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Rate coefficients for the reactions of C2(a(3)Pi(u)) and C2(X(1)Sigma(g)(+)) with various hydrocarbons (CH4, C 2 H 2 , C 2 H 4 , C 2 H 6 , and C3H8): a gas-phase experimental study over the temperature range 24-300 K.[external_link_head] PubMed Páramo, Alejandra; Canosa, André; Le Picard, Sébastien D; Sims, Ian R updating The kinetics of reactions of C2(a(3)Pi(u)) and C2(X(1)Sigma(g)(+)) with various hydrocarbons (CH4, C2H2, C2H4, C2H6, and C3H8) have been studied in a uniform supersonic flow expansion over the temperature range 24-300 K. Rate coefficients have been obtained by using the pulsed laser photolysis-laser induced fluorescence technique, where both radicals were produced at the same time but detected separately. The reactivity of the triplet state was found to be significantly lower than that of the singlet ground state for all reactants over the whole temperature range of the study. Whereas C2(X(1)Sigma(g)(+)) reacts with a rate coefficient close to the gas kinetic limit with all hydrocarbons studied apart from CH4, C2(a(3)Pi(u)) appears to be more sensitive to the molecular and electronic structure of the reactant partners. The latter reacts at least one order of magnitude faster with unsaturated hydrocarbons than with alkanes, and the rate coefficients increase very significantly with the size of the alkane. Results are briefly discussed in terms of their potential astrophysical impact.
Rate Coefficients of C2H with C 2 H 4 , C 2 H 6 , and H2 from 150 to 359 KNASA Technical Reports Server (NTRS) Opansky, Brian J.; Leone, Stephen R. updating Rate coefficients for the reactions C2H with C2H4, C2H6, and H2 are measured over the temperature range 150-359 K using transient infrared laser absorption spectroscopy. The ethynyl radical is formed by photolysis of C2H2 with a pulsed excimer laser at 193 nm, and its transient absorption is monitored with a color center laser on the Q(sub 11)(9) line of the A(sup 2) Pi-Chi(sup 2) Sigma transition at 3593.68 cm(exp -1). Over the experimental temperature range 150-359 K the rate constants of C2H with C2H4, C2H6, and H2 can be fitted to the Arrhenius expressions k(sub C2H4) = (7.8 +/- 0.6) x 10(exp -11) exp[(134 +/- 44)/T], k(sub C2H6) = (3.5 +/- 0.3) x 10(exp -11) exp[(2.9 +/- 16)/T], and k(sub H2) = (1.2 +/- 0.3) x 10(exp -11) exp[(-998 +/- 57)]/T cm(exp 3) molecule(exp -1) sec(exp -1). The data for C2H with C2H4 and C2H6 indicate a negligible activation energy to product formation shown by the mild negative temperature dependence of both reactions. When the H2 data are plotted together with the most recent high-temperature results from 295 to 854 K, a slight curvature is observed. The H2 data can be fit to the non-Arrhenius form k(sub H2) = 9.2 x 10(exp -18) T(sup 2.17 +/- 0.50) exp[(-478 +/- 165)/T] cm(exp 3) molecules(exp -1) sec(exp -1). The curvature in the Arrhenius plot is discussed in terms of both quantum mechanical tunneling of the H atom from H2 to the C2H radical and bending mode contributions to the partition function.
Meridional Variations of C 2 H 2 and C 2 H 6 in Jupiter's Atmosphere from Cassini CIRS Infrared SpectraNASA Technical Reports Server (NTRS) Nixon, C. A.; Achterberg, R. K.; Conrath, B. J.; Irwin, P. G. J.; Fouchet, T.; Parrish, P. D.; Romani, P. N.; Abbas, M.; LeClair, A.; Strobel, D. updating Hydrocarbons such as acetylene (C2H2) and ethane (C2H6) are important tracers in Jupiter's atmosphere, constraining our models of the chemical and dynamical processes. However, our knowledge of the vertical and meridional variations of their abundances has remained sparse. During the flyby of the Cassini spacecraft in December 2000, the Composite Infrared Spectrometer (CIRS) instrument was used to map the spatial variation of emissions from 10-1400 cm(sup -updating microns). In this paper we analyze a zonally-averaged set of CIRS spectra taken at the highest (0.5 cm(sup -1)) resolution, to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the v4 band of CH4, and in the troposphere at 150-400 mbar, via the H2 absorption at 600-800 cm(sup -1). Simultaneously, we retrieve the abundances of C2H2 and C2H6 via the v5 and vg bands respectively. Tropospheric absorption and stratospheric emission are highly anti-correlated at the CIRS resolution, introducing a non-uniqueness into the retrievals, such that vertical gradient and column abundance cannot both be found without additional constraints. Assuming profile gradients from photochemical calculations, we show that the column abundance of C2H2 decreases sharply towards the poles by a factor approximately 4, while C2H6 is unchanged in the north and increasing in the south, by a factor approximately 1.8. An explanation for the meridional trends is proposed in terms of a combination of photochemistry and dynamics. Poleward, the decreasing UV flux is predicted to decrease the abundances of C2H2 and C2H6 by factors 2.7 and 3.5 respectively at a latitude 70 deg. However, the lifetime of C2H6 in the stratosphere (5 x 10(exp 9)) is much longer than the dynamical timescale for meridional motions inferred from SL-9 debris (5 x 10(exp 8 s)), and therefore the constant or rising abundance towards high latitudes likely indicates that meridional mixing dominates over photochemical effects. For C2H2, the opposite
Meridional Variations of C 2 H 2 and C 2 H 6 in Jupiter's Atmosphere from Cassini CIRS Infrared SpectraNASA Technical Reports Server (NTRS) Nixon, C. A.; Achterberg, R. K.; Conrath, B. J.; Irwin, P. G. J.; Fouchet, T.; Parrish, P. D.; Abbas, M.; LeClaire, A.; Romani, P. N.; Simon-Miller, A. A. updating The abundances of hydrocarbons such as acetylene (C2H2) and ethane (C2H6) in Jupiter's atmosphere are important physical quantities, constraining our models of the chemical and dynamical processes. However, our knowledge of these quantities and their vertical and latitudinal variations has remained sparse. The flyby of the Cassini spacecraft with Jupiter at the end of 2000 provided an excellent opportunity to observe the infrared spectrum with the Composite Infrared Spectrometer (CIRS) instrument, mapping the spatial variation of emissions from 10-1400 cm-1. CIRS spectra taken at the highest resolution (0.5 cm-1) in early December 2000 have been analysed to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the v4 of CH4, and in the troposphere at 100-400 mbar, via the hydrogen collision-induced continuum absorption at 600-800 cm. Simultaneously, we have searched for meridional abundance variations in C2H2 and C2H6 via the v5 and vg bands respectively. Tropospheric absorption and stratospheric emission are highly anti-correlated at the CIM resolution, introducing a non-uniqueness into the retrievals, which means that vertical gradient and column abundance cannot be simultaneously found without additional constraints. If we assume the profile shapes from photochemical model calculations, we show that the column abundance of C2H2 must decrease sharply towards the poles, while C2H6 is constant or slightly increasing. The relevance of these results to current photochemical and dynamical knowledge of Jupiter's atmosphere is discussed.
Observations of CH4, C 2 H 6 , and C 2 H 2 in the stratosphere of JupiterNASA Technical Reports Server (NTRS) Sada, P. V.; Bjoraker, G. L.; Jennings, D. E.; McCabe, G. H.; Romani, P. N. updating We have performed high-resolution spectral observations at mid-infrared wavelengths of CH4 (8.14 micrometers), C2H6 (12.16 micrometers), and C2H2 (13.45 micrometers) on Jupiter. These emission features probe the stratosphere of the planet and provide information on the carbon-based photochemical processes taking place in that region of the atmosphere. The observations were performed using our cryogenic echelle spectrometer CELESTE, in conjunction with the McMath-Pierce 1.5-m solar telescope between November 1994 and February 1995. We used the methane observations to derive the temperature profile of the jovian atmosphere in the 1-10 mbar region of the stratosphere. This profile was then used in conjunction with height-dependent mixing ratios of each hydrocarbon to determine global abundances for ethane and acetylene. The resulting mixing ratios are updating) x 10(-6) for C2H6 (5 mbar pressure level), and 2.3 +/- 0.5 x 10(-8) for C2H2 (8 mbar pressure level), where the quoted uncertainties are derived from model variations in the temperature profile which match the methane observation uncertainties. c1998 Academic Press.
High-resolution spectroscopy of Saturn at 3 microns: CH 4, CH 3D, C 2 H 2 , C 2 H 6 , PH 3, clouds, and hazeNASA Astrophysics Data System (ADS) Kim, Joo Hyeon; Kim, Sang J.; Geballe, Thomas R.; Kim, Sungsoo S.; Brown, Linda R. updating We report observation and analysis of a high-resolution updating μm spectrum of the southern temperate region of Saturn obtained with NIRSPEC at Keck II. The spectrum reveals absorption and emission lines of five molecular species as well as spectral features of haze particles. The ν+ν band of CH 3D is detected in absorption between 2.87 and 2.92 μm; and we derived from it a mixing ratio approximately consistent with the Infrared Space Observatory result. The ν band of C 2H 2 also is detected in absorption between 2.95 and 3.05 μm; analysis indicates a sudden drop in the C 2H 2 mixing ratio at 15 mbar (130 km above the 1 bar level), probably due to condensation in the low stratosphere. The presence of the ν+ν+ν band of C 2H 6 near 3.07 μm, first reported by Bjoraker et al. [Bjoraker, G.L., Larson, H.P., Fink, U., 1981. Astrophys. J. 248, 856-862], is confirmed, and a C 2H 6 condensation altitude of 10 mbar (140 km) in the low stratosphere is determined. We assign weak emission lines within the 3.3 μm band of CH 4 to the ν band of C 2H 6, and derive a mixing ratio of 9±4×10 for this species. Most of the C 2H 6 3.3 μm line emission arises in the altitude range 460-620 km (at ˜μbar pressure levels), much higher than the 160-370 km range where the 12 μm thermal molecular line emission of this species arises. At updating μm the major absorber is tropospheric PH 3. The cloud level determined here and at updating is 390-460 mbar (˜30 km), somewhat higher than found by Kim and Geballe [Kim, S.J., Geballe, T.R., 2005. Icarus 179, 449-458] from analysis of a low resolution spectrum. A broad absorption feature at 2.96 μm, which might be due to NH 3 ice particles in saturnian clouds, is also present. The effect of a haze layer at about 125 km (˜12 mbar level) on the updating μm spectrum, which was not apparent in the low resolution spectrum, is clearly evident in the high resolution data, and the spectral properties of the haze particles suggest that
Photoabsorption and photoionization cross sections of NH3, PH3, H2S, C 2 H 2 , and C 2 H 4 in the VUV regionNASA Technical Reports Server (NTRS) Xia, T. J.; Chien, T. S.; Wu, C. Y. Robert; Judge, D. L. updating Using synchrotron radiation as a continuum light source, the photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 have been measured from their respective ionization thresholds to 1060 A. The vibrational constants associated with the nu(2) totally symmetric, out-of-plane bending vibration of the ground electronic state of PH3(+) have been obtained. The cross sections and quantum yields for producing neutral products through photoexcitation of these molecules in the given spectral regions have also been determined. In the present work, autoionization processes were found to be less important than dissociation and predissociation processes in NH3, PH3, and C2H4. Several experimental techniques have been employed in order to examine the various possible systematic errors critically.
MICROWAVE SPECTRA AND GEOMETRIES OF C 2 H _{2 \\cdots AgI} and C 2 H _{4 \\cdots AgI}NASA Astrophysics Data System (ADS) Stephens, Susanna L.; Tew, David Peter; Walker, Nick; Legon, Anthony updating A chirped-pulse Fourier transform microwave spectrometer has been used to measure the microwave spectra of both C2H_{2\\cdots AgI} and C2H_{4\\cdots AgI}. These complexes are generated via laser ablation at 532 nm of a silver surface in the presence of CF3I and either C2H_{2} or C2H_{4} and argon and are stabilized by a supersonic expansion. Rotational (A0, B0, C0) and centrifugal distortion constants (ΔJ and ΔJK) of each molecule have been determined as well the nuclear electric quadrupole coupling constants the iodine atom (χaa(I) and χbb-χcc(I)). The spectrum of each molecule is consistent with a C2v structure in which the metal atom interacts with the π-orbital of the ethene or ethyne molecule. Isotopic substitutions of atoms within the C2H_{2} or C2H_{4} subunits are in progress and in conjunction with high level ab initio calculations will allow for accurate determination of the geometry of each molecule. These to complexes are put in the context of the recently studied H2S\\cdots AgI, OC\\cdotsAgI, H3N\\cdots AgI and (CH3)_{3N\\cdots AgI}. S.Z. Riaz, S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, Chem. Phys. Let., 531, updating) S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, J. Chem. Phys., 136(6), updating) D.M. Bittner, D.P. Zaleski, S.L. Stephens, N.R. Walker, A.C. Legon, Study in progress.
Reactions of Fe+ and FeO+ with C 2 H 2 , C 2 H 4 , and C 2 H 6 : Temperature-Dependent KineticsDTIC Science & Technology updating studies to lead to the development of efficient quantum chemical calculation methods by offering benchmarks for testing and refinement. Due to the...EXPERIMENTAL METHODS All measurements were performed on the Air Force Research Laboratory’s variable temperature selected ion flow tube (VT- SIFT) instrument...correct within error, indicating that they are in the low-pressure limit,52,53 and the termolecular rate constant is obtained from the slope. In contrast
Concentrations of ethane (C 2 H 6 ) in the lower stratosphere and upper troposphere and acetylene (C 2 H 2 ) in the upper troposphere deduced from Atmospheric Trace Molecule Spectroscopy/Spacelab 3 spectraNASA Technical Reports Server (NTRS) Rinsland, C. P.; Russell, J. M., III; Zander, R.; Farmer, C. B.; Norton, R. H. updating This paper reports the results of the spectroscopic analysis of C2H6 and C2H2 absorption spectra obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument flown on the Shuttle as part of the Spacelab 3 mission. The spectra were recorded during sunset occultations occurring between 25 deg N and 31 deg N latitudes, yielding volume-mixing ratio profiles of C2H6 in the lower stratosphere and the upper troposphere, and an upper tropospheric profile of C2H2. These results compare well with previous in situ and remote sounding data obtained at similar latitudes and with model calculations. The results demonstrate the feasibility of the ATMOS instrument to sound the lower atmosphere from space.
Calculations of thermal radiation transfer of C 2 H 2 and C 2 H 4 together with H2O, CO2, and CO in a one-dimensional enclosure using LBL and SNB modelsNASA Astrophysics Data System (ADS) Qi, Chaobo; Zheng, Shu; Zhou, Huaichun updating Generally, the involvement of hydrocarbons such as C2H4 and its derivative C2H2 in thermal radiation has not been accounted in the numerical simulation of their flames, which may cause serious error for estimation of temperature in the early stage of combustion. At the first, the Statistical Narrow-Band (SNB) model parameters for C2H2 and C2H4 are generated from line by line (LBL) calculations. The distributions of the concentrations of radiating gases such as H2O, CO2, CO, C2H2 and C2H4, and the temperature along the centerline of a laminar ethylene/air diffusion flame were chosen to form a one-dimensional, planar enclosure to be tested in this study. Thermal radiation transfer in such an enclosure was calculated using the LBL approach and the SNB model, most of the relative errors are less than 8% and the results of these two models shows an excellent agreement. Below the height of 20 mm, which is the early stage of the flame, the average fraction contributed by C2H2 and C2H4 in the radiative heat source is 33.8%, while that by CO is only 5.8%. This result indicates that the involvement of C2H2 and C2H4 in radiation heat transfer needs to be taken into account in the numerical modeling of the ethylene/air diffusion flame, especially in the early stage of combustion.
Total reaction cross sections of electronic state-specified transition metal cations: V + +C 2 H 6 , C3H8, and C 2 H 4 at 0.2 eVNASA Astrophysics Data System (ADS) Sanders, Lary; Hanton, Scott D.; Weisshaar, James C. updating We describe a crossed beam experiment which measures total cross sections for reaction of electronic state-specified V+ with small hydrocarbons at well-defined collision energy E=0.2 eV. The V+ state distribution created at each ionizing wavelength is directly measured by angle-integrated photoelectron spectroscopy (preceding paper). Reactant and product ions are collected and analyzed by pulsed time-of-flight mass spectrometry following a reaction time of 6 μs. Tests of the performance of the apparatus are described in detail. Our experiment defines the reactant V+ electronic state distribution and the collision energy much more precisely than previous work. For all three hydrocarbons C2H6, C3H8, and C2H4, H2 elimination products dominate at 0.2 eV. We observe a dramatic dependence of cross section on the V+ electronic term. The second excited term 3d34s(3F) is more reactive than either lower energy quintet term 3d4(5D) or 3d34s(5F) by a factor of ≥270, 80, and ≥6 for the C2H6, C3H8, and C2H4 reactions, respectively. The 3d34s(3F) reaction cross sections at 0.2 eV are 20±11 Å2, 37±19 Å2, and 2.7±1.6 Å2, respectively, compared with Langevin cross sections of ˜80 Å2. For the C2H6 and C3H8 reactions, cross sections are independent of initial spin-orbit level J within the 3F term to the limits of our accuracy. Comparison with earlier work by Armentrout and co-workers shows that electronic excitation to d3s(3F) is far more effective at promoting H2 elimination than addition of the same total kinetic energy to reactants. Electron spin is clearly a key determinant of V+ reactivity with small hydrocarbons. We suggest that triplet V+ reacts much more efficiently than quintet V+ because of its ability to conserve total electron spin along paths to insertion in a C-H bond of the hydrocarbon.
The composition of Saturn's atmosphere at northern temperate latitudes from Voyager IRIS spectra - NH3, PH3, C 2 H 2 , C 2 H 6 , CH3D, CH4, and the Saturnian D/H isotopic ratioNASA Technical Reports Server (NTRS) Courtin, R.; Gautier, D.; Marten, A.; Bezard, B.; Hanel, R. updating The vertical distributions and mixing ratios of minor constituents in the northern hemisphere of Saturn are investigated. Results are obtained for NH3, PH3, C2H2, C2H6, CH3D, and CH4; the D/H ratio is obtained from the CH4 and CH3D abundances. The NH3 mixing ratio in the upper atmosphere is found to be compatible with the saturated partial pressure. The inferred PH3/H2 ratio of 1.4 + or - 0.8 x 10 to the -6th is higher than the value derived from the solar P/H ratio. The stratospheric C2H2/H2 and C2H6/H2 ratios are, respectively, 2.1 + or - 1.4 x 10 to the -7th and 3.0 + or - 1.1 x 10 to the -6th; the latter decreases sharply below the 20-50 mbar level. The results for CH3D/H2 and CH4/H2 imply an enrichment of Saturn's upper atmosphere in carbon by a factor of at least three over the solar abundance. The interpretation of two NH3 lines in the five-micron window suggests a NH3/H2 ratio at the two bar level below the solar value.
Covariance mapping of two-photon double core hole states in C 2 H 2 and C 2 H 6 produced by an x-ray free electron laserDOE PAGES Mucke, M; Zhaunerchyk, V; Frasinski, L J; ... updating Few-photon ionization and relaxation processes in acetylene (C 2H 2) and ethane (C 2H 6) were investigated at the linac coherent light source x-ray free electron laser (FEL) at SLAC, Stanford using a highly efficient multi-particle correlation spectroscopy technique based on a magnetic bottle. The analysis method of covariance mapping has been applied and enhanced, allowing us to identify electron pairs associated with double core hole (DCH) production and competing multiple ionization processes including Auger decay sequences. The experimental technique and the analysis procedure are discussed in the light of earlier investigations of DCH studies carried out at the samemore » FEL and at third generation synchrotron radiation sources. In particular, we demonstrate the capability of the covariance mapping technique to disentangle the formation of molecular DCH states which is barely feasible with conventional electron spectroscopy methods.« less
On the Stark effect in open shell complexes exhibiting partially quenched electronic angular momentum: Infrared laser Stark spectroscopy of OH–C 2 H 2 , OH–C 2 H 4 , and OH–H 2ODOE PAGES Moradi, Christopher P.; Douberly, Gary E. updating The Stark effect is considered for polyatomic open shell complexes that exhibit partially quenched electronic angular momentum. Matrix elements of the Stark Hamiltonian represented in a parity conserving Hund's case (a) basis are derived for the most general case, in which the permanent dipole moment has projections on all three inertial axes of the system. Transition intensities are derived, again for the most general case, in which the laser polarization has projections onto axes parallel and perpendicular to the Stark electric field, and the transition dipole moment vector is projected onto all three inertial axes in the molecular frame. Asmore » a result, simulations derived from this model are compared to experimental rovibrational Stark spectra of OH-C 2H 2, OH-C 2H 4, and OH-H 2O complexes formed in helium nanodroplets.« less
A novel Zn-based heterocycle metal-organic framework for high C 2 H 2 /C 2 H 4 , CO2/CH4 and CO2/N2 separationsNASA Astrophysics Data System (ADS) Zhang, Ling; Jiang, Ke; Yang, Yu; Cui, Yuanjing; Chen, Banglin; Qian, Guodong updating Efficient separation of the small gas molecules especially the hydrocarbons is essential to social economy. The microporous metal-organic frameworks (MOFs) are taking precedence in this respect by virtue of their irreplaceable advantages. Herein, the new organic linker 5-(5-carboxypyridin-3-yl)isophthalic acid simplified as H3L-N has been excavated to construct successfully the novel Zn-based heterocycle metal-organic framework ZnL·(DMF)1.5·(H2O)6.0 (ZJU-197, ZJU = Zhejiang University, DMF = N,N-dimethylformamide). ZJU-197 has been structurally characterized and explored in details for gas separation. It is commendable that the activated ZJU-197a has exhibited excellent C2H2/C2H4, CO2/CH4 and CO2/N2 separations simultaneously with IAST selectivity of 137.8, 53.0 and 514.1 respectively at ambient conditions.
Shock-tube measurements of carbon to oxygen atom ratios for incipient soot formation with C 2 H 2 , C 2 H 4 and C 2 H 6 fuelsNASA Technical Reports Server (NTRS) Radcliffe, S. W.; Appleton, J. P. updating The critical atomic carbon to oxygen ratios, Phi sub C, for incipient soot formation in shock heated acetylene, ethylene, ethane/oxygen/ argon mixtures was measured over the temperature range 2000 K to 2500 K for reactant partial pressures between 0.1 and 0.4 atoms. Absorption of light from a He-Ne laser at 6328A was was used to detect soot. It was observed that the values of Phi sub C for all three fuels increased uniformly with temperature such that at the highest temperatures Phi sub C was considerably greater than unity, i.e. greater than the value of about unity at which solid carbon should have been precipitated on a thermochemical equilibrium basis. Observations were made over periods extending up to about one millisecond, which was well in excess of the time required for the major heat release of the combustion reactions. The relevance of these experimental findings to the problem of soot formation in gas turbine combustion chambers is discussed.
Satellite Boreal Measurements over Alaska and Canada During June-July 2004: Simultaneous Measurements of Upper Tropospheric CO, C 2 H 6 , HCN, CH3Cl, CH4, C 2 H 2 , CH2OH, HCOOH, OCS, and SF6 Mixing RatiosNASA Technical Reports Server (NTRS) Rinsland, Curtis P.; Dufour, Gaelle; Boone, Chris D.; Bernath, Peter F.; Chiou, Linda; Coheur, Pierre-Francois; Turquety, Solene; Clerbaux, Cathy updating Simultaneous ACE (Atmospheric Chemistry Experiment) upper tropospheric CO, C2H6, HCN, CH3Cl, CH4 , C2H2 , CH30H, HCOOH, and OCS measurements show plumes up to 185 ppbv (10 (exp -9) per unit volume) for CO, 1.36 ppbv for C2H6, 755 pptv (10(exp -12) per unit volume) for HCN, 1.12 ppbv for CH3C1, 1.82 ppmv, (10(exp -6) per unit volume) for CH4, 0.178 ppbv for C2H2, 3.89 ppbv for CH30H, 0.843 ppbv for HCOOH, and 0.48 ppbv for OCS in western Canada and Alaska at 50 deg N-68 deg N latitude between 29 June and 23 July 2004. Enhancement ratios and emission factors for HCOOH, CH30H, HCN, C2H6, and OCS relative to CO at 250-350 hPa are inferred from measurements of young plumes compared with lower mixing ratios assumed to represent background conditions based on a CO emission factor derived from boreal measurements. Results are generally consistent with the limited data reported for various vegetative types and emission phases measured in extratropical forests including boreal forests. The low correlation between fire product emission mixing ratios and the S176 mixing ratio is consistent with no significant SF6 emissions from the biomass fires.
Collisions of slow polyatomic ions with surfaces: dissociation and chemical reactions of C 2 H 2 +*, C2H3+, C 2 H 4 +*, C2H5+, and their deuterated variants C2D2+* and C2D4+* on room-temperature and heated carbon surfaces.PubMed Jasík, Juraj; Zabka, Jan; Feketeova, Linda; Ipolyi, Imre; Märk, Tilmann D; Herman, Zdenek updating Interaction of C2Hn+ (n = 2-5) hydrocarbon ions and some of their isotopic variants with room-temperature and heated (600 degrees C) highly oriented pyrolytic graphite (HOPG) surfaces was investigated over the range of incident energies 11-46 eV and an incident angle of 60 degrees with respect to the surface normal. The work is an extension of our earlier research on surface interactions of CHn+ (n = 3-5) ions. Mass spectra, translational energy distributions, and angular distributions of product ions were measured. Collisions with the HOPG surface heated to 600 degrees C showed only partial or substantial dissociation of the projectile ions; translational energy distributions of the product ions peaked at about 50% of the incident energy. Interactions with the HOPG surface at room temperature showed both surface-induced dissociation of the projectiles and, in the case of radical cation projectiles C2H2+* and C2H4+*, chemical reactions with the hydrocarbons on the surface. These reactions were (i) H-atom transfer to the projectile, formation of protonated projectiles, and their subsequent fragmentation and (ii) formation of a carbon chain build-up product in reactions of the projectile ion with a terminal CH3-group of the surface hydrocarbons and subsequent fragmentation of the product ion to C3H3+. The product ions were formed in inelastic collisions in which the translational energy of the surface-excited projectile peaked at about 32% of the incident energy. Angular distributions of reaction products showed peaking at subspecular angles close to 68 degrees (heated surfaces) and 72 degrees (room-temperature surfaces). The absolute survival probability at the incident angle of 60 degrees was about 0.1% for C2H2+*, close to 1% for C2H4+* and C2H5+, and about 3-6% for C2H3+.
Detection of C 2 H 4 Neptune from ISO/PHT-S ObservationsNASA Technical Reports Server (NTRS) Schulz, B.; Encrenaz, Th.; Bezard, B.; Romani, P. N.; Lellouch, E.; Atreya, S. K. updating The 6-12 micrometer spectrum of Neptune has been recorded with the PHT-S instrument of the Infrared Space Observatory (ISO) at a resolution of 0.095 micrometer. In addition to the emissions of CH4, CH3D and C2H6 previously identified, the spectrum shows the first firm identification of ethylene C2H4. The inferred column density above the 0.2-mbar level is in the range (1.1 - 3) x 10(exp 14) molecules/cm. To produce this low amount, previous photochemical models invoked rapid mixing between the source and sink regions of C2H4. We show that this requirement can be relaxed if recent laboratory measurements of CH4 photolysis branching ratios at Lyman alpha are used.

Infrared spectra of C 2 H 4 dimer and trimerNASA Astrophysics Data System (ADS) Barclay, A. J.; Esteki, K.; McKellar, A. R. W.; Moazzen-Ahmadi, N. updating Spectra of ethylene dimers and trimers are studied in the ν11 and (for the dimer) ν9 fundamental band regions of C2H4 (≈2990 and 3100 cm-1) using a tunable optical parametric oscillator source to probe a pulsed supersonic slit jet expansion. The deuterated trimer has been observed previously, but this represents the first rotationally resolved spectrum of (C2H4)3. The results support the previously determined cross-shaped (D2d) dimer and barrel-shaped (C3h or C3) trimer structures. However, the dimer spectrum in the ν9 fundamental region of C2H4 is apparently very perturbed and a previous rotational analysis is not well verified.
Theoretical kinetics of O + C 2 H 4DOE PAGES Li, Xiaohu; Jasper, Ahren W.; Zádor, Judit; ... updating The reaction of atomic oxygen with ethylene is a fundamental oxidation step in combustion and is prototypical of reactions in which oxygen adds to double bonds. For 3O+C 2H 4 and for this class of reactions generally, decomposition of the initial adduct via spin-allowed reaction channels on the triplet surface competes with intersystem crossing (ISC) and a set of spin-forbidden reaction channels on the ground-state singlet surface. The two surfaces share some bimolecular products but feature different intermediates, pathways, and transition states. In addition, the overall product branching is therefore a sensitive function of the ISC rate. The 3O+C 2Hmore » 4 reaction has been extensively studied, but previous experimental work has not provided detailed branching information at elevated temperatures, while previous theoretical studies have employed empirical treatments of ISC. Here we predict the kinetics of 3O+C 2H 4 using an ab initio transition state theory based master equation (AITSTME) approach that includes an a priori description of ISC. Specifically, the ISC rate is calculated using Landau–Zener statistical theory, consideration of the four lowest-energy electronic states, and a direct classical trajectory study of the product branching immediately after ISC. The present theoretical results are largely in good agreement with existing low-temperature experimental kinetics and molecular beam studies. Good agreement is also found with past theoretical work, with the notable exception of the predicted product branching at elevated temperatures. Above ~1000 K, we predict CH 2CHO+H and CH 2+CH 2O as the major products, which differs from the room temperature preference for CH 3+HCO (which is assumed to remain at higher temperatures in some models) and from the prediction of a previous detailed master equation study.« less
Identification and measurement of atmospheric ethane (C 2 H 6 ) from a 1951 infrared solar spectrumNASA Technical Reports Server (NTRS) Rinsland, Curtis P.; Levine, Joel S. updating C2H6 absorption features in the 2980/cm spectral region of the solar spectrum recorded in April, 1951 were analyzed to determine the total vertical column amount and average free tropospheric mixing ratio of C2H6 above Jungfraujoch in the Swiss Alps. The PQ1 subbranch is the best isolated of the three C2H6 features in the 1951 spectrum, with an equivalent width of 0.0099 + or - 0.0025/cm. Results give a total vertical column amount of 9.7 x 10 to the 15th C2H6 molecules/sq cm, with an accuracy of + or - 30 percent. March 1981 measurements from this region give a mixing ratio of about 2.0 ppbv, 2.2 times larger than the 1951 value, suggesting a long-term increase in the free tropospheric C2H6 concentration over western Europe.
The Anharmonic Force Field of Ethylene, C 2 H 4 , by Means of Accurate Ab Initio CalculationsNASA Technical Reports Server (NTRS) Martin, Jan M. L.; Lee, Timothy J.; Taylor, Peter R.; Francois, Jean-Pierre; Langhoff, Stephen R. (Technical Monitor) updating The quartic force field of ethylene, C2H4, has been calculated ab initio using augmented coupled cluster, CCSD(T), methods and correlation consistent basis sets of spdf quality. For the C-12 isotopomers C2H4, C2H3D, H2CCD2, cis-C2H2D2, trans-C2H2D2, C2HD3, and C2D4, all fundamentals could be reproduced to better than 10 per centimeter, except for three cases of severe Fermi type 1 resonance. The problem with these three bands is identified as a systematic overestimate of the Kiij Fermi resonance constants by a factor of two or more; if this is corrected for, the predicted fundamentals come into excellent agreement with experiment. No such systematic overestimate is seen for Fermi type 2 resonances. Our computed harmonic frequencies suggest a thorough revision of the accepted experimentally derived values. Our computed and empirically corrected re geometry differs substantially from experimentally derived values: both the predicted rz geometry and the ground-state rotational constants are, however, in excellent agreement with experiment, suggesting revision of the older values. Anharmonicity constants agree well with experiment for stretches, but differ substantially for stretch-bend interaction constants, due to equality constraints in the experimental analysis that do not hold. Improved criteria for detecting Fermi and Coriolis resonances are proposed and found to work well, contrary to the established method based on harmonic frequency differences that fails to detect several important resonances for C2H4 and its isotopomers. Surprisingly good results are obtained with a small spd basis at the CCSD(T) level. The well-documented strong basis set effect on the v8 out-of-plane motion is present to a much lesser extent when correlation-optimized polarization functions are used. Complete sets of anharmonic, rovibrational coupling, and centrifugal distortion constants for the isotopomers are available as supplementary material to the paper.
Experimental ion mobility measurements in Xe-C 2 H 6NASA Astrophysics Data System (ADS) Perdigoto, J. M. C.; Cortez, A. F. V.; Veenhof, R.; Neves, P. N. B.; Santos, F. P.; Borges, F. I. G. M.; Conde, C. A. N. updating In this paper we present the results of the ion mobility measurements made in gaseous mixtures of xenon (Xe) with ethane (C2H6) for pressures ranging from 6 to 10 Torr (8-10.6 mbar) and for low reduced electric fields in the 10 Td to 25 Td range (2.4-6.1 kVṡcm-1ṡ bar-1), at room temperature. The time of arrival spectra revealed two peaks throughout the entire range studied which were attributed to ion species with 3-carbons (C3H5+, C3H6+ C3H8+ and C3H9+) and with 4-carbons (C4H7+, C4H9+ and C4H10+). Besides these, and for Xe concentrations above 70%, a bump starts to appear at the right side of the main peak for reduced electric fields higher than 20 Td, which was attributed to the resonant charge transfer of C2H6+ to C2H6 that affects the mobility of its ion products (C3H8+ and C3H9+). The time of arrival spectra for Xe concentrations of 20%, 50%, 70% and 90% are presented, together with the reduced mobilities as a function of the Xe concentration calculated from the peaks observed for the low reduced electric fields and pressures studied.
A SIFT ion-molecule study of some reactions in Titan's atmosphere. reactions of N(+), N(2)(+), and HCN(+) with CH(4), C (2 )H (2 ), and C (2 )H (4 )NASA Technical Reports Server (NTRS) Anicich, Vincent G.; Wilson, Paul; McEwan, Murray J. updating The results of a study of the ion-molecule reactions of N(+), N(2)(+), and HCN(+) with methane, acetylene, and ethylene are reported. These studies were performed using the FA-SIFT at the University of Canterbury. The reactions studied here are important to understanding the ion chemistry in Titan's atmosphere. N(+) and N(2)(+) are the primary ions formed by photo-ionization and electron impact in Titan's ionosphere and drive Titan's ion chemistry. It is therefore very important to know how these ions react with the principal trace neutral species in Titan's atmosphere: Methane, acetylene, and ethylene. While these reactions have been studied before the product channels have been difficult to define as several potential isobaric products make a definitive answer difficult. Mass overlap causes difficulties in making unambiguous species assignments in these systems. Two discriminators have been used in this study to resolve the mass overlap problem. They are deuterium labeling and also the differences in reactivities of each isobar with various neutral reactants. Several differences have been found from the products in previous work. The HCN(+) ion is important in both Titan's atmosphere and in the laboratory.
Bond-rearrangement and ionization mechanisms in the photo-double-ionization of simple hydrocarbons (C 2 H 4 , C 2H 3F, and 1,1-C 2 H 2 F 2) near and above thresholdDOE PAGES Gaire, B.; Gatton, A. S.; Wiegandt, F.; ... updating We have investigated bond-rearrangement driven by photo-double-ionization (PDI) near and above the double ionization threshold in a sequence of carbon-carbon double bonded hydrocarbon molecules: ethylene, fluoroethylene, and 1,1-difluoroethylene. We employ the kinematically complete cold target recoil ion momentum spectroscopy (COLTRIMS) method to resolve all photo-double-ionization events leading to two-ionic fragments. We observe changes in the branching ratios of different dissociative ionization channels depending on the presence of none, one, or two fluorine atoms. The role of the fluorine atom in the bond-rearrangement channels is intriguing as evident by the re-ordering of the threshold energies of the PDI in the fluorinatedmore » molecules. These effects offer a compelling argument that the electronegativity of the fluorine (or the polarity of the molecule) strongly influences the potential energy surfaces of the molcules and drives bond-rearrangement during the dissociation process. The energy sharing and the relative angle between the 3D-momentum vectors of the two electrons provide clear evidence of direct and indirect PDI processes.« less
Implications for Extraterrestrial Hydrocarbon Chemistry: Analysis of Ethylene (C 2 H 4 ) and D4-Ethylene (C2D4) Ices Exposed to Ionizing Radiation via Combined Infrared Spectroscopy and Reflectron Time-of-flight Mass SpectrometryNASA Astrophysics Data System (ADS) Abplanalp, Matthew J.; Kaiser, Ralf I. updating The processing of the hydrocarbon ice, ethylene (C2H4/C2D4), via energetic electrons, thus simulating the processes in the track of galactic cosmic-ray particles, was carried out in an ultrahigh vacuum apparatus. The chemical evolution of the ices was monitored online and in situ utilizing Fourier transform infrared spectroscopy (FTIR) and during temperature programmed desorption, via a quadrupole mass spectrometer utilizing electron impact ionization (EI-QMS) and a reflectron time-of-flight mass spectrometer utilizing a photoionization source (PI-ReTOF-MS). Several previous in situ studies of ethylene ice irradiation using FTIR were substantiated with the detection of six products: [CH4 (CD4)], acetylene [C2H2 (C2D2)], the ethyl radical [C2H5 (C2D5)], ethane [C2H6 (C2D6)], 1-butene [C4H8 (C4D8)], and n-butane [C4H10 (C4D10)]. Contrary to previous gas phase studies, the PI-ReTOF-MS detected several groups of hydrocarbon with varying degrees of saturation: C n H2n+2 (n = 4-10), C n H2n (n = 2-12, 14, 16), C n H2n-2 (n = 3-12, 14, 16), C n H2n-4 (n = 4-12, 14, 16), C n H2n-6 (n = 4-10, 12), C n H2n-8 (n = 6-10), and C n H2n-10 (n = 6-10). Multiple laboratory studies have shown the facile production of ethylene from methane, which is a known ice constituent in the interstellar medium. Various astrophysically interesting molecules can be associated with the groups detected here, such as allene/methylacetylene (C3H4) or 1, 3-butadiene (C4H6) and its isomers, which have been shown to lead to polycyclic aromatic hydrocarbons. Finally, several hydrocarbon groups detected here are unique to ethylene ice versus ethane ice and may provide understanding of how complex hydrocarbons form in astrophysical environments.
CW deuterium fluoride chemical laser with reactant combination C 2 H 4 /NF3NASA Astrophysics Data System (ADS) Jiang, Zhongfu; Hua, Weihong updating The characters of combustion driven cw deuterium fluoride (DF) chemical laser with C2H4/NF3 reactant were numerically investigated. The numerical simulation was carried out using compressibility scaling method--a finite difference technique for the numerical integration of the steady and unsteady Navier-stokes equations for reactive flow. The small signal gain and the flow field were calculated. The numerical results shown that active zone length of the cw DF chemical laser with C2H4/NF3 is very long, which is about 6 cm, and the average cavity pressure is about 7 torr as the combustion pressure is about 1.5 atm. These results shown that the DF chemical laser with C2H4/NF3 is suitable for high cavity pressure performance.
The Abundance of C 2 H 4 in the Circumstellar Envelope of IRC+10216.PubMed Fonfría, J P; Hinkle, K H; Cernicharo, J; Richter, M J; Agúndez, M; Wallace, L updating High spectral resolution mid-IR observations of ethylene (C 2 H 4 ) towards the AGB star IRC+10216 were obtained using the Texas Echelon Cross Echelle Spectrograph (TEXES) at the NASA Infrared Telescope Facility (IRTF). Eighty ro-vibrational lines from the 10.5 µ m vibrational mode ν 7 with J ≲ 30 were detected in absorption. The observed lines are divided into two groups with rotational temperatures of 105 and 400 K (warm and hot lines). The warm lines peak at ≃ -14 km s -1 with respect to the systemic velocity, suggesting that they are mostly formed outwards from ≃ 20 R ⋆ . The hot lines are centered at -10 km s -1 indicating that they come from a shell between 10 and 20 R ⋆ . 35% of the observed lines are unblended and can be fitted with a code developed to model the emission of a spherically symmetric circumstellar envelope. The analysis of several scenarios reveal that the C 2 H 4 abundance relative to H 2 in the range 5 - 20 R ⋆ is 6.9 × 10 -8 in average and it could be as high as 1.1 × 10 -7 . Beyond 20 R ⋆ , it is 8.2 × 10 -8 . The total column density is (6.5 ± 3.0) × 10 15 cm -2 . C 2 H 4 is found to be rotationally under local thermodynamical equilibrium (LTE) and vibrationally out of LTE. One of the scenarios that best reproduce the observations suggests that up to 25% of the C 2 H 4 molecules at 20 R ⋆ could condense onto dust grains. This possible depletion would not influence significantly the gas acceleration although it could play a role in the surface chemistry on the dust grains.
The Abundance of C 2 H 4 in the Circumstellar Envelope of IRC+10216PubMed Central Fonfría, J. P.; Hinkle, K. H.; Cernicharo, J.; Richter, M. J.; Agúndez, M. updating High spectral resolution mid-IR observations of ethylene (C2H4) towards the AGB star IRC+10216 were obtained using the Texas Echelon Cross Echelle Spectrograph (TEXES) at the NASA Infrared Telescope Facility (IRTF). Eighty ro-vibrational lines from the 10.5 µm vibrational mode ν7 with J ≲ 30 were detected in absorption. The observed lines are divided into two groups with rotational temperatures of 105 and 400 K (warm and hot lines). The warm lines peak at ≃ −14 km s−1 with respect to the systemic velocity, suggesting that they are mostly formed outwards from ≃ 20R⋆. The hot lines are centered at −10 km s−1 indicating that they come from a shell between 10 and 20R⋆. 35% of the observed lines are unblended and can be fitted with a code developed to model the emission of a spherically symmetric circumstellar envelope. The analysis of several scenarios reveal that the C2H4 abundance relative to H2 in the range 5 − 20R⋆ is 6.9 × 10−8 in average and it could be as high as 1.1 × 10−7. Beyond 20R⋆, it is 8.2 × 10−8. The total column density is (6.5 ± 3.0) × 1015 cm−2. C2H4 is found to be rotationally under local thermodynamical equilibrium (LTE) and vibrationally out of LTE. One of the scenarios that best reproduce the observations suggests that up to 25% of the C2H4 molecules at 20R⋆ could condense onto dust grains. This possible depletion would not influence significantly the gas acceleration although it could play a role in the surface chemistry on the dust grains. PMID:updating
Detection of interstellar ethylene oxide (c-C 2 H 4 O).PubMed Dickens, J E; Irvine, W M; Ohishi, M; Ikeda, M; Ishikawa, S; Nummelin, A; Hjalmarson, A updating We report the identification of 10 transitions that support the detection of the small cyclic molecule ethylene oxide (c-C2H4O) in Sgr B2N. Although one of these transitions is severely blended, so that an accurate intensity and line width could not be determined, and two other lines are only marginally detected, we have done Gaussian fits to the remaining seven lines and have performed a rotation diagram analysis. Our results indicate a rotation temperature T(rot) = 18 K and a molecular column density N(c-C2H4O) = 3.3 x 10(14) cm-2, corresponding to a fractional abundance relative to molecular hydrogen of order 6 x 10(-11). This is a factor of more than 200 higher than the abundance for this molecule suggested by the "new standard" chemistry model of Lee, Bettens, & Herbst. This result suggests that grain chemistry might play an effective role in the production of c-C2H4O. No transitions of this molecule were detected in either Sgr B2M or Sgr B2NW.
Theoretical analysis of factors controlling the nonalternating CO/C (2 )H (4 ) copolymerization.PubMed Haras, Alicja; Michalak, Artur; Rieger, Bernhard; Ziegler, Tom updating A [P-O]Pd catalyst based on o-alkoxy derivatives of diphenylphosphinobenzene sulfonic acid (I) has recently been shown by Drent et al. to perform nonalternating CO/C(2)H(4) copolymerization with subsequent incorporation of ethylene units into the polyketone chain. The origin of the nonalternation is investigated in a theoretical study of I, where calculated activation barriers and reaction heats of all involved elementary steps are used to generate a complete kinetic model. The kinetic model is able to account for the observed productivity and degree of nonalternation as a function of temperature. Consistent with the energy changes obtained for the real catalyst model, the selectivity toward a nonalternating distribution of both comonomers appears to be mainly a result of a strong destabilization of the Pd-acyl complex.
A combined crossed molecular beams and theoretical study of the reaction CN + C 2 H 4NASA Astrophysics Data System (ADS) Balucani, Nadia; Leonori, Francesca; Petrucci, Raffaele; Wang, Xingan; Casavecchia, Piergiorgio; Skouteris, Dimitrios; Albernaz, Alessandra F.; Gargano, Ricardo updating The CN + C2H4 reaction has been investigated experimentally, in crossed molecular beam (CMB) experiments at the collision energy of 33.4 kJ/mol, and theoretically, by electronic structure calculations of the relevant potential energy surface and Rice-Ramsperger-Kassel-Marcus (RRKM) estimates of the product branching ratio. Differently from previous CMB experiments at lower collision energies, but similarly to a high energy study, we have some indication that a second reaction channel is open at this collision energy, the characteristics of which are consistent with the channel leading to CH2CHNC + H. The RRKM estimates using M06L electronic structure calculations qualitatively support the experimental observation of C2H3NC formation at this and at the higher collision energy of 42.7 kJ/mol of previous experiments.
Modelling of c-C 2 H 4 O Formation on Grain-SurfacesNASA Astrophysics Data System (ADS) Occhiogrosso, Angela; Viti, S.; Ward, M. D.; Price, S. D. updating Ethylene oxide (c-C2H4O) is a ring-shaped organic compound that may lead to the synthesis of amino acids and the early metabolic pathways in the interstellar medium (ISM) (Cleaves 2003; Miller & Schlesinger 1993). This molecule has been detected towards several high-mass star forming regions (Ikeda et al. 2001) but to date, its observational abundances cannot be reproduced by chemical models. We include new experimental results in the UCL_CHEM chemical model with the aim of reproducing the abundances of ethylene oxide across high-mass sources. In particular, we focused on the solid state reaction investigated by Ward & Price (2011). By comparing our theoretical column densities with those from the observations we found that the reaction between atomic oxygen and ethylene on grains is a viable route of formation for ethylene oxide (Occhiogrosso et al., accepted by MNRAS).
Exploring the dynamics of reaction N((2)D)+C 2 H 4 with crossed molecular-beam experiments and quantum-chemical calculations.PubMed Lee, Shih-Huang; Chin, Chih-Hao; Chen, Wei-Kan; Huang, Wen-Jian; Hsieh, Chu-Chun updating We conducted the title reaction using a crossed molecular-beam apparatus, quantum-chemical calculations, and RRKM calculations. Synchrotron radiation from an undulator served to ionize selectively reaction products by advantage of negligibly small dissociative ionization. We observed two products with gross formula C(2)H(3)N and C(2)H(2)N associated with loss of one and two hydrogen atoms, respectively. Measurements of kinetic-energy distributions, angular distributions, low-resolution photoionization spectra, and branching ratios of the two products were carried out. Furthermore, we evaluated total branching ratios of various exit channels using RRKM calculations based on the potential-energy surface of reaction N((2)D)+C(2)H(4) established with the method CCSD(T)/6-311+G(3df,2p)//B3LYP/6-311G(d,p)+ZPE[B3LYP/6-311G(d,p)]. The combination of experimental and computational results allows us to reveal the reaction dynamics. The N((2)D) atom adds to the C=C π-bond of ethene (C(2)H(4)) to form a cyclic complex c-CH(2)(N)CH(2) that directly ejects a hydrogen atom or rearranges to other intermediates followed by elimination of a hydrogen atom to produce C(2)H(3)N; c-CH(2)(N)CH+H is the dominant product channel. Subsequently, most C(2)H(3)N radicals, notably c-CH(2)(N)CH, further decompose to CH(2)CN+H. This work provides results and explanations different from the previous work of Balucani et al. [J. Phys. Chem. A, 2000, 104, 5655], indicating that selective photoionization with synchrotron radiation as an ionization source is a good choice in chemical dynamics research.
The Relationship of HCN, C 2 H 6 , & H2O in Comets: A Key Clue to Origins?NASA Astrophysics Data System (ADS) Mumma, Michael J.; Charnley, Steven B.; Cordiner, Martin; Paganini, Lucas; Villanueva, Geronimo Luis updating Background: HCN, C2H6, and H2O are three of the best characterized volatiles in comets. It is often assumed that all three are primary volatiles, native to the nucleus. Here, we compare their properties in 26 comets (9 JFC and 17 Oort-cloud), making 6 points:1. Both HCN and C2H6 are poor proxies for water production. The production rate ratio (Q-ratio) of each trace gas relative to water varies by a factor of six among these comets.2. All 26 comets have Q-ratios HCN/C2H6 > 0.1. In 18 comets the Q-ratios HCN/H2O and C2H6/H2O are correlated, with a mean ratio of 0.33. In 6 comets undergoing complete disruption, this Q-ratio exceeds 0.5.3. Q-ratios HCN/C2H6 are not correlated with Q(H2O), nor are they correlated with dynamical class (Oort cloud vs. JFC).4. The nucleus-centered rotational temperatures measured for H2O and other primary species (C2H6, CH3OH) usually agree within error, but those for HCN are often slightly cooler. Could this mean that HCN is not fully developed in the warm near-nucleus region, and instead is at least in part a product species?5. With its strong dipole moment and H-bonding character, HCN should be linked more strongly in the nuclear ice to other molecules with similar properties (H2O, CH3OH), but instead its spatial release in some comets seems strongly coupled to volatiles that lack a dipole moment and thus do not form H-bonds (methane, ethane). Is HCN produced in part from an apolar precursor?6. ALMA maps of HCN and the dust continuum show a slight displacement in their centroids. Is this the signature of extended production of HCN?HCN as a product species: Points 4-6 suggest that HCN may have a significant distributed source. The astrochemical species ammonium cyanide is a strong candidate for this HCN precursor; at moderately low temperatures (
ExoMol molecular line lists - XXVII: spectra of C 2 H 4NASA Astrophysics Data System (ADS) Mant, Barry P.; Yachmenev, Andrey; Yurchenko, Jonathan Tennyson Sergei N. updating A new line list for ethylene, 12C21H4 is presented. The line list is based on high level ab initiopotential energy and dipole moment surfaces. The potential energy surface is refined by fitting to experimental energies. The line list covers the range up to 7000 cm-1(1.43 μm) with all ro-vibrational transitions (50 billion) with the lower state below 5000 cm-1included and thus should be applicable for temperatures up to 700 K. A technique for computing molecular opacities from vibrational band intensities is proposed and used to provide temperature dependent cross sections of ethylene for shorter wavelength and higher temperatures. When combined with realistic band profiles (such as the proposed three-band model), the vibrational intensity technique offers a cheap but reasonably accurate alternative to the full ro-vibrational calculations at high temperatures and should be reliable for representing molecular opacities. The C2H4 line list, which is called MaYTY, is rmade available in electronic form from the CDS (http://cdsarc.u-strasbg.fr) and ExoMol (www.exomol.com) databases.
Gas-phase nitrosation of ethylene and related events in the C 2 H 4 NO+ landscape.PubMed Gerbaux, Pascal; Dechamps, Noemie; Flammang, Robert; Nam, Pham Cam; Nguyen, Minh Tho; Djazi, Fayçal; Berruyer, Florence; Bouchoux, Guy updating The C2H4NO(+) system has been examined by means of quantum chemical calculations using the G2 and G3B3 approaches and tandem mass spectrometry experiments. Theoretical investigation of the C2H4NO(+) potential-energy surface includes 19 stable C2H4NO(+) structures and a large set of their possible interconnections. These computations provide insights for the understanding of the (i) addition of the nitrosonium cation NO(+) to the ethylene molecule, (ii) skeletal rearrangements evidenced in previous experimental studies on comparable systems, and (iii) experimental identification of new C2H4NO(+) structures. It is predicted from computation that gas-phase nitrosation of ethylene may produce C2H4(*)NO(+) adducts, the most stable structure of which is a pi-complex, 1, stabilized by ca. 65 kJ/mol with respect to its separated components. This complex was produced in the gas phase by a transnitrosation process involving as reactant a complex between water and NO(+) (H2O.NO(+)) and the ethylene molecule and fully characterized by collisional experiments. Among the other C 2H 4NO (+) structures predicted by theory to be protected against dissociation or isomerization by significant energy barriers, five were also experimentally identified. These finding include structures CH3CHNO(+) (5), CH 3CNOH (+) ( 8), CH3NHCO(+) (18), CH3NCOH(+) (19), and an ion/neutral complex CH2O...HCNH(+) (12).
Tetrahedral silsesquioxane-C 2 H 2 Ti complex for hydrogen storageNASA Astrophysics Data System (ADS) Konda, Ravinder; Tavhare, Priyanka; Ingale, Nilesh; Chaudhari, Ajay updating The interaction of molecular hydrogen with tetrahedral silsesquioxane (T4)-C2H2Ti complex has been studied using Density Functional Theory with M06-2X functional and MP2 method with 6-311++G** basis set. T4-C2H2Ti complex can absorb maximum five hydrogen molecules with the gravimetric hydrogen storage capacity of 3.4 wt %. Adsorption energy calculations show that H2 adsorption on T4-C2H2Ti complex is favorable at room temperature by both the methods. We have studied the effect of temperature and pressure on Gibbs free energy corrected adsorption energies. Molecular dynamics simulations for H2 adsorbed T4-C2H2Ti complex have also been performed at 300K and show that loosely bonded H2 molecule flies away within 1fs. Various interaction energies within the complex are studied. Stability of a complex is predicted by means of a gap between Highest Occupied Molecular Orbital (HUMO) and Lowest Unoccupied Molecular Orbital (LUMO). The H2 desorption temperature for T4-C2H2Ti complex is calculated with Van't Hoff equation and it is found to be 229K.

Electron-Impact Total Ionization Cross Sections of CH and C 2 H 2PubMed Central Kim, Yong-Ki; Ali, M. Asgar; Rudd, M. Eugene updating Electron-impact total ionization cross sections for the CH radical and C2H2 (acetylene) have been calculated using the Binary-Encounter-Bethe (BEB) model. The BEB model combines the Mott cross section and the asymptotic form of the Bethe theory, and has been shown to generate reliable ionization cross sections for a large variety of molecules. The BEB cross sections for CH and C2H2 are in good agreement with the available experimental data from ionization thresholds to hundreds of eV in incident energies. PMID:updating
The Effect of N2 Photoabsorption Cross Section Resolution on C 2 H 6 Production in Titan’s IonosphereNASA Astrophysics Data System (ADS) Luspay-Kuti, Adrienn; Mandt, Kathleen E.; Plessis, Sylvain; Greathouse, Thomas K. updating Titan’s rich organic chemistry begins with the photochemistry of only two molecules: N2 and CH4. The details on how higher-order hydrocarbons and nitriles are formed from these molecules have key implications for both the structure and evolution of Titan’s atmosphere, and for its surface-atmosphere interactions. Of high importance is the production of C2H6, which is a sink for CH4, and a main component in the polar lakes. Results of photochemical models, though, may be sensitive to the choice of input parameters, such as the N2 photoabsorption cross section resolution, as previously shown for nitrogen (Liang et al. (2007) ApJL 664, 115-118), and CH4 (Lavvas et al. (2011) Icarus 213, 233-251). Here we investigate the possibility of the same effect on the production rates of C2H6. We modeled production and loss rates, as well as mixing ratio and density profiles between an altitude of 600 and 1600 km for low and high resolution N2 cross sections via a coupled ion-neutral-thermal model (De La Haye et al. (2008) Icarus 197, 110-136; Mandt et al. (2012) JGR 117, E10006). Our results show a clear impact of photoabsorption cross section resolution used on all neutral and ion species contributing to C2H6 production. The magnitude of the influence varies amongst species. Ethane production profiles exhibit a significant increase with better resolution; a factor of 1.2 between 750 and 950 km, and a factor of 1.1 in the total column-integrated production rate. These values are lower limits, as additional reactions involving C2H5 not included in the model may also contribute to the production rates. The clear effect on C2H6 (which is not a parent molecule, nor does it bear nitrogen) may have important implications for other molecules in Titan’s atmosphere as well. The possible non-negligible impact of an isotope of nitrogen may argue for the inclusion of isotopes in photochemical models. For future analysis, development of a more efficient and streamlined model called
Q branches of the nu7 fundamental of ethane (C 2 H 6 ) Integrated intensity measurements for atmospheric measurement applicationsNASA Technical Reports Server (NTRS) Rinsland, C. P.; Harvey, G. A.; Levine, J. S.; Smith, M. A. H.; Malathy Devi, V.; Thakur, K. B. updating Laboratory spectra covering the nu7 band of ethane (C2H6) have been recorded, and measurements of integrated intensities of selected Q branches from these spectra are reported. The method by which the spectra were obtained is described, and a typical spectrum covering the PQ3 branch at 2976.8/cm is shown along with a plot of equivalent width vs. optical density for this branch. The values of the integrated intensities reported for each branch are the means of five different optical densities.
Detection of NO sub x,C 2 H 4 concentrations by using CO and CO2 lasersNASA Technical Reports Server (NTRS) Gengchen, W.; Qinxin, K. updating A laser, especially the infrared line tunable laser, opens up a new way to monitor the atmospheric environment, and already has gotten effective practical application. One of the most serious problems in open path remote measurement at atmospheric pressure is the broadening effect which leads to increased linewidths, spectral interferences, and, as a result, tends to reduce detection sensitivity, so measuring laser wavelengths should be selected carefully, and interaction between the measuring wavelength and gas to be measured must be known very well. Therefore, N2O, No, NO2, CH4, NH3 and C2H4 absorption properties at some lines of CO and CO2 line tunable lasers were studied. The absorption coefficients of NO, NO2, and C2H4; some results on detection of NO sub x, C2H4 concentrations in both laboratory and field; and selection of measuring wavelengths and error analysis are discussed.
Gas-phase hydrogen atom abstraction reactions of S- with H2, CH4, and C 2 H 6NASA Astrophysics Data System (ADS) Angel, Laurence A.; Dogbevia, Moses K.; Rempala, Katarzyna M.; Ervin, Kent M. updating Reaction cross sections, product axial velocity distributions, and potential energy surfaces are presented for the hydrogen atom abstraction reactions S-+RH→R+HS- (R=H, CH3, C2H5) as a function of collision energy. The observed threshold energy, E0, for S-+H2→H+HS- agrees with the reaction endothermicity, ΔrH0. At low collision energies, the H+HS- products exhibit symmetric, low-recoil-velocity scattering, consistent with statistical reaction behavior. The S-+CH4→CH3+HS- and S-+C2H6→C2H5+HS reactions, in contrast, show large excess threshold energies when compared to ΔrH0. The excess energies are partly explained by a potential energy barrier separating products from reactants. However, additional dynamical constraints must account for more than half of the excess threshold energy. The observed behavior seems to be general for collisional activation of anion-molecule reactions that proceed through a tight, late transition state. For RH=CH4 and C2H6, the HS- velocity distributions show anisotropic backward scattering at low collision energies indicating small impact parameters and a direct rebound reaction mechanism. At higher collision energies, there is a transition to HS- forward scattering and high velocities consistent with grazing collisions and a stripping mechanism.
Balloon-borne and aircraft infrared measurements of ethane (C 2 H 6 ) in the upper troposphere and lower stratosphereNASA Technical Reports Server (NTRS) Goldman, A.; Murcray, F. J.; Murcray, D. G.; Rinsland, C. P.; Coffey, M. T.; Mankin, W. G. updating Quantitative infrared measurements of ethane (C2H6) in the upper troposphere and lower stratosphere are reported. The results have been obtained from the analysis of absorption features of the nu9 band at 12.2 microns, which have been identified in high-resolution balloon-borne and aircraft solar absorption spectra. The balloon-borne spectral data were recorded at sunset with the 0.02/cm resolution University of Denver interferometer system, from a float altitude of 33.5 km near Alamogordo, New Mexico, on March 23, 1981. The aircraft spectra were recorded at sunset in July 1978 with a 0.06/cm resolution interferometer aboard a jet aircraft at 12 km altitude, near 35 deg N, 96 deg W. The balloon analysis indicates the C2H6 mixing ratio decreased from 3.5 ppbv near 8.8 km to 0.91 ppbv near 12.1 km. The results are consistent with the column value obtained from the aircraft data.
Electron Impact Ionization and Dissociative Ionization of C 2 H 2NASA Technical Reports Server (NTRS) Srivastava, S. K. updating By utilizing a crossed electron beam collision geometry, a combination of time-of-flight (TOF) and quadrupole mass spectrometers, and the relative flow technique1 normalized values of cross sections and appearance energies (AP) were obtained for the formation of singly and multiply ionized species resulting from the ionization and dissociation of C2H2. Details ont he apparatus and technique have been published previously.2,3.
Characterization of interferences to in situ observations of δ13CH4 and C 2 H 6 when using a cavity ring-down spectrometer at industrial sitesNASA Astrophysics Data System (ADS) Assan, Sabina; Baudic, Alexia; Guemri, Ali; Ciais, Philippe; Gros, Valerie; Vogel, Felix R. updating Due to increased demand for an understanding of CH4 emissions from industrial sites, the subject of cross sensitivities caused by absorption from multiple gases on δ13CH4 and C2H6 measured in the near-infrared spectral domain using CRDS has become increasingly important. Extensive laboratory tests are presented here, which characterize these cross sensitivities and propose corrections for the biases they induce. We found methane isotopic measurements to be subject to interference from elevated C2H6 concentrations resulting in heavier δ13CH4 by +23.5 ‰ per ppm C2H6 / ppm CH4. Measured C2H6 is subject to absorption interference from a number of other trace gases, predominantly H2O (with an average linear sensitivity of 0.9 ppm C2H6 per % H2O in ambient conditions). Yet, this sensitivity was found to be discontinuous with a strong hysteresis effect and we suggest removing H2O from gas samples prior to analysis. The C2H6 calibration factor was calculated using a GC and measured as 0.5 (confirmed up to 5 ppm C2H6). Field tests at a natural gas compressor station demonstrated that the presence of C2H6 in gas emissions at an average level of 0.3 ppm shifted the isotopic signature by 2.5 ‰, whilst after calibration we find that the average C2H6 : CH4 ratio shifts by +0.06. These results indicate that, when using such a CRDS instrument in conditions of elevated C2H6 for CH4 source determination, it is imperative to account for the biases discussed within this study.
Laboratory IR Studies and Astrophysical Implications of C 2 H 2 -Containing Binary IcesNASA Technical Reports Server (NTRS) Knez, C.; Moore, M.; Ferrante, R.; Hudson, R. updating Studies of molecular hot cores and protostellar environments have shown that the observed abundance of gas-phase acetylene (C2H2) cannot be matched by chemical models without the inclusion of C2H2 molecules subliming from icy grain mantles. Searches for infrared (IR) spectral features of solid-phase acetylene are under way, but few laboratory reference spectra of C2H2 in icy mixtures, which are needed for spectral fits to observational data, have been published. Here, we report a systematic study of the IR spectra of condensed-phase pure acetylene and acetylene in ices dominated by carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), and water (H2O). We present new spectral data for these ices, including band positions and intrinsic band strengths. For each ice mixture and concentration, we also explore the dependence of acetylene's nu5-band position (743 cm-1, 13.46 micrometers) and FWHM on temperature. Our results show that the nu5 feature is much more cleanly resolved in ices dominated by non-polar and low-polarity molecules, specifically CO, CO2, and CH4, than in mixtures dominated by H2O-ice. We compare our laboratory ice spectra with observations of a quiescent region in Serpens.
Suggestion for search of ethylene oxide (c-C 2 H 4 O) in a cosmic objectNASA Astrophysics Data System (ADS) Sharma, M. K.; Sharma, M.; Chandra, S. updating Ethylene oxide (c-C2H4O) and its isomer acetaldehyde (CH3CHO) are important organic molecules because of their potential role in the formation of amino acids. The c-C2H4O molecule is a b-type asymmetric top molecule and owing to half-spin of each of the four hydrogen atoms, it has two distinct ortho (nuclear spin one) and para (nuclear spin zero and two) species. It has been detected in the Sgr B2N. Using the rotational and centrifugal distortion constants along with the electric dipole moment, we have calculated energies of 100 rotational levels of each of the ortho and para species of c-C2H4O molecule and the Einstein A-coefficients for radiative transitions between the levels. The values of Einstein A-coefficients along with the scaled values for the collisional rate coefficients are used for solving a set of statistical equilibrium equations coupled with the equations of radiative transfer. Brightness-temperatures of five rotational transitions of each of the ortho and para species of c-C2H4O molecule are investigated. Out of these ten transitions, three transitions are found to show the anomalous absorption and rest seven are found to show the emission feature. We have also investigated seven transitions observed unblended in the Sgr B2(N). We have found that the transitions 3_{3 0} - 3_{2 1} (23.134 GHz), 2_{2 0} - 2_{1 1} (15.603 GHz), 3_{3 1} - 3_{2 2} (39.680 GHz) and 1_{1 1} - 0_{0 0} (39.582 GHz) may play important role for the identification of ethylene oxide in a cosmic object.
MARVEL analysis of the measured high-resolution rovibrational spectra of C 2 H 2NASA Astrophysics Data System (ADS) Chubb, Katy L.; Joseph, Megan; Franklin, Jack; Choudhury, Naail; Furtenbacher, Tibor; Császár, Attila G.; Gaspard, Glenda; Oguoko, Patari; Kelly, Adam; Yurchenko, Sergei N.; Tennyson, Jonathan; Sousa-Silva, Clara updating Rotation-vibration energy levels are determined for the electronic ground state of the acetylene molecule, 12C2H2, using the Measured Active Rotational-Vibrational Energy Levels (MARVEL) technique. 37,813 measured transitions from 61 publications are considered. The distinct components of the spectroscopic network linking ortho and para states of the molecule are considered separately. The 20,717 ortho and 17,096 para transitions measured experimentally are used to determine 6013 ortho and 5200 para energy levels. The MARVEL results are compared with alternative compilations based on the use of effective Hamiltonians.
Grafting of carboxyl groups using CO2/C 2 H 4 /Ar pulsed plasma: Theoretical modeling and XPS derivatizationNASA Astrophysics Data System (ADS) Manakhov, Anton; Kiryukhantsev-Korneev, Philip; Michlíček, Miroslav; Permyakova, Elizaveta; Dvořáková, Eva; Polčák, Josef; Popov, Zakhar; Visotin, Maxim; Shtansky, Dmitry V. updating The grafting of carboxyl groups enhances cell adhesion and can be used for immobilization of different biomolecules onto plasma-treated materials. The process, however, was not well optimized due to lack of clear understanding of the mechanisms of carboxylic group incorporation into plasma and their grafting to polymer surface. In this work the deposition of COOH plasma polymers from CO2/C2H4/Ar pulsed discharge has been studied depending on the gas mixture and duty cycle. We have demonstrated that the CO2/C2H4/Ar plasma with adjustable thickness of COOH functionalized layer and high stability of the grafted functions in water is a better solution for the COOH surface functionalization compared to the thoroughly analyzed CO2 plasma. The concentration of different carbon environments and the density of COOH groups have been measured by using chemical derivatization combined with X-ray photoelectron spectroscopy. It has been found that the CO2/C2H4/Ar plasma mainly contains ester groups (COOC), the COOH/COOC ratio being between 0.03 and 0.08. The water stability of the COOH groups was significantly higher compared to ester environment, so immersing in water for 24 h allowed to increase the COOH/COOC ratio by a factor of 3. The mechanisms of the CO2 molecule attachment to hydrocarbon chains on the polymer surface and those located inside the plasma were modeled using ab initio calculations.
Line Parameters of Ethane (12C _2 H _6 ) at 12 μm with Constrained Multispectrum FittingNASA Astrophysics Data System (ADS) Devi, V. Malathy; Benner, D. Chris; Rinsland, C. P.; Smith, M. A. H.; Sams, R. L.; Blake, T. A.; Flaud, J.-M.; Sung, K.; Brown, L. R.; Mantz, A. W. updating A multispectrum nonlinear least squares technique was applied to simultaneously fit 43 infrared absorption spectra of C_2H_6 between 795 and 850 cm-1. The high resolution (updating cm-1) spectra were recorded with two different Bruker Fourier transform spectrometers at PNNL and JPL to support Earth and planetary atmosphere studies, e.g. Titan's cold stratosphere. Accurate line positions and absolute intensities at room temperature were retrieved for over 1750 transitions of ν_9. N_2- and self-broadened halfwidth coefficients with their temperature dependences were obtained for over 1330 lines using sample temperatures between ˜150 and 298 K. Constraints to intensity ratios, torsional splittings, halfwidth coefficients and their temperature dependence exponents were incorporated in the analysis to determine these parameters for both torsional split components. The variations of the observed halfwidth coefficients and their temperature dependences with respect to J, K quanta are discussed. No pressure-induced shifts were measured or even required to fit the spectra to their noise levels. Present results are compared with previously reported measurements and predictions. D. Chris Benner, C. P. Rinsland, V. M. Devi, M. A. H. Smith, and D. A. Atkins, JQSRT 1995;53:705-21. Part of the research described in this paper was performed at the Jet Propulsion Laboratory, California Institute of Technology, the College of William and Mary, Connecticut College, and NASA Langley Research Center under contracts and cooperative agreements with the National Aeronautics and Space Administration.
The Temperature Dependence of the Partition of CH4 and C 2 H 6 in Structure I HydratesNASA Astrophysics Data System (ADS) Cheng, H.; Lu, W. updating At present, we mainly use hydrocarbon gas and carbon isotope composition to determine the gas source of natural gas hydrate. Judging the type of gas source plays a key role in the evaluation of hydrate reservoirs, but there is still controversy over this approach. Considering the crystal properties of hydrate, the process of aggregation and decomposition of natural gas hydrates may have an important effect on the gas composition. We used CH4 (C1), C2H6 (C2) and their mixture as gas sources to synthesize hydrates from aqueous solution in high-pressure capillary tubes. Gas concentration in hydrates grew at different temperatures was measured with quantitative Raman spectroscopy. The results show that concentrations of gas in pure methane and pure ethane hydrates increase with temperature. The results of the mixture are similar to pure gas below 288.15 K, the concentration of C1 in small cages (SC, 512) slowly increased, but the competitive relationship between methane and ethane in large cages (LC, 51262) become obvious after 288.15 K. From 278.15 K to 294.15 K, the value of C1/C2 decreased from 26.38 to 6.61, gradually closing to the original gas composition of 4. We find that gas hydrates are more likely to gather C1 when they accumulate. The lower the temperature is, the more obvious it will be, and the closer the value of C1/C2 is to the microbial gases.
Infrared Spectroscopic Measurements of the Ethane (C 2 H 6 ) Total Column Abundance Above Mauna Loa, Hawaii: Seasonal VariationsNASA Technical Reports Server (NTRS) Rinsland, C. P.; Goldman, A.; Murcray, F. J.; David, S. J.; Blatherwick, R. D.; Murcray, D. G. updating About 200 i.r. solar spectra recorded at 0.01/ cm resolution on 71 days between November 1991 and July 1993 at the Network for the Detection of Stratospheric Change (NDSC) station at Mauna Loa, Hawaii (latitude 19.53 deg N, longitude 155.58 deg W, elevation 3.459 km) have been analyzed with a nonlinear least-squares spectral fitting technique to study temporal variations in the total column of atmospheric ethane (C2H6) above the site. The results were derived from the analysis of the unresolved nu(sub 7) band (sup P)Q(sub 3) subbranch at 2976.8/cm. A distinct seasonal cycle is observed with a factor of 2 variation, a maximum total column of 1.1 6 x 10(exp 16) mol /sq cm at the end of winter, and a minimum total column of 0.53 x 10(exp 16) mol/sq cm at the end of summer. Our measurements are compared with previous observations and model predictions.
Infrared spectroscopic measurements of the ethane (C 2 H 6 ) total column abundance above Mauna Loa, Hawaii -- seasonal variationsNASA Technical Reports Server (NTRS) Rinsland, C. P.; Goldman, A.; Murcray, F. J.; David, S. J.; Blatherwick, R. D.; Murcray, D. G. updating About 200 i.r. solar spectra recorded at 0.01/cm resolution on 71 days between November 1991 and July 1993 at the Network for the Detection of Stratospheric Change (NDSC) station at Mauna Loa, Hawaii (latitude 19.53 deg N, longitude 155.58 deg W, elevation 3.459 km) have been analyzed with a nonlinear least-squares spectral fitting technique to study temporal variations in the total column of atmospheric ethane (C2H6) above the site. The results were derived from the analysis of the unresolved nu(sub 7) band (P)Q(sub 3) subbranch at 2976.8/cm. A distinct seasonal cycle is observed with a factor of 2 variation, a maximum total column of 1.16 x 10(exp 16) mol/sq cm at the end of winter, and a minimum total column of 0.53 x 10(exp 16) mol/sq cm at the end of summer. Our measurements are compared with previous observations and model predictions.
A Newly Developed Fluorescence Model for C 2 H 6 ν5 and Application to Cometary Spectra Acquired with NIRSPEC at Keck IINASA Astrophysics Data System (ADS) Radeva, Yana L.; Mumma, Michael J.; Villanueva, Geronimo L.; A'Hearn, Michael F. updating Accurate rotational temperatures are essential for extracting production rates for parent volatiles in comets. Two strong bands of ethane (ν7 at 2985.39 cm-1 and ν5 at 2895.67 cm-1) are seen in infrared cometary spectra, but the Q-branches of ν7 are not resolved by current instruments and cannot provide an accurate rotational temperature with current models. We developed a fluorescence model for the C2H6 ν5 band that can be used to derive a rotational temperature. We applied our C2H6 ν5 model to high-resolution infrared spectra of the comets C/2004 Q2 Machholz and C/2000 WM1 (LINEAR), acquired with the Near-infrared Echelle Spectrograph on the Keck II telescope. We demonstrate agreement among the rotational temperatures derived from C2H6 ν5 and other species, and between mixing ratios derived from C2H6 ν5 and C2H6 ν7. As a symmetric hydrocarbon, C2H6 is observed only in the infrared, and it is now the fifth molecule (along with H2O, HCN, CO, and H2CO) for which we can derive a reliable rotational temperature from cometary infrared spectra.
Laboratory Studies on the Formation of Three C 2 H 4 O Isomers-Acetaldehyde (CH3CHO), Ethylene Oxide (c-C 2 H 4 O), and Vinyl Alcohol (CH2CHOH)-in Interstellar and Cometary IcesNASA Astrophysics Data System (ADS) Bennett, Chris J.; Osamura, Yoshihiro; Lebar, Matt D.; Kaiser, Ralf I. updating Laboratory experiments were conducted to unravel synthetic routes to form three C2H4O isomers-acetaldehyde (CH3CHO), ethylene oxide (c-C2H4O), and vinyl alcohol (CH2CHOH)-in extraterrestrial ices via electronic energy transfer processes initiated by electrons in the track of MeV ion trajectories. Here we present the results of electron irradiation on a 2:1 mixture of carbon dioxide (CO2) and ethylene (C2H4). Our studies suggest that suprathermal oxygen atoms can add to the carbon-carbon π bond of an ethylene molecule to form initially an oxirene diradical (addition to one carbon atom) and the cyclic ethylene oxide molecule (addition to two carbon atoms) at 10 K. The oxirene diradical can undergo a [1, 2]-H shift to the acetaldehyde molecule. Both the ethylene oxide and the acetaldehyde isomers can be stabilized in the surrounding ice matrix. To a minor amount, suprathermal oxygen atoms can insert into a carbon-hydrogen bond of the ethylene molecule, forming vinyl alcohol. Once these isomers have been synthesized inside the ice layers of the coated grains in cold molecular clouds, the newly formed molecules can sublime as the cloud reaches the hot molecular core stage. These laboratory investigations help to explain astronomical observations by Nummelin et al. and Ikeda et al. toward massive star-forming regions and hot cores, where observed fractional abundances of these isomers are higher than can be accounted for by gas-phase reactions alone. Similar synthetic routes could help explain the formation of acetaldehyde and ethylene oxide in comet C/1995 O1 (Hale-Bopp) and also suggest a presence of both isomers in Titan's atmosphere.
Conversion of CO2 and C 2 H 6 to propanoic acid over a Au-exchanged MCM-22 zeolite.PubMed Sangthong, Winyoo; Probst, Michael; Limtrakul, Jumras updating Finding novel catalysts for the direct conversion of CO2 to fuels and chemicals is a primary goal in energy and environmental research. In this work, density functional theory (DFT) is used to study possible reaction mechanisms for the conversion of CO2 and C2H6 to propanoic acid over a gold-exchanged MCM-22 zeolite catalyst. The reaction begins with the activation of ethane to produce a gold ethyl hydride intermediate. Hydrogen transfers to the framework oxygen leads then to gold ethyl adsorbed on the Brønsted-acid site. The energy barriers for these steps of ethane activation are 9.3 and 16.3 kcal mol(-1), respectively. Two mechanisms of propanoic acid formation are investigated. In the first one, the insertion of CO2 into the Au-H bond of the first intermediate yields gold carboxyl ethyl as subsequent intermediate. This is then converted to propanoic acid by forming the relevant C-C bond. The activation energy of the rate-determining step of this pathway is 48.2 kcal mol(-1). In the second mechanism, CO2 interacts with gold ethyl adsorbed on the Brønsted-acid site. Propanoic acid is formed via protonation of CO2 by the Brønsted acid and the simultaneous formation of a bond between CO2 and the ethyl group. The activation energy there is 44.2 kcal mol(-1), favoring this second pathway at least at low temperatures. Gold-exchanged MCM-22 zeolite can therefore, at least in principle, be used as the catalyst for producing propanoic acid from CO2 and ethane. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
C 2 H 2 type of zinc finger transcription factors in foxtail millet define response to abiotic stresses.PubMed Muthamilarasan, Mehanathan; Bonthala, Venkata Suresh; Mishra, Awdhesh Kumar; Khandelwal, Rohit; Khan, Yusuf; Roy, Riti; Prasad, Manoj updating C2H2 type of zinc finger transcription factors (TFs) play crucial roles in plant stress response and hormone signal transduction. Hence considering its importance, genome-wide investigation and characterization of C2H2 zinc finger proteins were performed in Arabidopsis, rice and poplar but no such study was conducted in foxtail millet which is a C4 Panicoid model crop well known for its abiotic stress tolerance. The present study identified 124 C2H2-type zinc finger TFs in foxtail millet (SiC2H2) and physically mapped them onto the genome. The gene duplication analysis revealed that SiC2H2s primarily expanded in the genome through tandem duplication. The phylogenetic tree classified these TFs into five groups (I-V). Further, miRNAs targeting SiC2H2 transcripts in foxtail millet were identified. Heat map demonstrated differential and tissue-specific expression patterns of these SiC2H2 genes. Comparative physical mapping between foxtail millet SiC2H2 genes and its orthologs of sorghum, maize and rice revealed the evolutionary relationships of C2H2 type of zinc finger TFs. The duplication and divergence data provided novel insight into the evolutionary aspects of these TFs in foxtail millet and related grass species. Expression profiling of candidate SiC2H2 genes in response to salinity, dehydration and cold stress showed differential expression pattern of these genes at different time points of stresses.

The Dissociation Energies of CH4 and C 2 H 2 RevisitedNASA Technical Reports Server (NTRS) Partridge, Harry; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor) updating The bond dissociation energies of CH4 and C2H2 and their fragments are investigated using basis set extrapolations and high levels of correlation. The computed bond dissociation energies (D(sub e)) are accurate to within 0.2 kcal/mol. The agreement with the experimental (D(sub 0)) values is excellent if we assume that the zero-point energy of C2H is 9.18 kcal/mol. The effect of core (1s) correlation on the bond dissociation energies of C-H bonds is shown to vary from 0.2 to 0.7 kcal/mol and that for C-C bonds varies from 0.4 to 2.2 kcal/mol.
The rate of the reaction between CN and C 2 H 2 at interstellar temperatures.PubMed Woon, D E; Herbst, E updating The rate coefficient for the important interstellar reaction between CN and C2H2 has been calculated as a function of temperature between 10 and 300 K. The potential surface for this reaction has been determined through ab initio quantum chemical techniques; the potential exhibits no barrier in the entrance channel but does show a small exit channel barrier, which lies below the energy of reactants. Phase-space calculations for the reaction dynamics, which take the exit channel barrier into account, show the same unusual temperature dependence as determined by experiment, in which the rate coefficient at first increases as the temperature is reduced below room temperature and then starts to decrease as the temperature drops below 50-100 K. The agreement between theory and experiment provides strong confirmation that the reaction occurs appreciably at cool interstellar temperatures.
Direct Detection of C _2 H _2 in Air and Human Breath by Cw-CrdsNASA Astrophysics Data System (ADS) Schmidt, Florian M.; Vaittinen, Olavi; Metsälä, Markus; Halonen, Lauri updating Continuous wave cavity ring-down spectroscopy (cw-CRDS) is an established cavity-enhanced absorption technique that can provide the necessary sensitivity, selectivity and fast acquisition time for many applications involving the detection of trace species. We present a simple but highly sensitive cw-CRDS spectrometer based on an external cavity diode laser operating in the near-infrared region. This instrument allows us to directly detect acetylene (C_2H_2) mixing ratios in air with a detection limit of 120 parts per trillion by volume (pptv) measuring on a C_2H_2 absorption line at updating cm-1. Acetylene is a combustion product that is routinely used in environmental monitoring as a marker for anthropogenic emissions. In a recent work, the spectrometer was employed to measure the level of acetylene in indoor and outdoor air in Helsinki. Continuous flow measurements with high time resolution (one minute) revealed strong fluctuations in the acetylene mixing ratio in outdoor air during daytime. Due to its non-invasive nature and fast response time, the analysis of exhaled breath for medical diagnostics is an excellent and straightforward alternative to methods using urine or blood samples. In an ongoing study, the cw-CRDS instrument is used to establish the baseline level of acetylene in the breath of the healthy population. An elevated amount of acetylene in breath could indicate exposure to combustion exhausts or other volatile organic compound (VOC) rich sources. The latest results of this investigation will be presented. F. M. Schmidt, O. Vaittinen, M. Metsälä, P. Kraus and L. Halonen, submitted for publication in Appl. Phys. B.
Isomerization, Perturbations, Calculations and the S_{1} State of C _{2 }H _{2 }NASA Astrophysics Data System (ADS) Baraban, J. H.; Changala, P. B.; Berk, J. R. P.; Field, R. W.; Stanton, J. F.; Merer, A. J. updating Preliminary analysis of the energy region of the cis-trans isomerization transition state on the S_{1} surface of C_{2}H_{2} has revealed novel patterns and surprising perturbations, including unusually large (and high-order) anharmonicities, as well as K-staggerings of several vibrational levels. These effects complicate the analysis considerably, and require new models and calculations to account for and predict features of the observed spectra. The ˜{A}-˜{X} spectrum of acetylene has been studied both experimentally and theoretically for almost a century, and this cycle of unexpected phenomena eliciting innovative responses is found throughout its history. Especially in the last ten years, progress in understanding the S_{1} state rovibrational level structure and cis-trans isomerization has been accelerated by combining the information available from both ab initio computation and spectroscopic observations. The resulting dialogue has then frequently suggested fruitful avenues for further experiments and calculations. Current challenges and recent results in understanding the cis-trans isomerization transition state region will be discussed in this context.
High-Resolution Fourier Transform Infrared Spectrum of the ν 12 Fundamental Band of Ethylene (C 2 H 4 )NASA Astrophysics Data System (ADS) Tan, T. L.; Lau, S. Y.; Ong, P. P.; Goh, K. L.; Teo, H. H. updating The infrared spectrum of the ν12 fundamental band of ethylene (C2H4) has been measured with an unapodized resolution of 0.004 cm-1 in the frequency range of updating cm-1 using the Fourier transform technique. By assigning and fitting a total of 1387 infrared transitions using a Watson's A-reduced Hamiltonian in the Ir representation, rovibrational constants for the upper state (v12 = 1) up to five quartic and three sextic centrifugal distortions terms were derived. They represent the most accurate constants for the band so far. The rms deviation of the fit was 0.00033 cm-1. The A-type ν12 band with a band center at updating ± 0.00003 cm-1 was found to be relatively free from local frequency perturbations. The inertial defect Δ12 was found to be 0.24201 ± 0.00002 u Å2.
Temperature, Oxygen, and Soot-Volume-Fraction Measurements in a Turbulent C 2 H 4 -Fueled Jet FlameSciTech Connect Kearney, Sean P.; Guildenbecher, Daniel Robert; Winters, Caroline updating We present a detailed set of measurements from a piloted, sooting, turbulent C 2 H 4 - fueled diffusion flame. Hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (CARS) is used to monitor temperature and oxygen, while laser-induced incandescence (LII) is applied for imaging of the soot volume fraction in the challenging jet-flame environment at Reynolds number, Re = 20,000. Single-laser shot results are used to map the mean and rms statistics, as well as probability densities. LII data from the soot-growth region of the flame are used to benchmark the soot source term for one-dimensional turbulence (ODT) modeling of this turbulentmore » flame. The ODT code is then used to predict temperature and oxygen fluctuations higher in the soot oxidation region higher in the flame.« less
Investigation of CO, C 2 H 6 and aerosols over Eastern Canada during BORTAS 2011 using ground-based and satellite-based observations and model simulationsNASA Astrophysics Data System (ADS) Griffin, Debora; Franklin, Jonathan; Parrington, Mark; Whaley, Cynthia; Hopper, Jason; Lesins, Glen; Tereszchuk, Keith; Walker, Kaley A.; Drummond, James R.; Palmer, Paul; Strong, Kimberly; Duck, Thomas J.; Abboud, Ihab; Dan, Lin; O'Neill, Norm; Clerbaux, Cathy; Coheur, Pierre; Bernath, Peter F.; Hyer, Edward; Kliever, Jenny updating We present the results of total column measurements of CO and C2H6 and aerosol optical depth (AOD) during the Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS-B) campaign over Eastern Canada. Ground-based observations, using Fourier transform spectrometers (FTSs) and sun photometers, were carried out in July and August 2011. They were taken in Halifax, Nova Scotia, which is an ideal location to monitor the outflow of boreal fires from North America, and in Toronto, Ontario. Measurements of enhanced fine mode AOD were highly correlated with enhancements in coincident trace gas (CO and C2H6) observations between 19 and 21 July 2011, which is typical for a smoke plume event. In this study, we will focus on the identification of the origin and the transport of this smoke plume. We use back-trajectories calculated by the Canadian Meteorological Centre (CMC) as well as FLEXPART forward-trajectories to demonstrate that the enhanced CO, C2H6 and fine mode AOD seen near Halifax and Toronto did originate from forest fires in Northwestern Ontario, that occurred between 17 and 19 July 2011. In addition, total column measurements of CO from the satellite-borne Infrared Atmospheric Sounding Interferometer (IASI) have been used to trace the smoke plume and to confirm the origin of the CO enhancement. Furthermore, the emission ratio (ERC2H6-CO) and the emission factor (EFC2H6) of C2H6 (with respect to the CO emission) were estimated from these ground-based observations. The C2H6 emission results from boreal fires in Northwestern Ontario agree well with C2H6 emission measurements from other boreal regions, and are relatively high compared to other geographical regions. The ground-based CO and C2H6 observations were compared with output from the 3-D global chemical transport model GEOS-Chem, using the inventory of the Fire Locating And Monitoring of Burning Emissions (FLAMBE). Good agreement was found for
Multilayer adsorption of C 2 H 4 and CF4 on graphite: Grand Canonical Monte Carlo simulationNASA Astrophysics Data System (ADS) Abdelatif, H.; Drir, M. updating We study the phase transitions in adsorbed multilayers by Grand Canonical Monte Carlo simulations (GCMC) of the lattice-gas model. The focus will be on ethylene (C2H4) and tetrafluoromethane (CF4) on a homogeneous graphite surface. Earlier simulations of these systems investigated structural properties, dynamical behaviors of adsorbed films and thermodynamic quantities such as isosteric heat. The main purpose of this study is to consider the adsorbed multilayers by the evaluation of the layering behavior, the wetting phenomena and the critical temperatures. The isotherms obtained for temperature from 50 K to 170 K reproduce a number of interesting features observed experimentally: (i) we observe an important number of layers in contrast with previous simulations, (ii) a finite number of layers at saturated pressure for low temperatures are found, (iii) the isotherms present vertical steps typical of layer-by-layer growth, at higher temperatures these distinct layers tend to disappear signifying that the film thickness increases continuously, (iv) a thin film to thick film transition near the triple point temperature is noticed. In addition to this qualitative description, quantitative information are determined including temperatures and relative pressures of layers formation, layer-critical-point temperatures and phase diagrams. Comparing the two systems, ethylene/graphite and tetrafluoromethane/graphite, we observe a qualitatively similar behavior.
Isotope effect in acetylene C 2 H 2 and C2D2 rotations on Cu(001)NASA Astrophysics Data System (ADS) Shchadilova, Yulia E.; Tikhodeev, Sergei G.; Paulsson, Magnus; Ueba, Hiromu updating A comprehensive analysis of the elementary processes behind the scanning tunneling microscope controlled rotation of C2H2 and C2D2, isotopologues of a single acetylene molecule adsorbed on the Cu(001) surface, is given, with a focus on the isotope effects. With the help of density-functional theory we calculate the vibrational modes of C2H2 and C2D2 on Cu(001) and estimate the anharmonic couplings between them, using a simple strings-on-rods model. The probability of the elementary processes, nonlinear and combination band, is estimated using the Keldysh diagram technique. This allows us to clarify the main peculiarities and the isotope effects of the C2H2 and C2D2 on Cu(001) rotation, discovered in the pioneering work [B. C. Stipe et al., Phys. Rev. Lett. 81, updating), 10.1103/PhysRevLett.81.1263], which have not been previously understood.
Ab initio and density functional study on the mechanism of the C 2 H 2 ++methanol reactionNASA Astrophysics Data System (ADS) Irle, Stephan; Morokuma, Keiji updating High level ab initio (G2MS and CASSCF) and density functional (B3LYP) calculations were carried out to study the mechanism of the ion-molecule reaction C2H2++CH3OH for four reaction channels: hydride abstraction from methanol (HA), proton transfer from acetylene cation (PT), charge transfer (CT), and covalent complex formation (CC) channel. For the CT channel, two pathways have been found: a usual nonadiabatic pathway via A'/A″ seam of crossing, and a low-energy adiabatic pathway through an initial intermediate; the latter may be the dominant process with favorable energies and a large impact parameter. The HA process involves a low-energy direct intermediate and a very low barrier to form C2H3+CH2OH+ and is also energetically favorable. The PT processes require passage over a high-energy transition state (TS) and are not important. One of the experimentally unobserved CC channels, formation of the COCC skeleton, is energetically favorable and there is no energetic reason for it not to take place; a "dynamic bottleneck" argument may have to be invoked to explain the experiment. The increase in reaction efficiency with the C-C stretch excitation may be justified by considering the TSs for two CT pathways, where the C-C distance changed substantially from that in the reactant C2H2+. Very qualitatively, the C2H2++CH3OH potential energy surface looks more like that of the C2H2++NH3 system than the C2H2++CH4 system, because of the differences in the ionization potentials: NH3˜CH3OHC2H2
Keep your fingers off my DNA: protein-protein interactions mediated by C 2 H 2 zinc finger domains.PubMed Brayer, Kathryn J; Segal, David J updating Cys2-His2 (C2H2) zinc finger domains (ZFs) were originally identified as DNA-binding domains, and uncharacterized domains are typically assumed to function in DNA binding. However, a growing body of evidence suggests an important and widespread role for these domains in protein binding. There are even examples of zinc fingers that support both DNA and protein interactions, which can be found in well-known DNA-binding proteins such as Sp1, Zif268, and Ying Yang 1 (YY1). C2H2 protein-protein interactions (PPIs) are proving to be more abundant than previously appreciated, more plastic than their DNA-binding counterparts, and more variable and complex in their interactions surfaces. Here we review the current knowledge of over 100 C2H2 zinc finger-mediated PPIs, focusing on what is known about the binding surface, contributions of individual fingers to the interaction, and function. An accurate understanding of zinc finger biology will likely require greater insights into the potential protein interaction capabilities of C2H2 ZFs.
FTMS studies of sputtered metal cluster ions (IV): size-selective effects in the chemistry of Fe{/n +} with NH3 and Pd{/n +} with D2 or C 2 H 4NASA Astrophysics Data System (ADS) Irion, M. P.; Selinger, A.; Schnabel, P. updating Fe{/n +} and Pd{/n +} clusters up to n=19 and n=25, respectively, are produced in an external ion source by sputtering of the respective metal foils with Xe+ primary ions at 20 keV. They are transferred to the ICR cell of a home-built Fourier transform mass spectrometer, where they are thermalized to nearly room temperature and stored for several tens of seconds. During this time, their reactions with a gas leaked in at low level are studied. Thus in the presence of ammonia, most Fe{/n +} clusters react by simply adsorbing intact NH3 molecules. Only Fe{4/+} ions show dehydrogenation/adsorption to Fe4(NH){/m +} intermediates ( m=1, 2) that in a complex scheme go on adsorbing complete NH3 units. To clarify the reaction scheme, one has to isolate each species in the ion cell, which often requires the ejection of ions very close in mass. This led to the development of a special isolation technique that avoids the use of isotopically pure metal samples. Pd{n/+} cluster ions ( n=2...9) dehydrogenate C2H4 in general to yield Pd n (C2H2)+, yet Pd{6/+} appear totally unreactive. Towards D2, Pd{7/+} ions seem inert, whereas Pd{8/+} adsorb up to two molecules.
Acetylene (C 2 H 2 ) and hydrogen cyanide (HCN) from IASI satellite observations: global distributions, validation, and comparison with modelNASA Astrophysics Data System (ADS) Duflot, V.; Wespes, C.; Clarisse, L.; Hurtmans, D.; Ngadi, Y.; Jones, N.; Paton-Walsh, C.; Hadji-Lazaro, J.; Vigouroux, C.; De Mazière, M.; Metzger, J.-M.; Mahieu, E.; Servais, C.; Hase, F.; Schneider, M.; Clerbaux, C.; Coheur, P.-F. updating We present global distributions of C2H2 and hydrogen cyanide (HCN) total columns derived from the Infrared Atmospheric Sounding Interferometer (IASI) for the years updating. These distributions are obtained with a fast method allowing to retrieve C2H2 abundance globally with a 5 % precision and HCN abundance in the tropical (subtropical) belt with a 10 % (25 %) precision. IASI data are compared for validation purposes with ground-based Fourier transform infrared (FTIR) spectrometer measurements at four selected stations. We show that there is an overall agreement between the ground-based and space measurements with correlation coefficients for daily mean measurements ranging from 0.28 to 0.81, depending on the site. Global C2H2 and subtropical HCN abundances retrieved from IASI spectra show the expected seasonality linked to variations in the anthropogenic emissions and seasonal biomass burning activity, as well as exceptional events, and are in good agreement with previous spaceborne studies. Total columns simulated by the Model for Ozone and Related Chemical Tracers, version 4 (MOZART-4) are compared to the ground-based FTIR measurements at the four selected stations. The model is able to capture the seasonality in the two species in most of the cases, with correlation coefficients for daily mean measurements ranging from 0.50 to 0.86, depending on the site. IASI measurements are also compared to the distributions from MOZART-4. Seasonal cycles observed from satellite data are reasonably well reproduced by the model with correlation coefficients ranging from -0.31 to 0.93 for C2H2 daily means, and from 0.09 to 0.86 for HCN daily means, depending on the considered region. However, the anthropogenic (biomass burning) emissions used in the model seem to be overestimated (underestimated), and a negative global mean bias of 1 % (16 %) of the model relative to the satellite observations was found for C2H2 (HCN).
The vanadium nitrogenase of Azotobacter chroococcum. Reduction of acetylene and ethylene to ethane.PubMed Central Dilworth, M J; Eady, R R; Eldridge, M E updating 1. The vanadium (V-) nitrogenase of Azobacter chroococcum transfers up to 7.4% of the electrons used in acetylene (C2H2) reduction for the formation of ethane (C2H6). The apparent Km for C2H2 (6 kPa) is the same for either ethylene (C2H4) or ethane (C2H6) formation and much higher than the reported Km values for C2H2 reduction to C2H4 by molybdenum (Mo-) nitrogenases. Reduction of C2H2 in 2H2O yields predominantly [cis-2H2]ethylene. 2. The ratio of electron flux yielding C2H6 to that yielding C2H4 (the C2H6/C2H4 ratio) is increased by raising the ratio of Fe protein to VFe protein and by increasing the assay temperature up to at least 40 degrees C. pH values above 7.5 decrease the C2H6/C2H4 ratio. 3. C2H4 and C2H6 formation from C2H2 by V-nitrogenase are not inhibited by H2. CO inhibits both processes much less strongly than it inhibits C2H4 formation from C2H2 with Mo-nitrogenase. 4. Although V-nitrogenase also catalyses the slow CO-sensitive reduction of C2H4 to C2H6, free C2H4 is not an intermediate in C2H6 formation from C2H2. 5. Propyne (CH3C identical to CH) is not reduced by the V-nitrogenase. 6. Some implications of these results for the mechanism of C2H6 formation by the V-nitrogenase are discussed. PMID:3162672
Destruction of C 2 H 4 O2 isomers in ice-phase by X-rays: Implication on the abundance of acetic acid and methyl formate in the interstellar mediumNASA Astrophysics Data System (ADS) Rachid, Marina G.; Faquine, Karla; Pilling, S. updating The C2H4O2 isomers methyl formate (HCOOCH3), acetic acid (CH3COOH) and glycoaldehyde (HOCH2CHO) have been detected in molecular clouds in the interstellar medium, as well as, hot cores, hot corinos and around protostellar objects. However, their abundances are very different, being methyl formate more abundant than the other two isomers. This fact may be related to the different destruction by ionizing radiation of these molecules. The goal of this work is experimentally study the photodissociation processes of methyl formate and acetic acid ices when exposed to broadband soft X-ray from 6 up to 2000 eV. The experiments were performed coupled to the SGM beamline in the Brazilian Synchrotron Light Source (LNLS/CNPEM) at Campinas, Brazil. The simulated astrophysical ices (12 K) were monitored throughout the experiment using infrared vibrational spectroscopy (FTIR). The analysis of processed ices allowed the determination of the effective destruction cross sections of the parent molecules as well as the effective formation cross section of daughter molecular species such as CO, CO2, H2O, CH4 and H2CO (only for methyl formate) and the hydrocarbons C2H6 and C5H10 (only for acetic acid). The half-lives of molecules at ices toward young stellar objects (YSOs) and inside molecular clouds (e.g. Sgr B2 and W51) due to the presence of incoming soft X-rays were estimated. We determined the effective formation rate and the branching ratios for assigned daughter species after the establishment of a chemical equilibrium. The main product from photodissociation of both methyl formate and acetic acid is CO, that can be formed by recombination of ions, formed during the photodissociation, in the ice surface. The relative abundance between methyl formate and acetic acid (NCH3COOH/NHCOOCH3) in different astronomical scenarios and their column density evolution in the presence of X-rays were calculated. Our results suggest that such radiation field can be one of the factors that
High pressure micromechanical force measurements of the effects of surface corrosion and salinity on CH4/C 2 H 6 hydrate particle-surface interactions.PubMed Wang, Shenglong; Hu, Sijia; Brown, Erika P; Nakatsuka, Matthew A; Zhao, Jiafei; Yang, Mingjun; Song, Yongchen; Koh, Carolyn A updating In order to investigate the mechanism of gas hydrate deposition and agglomeration in gas dominated flowlines, a high-pressure micromechanical force (MMF) apparatus was applied to directly measure CH 4 /C 2 H 6 hydrate adhesion/cohesion forces under low temperature and high pressure conditions. A CH 4 /C 2 H 6 gas mixture was used as the hydrate former. Adhesion forces between hydrate particles and carbon steel (CS) surfaces were measured, and the effects of corrosion on adhesion forces were analyzed. The influences of NaCl concentration on the cohesion force between CH 4 /C 2 H 6 hydrate particles were also studied for gas-dominated systems. It was observed that there was no measurable adhesion force for pristine (no corrosion) and corroded surfaces, when there was no condensed water or water droplet on these surfaces. With water on the surface (the estimated water amount was around 1.7 μg mm -2 ), a hydrate film growth process was observed during the measurement. CS samples were soaked in NaCl solution to obtain different extents of corrosion on surfaces, and adhesion measurements were performed on both pristine and corroded samples. The adhesion force was found to increase with increasing soak times in 5 wt% NaCl (resulting in more visual corrosion) by up to 500%. For the effect of salinity on cohesion forces, it was found that the presence of NaCl decreased the cohesion force between hydrate particles, and a possible explanation of this phenomenon was given based on the capillary liquid bridge model.
Local- and regional-scale measurements of CH4, δ13CH4, and C 2 H 6 in the Uintah Basin using a mobile stable isotope analyzerNASA Astrophysics Data System (ADS) Rella, C. W.; Hoffnagle, J.; He, Y.; Tajima, S. updating In this paper, we present an innovative CH4, δ13CH4, and C2H6 instrument based on cavity ring-down spectroscopy (CRDS). The design and performance of the analyzer is presented in detail. The instrument is capable of precision of less than 1 ‰ on δ13CH4 with 1 in. of averaging and about 0.1 ‰ in an hour. Using this instrument, we present a comprehensive approach to atmospheric methane emissions attribution. Field measurements were performed in the Uintah Basin (Utah, USA) in the winter of 2013, using a mobile lab equipped with the CRDS analyzer, a high-accuracy GPS, a sonic anemometer, and an onboard gas storage and playback system. With a small population and almost no other sources of methane and ethane other than oil and gas extraction activities, the Uintah Basin represents an ideal location to investigate and validate new measurement methods of atmospheric methane and ethane. We present the results of measurements of the individual fugitive emissions from 23 natural gas wells and six oil wells in the region. The δ13CH4 and C2H6 signatures that we observe are consistent with the signatures of the gases found in the wells. Furthermore, regional measurements of the atmospheric CH4, δ13CH4, and C2H6 signatures throughout the basin have been made, using continuous sampling into a 450 m long tube and laboratory reanalysis with the CRDS instrument. These measurements suggest that 85 ± 7 % of the total emissions in the basin are from natural gas production.
Beyond 3 Au from the Sun: the Hypervolatiles CH4, C 2 H 6 , and CO in the Distant Comet C2006 W3 (Christensen)NASA Technical Reports Server (NTRS) Bonev, Boncho P.; Villanueva, Geronimo L.; Disanti, Michael A.; Boehnhardt, Hermann; Lippi, Manuela; Gibb, Erika L.; Paganini, Lucas; Mumma, Michael J. updating Comet C/2006 W3 (Christensen) remained outside a heliocentric distance (Rh) of 3.1 au throughout its apparition, but it presented an exceptional opportunity to directly sense a suite of molecules released from its nucleus. The Cryogenic Infrared Echelle Spectrograph at ESO-VLT detected infrared emissions from the three hypervolatiles (CO, CH4, and C2H6) that have the lowest sublimation temperatures among species that are commonly studied in comets by remote sensing. Even at Rh 3.25 au, the production rate of each molecule exceeded those measured for the same species in a number of other comets, although these comets were observed much closer to the Sun. Detections of CO at Rh = 3.25, 4.03, and 4.73 au constrained its post-perihelion decrease in production rate, which most likely dominated the outgassing. At 3.25 au, our measured abundances scaled as CO/CH4/C2H6 approx. = 100/4.4/2.1. The C2H6/CH4 ratio falls within the range of previously studied comets at Rh
Production and optical constraints of ice tholin from charged particle irradiation of (1:6) C 2 H 6 /H2O at 77 KNASA Astrophysics Data System (ADS) Khare, B. N.; Thompson, W. R.; Cheng, L.; Chyba, C.; Sagan, C.; Arakawa, E. T.; Meisse, C.; Tuminello, P. S. updating Fifty separate irradiations of a 6:1 mixture of H2O/C2H6 ice conducted over a 5-month period have yielded sufficient tholin for the determination of its physical constants in the 0.06 to 40 micron range. While the imaginary part of the refractive index k was obtained by transmission measurements on thin-film samples and Kramers-Kronig analysis (KKA), the real part of the refractive index was obtained by KKA and ellipsometry; these data may prove useful in cometary and outer solar system spectrometric interpretation.
Beyond Crystal Engineering: Significant Enhancement of C 2 H 2 /CO2 Separation by Constructing Composite Material.PubMed Wu, Hui Qiong; Yan, Chang Sheng; Luo, Feng; Krishna, Rajamani updating Different from the established crystal engineering method for enhancing gas-separation performance, we demonstrate herein a distinct approach. In contrast to the pristine MOF (metal-organic framework) material, the C 2 H 2 /CO 2 separation ability for the resultant Ag NPs (nanoparticle)@Fe 2 O 3 @MOF composite material, estimated from breakthrough calculations, is greatly enhanced by 2 times, and further magnified up to 3 times under visible light irradiation.

Identification and expression of C 2 H 2 transcription factor genes in Carica papaya under abiotic and biotic stresses.PubMed Jiang, Ling; Pan, Lin-jie updating C2H2 proteins belong to a group of transcription factors (TFs) existing as a superfamily that plays important roles in defense responses and various other physiological processes in plants. The present study aimed to screen for and identify C2H2 proteins associated with defense responses to abiotic and biotic stresses in Carica papaya L. Data were collected for 47,483 papaya-expressed sequence tags (ESTs). The full-length cDNA nucleotide sequences of 87 C2H2 proteins were predicated by BioEdit. All 91 C2H2 proteins were aligned, and a phylogenetic tree was constructed using DNAman. The expression levels of 42 C2H2 were analyzed under conditions of salt stress by quantitative reverse transcriptase-polymerase chain reaction (qRT-PCR). Methyl jasmonate treatment rapidly upregulated ZF(23.4) and ZF(30,912.1) by 18.6- and 21.7-fold, respectively. ZF(1.3), ZF(138.44), ZF(94.49), ZF(29.160), and ZF(20.206) were found to be downregulated after low temperature treatment at very significant levels (p
The CU mobile Solar Occultation Flux instrument: structure functions and emission rates of NH3, NO2 and C 2 H 6NASA Astrophysics Data System (ADS) Kille, Natalie; Baidar, Sunil; Handley, Philip; Ortega, Ivan; Sinreich, Roman; Cooper, Owen R.; Hase, Frank; Hannigan, James W.; Pfister, Gabriele; Volkamer, Rainer updating We describe the University of Colorado mobile Solar Occultation Flux instrument (CU mobile SOF). The instrument consists of a digital mobile solar tracker that is coupled to a Fourier transform spectrometer (FTS) of 0.5 cm-1 resolution and a UV-visible spectrometer (UV-vis) of 0.55 nm resolution. The instrument is used to simultaneously measure the absorption of ammonia (NH3), ethane (C2H6) and nitrogen dioxide (NO2) along the direct solar beam from a moving laboratory. These direct-sun observations provide high photon flux and enable measurements of vertical column densities (VCDs) with geometric air mass factors, high temporal resolution of 2 s and spatial resolution of 5-19 m. It is shown that the instrument line shape (ILS) of the FTS is independent of the azimuth and elevation angle pointing of the solar tracker. Further, collocated measurements next to a high-resolution FTS at the National Center for Atmospheric Research (HR-NCAR-FTS) show that the CU mobile SOF measurements of NH3 and C2H6 are precise and accurate; the VCD error at high signal to noise ratio is 2-7 %. During the Front Range Air Pollution and Photochemistry Experiment (FRAPPE) from 21 July to 3 September 2014 in Colorado, the CU mobile SOF instrument measured median (minimum, maximum) VCDs of updating, 45) × 1016 molecules cm-2 NH3, updating, 2.23) × 1016 molecules cm-2 NO2 and updating, 7.7) × 1016 molecules cm-2 C2H6. All gases were detected in larger 95 % of the spectra recorded in urban, semi-polluted rural and remote rural areas of the Colorado Front Range. We calculate structure functions based on VCDs, which describe the variability of a gas column over distance, and find the largest variability for NH3. The structure functions suggest that currently available satellites resolve about 10 % of the observed NH3 and NO2 VCD variability in the study area. We further quantify the trace gas emission fluxes of NH3 and C2H6 and production rates of NO2 from concentrated animal feeding
First-principles analysis of C 2 H 2 molecule diffusion and its dissociation process on the ferromagnetic bcc-Fe110 surface.PubMed Ikeda, Minoru; Yamasaki, Takahiro; Kaneta, Chioko updating Using the projector-augmented plane wave method, we study diffusion and dissociation processes of C(2)H(2) molecules on the ferromagnetic bcc-Fe(110) surface and investigate the formation process of graphene created by C(2)H(2) molecules. The most stable site for C(2)H(2) on the Fe surface is a hollow site and its adsorption energy is - 3.5 eV. In order to study the diffusion process of the C(2)H(2) molecule, the barrier height energies for the C atom, C(2)-dimer and CH as well as the C(2)H(2) molecule are estimated using the nudged elastic band method. The barrier height energy for C(2)H(2) is 0.71 eV and this indicates that the C(2)H(2) diffuses easily on this FM bcc-Fe(110) surface. We further investigate the two step dissociation process of C(2)H(2) on Fe. The first step is the dissociation of C(2)H(2) into C(2)H and H, and the second step is that of C(2)H into C(2) and H. Their dissociation energies are 0.9 and 1.2 eV, respectively. These energies are relatively small compared to the dissociation energy 7.5 eV of C(2)H(2) into C(2)H and H in the vacuum. Thus, the Fe surface shows catalytic effects. We further investigate the initial formation process of graphene by increasing the coverage of C(2)H(2). The formation process of the benzene molecule on the FM bcc(110) surface is also discussed. We find that there exists a critical coverage of C(2)H(2) which characterizes the beginning of the formation of the graphene.
High Spectral Resolution SOFIA/EXES Observations of C 2 H 2 toward Orion IRc2NASA Astrophysics Data System (ADS) Rangwala, Naseem; Colgan, Sean W. J.; Le Gal, Romane; Acharyya, Kinsuk; Huang, Xinchuan; Lee, Timothy J.; Herbst, Eric; deWitt, Curtis; Richter, Matt; Boogert, Adwin; McKelvey, Mark updating We present high spectral resolution observations from 12.96 to 13.33 microns toward Orion IRc2 using the mid-infrared spectrograph, Echelon-Cross-Echelle Spectrograph (EXES), at Stratospheric Observatory for Infrared Astronomy (SOFIA). These observations probe the physical and chemical conditions of the Orion hot core, which is sampled by a bright, compact, mid-infrared background continuum source in the region, IRc2. All 10 of the rovibrational C2H2 transitions expected in our spectral coverage are detected with high signal-to-noise ratios (S/Ns), yielding continuous coverage of the R-branch lines from J = 9–8 to J = 18–17, including both ortho and para species. Eight of these rovibrational transitions are newly reported detections. The isotopologue, 13CCH2, is clearly detected with a high S/N. This enabled a direct measurement of the 12C/13C isotopic ratio for the Orion hot core of 14 ± 1 and an estimated maximum value of 21. We also detected several HCN rovibrational lines. The ortho and para C2H2 ladders are clearly separate, and tracing two different temperatures, 226 K and 164 K, respectively, with a non-equilibrium ortho to para ratio (OPR) of 1.7 ± 0.1. Additionally, the ortho and para V LSR values differ by about 1.8 ± 0.2 km s‑1, while the mean line widths differ by 0.7 ± 0.2 km s‑1, suggesting that these species are not uniformly mixed along the line of sight to IRc2. We propose that the abnormally low C2H2 OPR could be a remnant from an earlier, colder phase, before the density enhancement (now the hot core) was impacted by shocks generated from an explosive event 500 years ago.
Detection of HCN and C 2 H 2 in ISO Spectra of Oxygen-Rich AGB StarsNASA Technical Reports Server (NTRS) Carbon, Duane F.; Chiar, Jean; Goorvitch, David; Kwak, Dochan (Technical Monitor) updating Cool oxygen-rich AGB stars were not expected to have organic molecules like HCN in either their photospheres or circumstellar envelopes (CSEs). The discovery of HCN and CS microwave emission from the shallowest CSE layers of these stars was a considerable surprise and much theoretical effort has been expended in explaining the presence of such organics. To further explore this problem, we have undertaken a systematic search of oxygen-rich AGB stellar spectra in the Infrared Space Observatory (ISO) data archive. Our purposes are to find evidence regarding critical molecular species that could be of value in choosing among the proposed theoretical models, to locate spectral features which might give clues to conditions deeper in the CSEs, and to lay the groundwork for future SIRTF (Space Infrared Telescope Facility) and SOFIA (Stratospheric Observatory for Infrared Astronomy) observations. Using carefully reduced observations, we have detected weak absorption features arising from HCN and possibly C2H2 in a small number of oxygen-rich AGB stars. The most compelling case is NML Cyg which shows both HCN (14 microns) and CO2 (15 microns). VY CMa, a similar star, shows evidence for HCN, but not CO2. Two S-type stars show evidence for the C-H bending transitions: W Aql at 14 microns (HCN) and both W Aql and S Cas at 13.7 microns (C2H2). Both W Aql and S Cas as well as S Lyr, a SC-type star, show 3 micron absorption which may arise from the C-H stretch of HCN and C2H2. In the case of NML Cyg, we show that the HCN and CO2 spectral features are formed in the CSE at temperatures well above those of the outermost CSE layers and derive approximate column densities. In the case of the S-stars, we discuss the evidence for the organic features and their photospheric origin.
Direct ab initio dynamics study of the reaction of C 2(A 3Π u) radical with C 2 H 6NASA Astrophysics Data System (ADS) Li, Na; Huo, Rui-Ping; Zhang, Xiang; Huang, Xu-Ri; Li, Ji-Lai; Sun, Chia-Chung updating The reaction of C 2 (A 3Π u) with C 2H 6 has been investigated at the BMC-CCSD//BB1K/6-311+G(2d, 2p) level. The classical barrier height for H-abstraction reaction is calculated to be 3.32 kcal/mol and the electron transfer behavior is also analyzed in detail. The rate constants are calculated by TST, CVT, and CVT/SCT over a wide temperature range 50-3000 K. The results indicate: (1) variational effect is small and nonclassical reflection effect is important to the H abstraction in high temperature region; and (2) variational effect is negligible and tunneling effect cooperating with the nonclassical reflection effect makes the rate constant temperature independence in low-temperature range. The CVT/SCT rate constants are in excellent agreement with experimental values.
Infrared Measurements of Atmospheric Ethane (C 2 H 6 ) From Aircraft and Ground-Based Solar Absorption Spectra in the 3000/ cm RegionNASA Technical Reports Server (NTRS) Coffey, M. T.; Mankin, W. G.; Goldman, A.; Rinsland, C. P.; Harvey, G. A.; Devi, V. Malathy; Stokes, G. M. updating A number or prominent Q-branches or the upsilon(sub 7) band or C2H6 have been identified near 3000/ cm in aircraft and ground-based infrared solar absorption spectra. The aircraft spectra provide the column amount above 12 km at various altitudes. The column amount is strongly correlated with tropopause height and can be described by a constant mixing ratio of 0.46 ppbv in the upper troposphere and a mixing ratio scale height of 3.9 km above the tropopause. The, ground-based spectra yield a column of 9.0 x 10(exp 15) molecules/sq cm above 2.1 km; combining these results implies a tropospheric mixing ratio of approximately 0.63 ppbv.
A theoretical investigation on optimal structures of ethane clusters (C 2 H 6 )n with n ≤ 25 and their building-up principle.PubMed Takeuchi, Hiroshi updating Geometry optimization of ethane clusters (C(2)H(6))(n) in the range of n ≤ 25 is carried out with a Morse potential. A heuristic method based on perturbations of geometries is used to locate global minima of the clusters. The following perturbations are carried out: (1) the molecule or group with the highest energy is moved to the interior of a cluster, (2) it is moved to stable positions on the surface of a cluster, and (3) orientations of one and two molecules are randomly modified. The geometry obtained after each perturbation is optimized by a quasi-Newton method. The global minimum of the dimer is consistent with that previously reported. The putative global minima of the clusters with 3 ≤ n ≤ 25 are first proposed and their building-up principle is discussed. Copyright © 2010 Wiley Periodicals, Inc.
Infrared measurements of atmospheric ethane (C 2 H 6 ) from aircraft and ground-based solar absorption spectra in the 3000/cm regionNASA Technical Reports Server (NTRS) Coffey, M. T.; Mankin, W. G.; Goldman, A.; Rinsland, C. P.; Harvey, G. A.; Devi, V. M.; Stokes, G. M. updating A number of prominent Q-branches of the nu-7 band of C2H6 have been identified near 3000/cm in aircraft and ground-based infrared solar absorption spectra. The aircraft spectra provide the column amount above 12 km at various altitudes. The column amount is strongly correlated with tropopause height and can be described by a constant mixing ratio of 0.46 ppbv in the upper troposphere and a mixing ratio scale height of 3.9 km above the tropopause. The ground-based spectra yield a column of 9.0 x 10 to the 15th molecules/sq cm above 2.1 km; combining these results implies a tropospheric mixing ratio of approximately 0.63 ppbv.
Particle Generation And Evolution In Silane (SiH4)/Acetylene (C 2 H 2 ) Flames In MicrogravityNASA Technical Reports Server (NTRS) Keil, D. G. updating The objective of this experimental program is to advance the understanding of the coupling of particle formation with gas phase combustion processes. The work utilizes the unique SiH4/C2H2 combustion system which generates particulate products ranging from high purity, white SiC to carbonaceous soot depending on equivalence ratio (Ref. 1). A goal of this work is to identify gas phase or particle formation processes that provide the enthalpy release needed to drive the combustion wave, and to locate the steps of the particle formation process that determine SiC stoichiometry and crystallinity. In a real sense, these SiH4/C2H2 flames act like highly sooty hydrocarbon flames, but with simpler chemistry. This simplification is expected to allow them to be used as surrogates to advance understanding of soot formation in such rich hydrocarbon flames. It is also expected that this improved understanding of SiC particle generation and evolution in these self-sustaining flames will advance the commercial potential of the flame process for the generation of high purity SiC powders.
A Layered Solution Crystal Growth Technique and the Crystal Structure of (C 6H 5C 2 H 4 NH 3) 2PbCl 4NASA Astrophysics Data System (ADS) Mitzi, D. B. updating Single crystals of the organic-inorganic perovskite (C6H5C2H4NH3)2PbCl4 have been grown at room temperature using a layered solution approach. The bottom solution layer, contained within a long straight tube, consists of PbCl2 dissolved in concentrated aqueous HCl. A less dense layer of methanol is carefully placed on top of the HCl/PbCl2 solution using a syringe. Finally, a stoichiometric quantity of C6H5C2H4NH2 (relative to the PbCl2) is added to the top of the column. As the layers slowly diffuse together, well-formed crystals of (C6H5C2H4NH3)2PbCl4 appear near the interface between the HCl/PbCl2 and C6H5C2H4NH2 solutions. The thick, plate-like crystals are well suited for X-ray crystallography studies. Room temperature intensity data were refined using a triclinic (Poverline1) cell (a=updating) Å, b=updating) Å, c=updating) Å, α= updating)°, β=updating)°, γ=updating)°, V=updating) Å3, Z=4, Rf/Rw=0.031/0.044). The organic-inorganic layered perovskite structure features well-ordered sheets of corner-sharing distorted PbCl6 octahedra separated by bilayers of phenethylammonium cations. Tilting and rotation of the PbCl6 octahedra within the perovskite sheets, coupled with organic cation ordering, leads to the unusual in-sheet 2ap×2ap superstructure, where ap is the lattice constant for the ideal cubic perovskite.
Distributions and Seasonal Variations of Tropospheric Ethene (C 2 H 4 ) from Atmospheric Chemistry Experiment (ACE-FTS) Solar Occultation SpectraNASA Technical Reports Server (NTRS) Herbin, H.; Hurtmans, D.; Clarisse, L.; Turquety, S.; Clerbaux, C.; Rinsland, Curtis P.; Boone, C.; Bernath, P. F.; Coheur, P.-F. updating This work reports the first measurements of ethene (C2H4) distributions in the upper troposphere. These are obtained by retrieving vertical profiles from 5 to 20 km from infrared solar occultation spectra recorded in 2005 and 2006 by the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS). Background volume mixin^ ratios (vmrs) ranging from a few to about 50 pptv (10(exp -1) are measured at the different altitudes, while for certain occultations, vmrs as high as 200 pptv are observed. Zonal distributions and vertically resolved latitudinal distributions are derived for the two year period analyzed, highlighting spatial - including a North-South gradient - as well as seasonal variations. We show the latter to be more pronounced at the highest latitudes, presumably as a result of less active photochemistry during winter. The observation of C2H4 enhancements in remote Arctic regions at high latitudes is consistent with the occurrence of fast transport processes of gaseous pollution from the continents leading to Arctic haze. Citation: Herbin, H., D. Hurtmans, L. Clarisse, S. Turquety, C. Clerbaux, C. P. Rinsland, C. Boone, P. F. Bernath, and P.-F. Colieur (2009), Distributions and seasonal variations of tropospheric ethene (C2H4) from Atmospheric Chemistry Experiment (ACE-FTS) solar occultation spectra,
Laser induced fluorescence of HCCO (DCCO) radical formed in O+C 2 H 2 (C2D2) reactionNASA Astrophysics Data System (ADS) Inoue, Gen; Suzuki, Makoto updating Laser induced fluorescence of HCCO (DCCO) radical have been obtained in the reaction of O(3P)+C2H2(C2D2) for the first time (X 2A'-2A`). The laser excitation spectra have been obtained over the wavelength region from 310 to 370 nm. The collision-free lifetimes for HCCO and DCCO are 0.14 and 3.8 μs, respectively. From the excitation and dispersed fluorescence spectra, some vibrational energies have been obtained in cm-1 unit: updating), 150-140 (n.a.), and updating) for the ground state HCCO (DCCO), and updating), updating), and updating) for the excited state HCCO (DCCO). The band origin ν00 is updating cm-1.
Genome-Wide Analysis of C 2 H 2 Zinc-Finger Family Transcription Factors and Their Responses to Abiotic Stresses in Poplar (Populus trichocarpa)PubMed Central Liu, Quangang; Wang, Zhanchao; Xu, Xuemei; Zhang, Haizhen; Li, Chenghao updating Background C2H2 zinc-finger (C2H2-ZF) proteins are a large gene family in plants that participate in various aspects of normal plant growth and development, as well as in biotic and abiotic stress responses. To date, no overall analysis incorporating evolutionary history and expression profiling of the C2H2-ZF gene family in model tree species poplar (Populus trichocarpa) has been reported. Principal Findings Here, we identified 109 full-length C2H2-ZF genes in P. trichocarpa, and classified them into four groups, based on phylogenetic analysis. The 109 C2H2-ZF genes were distributed unequally on 19 P. trichocarpa linkage groups (LGs), with 39 segmental duplication events, indicating that segmental duplication has been important in the expansion of the C2H2-ZF gene family. Promoter cis-element analysis indicated that most of the C2H2-ZF genes contain phytohormone or abiotic stress-related cis-elements. The expression patterns of C2H2-ZF genes, based on heatmap analysis, suggested that C2H2-ZF genes are involved in tissue and organ development, especially root and floral development. Expression analysis based on quantitative real-time reverse transcription polymerase chain reaction indicated that C2H2-ZF genes are significantly involved in drought, heat and salt response, possibly via different mechanisms. Conclusions This study provides a thorough overview of the P. trichocarpa C2H2-ZF gene family and presents a new perspective on the evolution of this gene family. In particular, some C2H2-ZF genes may be involved in environmental stress tolerance regulation. PtrZFP2, 19 and 95 showed high expression levels in leaves and/or roots under environmental stresses. Additionally, this study provided a solid foundation for studying the biological roles of C2H2-ZF genes in Populus growth and development. These results form the basis for further investigation of the roles of these candidate genes and for future genetic engineering and gene functional studies in Populus. PMID
Special hydrogen bonds observed in two monovalent metal carboxylate-phosphinates: {NaH(Phsbnd PO2sbnd C 2 H 4 sbnd COOH)2}∞ and {[KH(Phsbnd PO2sbnd C 2 H 4 sbnd COOH)2]·H2O}∞NASA Astrophysics Data System (ADS) Zhao, Cui-Cui; Zhang, Jian-Wei; Zhou, Zhong-Gao; Du, Zi-Yi updating The addition of strong base such as sodium hydroxide or potassium hydroxide to the aqueous solution of (2-carboxyethyl)(phenyl)phosphinic acid afforded two novel monovalent metal carboxylate-phosphinates, namely, {NaH(Phsbnd PO2sbnd C2H4sbnd COOH)2}∞ (1) and {[KH(Phsbnd PO2sbnd C2H4sbnd COOH)2]·H2O}∞ (2). They represent the first examples of phosphinate containing short, symmetric or almost symmetric O&ctdot;H&ctdot;O hydrogen bonds.
Reinvestigation of the elementary chemical kinetics of the reaction C2H5(•) + HBr (HI) → C 2 H 6 + Br(•) (I(•)) in the range 293-623 K and its implication on the thermochemical parameters of C2H5(•) free radical.PubMed Leplat, N; Wokaun, A; Rossi, M J updating A reinvestigation of the absolute rate constants of the metathesis reactions C2H5• + HBr → C2H6 + Br• (R1) and C2H5• + HI → C2H6 + I• (R2) has been performed and led to the following Arrhenius expressions: k1 = 3.69(±0.95) × 10–11 exp(−10.62(±0.66)/RT), k2 = 1.20(±0.38) × 10–11 exp(−7.12(±1.059)/RT) in the temperature range 293–623 K (A/cm3 molecule–1 s–1, Ea/kJ mol–1). The study has been performed using a Knudsen reactor coupled to single-photon (VUV) photoionization mass spectrometer (SPIMS). Hydrocarbon free radicals have been generated externally before admission into the Knudsen reactor according to two different chemical schemes, enabling the generation of thermalized C2H5• free radicals. A minor correction to k1 and k2 for the wall loss of C2H5• (kw) has been applied throughout the temperature range. The obtained results are consistent regarding both the disappearance of C2H5• and the formation of closed shell products (n-C4H10, C2H4, C2H6), indicating that the chemical mechanism is largely understood and complete. Thermochemical parameters for C2H5• free radical resulting from the present kinetic measurements are discussed and point toward a slightly lower value for the standard heat of formation ΔfH298°(C2H5•) compared to some presently recommended values. On the basis of the present results and suitable data on the reverse reaction taken from the literature, we recommend ΔfH298°(C2H5•) = 117.3 ± 3.1 kJ/mol resulting from an average of “third law” evaluations using S298°(C2H5•) = 242.9 ± 4.6 J/K mol. The present work yields a standard heat of formation in satisfactory agreement with the results obtained by W. Tsang (ΔfH298°(C2H5•) = 119 ± 2 kJ/mol) despite using two very different experimental techniques.
Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C 2 H 4 F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)NASA Astrophysics Data System (ADS) Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V. This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)' providing data from direct measurement of pressure and mole fraction in vapor phase at variable mole fraction in liquid phase and constant temperature.
Ab initio rate constants from hyperspherical quantum scattering: Application to H+C 2 H 6 and H+CH3OHNASA Astrophysics Data System (ADS) Kerkeni, Boutheïna; Clary, David C. updating The dynamics and kinetics of the abstraction reactions of H atoms with ethane and methanol have been studied using a quantum mechanical procedure. Bonds being broken and formed are treated with explicit hyperspherical quantum dynamics. The ab initio potential energy surfaces for these reactions have been developed from a minimal number of grid points (average of 48 points) and are given by analytical functionals. All the degrees of freedom except the breaking and forming bonds are optimized using the second order perturbation theory method with a correlation consistent polarized valence triple zeta basis set. Single point energies are calculated on the optimized geometries with the coupled cluster theory and the same basis set. The reaction of H with C2H6 is endothermic by 1.5 kcal/mol and has a vibrationally adiabatic barrier of 12 kcal/mol. The reaction of H with CH3OH presents two reactive channels: the methoxy and the hydroxymethyl channels. The former is endothermic by 0.24 kcal/mol and has a vibrationally adiabatic barrier of 13.29 kcal/mol, the latter reaction is exothermic by 7.87 kcal/mol and has a vibrationally adiabatic barrier of 8.56 kcal/mol. We report state-to-state and state-selected cross sections together with state-to-state rate constants for the title reactions. Thermal rate constants for these reactions exhibit large quantum tunneling effects when compared to conventional transition state theory results. For H+CH3OH, it is found that the CH2OH product is the dominant channel, and that the CH3O channel contributes just 2% at 500 K. For both reactions, rate constants are in good agreement with some measurements.
Pressure dependence of the absolute rate constant for the reaction OH + C 2 H 2 from 228 to 413KNASA Technical Reports Server (NTRS) Michael, J. V.; Nava, D. F.; Borokowski, R. P.; Payne, W. A.; Stief, L. J. updating The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.
Structure, Stabilities, Thermodynamic Properties, and IR Spectra of Acetylene Clusters (C 2 H 2 )n=2-5.PubMed Karthikeyan, S; Lee, Han Myoung; Kim, Kwang S updating There are no clear conclusions over the structures of the acetylene clusters. In this regard, we have carried out high-level calculations for acetylene clusters (C2H2)2-5 using dispersion-corrected density functional theory (DFT-D), Møller-Plesset second-order perturbation theory (MP2); and coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] at the complete basis set limit. The lowest energy structure of the acetylene dimer has a T-shaped structure of C2v symmetry, but it is nearly isoenergetic to the displaced stacked structure of C2h symmetry. We find that the structure shows the quantum statistical distribution for configurations between the T-shaped and displaced stacked structures for which the average angle (|θ̃|) between two acetylene molecules would be 53-78°, close to the T-shaped structure. The trimer has a triangular structure of C3h symmetry. The tetramer has two lowest energy isomers of S4 and C2h symmetry in zero-point energy (ZPE)-uncorrected energy (ΔEe), but one lowest energy isomer of C2v symmetry in ZPE-corrected energy (ΔE0). For the pentamer, the global minimum structure is C1 symmetry with eight sets of T-type π-H interactions and a set of π-π interactions. Our high-level ab initio calculations are consistent with available experimental data.

Estimates of methane emissions from India using CH4-CO-C 2 H 6 relationships from CARIBIC observations in monsoon convective outflowNASA Astrophysics Data System (ADS) Baker, A. K.; Rauthe-Schöch, A.; Schuck, T. J.; van Velthoven, P. F.; Slemr, F.; Brenninkmeijer, C. A. updating A large fraction of methane sources are anthropogenic, and include fossil fuel use, biomass/biofuel burning, agriculture and waste treatment. Recently, much attention regarding emissions of greenhouse gases has focused on large, developing nations, as their emissions are expected to rise rapidly over the coming decades. As the second most populous country in the world, and one of the fastest growing economies, India has been of particular interest. Arguably the most important feature of meteorology in India is the Asian summer monsoon. During the monsoon period there exists persistent deep convection over Southern Asia, and the composition of convected air masses is strongly influenced by emissions from India. This ultimately results in a well-mixed air parcel containing air from India being transported to the upper troposphere. Over the course of the 2008 monsoon period the CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) passenger aircraft conducted monthly measurement flights which probed this outflow. Data collected during these flights provides a unique opportunity to examine sources of atmospheric species in India. Here we use measurements of methane (CH4), carbon monoxide (CO) and ethane (C2H6) from whole air samples collected during CARIBIC flights to estimate emissions of methane and to quantify those emissions related to flooding during the monsoon. Methane data from the monsoon period show enhancements inside the monsoon plume, which increase as the monsoon progresses. Using emission data for CO and ΔCH4/ΔCO derived from CARIBIC measurements, we estimate total methane emissions to be ~40 Tg yr-1. Relationships of methane to ethane, which shares the bulk of its sources with methane but lacks a biological component, are further used to estimate the fraction of “extra” emissions from biological activity related to increased monsoon rains. This additional methane is a considerable fraction of
HIGH-RESOLUTION FOURIER TRANSFORM INFRARED SPECTRUM OF THE ν2 + ν12 BAND OF ETHYLENE (12C 2 H 4 )NASA Astrophysics Data System (ADS) Lebron, G. B.; Tan, T. L. updating The high-resolution Fourier transform infrared absorption spectrum of the ν2 + ν12 combination band of normal ethylene (12C2H4) in the updating cm-1 region was recorded at a resolution of 0.0063 cm-1 and at an ambient temperature of 296 K. Upper state rovibrational analysis was carried out using a standard Watson's Hamiltonian in asymmetric reduction in Ir representation. The band center, rotational constants and centrifugal distortion constants up to quartic terms of the upper ν2 + ν12 = 1 state were determined from the final fit that included 102 infrared transitions. The root-mean-square deviation of the fit was updating cm-1.
Pulsed-laser excitation of acoustic modes in open high-Q photoacoustic resonators for trace gas monitoring: results for C 2 H 4NASA Astrophysics Data System (ADS) Brand, Christian; Winkler, Andreas; Hess, Peter; Miklós, András; Bozóki, Zoltán; Sneider, János updating The pulsed excitation of acoustic resonances was studied with a continuously monitoring photoacoustic detector system. Acoustic waves were generated in C2H4/N 2 gas mixtures by light absorption of the pulses from a transversely excited atmospheric CO2 laser. The photoacoustic part consisted of high-Q cylindrical resonators (Q factor 820 for the first radial mode in N2) and two adjoining variable acoustic filter systems. The time-resolved signal was Fourier transformed to a frequency spectrum of high resolution. For the first radial mode a Lorentzian profile was fitted to the measured data. The outside noise suppression and the signal-to-noise ratio were investigated in a normal laboratory environment in the flow-through mode. The acoustic and electric filter system combined with the
Band gap narrowing in n-type and p-type 3C -, 2 H -, 4 H-, 6H-SiC, and SiNASA Astrophysics Data System (ADS) Persson, C.; Lindefelt, U.; Sernelius, B. E. updating Doping-induced energy shifts of the conduction band minimum and the valence band maximum have been calculated for n-type and p-type 3C-, 2H-, 4H-, 6H-SiC, and Si. The narrowing of the fundamental band gap and of the optical band gap are presented as functions of ionized impurity concentration. The calculations go beyond the common parabolic treatments of the ground state energy dispersion by using energy dispersion and overlap integrals from band structure calculations. The nonparabolic valence band curvatures influence strongly the energy shifts especially in p-type materials. The utilized method is based on a zero-temperature Green's function formalism within the random phase approximation with local field correction according to Hubbard. We have parametrized the shifts of the conduction and the valence bands and made comparisons with recently published results from a semi-empirical model.
Detonation re-initiation in a concentric tube arrangement for C _2 H _2 /O_2/Ar mixturesNASA Astrophysics Data System (ADS) Wu, Y.; Lee, J. H. S.; Weng, C. updating Re-initiation of detonation in a concentric tube arrangement where a detonation exiting from a small diameter inner tube to a large diameter outer tube has been investigated. The outer tube diameter D is 50.8 mm and inner tube diameters d are 38, 25.4, and 12.7 mm giving diameter ratios D/d=1.34, 2, and 4. Stoichiometric C_2H_2-O_2 mixtures with argon dilution of 0, 25, 50, and 70% are used in the present study. Velocity measurements are made using photodiodes, and smoked foils downstream of the exit of the inner tube are also used to record the re-initiation process. Upon exit from the inner tube, the detonation suffers an abrupt decrease in velocity and at critical conditions, the velocity downstream of the exit is of the order of 50% of the Chapman-Jouguet velocity. It is found that re-initiation generally occurs within 10 tube diameters downstream of the exit. If re-initiation is not successful, the detonation continues to propagate at a low velocity for distances of the order of 30 tube diameters without any indication of flame acceleration of deflagration-to-detonation transition (DDT). Thus, the re-initiation process is clearly defined and distinct from the usual DDT in a smooth tube. The critical d/λ value ratio in the concentric tube is significantly lower than the usual unconfined case of d/λ =13 where λ is the detonation cell size. Thus, it is a result of re-initiation at the Mach stem of the reflected shock from the wall of the outer concentric tube. If re-initiation is not successful upon the first reflection, then subsequent multiple reflections at the tube axis and wall of the outer tube can also result in re-initiation. However, this is only observed for undiluted mixtures. For high-argon-diluted mixtures, re-initiation only occurs at the Mach stem of the first reflection.
Investigation of CO, C 2 H 6 and aerosols in a boreal fire plume over eastern Canada during BORTAS 2011 using ground- and satellite-based observations, and model simulationsNASA Astrophysics Data System (ADS) Griffin, D.; Walker, K. A.; Franklin, J. E.; Parrington, M.; Whaley, C.; Hopper, J.; Drummond, J. R.; Palmer, P. I.; Strong, K.; Duck, T. J.; Abboud, I.; Bernath, P. F.; Clerbaux, C.; Coheur, P.-F.; Curry, K. R.; Dan, L.; Hyer, E.; Kliever, J.; Lesins, G.; Maurice, M.; Saha, A.; Tereszchuk, K.; Weaver, D. updating We present the results of total column measurements of CO, C2H6 and fine mode aerosol optical depth (AOD) during the "Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites" (BORTAS-B) campaign over Eastern Canada. Ground-based observations, using Fourier transform spectrometers (FTSs) and sun photometers, were carried out in July and August 2011. These measurements were taken in Halifax, Nova Scotia, which is an ideal location to monitor the outflow of boreal fires from North America, and also in Toronto, Ontario. Measurements of fine mode AOD enhancements were highly correlated with enhancements in coincident trace gas (CO and C2H6) observations between 19 and 21 July 2011, which is typical for a smoke plume event. In this paper, we focus on the identification of the origin and the transport of this smoke plume. We use back-trajectories calculated by the Canadian Meteorological Centre as well as FLEXPART forward-trajectories to demonstrate that the enhanced CO, C2H6 and fine mode AOD seen near Halifax and Toronto originated from forest fires in Northwestern Ontario that occurred between 17 and 19 July 2011. In addition, total column measurements of CO from the satellite-borne Infrared Atmospheric Sounding Interferometer (IASI) have been used to trace the smoke plume and to confirm the origin of the CO enhancement. Furthermore, the emission ratio (ERC2H6/CO) and the emission factor (EFC2H6) of C2H6 (with respect to the CO emission) were estimated from these ground-based observations. These C2H6 emission results from boreal fires in Northwestern Ontario agree well with C2H6 emission measurements from other boreal regions, and are relatively high compared to fires from other geographical regions. The ground-based CO and C2H6 observations were compared with outputs from the 3-D global chemical transport model GEOS-Chem, using the Fire Locating And Monitoring of Burning Emissions (FLAMBE) inventory
Investigation of CO, C 2 H 6 and aerosols in a boreal fire plume over eastern Canada during BORTAS 2011 using ground- and satellite-based observations and model simulationsNASA Astrophysics Data System (ADS) Griffin, D.; Walker, K. A.; Franklin, J. E.; Parrington, M.; Whaley, C.; Hopper, J.; Drummond, J. R.; Palmer, P. I.; Strong, K.; Duck, T. J.; Abboud, I.; Bernath, P. F.; Clerbaux, C.; Coheur, P.-F.; Curry, K. R.; Dan, L.; Hyer, E.; Kliever, J.; Lesins, G.; Maurice, M.; Saha, A.; Tereszchuk, K.; Weaver, D. updating We present the results of total column measurements of CO, C2H6 and fine-mode aerosol optical depth (AOD) during the "Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites" (BORTAS-B) campaign over eastern Canada. Ground-based observations, using Fourier transform spectrometers (FTSs) and sun photometers, were carried out in July and August 2011. These measurements were taken in Halifax, Nova Scotia, which is an ideal location to monitor the outflow of boreal fires from North America, and also in Toronto, Ontario. Measurements of fine-mode AOD enhancements were highly correlated with enhancements in coincident trace gas (CO and C2H6) observations between 19 and 21 July 2011, which is typical for a smoke plume event. In this paper, we focus on the identification of the origin and the transport of this smoke plume. We use back trajectories calculated by the Canadian Meteorological Centre as well as FLEXPART forward trajectories to demonstrate that the enhanced CO, C2H6 and fine-mode AOD seen near Halifax and Toronto originated from forest fires in northwestern Ontario that occurred between 17 and 19 July 2011. In addition, total column measurements of CO from the satellite-borne Infrared Atmospheric Sounding Interferometer (IASI) have been used to trace the smoke plume and to confirm the origin of the CO enhancement. Furthermore, the enhancement ratio - that is, in this case equivalent to the emission ratio (ERC2H6/CO) - was estimated from these ground-based observations. These C2H6 emission results from boreal fires in northwestern Ontario agree well with C2H6 emission measurements from other boreal regions, and are relatively high compared to fires from other geographical regions. The ground-based CO and C2H6 observations were compared with outputs from the 3-D global chemical transport model GEOS-Chem, using the Fire Locating And Modeling of Burning Emissions (FLAMBE) inventory. Agreement within the
Assembly of [Cu2(COO)4] and [M3(μ3-O)(COO)6] (M = Sc, Fe, Ga, and In) building blocks into porous frameworks towards ultra-high C 2 H 2 /CO2 and C 2 H 2 /CH4 separation performance.PubMed Zhang, Jian-Wei; Hu, Man-Cheng; Li, Shu-Ni; Jiang, Yu-Cheng; Qu, Peng; Zhai, Quan-Guo updating A porous MOF platform (SNNU-65s) formed by creatively combining paddle-wheel-like [Cu 2 (COO) 4 ] and trigonal prismatic [M 3 (μ 3 -O)(COO) 6 ] building blocks was designed herein. The mixed and high-density open metal sites and the OH-functionalized pore surface promote SNNU-65s to exhibit ultra-high C 2 H 2 uptake and separation performance. Impressively, SNNU-65-Cu-Ga stands out for the highest C 2 H 2 /CO 2 (18.7) and C 2 H 2 /CH updating) selectivity among all the reported MOFs at room temperature.
Infrared Solar Spectroscopic Measurements of Free Tropospheric CO, C 2 H 6 , and HCN above Mauna Loa, Hawaii: Seasonal Variations and Evidence for Enhanced Emissions from the Southeast Asian Tropical Fires of updatingNASA Technical Reports Server (NTRS) Rinsland, C. P.; Goldman, A.; Murcray, F. J.; Stephen, T. M.; Pougatchev, N. S.; Fishman, J.; David, S. J.; Blatherwick, R. D.; Novelli, P. C.; Jones, N. B. updating High spectral resolution (0.003 per cm) infrared solar absorption measurements of CO, C2H6, and HCN have been recorded at the Network for the Detection of Stratospheric Change station on Mauna Loa, Hawaii, (19.5N, 155.6W, altitude 3.4 km). The observations were obtained on over 250 days between August 1995 and February 1998. Column measurements are reported for the 3.4-16 km altitude region, which corresponds approximately to the free troposphere above the station. Average CO mixing ratios computed for this layer have been compared with flask sampling CO measurements obtained in situ at the station during the same time period. Both show asymmetrical seasonal cycles superimposed on significant variability. The first 2 years of observations exhibit a broad January-April maximum and a sharper CO minimum during late summer. The C2H6 and CO 3.4-16 km columns were highly correlated throughout the observing period with the C2H6/CO slope intermediate between higher and lower values derived from similar infrared spectroscopic measurements at 32'N and 45'S latitude, respectively. Variable enhancements in CO, C2H6, and particularly HCN were observed beginning in about September 1997. The maximum HCN free tropospheric monthly mean column observed in November 1997 corresponds to an average 3.4-16 km mixing ratio of 0.7 ppbv (1 ppbv = 10(exp -9) per unit volume), more than a factor of 3 above the background level. The HCN enhancements continued through the end of the observational series. Back-trajectory calculations suggest that the emissions originated at low northern latitudes in southeast Asia. Surface CO mixing ratios and the C2H6 tropospheric columns measured during the same time also showed anomalous autumn 1997 maxima. The intense and widespread tropical wild fires that burned during the strong El Nino warm phase of updating are the likely source of the elevated emission products.
Laser-induced fluorescence studies of excited Sr reactions: II. Sr(3P1)+CH3F, C2H5F, C 2 H 4 F2NASA Astrophysics Data System (ADS) Teule, J. M.; Janssen, M. H. M.; Bulthuis, J.; Stolte, S. updating The vibrational and rotational energy distributions of ground state SrF(X 2Σ) formed in the reactions of electronically excited Sr(3P1) with methylfluoride, ethylfluoride, and 1,1-difluoroethane have been studied by laser-induced fluorescence. Although the reactions of ground state Sr with these reactants are exothermic, no SrF products are observed for those reactions in this study. The fraction of available energy disposed into the sum of rotational and vibrational energy of the SrF(X 2Σ) product is approximately the same for all three reactions, i.e., 40%. The reaction of Sr(3P1) with CH3F results in very low vibrational excitation in the SrF reaction product. The product vibration increases in going to C2H5F and C2H4F2. It is concluded that the alkyl group influences the energy disposal mechanism in these reactions, and some suggestions are given for a partial explanation of the observations.
Multireference configuration interaction study of the mixed Valence-Rydberg character of the C 2 H 4 1(π,π*) V stateNASA Astrophysics Data System (ADS) Krebs, Stefan; Buenker, Robert J. updating The spatial extension of the C2H41(π,π*) V state is investigated by means of low selection threshold multireference configuration interaction (CI) calculations employing two atomic orbital (AO) basis sets with different numbers of polarization and Rydberg functions. The results are shown to be nearly independent of the choice of one-electron basis (ground N, triplet T, and singlet V self-consistent field molecular orbitals (SCF MOs)) in forming the many-electron basis for the configuration interaction indicating that the AO basis limit has been closely approached in each case. The calculations indicate that the value for the ≡V matrix element falls in the 18±1 a02 range, 50% larger than the corresponding values computed for N and T, respectively, for the corresponding N and T states. This result is interpreted to be a consequence of the mixing of diabatic 1(π,π*) valence and 1(π,dπ) Rydberg states in the Franck-Condon region of the V-N transition. The corresponding excitation energy is computed to lie in the updating eV range, indicating that there is a distinct nonverticality in the measured absorption spectrum which is caused in part by nonadiabatic interactions between the V and 1(π,3py) Rydberg states as a result of torsional motion of the C2H4 molecule.
Precise ro-vibrational analysis of molecular bands forbidden in absorption: The ν8 +ν10 band of the 12C 2 H 4 moleculeNASA Astrophysics Data System (ADS) Ulenikov, O. N.; Gromova, O. V.; Bekhtereva, E. S.; Kashirina, N. V.; Bauerecker, S.; Horneman, V.-M. updating The highly accurate (experimental accuracy in line positions ∼ (1 - 2) ×10-4 cm-1) ro-vibrational spectrum of the ν8 +ν10 band of the 12C2H4 molecule was recorded for the first time with high resolution Fourier transform spectrometry and analyzed in the region of updating cm-1 using the Hamiltonian model which takes into account Coriolis resonance interactions between the studied ν8 +ν10 band, which is forbidden in absorption, and the bands ν4 +ν8 and ν7 +ν8 . About 1570 transitions belonging to the ν8 +ν10 band were assigned in the experimental spectra with the maximum values of quantum numbers Jmax. = 35 and Kamax . = 18 . On that basis, a set of 38 vibrational, rotational, centrifugal distortion, and resonance interaction parameters was obtained from the fit. They reproduce values of 598 initial "experimental" ro-vibrational energy levels (positions of about 1570 experimentally recorded and assigned transitions) with the rms error drms = 0.00045 cm-1 (drms = 0.00028 cm-1 when upper ro-vibrational energies obtained from blended and very weak transitions were deleted from the fit).
Dewetting behavior of polystyrene film filled with (C6H5C 2 H 4 NH3)2PbI4NASA Astrophysics Data System (ADS) Xue, Longjian; Cheng, Ziyong; Fu, Jun; Han, Yanchun updating The dewetting behavior of thin (about 30 nm) polystyrene (PS) films filled with different amount of (C6H5C2H4NH3)2PbI4 (PhE-PbI4) on the silicon substrate with a native oxide layer was investigated. For different additive concentrations, PhE-PbI4 showed different spatial distributions in the PS films, which had a strong influence on the film wettability, dewetting dynamics, and mechanism. With 0.5 wt % additive, PhE-PbI4 formed a noncontinuous diffusion layer, which caused a continuous hole nucleation in the film. With about 1 wt % additive, a continuous gradient distribution layer of PhE-PbI4 formed in the film, which inhibited the dewetting. When the concentration is higher (2 wt %), large PhE-PbI4 aggregates, in addition to the PhE-PbI4 continuous layer, formed in the film. These large aggregates (larger than radius of gyration of PS) migrated to the interface, resulting in the hole nucleation and eventually the complete dewetting of the film.
Chemistry through cocrystals: pressure-induced polymerization of C 2 H 2 ·C 6H 6 to an extended crystalline hydrocarbonSciTech Connect Ward, Matthew D.; Huang, Haw-Tyng; Zhu, Li The 1:1 acetylene–benzene cocrystal, C 2H 2·C 6H 6, was synthesized under pressure in a diamond anvil cell (DAC) and its evolution under pressure was studied with single-crystal X-ray diffraction and Raman spectroscopy.
Chemistry through cocrystals: pressure-induced polymerization of C 2 H 2 ·C 6H 6 to an extended crystalline hydrocarbonSciTech Connect Ward, Matthew D.; Huang, Haw-Tyng; Zhu, Li The 1 : 1 acetylene–benzene cocrystal, C 2H 2·C 6H 6, was synthesized under pressure in a diamond anvil cell (DAC) and its evolution under pressure was studied with single-crystal X-ray diffraction and Raman spectroscopy.
The decomposition of mixed oxide Ag2Cu2O3: Structural features and the catalytic properties in CO and C 2 H 4 oxidationNASA Astrophysics Data System (ADS) Svintsitskiy, Dmitry A.; Kardash, Tatyana Yu.; Slavinskaya, Elena M.; Stonkus, Olga A.; Koscheev, Sergei V.; Boronin, Andrei I. updating The mixed silver-copper oxide Ag2Cu2O3 with a paramelaconite crystal structure is a promising material for catalytic applications. The as-prepared sample of Ag2Cu2O3 consisted of brick-like particles extended along the [001] direction. A combination of physicochemical techniques such as TEM, XPS and XRD was applied to investigate the structural features of this mixed silver-copper oxide. The thermal stability of Ag2Cu2O3 was investigated using in situ XRD under different reaction conditions, including a catalytic CO + O2 mixture. The first step of Ag2Cu2O3 decomposition was accompanied by the appearance of ensembles consisting of silver nanoparticles with sizes of 5-15 nm. Silver nanoparticles were strongly oriented to each other and to the surface of the initial Ag2Cu2O3 bricks. Based on the XRD data, it was shown that the release of silver occurred along the a and b axes of the paramelaconite structure. Partial decomposition of Ag2Cu2O3 accompanied by the formation of silver nanoparticles was observed during prolonged air storage under ambient conditions. The high reactivity is discussed as a reason for spontaneous decomposition during Ag2Cu2O3 storage. The full decomposition of the mixed oxide into metallic silver and copper (II) oxide took place at temperatures higher than 300 °C regardless of the nature of the reaction medium (helium, air, CO + O2). Catalytic properties of partially and fully decomposed samples of mixed silver-copper oxide were measured in low-temperature CO oxidation and C2H4 epoxidation reactions.
Prediction of the PVTx and VLE properties of natural gases with a general Helmholtz equation of state. Part I: Application to the CH4-C 2 H 6 -C3H8-CO2-N2 systemNASA Astrophysics Data System (ADS) Mao, Shide; Lü, Mengxin; Shi, Zeming updating A general equation of state (EOS) explicit in Helmholtz free energy has been developed to predict the pressure-volume-temperature-composition (PVTx) and vapor-liquid equilibrium (VLE) properties of the CH4-C2H6-C3H8-CO2-N2 fluid mixtures (main components of natural gases). This EOS, which is a function of temperature, density and composition, with four mixing parameters used, is based on the improved EOS of Sun and Ely (2004) for the pure components (CH4, C2H6, C3H8, CO2 and N2) and contains a simple generalized departure function presented by Lemmon and Jacobsen (1999). Comparison with the experimental data available indicates that the EOS can calculate the PVTx and VLE properties of the CH4-C2H6-C3H8-CO2-N2 fluid mixtures within or close to experimental uncertainties up to 623 K and 1000 bar within full range of composition. Isochores of the CH4-C2H6-C3H8-CO2-N2 system can be directly calculated from this EOS to interpret the corresponding microthermometric and Raman analysis data of fluid inclusions. The general EOS can calculate other thermodynamic properties if the ideal Helmholtz free energy of fluids is combined, and can also be extended to the multi-component natural gases including the secondary alkanes (carbon number above three) and none-alkane components such as H2S, SO2, O2, CO, Ar and H2O. This part of work will be finished in the near future.
Hydrogen addition reactions of aliphatic hydrocarbons in cometsNASA Astrophysics Data System (ADS) Kobayashi, Hitomi; Watanabe, N.; Watanabe, Y.; Fukushima, T.; Kawakita, H. updating Comets are thought as remnants of early solar nebula. Their chemical compositions are precious clue to chemical and physical evolution of the proto-planetary disk. Some hydrocarbons such as C2H6, C2H2 and CH4 in comets have been observed by using near-infrared spectroscopy. Although the compositions of C2H6 were about 1% relative to the water in normal comets, there are few reports on the detection of C2H6 in ISM. Some formation mechanisms of C2H6 in ISM have been proposed, and there are two leading hypotheses; one is the dimerizations of CH3 and another is the hydrogen addition reactions of C2H2 on cold icy grains. To evaluate these formation mechanisms for cometary C2H6 quantitatively, it is important to search the C2H4 in comets, which is the intermediate product of the hydrogen addition reactions toward C2H6. However, it is very difficult to detect the C2H4 in comets in NIR (3 microns) regions because of observing circumstances. The hydrogen addition reactions of C2H2 at low temperature conditions are not well characterized both theoretically and experimentally. For example, there are no reports on the reaction rate coefficients of those reaction system. To determine the production rates of those hydrogen addition reactions, we performed the laboratory experiments of the hydrogenation of C2H2 and C2H4. We used four types of the initial composition of the ices: pure C2H4, pure C2H2, C2H2 on amorphous solid water (ASW) and C2H4 on ASW at three different temperatures of 10, 20, and 30K. We found 1) reactions are more efficient when there are ASW in the initial compositions of the ice; 2) hydrogenation of C2H4 occur more rapid than that of C2H2.
A theoretical study of the hydrogen bonding between the vic-, cis- and trans-C 2 H 2 F 2 isomers and hydrogen fluorideNASA Astrophysics Data System (ADS) Rusu, Victor H.; da Silva, João Bosco P.; Ramos, Mozart N. updating MP2/6-31++G(d,p) and B3LYP/6-31++G(d,p) theoretical calculations have been employed to investigate the hydrogen bonding formation involving the vic-, cis- and trans-C 2H 2F 2 isomers and hydrogen fluoride. Our calculations have revealed for each isomer the preferential existence of two possible hydrogen-bonded complexes: a non-cyclic complex and a cyclic complex. For all the three isomers the binding energies for the non-cyclic and cyclic hydrogen complexes are essentially equal using both the MP2 and B3LYP calculations, being that the cyclic structure is slightly more stable. For instance, the binding energies including BSSE and ZPE corrections for the non-cyclic and cyclic structures of cis-C 2H 2F···HF are 8.7 and 9.0 kJ mol -1, respectively, using B3LYP calculations. The cyclic complex formation reduces the polarity, in contrast to what occurs with the non-cyclic complex. This result is more accentuated in vic-C 2H 2F 2···HF. In this latter, Δ μ(cyclic) is -3.07 D, whereas Δ μ(non-cyclic) is +1.92 D using B3LYP calculations. Their corresponding MP2 values are +0.44 D and -1.89 D, respectively. As expected, the complexation produces an H sbnd F stretching frequency downward shift, whereas its IR intensity is enhanced. On the other hand, the vibrational modes of the vic-, cis- and trans-C 2H 2F 2 isomers are little affected by complexation. The new vibrational modes due to hydrogen bonding formation show several interesting features, in particular the HF bending modes which are pure rotations in the free molecule.
Classical Trajectory Study of Collision Energy Transfer between Ne and C 2 H 2 on a Full Dimensional Accurate Potential Energy Surface.PubMed Liu, Yang; Huang, Yin; Ma, Jianyi; Li, Jun updating Collision energy transfer plays an important role in gas phase reaction kinetics and relaxation of excited molecules. However, empirical treatments are generally adopted for the collisional energy transfer in the master equation based approach. In this work, classical trajectory approach is employed to investigate the collision energy transfer dynamics in the C 2 H 2 -Ne system. The entire potential energy surface is described as the sum of the C 2 H 2 potential and interaction potential between C 2 H 2 and Ne. It is highlighted that both parts of the entire potential are highly accurate. In particular, the interaction potential is fit to ∼41 300 configurations determined at the level of CCSD(T)-F12a/cc-pCVTZ-F12 with the counterpoise correction. Collision energy transfer dynamics are then carried out on this benchmark potential and the widely used Lennard-Jones and Buckingham interaction potentials. Energy transfers and related probability densities at different collisional energies are reported and discussed.

Infrared Solar Spectroscopic Measurements of Free Tropospheric CO, C 2 H 6 , and HCN above Mauna Loa, Hawaii: Seasonal Variations and Evidence for Enhanced Emissions from the Southeast Asian Fires of updating. RevisedNASA Technical Reports Server (NTRS) Rinsland, C. P.; Goldman, A.; Murcray, F. J.; Stephen, T. M.; Pougatchev, N. S.; Fishman, J.; David, S. J.; Blatherwick, R. D.; Novelli, P. C.; Jones, N. B.; updating High spectral resolution (0.003/ cm) infrared solar absorption measurements of CO, C2H6, and HCN have been recorded at the Network for the Detection of Stratospheric Change station on Mauna Loa, Hawaii, (19.5 deg N, 155.6 deg W, altitude 3.4 km). The observations were obtained on over 250 days between August 1995 and February 1998. Column measurements are reported for the updating km altitude region, which corresponds approximately to the free troposphere above the station. Average CO mixing ratios computed for this layer have been compared with flask sampling CO measurements obtained in situ at the station during the same time period. Both show asymmetrical seasonal cycles superimposed on significant variability. The first two years of observations exhibit a broad January-April maximum and a sharper CO minimum during late summer. The C2H6 and CO updating km columns were highly correlated throughout the observing period with the C2H6/CO slope intermediate between higher and lower values derived from similar infrared spectroscopic measurements at 32 deg N and 45 deg S latitude, respectively. Variable enhancements in CO, C2H6, and particularly HCN were observed beginning in about September 1997. The maximum HCN free tropospheric monthly mean column observed in November 1997 corresponds to an average updating km mixing ratio of 0.7 ppbv (1 ppbv = 10(exp -9) per unit volume), more than a factor of 3 above the background level. The HCN enhancements continued through the end of the observational series. Back-trajectory calculations suggest that the emissions originated at low northern latitudes in southeast Asia. Surface CO mixing ratios and the C2H6 tropospheric columns measured during the same time also showed anomalous autumn 1997 maxima. The intense and widespread tropical wild fires that burned during 3 the strong El Nino warm phase of updating are the likely source of the elevated emission products.
NbCZF1, a Novel C 2 H 2 -Type Zinc Finger Protein, as a New Regulator of SsCut-Induced Plant Immunity in Nicotiana benthamiana.PubMed Zhang, Huajian; Zhao, Tongyao; Zhuang, Peitong; Song, Zhiqiang; Du, Hui; Tang, Zhaozhao; Gao, Zhimou updating SsCut, which functions as an elicitor, can induce plant immunity. In this study, we utilized Nicotiana benthamiana and virus-induced gene silencing to decrease the expression of > 2,500 genes individually. Using this forward genetics approach, several genes were identified that, when silenced, compromised SsCut-triggered cell death based on a cell death assay. A C 2 H 2 -type zinc finger gene was isolated from N. benthamiana Sequence analysis indicated that the gene encodes a 27 kDa protein with 253 amino acids containing two typical C 2 H 2 -type zinc finger domains; this gene was named NbCZF1 We found that SsCut-induced cell death could be inhibited by virus-induced gene silencing of NbCZF1 in N. benthamiana In addition, SsCut induces stomatal closure, accompanied by reactive oxygen species (ROS) production by NADPH oxidases and nitric oxide (NO) production. NbCZF1-silenced plants showed impaired SsCut-induced stomatal closure, decreased SsCut-induced production of ROS and NO in guard cells and reduced SsCut-induced resistance against Phytophthora nicotianae Taken together, these results demonstrate that the NbCZF1-ROS-NO pathway mediates multiple SsCut-triggered responses, including stomatal closure, hypersensitive responses and defense-related gene expression. This is the first report describing the function of a C 2 H 2 -type zinc finger protein in N. benthamiana. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: nguyenquanghuy@gmail.com
A new metal-organic framework for separation of C 2 H 2 /CH4 and CO2/CH4 at room temperatureNASA Astrophysics Data System (ADS) Duan, Xing; Zhou, You; Lv, Ran; Yu, Ben; Chen, Haodong; Ji, Zhenguo; Cui, Yuanjing; Yang, Yu; Qian, Guodong updating A 3D microporous metal-organic framework with open Cu2+ sites and suitable pore space, [Cu2(L)(H2O)2]·(H2O)4(DMF)8 (ZJU-15, H4L = 5,5‧-(9H-carbazole-2,7-diyl)diisophthalic acid; DMF = N,N-dimethylformamide; ZJU = Zhejiang University), has been constructed and characterized. The activated ZJU-15a has three different types of cages and exhibits BET surface area of 1660 m2 g-1, and can separate gas mixture of C2H2/CH4 and CO2/CH4 at room temperature.
Oscillations and patterns in a model of simultaneous CO and C 2 H 2 oxidation and NO(x) reduction in a cross-flow reactor.PubMed Hadač, Otto; Kohout, Martin; Havlica, Jaromír; Schreiber, Igor updating A model describing simultaneous catalytic oxidation of CO and C2H2 and reduction of NOx in a cross-flow tubular reactor is explored with the aim of relating spatiotemporal patterns to specific pathways in the mechanism. For that purpose, a detailed mechanism proposed for three-way catalytic converters is split into two subsystems, (i) simultaneous oxidation of CO and C2H2, and (ii) oxidation of CO combined with NOx reduction. The ability of these two subsystems to display mechanism-specific dynamical effects is studied initially by neglecting transport phenomena and applying stoichiometric network and bifurcation analyses. We obtain inlet temperature - inlet oxygen concentration bifurcation diagrams, where each region possessing specific dynamics - oscillatory, bistable and excitable - is associated with a dominant reaction pathway. Next, the spatiotemporal behaviour due to reaction kinetics combined with transport processes is studied. The observed spatiotemporal patterns include phase waves, travelling fronts, pulse waves and spatiotemporal chaos. Although these types of pattern occur generally when the kinetic scheme possesses autocatalysis, we find that some of their properties depend on the underlying dominant reaction pathway. The relation of patterns to specific reaction pathways is discussed.
Regulation of trichome development in tobacco by JcZFP8, a C 2 H 2 zinc finger protein gene from Jatropha curcas L.PubMed Shi, Xiaodong; Gu, Yuxi; Dai, Tingwei; Wu, Yang; Wu, Peng; Xu, Ying; Chen, Fang [external_link offset=1] updating Trichomes are epidermal outgrowths of plant tissues that can secrete or store large quantities of secondary metabolites, which contribute to plant defense responses against stress. The use of bioengineering methods for regulating the development of trichomes and metabolism is a widely researched topic. In the present study, we demonstrate that JcZFP8, a C2H2 zinc finger protein gene from Jatropha curcas L., can regulate trichome development in transgenic tobacco. To understand the underlying mechanisms, we performed transcriptome profiling of overexpression JcZFP8 transgenic plants and wild-type tobacco. Based on the analysis of differentially expressed genes, we determined that genes of the plant hormone signal transduction pathway was significantly enriched, suggesting that these pathways were modulated in the transgenic plants. In addition, the transcript levels of the known trichome-related genes in Arabidopsis were not significantly changed, whereas CycB2 and MYB genes were differentially expressed in the transgenic plants. Despite tobacco and Arabidopsis have different types of trichomes, all the pathways were associated with C2H2 zinc finger protein genes. Our findings help us to understand the regulation of multicellular trichome formation and suggest a new metabolic engineering method for the improvement of plants. Copyright © 2018 Elsevier B.V. All rights reserved.
Dynamics of C 2 H 2 3 +→H++H++C 2 + investigated by 50-keV/u Ne8 + impactNASA Astrophysics Data System (ADS) Xu, S.; Zhu, X. L.; Feng, W. T.; Guo, D. L.; Zhao, Q.; Yan, S.; Zhang, P.; Zhao, D. M.; Gao, Y.; Zhang, S. F.; Yang, J.; Ma, X. updating Breakup dynamics of C2H 2 3 + → H++H++C 2 + induced by 50-keV/u Ne8 + ion impact is investigated employing a reaction microscope. All three ionic fragments in the final state are detected in coincidence, and their momentum vectors as well as the kinetic energies are determined. The kinetic-energy correlation spectrum of the two protons displays very rich structures. Utilizing the Newton diagrams and the Dalitz plots, different dissociation mechanisms corresponding to these structures are identified. It was found that, besides the concerted and sequential breakup, fragmentation mechanisms associated with different vibration modes including molecular bending and asymmetric stretching also make significant contributions. We analyzed the correlation between different fragmentation mechanisms and the kinetic-energy release (KER) and found that the sequential process occurs with higher KER while, in contrast, the concerted process mainly contributes to the lower KER. This behavior is entirely opposite to the breakup of the CO2 molecule.
High-resolution, VUV (147-201 nm) photoabsorption cross sections for C 2 H 2 at 195 and 295 KNASA Technical Reports Server (NTRS) Smith, Peter L.; Yoshino, Kouichi; Parkinson, W. H.; Ito, Kenji; Stark, Glenn updating Results of measurements of photoabsorption cross sections of acetylene at 195 and 295 K in the wavelength range of 147-201 nm are reported. Short-wavelength data are obtained at 0.002 nm intervals, but no structure was observed on that scale. Emission and absorption lines from contaminant species in xenon and hydrogen discharges are used to determine the correct wavelength scale for the data. The uncertainty in the relative wavelengths is estimated to be about 0.004 nm, whereas the absolute wavelength values are accurate to + or - 0.043 nm. No significant photodestruction of C2H2 was found during the measurements. Cross-section values determined at the beginning portions of the measurements are indistinguishable from the values determined at the ends, thus demonstrating that there was no loss of absorbers.
MHY1 Encodes a C 2 H 2 -Type Zinc Finger Protein That Promotes Dimorphic Transition in the Yeast Yarrowia lipolyticaPubMed Central Hurtado, Cleofe A. R.; Rachubinski, Richard A. updating The yeast-to-hypha morphological transition (dimorphism) is typical of many pathogenic fungi. Dimorphism has been attributed to changes in temperature and nutritional status and is believed to constitute a mechanism of response to adverse conditions. We have isolated and characterized a gene, MHY1, whose transcription is dramatically increased during the yeast-to-hypha transition in Yarrowia lipolytica. Deletion of MHY1 is viable and has no effect on mating, but it does result in a complete inability of cells to undergo mycelial growth. MHY1 encodes a C2H2-type zinc finger protein, Mhy1p, which can bind putative cis-acting DNA stress response elements, suggesting that Mhy1p may act as a transcription factor. Interestingly, Mhy1p tagged with a hemagglutinin epitope was concentrated in the nuclei of actively growing cells found at the hyphal tip. PMID:updating
Multifunctional Involvement of a C 2 H 2 Zinc Finger Protein (PbZfp) in Malaria Transmission, Histone Modification, and Susceptibility to DNA Damage ResponsePubMed Central Gopalakrishnan, Anusha M.; Aly, Ahmed S. I.; Aravind, L. updating ABSTRACT In sexually reproducing organisms, meiosis is an essential step responsible for generation of haploid gametes from diploid somatic cells. The quest for understanding regulatory mechanisms of meiotic recombination in Plasmodium led to identification of a gene encoding a protein that contains 11 copies of C2H2 zinc fingers (ZnF). Reverse genetic approaches were used to create Plasmodium berghei parasites either lacking expression of full-length Plasmodium berghei zinc finger protein (PbZfp) (knockout [KO]) or expressing PbZfp lacking C-terminal zinc finger region (truncated [Trunc]). Mice infected with KO parasites survived two times longer (P 95% oocyst reduction). KO parasites revealed a total lack of trimethylation of histone 3 at several lysine residues (K4, K27, and K36) without any effect on acetylation patterns (H3K9, H3K14, and H4K16). Reduced DNA damage and reduced expression of topoisomerase-like Spo11 in the KO parasites with normal Rad51 expression further suggest a functional role for PbZfp during genetic recombination that involves DNA double-strand break (DSB) formation followed by DNA repair. These finding raise the possibility of some convergent similarities of PbZfp functions to functions of mammalian PRDM9, also a C2H2 ZnF protein with histone 3 lysine 4 (H3K4) methyltransferase activity. These functions include the major role played by the latter in binding recombination hotspots in the genome during meiosis and trimethylation of the associated histones and subsequent chromatin recruitment of topoisomerase-like Spo11 to catalyze DNA DSB formation and DMC1/Rad51-mediated DNA repair and homologous recombination. PMID:updating
Separating methane emissions from agricultural sources and natural gas: direct measurements of excess columns of CH4, C 2 H 6 and NH3 in the Colorado Front RangeNASA Astrophysics Data System (ADS) Kille, N.; Chiu, R.; Frey, M.; Hase, F.; Kumar Sha, M.; Blumenstock, T.; Hannigan, J. W.; Volkamer, R. M. updating Methane (CH4) is a major greenhouse gas emitted from biogenic, thermogenic, and pyrogenic sources. Here we demonstrate a novel approach to separate sources of CH4 emissions based on a network of small portable sensors performing column measurements in the Northern Colorado Front Range (NCFR). In the study area CH4 is emitted from biogenic sources such as concentrated animal feeding operations (CAFOs) and natural gas production and storage. In March 2015 we deployed a network of five Fourier Transform Spectrometers (FTS) to characterize the regional scale methane dome in Colorado's Denver-Julesburg Basin based on excess vertical column measurements (the column enhancement inside the dome over background). Three EM27sun FTS measured CH4, oxygen (O2) and water vapor (H2O) columns at Eaton, CO (inside the dome) and at two boundary sites; the CU mobile SOF (Solar Occultation Flux) measured ethane (C2H6), ammonia (NH3), and H2O at Eaton, CO. The column averaged dry air mole fractions XCH4, XC2H6, and XNH3 were determined using O2 columns for air mass factor normalization, and background column was subtracted to derive excess vertical columns of DXCH4, DXC2H6, DXNH3 at Eaton, CO. Eaton is located both near CAFOs and at the northern edge of oil and natural gas production wells. Our approach for source apportioning methane employs a linear regression analysis that explains DXCH4 in terms of DXC2H6 as tracer for natural gas sources, and DXNH3 as tracer for CAFO emissions. The results of the source apportionment are compared with literature values of the NH3/CH4 and C2H6/CH4 ratio to evaluate the method of excess columns, which is independent of boundary layer height.
On the Formation of the C 2 H 6 O Isomers Ethanol (C2H5OH) and Dimethyl Ether (CH3OCH3) in Star-forming RegionsNASA Astrophysics Data System (ADS) Bergantini, Alexandre; Maksyutenko, Pavlo; Kaiser, Ralf I. updating The structural isomers ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3) were detected in several low-, intermediate-, and high-mass star-forming regions, including Sgr B2, Orion, and W33A, with the relative abundance ratios of ethanol/dimethyl ether varying from about 0.03 to 3.4. Until now, no experimental data regarding the formation mechanisms and branching ratios of these two species in laboratory simulation experiments could be provided. Here, we exploit tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) to detect and analyze the production of complex organic molecules (COMs) resulting from the exposure of water/methane (H2O/CH4) ices to energetic electrons. The main goal is to understand the formation mechanisms in star-forming regions of two C2H6O isomers: ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3). The results show that the experimental branching ratios favor the synthesis of ethanol versus dimethyl ether (31 ± 11:1). This finding diverges from the abundances observed toward most star-forming regions, suggesting that production routes on interstellar grains to form dimethyl ether might be missing; alternatively, ethanol can be overproduced in the present simulation experiments, such as via radical-radical recombination pathways involving ethyl and hydroxyl radicals. Finally, the PI-ReTOF-MS data suggest the formation of methylacetylene (C3H4), ketene (CH2CO), propene (C3H6), vinyl alcohol (CH2CHOH), acetaldehyde (CH3CHO), and methyl hydroperoxide (CH3OOH), in addition to ethane (C2H6), methanol (CH3OH), and CO2 detected from infrared spectroscopy. The yield of all the confirmed species is also determined.
FTIR investigation of the H2, N2, and C 2 H 4 molecular complexes formed on the Cr(II) sites in the Phillips catalyst: a preliminary step in the understanding of a complex system.PubMed Groppo, E; Lamberti, C; Bordiga, S; Spoto, G; Damin, A; Zecchina, A updating This work reports the first complete FTIR characterization of H2, N2 and C2H4 molecular complexes formed on the Cr(II) sites in the Phillips catalyst. The use of a silica aerogel as support for Cr(II) sites, substituting the conventional aerosil material, allowed us to obtain a remarkable increase in the signal-to-noise ratio of the IR spectra of adsorbed species. The improvement is directly related to an increase of the surface area of the support (approximately 700 m2 g(-1)) and to an almost complete absence of scattering [Groppo et al., Chem. Mater. 2005, 17, updating]. The use of this support and the adoption of suitable experimental conditions results, for the first time, in the clear observation of H2 and N2 adducts formed on two different types of Cr(II) sites, thus yielding important information on the coordinative state of the Cr(II) ions, which well agrees with the evidences provided in the past by other probe molecules. Furthermore, we report the first complete characterization of the C2H4 pi-complexes formed on Cr(II) sites. These results are particularly important in the view of the understanding of the polymerization mechanism, since the C2H4 coordination and the formation of pi-bonded complexes are the first steps of the reaction.
Reactions of vanadium dioxide molecules with acetylene: infrared spectra of VO2(η(2)-C 2 H 2 )(x) (x = 1, 2) and OV(OH)CCH in solid neon.PubMed Zhou, Xiaojie; Chen, Mohua; Zhou, Mingfei updating Reactions of vanadium dioxide molecules with acetylene have been studied by matrix isolation infrared spectroscopy. Reaction intermediates and products are identified on the basis of isotopic substitutions as well as density functional frequency calculations. Ground state vanadium dioxide molecule reacts with acetylene in forming the side-on-bonded VO2(η(2)-C2H2) and VO2(η(2)-C2H2)2 complexes spontaneously on annealing in solid neon. The VO2(η(2)-C2H2) complex is characterized to have a (2)B2 ground state with C2v symmetry, whereas the VO2(η(2)-C2H2)2 complex has a (2)A ground state with C2 symmetry. The VO2(η(2)-C2H2) and VO2(η(2)-C2H2)2 complexes are photosensitive. The VO2(η(2)-C2H2) complex rearranges to the OV(OH)CCH molecule upon UV-vis light excitation.
Underlying theory of a model for the Renner-Teller effect in tetra-atomic molecules: X(2)Πu electronic state of C 2 H 2 (+).PubMed Perić, M; Jerosimić, S; Mitić, M; Milovanović, M; Ranković, R updating In the present study, we prove the plausibility of a simple model for the Renner-Teller effect in tetra-atomic molecules with linear equilibrium geometry by ab initio calculations of the electronic energy surfaces and non-adiabatic matrix elements for the X(2)Πu state of C2H2 (+). This phenomenon is considered as a combination of the usual Renner-Teller effect, appearing in triatomic species, and a kind of the Jahn-Teller effect, similar to the original one arising in highly symmetric molecules. Only four parameters (plus the spin-orbit constant, if the spin effects are taken into account), which can be extracted from ab initio calculations carried out at five appropriate (planar) molecular geometries, are sufficient for building up the Hamiltonian matrix whose diagonalization results in the complete low-energy (bending) vibronic spectrum. The main result of the present study is the proof that the diabatization scheme, hidden beneath the apparent simplicity of the model, can safely be carried out, at small-amplitude bending vibrations, without cumbersome computation of non-adiabatic matrix elements at large number of molecular geometries.
Transcriptional repression mediated by the KRAB domain of the human C 2 H 2 zinc finger protein Kox1/ZNF10 does not require histone deacetylation.PubMed Lorenz, P; Koczan, D; Thiesen, H J updating The KRAB domain of human Kox1, a member of the KRAB C2H2 zinc finger family, confers strong transcriptional repressor activities even to remote promoter positions. Here, HDAC inhibitors were used to demonstrate that histone deacetylation is not required for mediating transcriptional repression of KRAB zinc finger proteins. Two reporter systems with either stably integrated or transiently transfected templates, both under control of strong viral promoters, were analyzed. Under all circumstances, HDAC inhibition did not alter the repression potential of the KRAB domain. In case of the stably integrated luciferase reporter gene system, neither expression levels of the KRAB fusion protein nor complex formation with its putative co-repressor TIF1beta were significantly changed. Furthermore, the TIF1beta/KRAB complex was devoid of mSin3A and HDAC1. In the transient transfection system, the transcriptional repression induced by TIF1beta and HP1alpha was not diminished by HDAC inhibitors, whereas the repressory activity of TIF1alpha was significantly affected. Thus, KRAB, TIF1beta and HP1alpha are likely to be functionally linked. In conclusion, HDAC activity is not essential for the strong transcriptional repressor activity mediated by the KRAB domain of Kox1 in particular and, presumably, by KRAB domains in general. This feature might be helpful in identifying and characterizing target genes under the control of
The C 2 H 2 transcription factor regulator of symbiosome differentiation represses transcription of the secretory pathway gene VAMP721a and promotes symbiosome development in Medicago truncatula.PubMed Sinharoy, Senjuti; Torres-Jerez, Ivone; Bandyopadhyay, Kaustav; Kereszt, Attila; Pislariu, Catalina I; Nakashima, Jin; Benedito, Vagner A; Kondorosi, Eva; Udvardi, Michael K updating Transcription factors (TFs) are thought to regulate many aspects of nodule and symbiosis development in legumes, although few TFs have been characterized functionally. Here, we describe regulator of symbiosome differentiation (RSD) of Medicago truncatula, a member of the Cysteine-2/Histidine-2 (C2H2) family of plant TFs that is required for normal symbiosome differentiation during nodule development. RSD is expressed in a nodule-specific manner, with maximal transcript levels in the bacterial invasion zone. A tobacco (Nicotiana tabacum) retrotransposon (Tnt1) insertion rsd mutant produced nodules that were unable to fix nitrogen and that contained incompletely differentiated symbiosomes and bacteroids. RSD protein was localized to the nucleus, consistent with a role of the protein in transcriptional regulation. RSD acted as a transcriptional repressor in a heterologous yeast assay. Transcriptome analysis of an rsd mutant identified 11 genes as potential targets of RSD repression. RSD interacted physically with the promoter of one of these genes, VAMP721a, which encodes vesicle-associated membrane protein 721a. Thus, RSD may influence symbiosome development in part by repressing transcription of VAMP721a and modifying vesicle trafficking in nodule cells. This establishes RSD as a TF implicated directly in symbiosome and bacteroid differentiation and a transcriptional regulator of secretory pathway genes in plants.
Infrared spectra of M-η2-C 2 H 2 and HMsbnd CCH produced in reactions of laser-ablated Fe and Os atoms with acetyleneNASA Astrophysics Data System (ADS) Cho, Han-Gook; Andrews, Lester updating The π- and Csbnd H insertion products (M-η2-C2H2 and HMsbnd CCH) are identified in the matrix infrared spectra from reactions of laser-ablated Fe and Os atoms with acetylene isotopomers, but the vinylidene product (H2CCM) is not, in contrast to the recently studied Ru case. The π-complex is produced in deposition and annealing, and it converts to the insertion complex during photolysis. While the vinylidene product is energetically comparable with the two primary products, the energy barrier is considerably higher in contrast to the Ru case. The relatively short Csbnd C bonds of the π-complexes indicate weak back-donations from the group 8 metals to the acetylene π∗ orbitals. The highly bent structure of HOssbnd CCH evidently originates from the high d contributions to the Csbnd Os and Ossbnd H bonds. The C2v structures of the vinylidene products arise from the p-d π bonding between C and M.
Competitive formation of b(2) and c (2 )-H 2 O ions from b(3) ions containing Asp residue during tandem mass spectrometry: the influence of neighboring Arg.PubMed Guo, Mengzhe; Guo, Cheng; Pan, Yuanjiang updating The fragmentation of b3 ions derived from protonated Arg-Xxx-Asp-Ala-Ala (Xxx = Ala, Asp, Glu, Cys) and Arg-Xxx-Glu-Ala-Ala was investigated by electrospray ionization tandem mass spectrometry (MS (n) ) with collision-induced dissociation. A particular ion, which is 1 Da less than b2 ion, is shown to be the c2-H2O ion. The mechanism for its formation involved the aspartic acid in the third position easily losing anhydride to form a c2 ion, which then lost water to form an eight-membered ring of azacyclooctane derivative under the participation of the guanidine of the N-terminal arginine. However, this phenomenon was not observed when the aspartic acid was replaced by glutamic acid. The Amber program was used to determine the conformation of the original c2 residue from the dynamic energy perspective, and then density functional theory-based calculations and changing N-terminal amino acid from arginine to phenylalanine supported this mechanism.
Isotropic C6, C8 and C10 interaction coefficients for CH 4, C 2 H 6 , C 3H 8, n-C 4H 10 and cyclo- C3H 6NASA Astrophysics Data System (ADS) Thomas, Gerald F.; Mulder, Fred; Meath, William J. updating The non-empirical generalized Kirkwood, Unsöld, and the single-Δ Unsöld methods (with double-zeta quality SCF wave-functions) are used to calculate isotropic dispersion (and induction) energy coefficients C2n, with n ⩽ 5, for interactions involving ground state CH 4, C 2H 6, C 3H 8, n-C 4H 10 and cyclo-C 3H 6. Results are also given for the related multipole polarizabilities α l, multipole sums S1/(0) and S1(-1) which are evaluated using sum rules, and the permanent multipole moments. for l = 1 (dipole) to l = 3 (octupole). Estimates of the reliability of the non-empirical methods, for the type of molecules considered, are obtained by a comparison with accurate literature values of α 1S1(-1) and C6. This, and the asymptotic properties of the multipolar expansion of the dispersion energy, the use to discuss recommended representation for the isotropic long range interaction energies through R-10 where R is the intermolecular separation.
Semiconducting perovskites (2-XC6H4C 2 H 4 NH3)2SnI4 (X = F, Cl, Br): steric interaction between the organic and inorganic layers.PubMed Xu, Zhengtao; Mitzi, David B; Dimitrakopoulos, Christos D; Maxcy, Karen R updating Two new semiconducting hybrid perovskites based on 2-substituted phenethylammonium cations, (2-XC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) (X = Br, Cl), are characterized and compared with the previously reported X = F compound, with a focus on the steric interaction between the organic and inorganic components. The crystal structure of (2-ClC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) is solved in a disordered subcell [C2/m, a = updating) A, b = 6.178(1) A, c = 6.190(1) A, beta = 90.42(3)(o), and Z = 2]. The structure is similar to the known (2-FC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) structure with regard to both the conformation of the organic cations and the bonding features of the inorganic sheet. The (2-BrC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) system adopts a fully ordered monoclinic cell [P2(1)/c, a = updating) A, b = updating) A, c = updating) A, beta = updating)(o), and Z = 2]. The organic cation adopts the anti conformation, instead of the gauche conformation observed in the X = F and Cl compounds, apparently because of the need to accommodate the additional volume of the bromo group. The steric effect of the bromo group also impacts the perovskite sheet, causing notable distortions, such as a compressed Sn-I-Sn bond angle (148.7(o), as compared with the average values of 153.3 and 154.8(o) for the fluoro and chloro compounds, respectively). The optical absorption features a substantial blue shift (lowest exciton peak: 557 nm, 2.23 eV) relative to the spectra of the fluoro and chloro compounds (588 and 586 nm, respectively). Also presented are transport properties for thin-film field-effect transistors (TFTs) based on spin-coated films of the two hybrid semiconductors.

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A Novel C 2 H 2 Transcription Factor that Regulates gliA Expression Interdependently with GliZ in Aspergillus fumigatusPubMed Central Schoberle, Taylor J.; Nguyen-Coleman, C. Kim; Herold, Jennifer; Yang, Ally; Weirauch, Matt; Hughes, Timothy R.; McMurray, John S.; May, Gregory S. updating Secondary metabolites are produced by numerous organisms and can either be beneficial, benign, or harmful to humans. Genes involved in the synthesis and transport of these secondary metabolites are frequently found in gene clusters, which are often coordinately regulated, being almost exclusively dependent on transcription factors that are located within the clusters themselves. Gliotoxin, which is produced by a variety of Aspergillus species, Trichoderma species, and Penicillium species, exhibits immunosuppressive properties and has therefore been the subject of research for many laboratories. There have been a few proteins shown to regulate the gliotoxin cluster, most notably GliZ, a Zn2Cys6 binuclear finger transcription factor that lies within the cluster, and LaeA, a putative methyltransferase that globally regulates secondary metabolism clusters within numerous fungal species. Using a high-copy inducer screen in A. fumigatus, our lab has identified a novel C2H2 transcription factor, which plays an important role in regulating the gliotoxin biosynthetic cluster. This transcription factor, named GipA, induces gliotoxin production when present in extra copies. Furthermore, loss of gipA reduces gliotoxin production significantly. Through protein binding microarray and mutagenesis, we have identified a DNA binding site recognized by GipA that is in extremely close proximity to a potential GliZ DNA binding site in the 5′ untranslated region of gliA, which encodes an efflux pump within the gliotoxin cluster. Not surprisingly, GliZ and GipA appear to work in an interdependent fashion to positively control gliA expression. PMID:updating
Tuberculate fruit gene Tu encodes a C 2 H 2 zinc finger protein that is required for the warty fruit phenotype in cucumber (Cucumis sativus L.).PubMed Yang, Xuqin; Zhang, Weiwei; He, Huanle; Nie, Jingtao; Bie, Beibei; Zhao, Junlong; Ren, Guoliang; Li, Yue; Zhang, Dabing; Pan, Junsong; Cai, Run updating Cucumber fruits that have tubercules and spines (trichomes) are known to possess a warty (Wty) phenotype. In this study, the tuberculate fruit gene Tu was identified by map-based cloning, and was found to encode a transcription factor (TF) with a single C2 H2 zinc finger domain. Tu was identified in all 38 Wty lines examined, and was completely absent from all 56 non-warty (nWty) lines. Cucumber plants transgenic for Tu (TCP) revealed that Tu was required for the Wty fruit phenotype. Subcellular localization showed that the fusion protein GFP-Tu was localized mainly to the nucleus. Based on analyses of semi-quantitative and quantitative reverse transcription polymerase chain reaction (RT-PCR), and mRNA in situ hybridization, we found that Tu was expressed specifically in fruit spine cells during development of fruit tubercules. Moreover, cytokinin (CTK) content measurements and cytological observations in Wty and nWty fruits revealed that the Wty fruit phenotype correlated with high endogenous CTK concentrations. As a result of further analyses on the transcriptomic profile of the nWty fruit epidermis and TCP fruit warts, expression of CTK-associated genes, and hormone content in nWty fruit epidermis, Wty fruit warts and epidermis, and TCP fruit warts and epidermis, we found that Tu probably promoted CTK biosynthesis in fruit warts. Here we show that Tu could not be expressed in the glabrous and tubercule-free mutant line gl that contained Tu, this result that futher confirmed the epistatic effect of the trichome (spine) gene Gl over Tu. Taken together, these data led us to propose a genetic pathway for the Wty fruit trait that could guide future mechanistic studies. © 2014 The Authors The Plant Journal © 2014 John Wiley & Sons Ltd.
The Putative C 2 H 2 Transcription Factor MtfA Is a Novel Regulator of Secondary Metabolism and Morphogenesis in Aspergillus nidulansPubMed Central Ramamoorthy, Vellaisamy; Dhingra, Sourabh; Kincaid, Alexander; Shantappa, Sourabha; Feng, Xuehuan; Calvo, Ana M. updating Secondary metabolism in the model fungus Aspergillus nidulans is controlled by the conserved global regulator VeA, which also governs morphological differentiation. Among the secondary metabolites regulated by VeA is the mycotoxin sterigmatocystin (ST). The presence of VeA is necessary for the biosynthesis of this carcinogenic compound. We identified a revertant mutant able to synthesize ST intermediates in the absence of VeA. The point mutation occurred at the coding region of a gene encoding a novel putative C2H2 zinc finger domain transcription factor that we denominated mtfA. The A. nidulans mtfA gene product localizes at nuclei independently of the illumination regime. Deletion of the mtfA gene restores mycotoxin biosynthesis in the absence of veA, but drastically reduced mycotoxin production when mtfA gene expression was altered, by deletion or overexpression, in A. nidulans strains with a veA wild-type allele. Our study revealed that mtfA regulates ST production by affecting the expression of the specific ST gene cluster activator aflR. Importantly, mtfA is also a regulator of other secondary metabolism gene clusters, such as genes responsible for the synthesis of terrequinone and penicillin. As in the case of ST, deletion or overexpression of mtfA was also detrimental for the expression of terrequinone genes. Deletion of mtfA also decreased the expression of the genes in the penicillin gene cluster, reducing penicillin production. However, in this case, over-expression of mtfA enhanced the transcription of penicillin genes, increasing penicillin production more than 5 fold with respect to the control. Importantly, in addition to its effect on secondary metabolism, mtfA also affects asexual and sexual development in A. nidulans. Deletion of mtfA results in a reduction of conidiation and sexual stage. We found mtfA putative orthologs conserved in other fungal species. PMID:updating
Vibration-rotation alchemy in acetylene (12C 2 H 2 ), ? at low vibrational excitation: from high resolution spectroscopy to fast intramolecular dynamicsNASA Astrophysics Data System (ADS) Perry, David S.; Miller, Anthony; Amyay, Badr; Fayt, André; Herman, Michel updating The link between energy-resolved spectra and time-resolved dynamics is explored quantitatively for acetylene (12C2H2), ? with up to 8600 cm-1 of vibrational energy. This comparison is based on the extensive and reliable knowledge of the vibration-rotation energy levels and on the model Hamiltonian used to fit them to high precision [B. Amyay, S. Robert, M. Herman, A. Fayt, B. Raghavendra, A. Moudens, J. Thiévin, B. Rowe, and R. Georges, J. Chem. Phys. 131, updating)]. Simulated intensity borrowing features in high resolution absorption spectra and predicted survival probabilities in intramolecular vibrational redistribution (IVR) are first investigated for the v 4 + v 5 and v 3 bright states, for J = 2, 30 and 100. The dependence of the results on the rotational quantum number and on the choice of vibrational bright state reflects the interplay of three kinds of off-diagonal resonances: anharmonic, rotational l-type, and Coriolis. The dynamical quantities used to characterize the calculated time-dependent dynamics are the dilution factor φ d, the IVR lifetime τ IVR , and the recurrence time τ rec. For the two bright states v 3 + 2v 4 and 7v 4, the collisionless dynamics for thermally averaged rotational distributions at T = 27, 270 and 500 K were calculated from the available spectroscopic data. For the 7v 4 bright state, an apparent irreversible decay of is found. In all cases, the model Hamiltonian allows a detailed calculation of the energy flow among all of the coupled zeroth-order vibration-rotation states.
Poster 1: Global frequency and intensity analysis of the ν10/ν7/ν4/ν12 band system of 12C 2 H 4 at 10 µm using the D2h Top Data SystemNASA Astrophysics Data System (ADS) Alkadrou, Abdulsamee; Bourgeois, Marie-Therese; Rotger, Maud; Boudon, Vincent; Vander Auwera, Jean updating A global frequency and intensity analysis of the infrared tetrad of 12C2H4 located in the updating cm-1 region was carried out using the tensorial formalism developed in Dijon for X2Y4 asymmetric-top molecules. It relies on spectroscopic information available in the literature and retrieved from high-resolution Fourier transform infrared spectra recorded in Brussels in the frame of either the present or previous work. In particular, 645 and 131 lines intensities have been respectively measured for the weak ν10 and ν4 bands. Including the Coriolis interactions affecting the upper vibrational levels 101, 71, 41 and 121 , a total of 10,737 line positions and 1,867 line intensities have been assigned and fitted with global root mean square deviations of updating cm-1 and 2.4 %, respectively. Relying on the results of the present work and available in the literature, a list of parameters for 65,420 lines in the ν10, ν7, ν4 and ν12 bands of 12C2H4 was generated. To the best of our knowledge, this is the first time that a global intensity analysis is carried out in this range of the ethylene spectrum.
Chanabayaite, Cu2(N3C 2 H 2 )Cl(NH3,Cl,H2O,□)4, a new mineral containing triazolate anionNASA Astrophysics Data System (ADS) Chukanov, N. V.; Zubkova, N. V.; Möhn, G.; Pekov, I. V.; Pushcharovsky, D. Yu.; Zadov, A. E. updating A new mineral, chanabayaite, has been discovered at a guano deposit located at Mt. Pabellón de Pica near the village of Chanabaya, Iquique Province, Tarapacá region, Chile. It is associated with salammoniac, halite, joanneumite, nitratine and earlier chalcopyrite. Chanabayaite occurs as blue translucent imperfect prismatic crystals, up to 0.05 × 0.1 × 0.5 mm in size, and their radial aggregates. Chanabayaite is brittle, with a Mohs' hardness of 2. The cleavage is perfect on (001) and imperfect on (100) and (010). D meas = 1.48(2) g/cm3, D calc = 1.464 g/cm3. The mineral is optically biaxial (-), α = 1.561(2), β = 1.615(3), γ = 1.620(2), 2 V meas = 25(10)°, 2 V calc = 33°. Pleochroism is strong, Z ≈ Y (deep blue) ≫ X (pale blue with gray tint). IR spectrum is given. The chemical composition (electron microprobe data for Cu, Fe and Cl; gas chromatography data for H, N, C and O) is as follows (wt %): 32.23 Cu, 1.14 Fe, 16.13 Cl, 3.1 H, 29.9 N, 12.2 C, 3.4 O, total is 98.1. The empirical formula is ( Z = 4): Cu1.92Fe0.08Cl1.72N8.09C3.85H11.66O0.81. The structural model was based on the single-crystal X-ray diffraction data ( R = 0.1627). Chanabayaite is orthorhombic, space group Imma, a = updating), b = updating), c = updating) Å, V = updating) Å3, Z = 2. In chanabayaite, chains of the corner-sharing Cu(l)-centered octahedra and single Cu(2)-centered octahedra are linked via 1,2,4-triazolate anions C2N3H2 -. NH3 and Cl- are additional ligands coordinating Cu2+. Chanabayaite is a transformational mineral species formed by leaching of Na and one third of Cl and partial dehydration of the protophase Na2Cu2Cl3(N3C2H2)2(NH3)2 • 4H2O. The strongest reflections in the powder X-ray diffraction pattern [ d, Å ( I, %) ( hkl)] are detected: updating), updating), updating), updating, 202), updating), updating, 413, 503), updating, 422, 404).
Selective Generation of the Radical Cation Isomers [CH3CN](•+) and [CH2CNH](•+) via VUV Photoionization of Different Neutral Precursors and Their Reactivity with C 2 H 4 .PubMed Polášek, Miroslav; Zins, Emilie-Laure; Alcaraz, Christian; Žabka, Ján; Křížová, Věra; Giacomozzi, Linda; Tosi, Paolo; Ascenzi, Daniela updating Experimental and theoretical studies have been carried out to demonstrate the selective generation of two different C2H3N(+) isomers, namely, the acetonitrile [CH3CN](•+) and the ketenimine [CH2CNH](•+) radical cations. Photoionization and dissociative photoionization experiments from different neutral precursors (acetonitrile and butanenitrile) have been performed using vacuum ultraviolet (VUV) synchrotron radiation in the 10-15 eV energy range, delivered by the DESIRS beamline at the SOLEIL storage ring. For butanenitrile (CH3CH2CH2CN) an experimental ionization threshold of 11.29 ± 0.05 eV is obtained, whereas the appearance energy for the formation of [CH2CNH](•+) fragments is 11.52 ± 0.05 eV. Experimental findings are fully supported by theoretical calculations at the G4 level of theory (ZPVE corrected energies at 0 K), giving a value of 11.33 eV for the adiabatic ionization energy of butanenitrile and an exothermicity of 0.49 for fragmentation into [CH2CNH](•+) plus C2H4, hampered by an energy barrier of 0.29 eV. The energy difference between [CH3CN](•+) and [CH2CNH](•+) is 2.28 eV (with the latter being the lowest energy isomer), and the isomerization barrier is 0.84 eV. Reactive monitoring experiments of the [CH3CN](•+) and [CH2CNH](•+) isomers with C2H4 have been performed using the CERISES guided ion beam tandem mass spectrometer and exploiting the selectivity of ethylene that gives exothermic charge exchange and proton transfer reactions with [CH3CN](•+) but not with [CH2CNH](•+) isomers. In addition, minor reactive channels are observed leading to the formation of new C-C bonds upon reaction of [CH3CN](•+) with C2H4, and their astrochemical implications are briefly discussed.
Thermally-induced first-order phase transition in the (FC6H4C 2 H 4 NH3)2[PbI4] photoluminescent organic-inorganic materialNASA Astrophysics Data System (ADS) Koubaa, M.; Dammak, T.; Garrot, D.; Castro, M.; Codjovi, E.; Mlayah, A.; Abid, Y.; Boukheddaden, K. updating The thermal properties of the perovskite slab alkylammonium lead iodide (FC6H4C2H4NH3)2[PbI4] are investigated using spectroscopic ellipsometry, differential scanning calorimetry, photoluminescence, and Raman spectroscopy. The spectroscopic ellipsometry, performed in the heating mode, clearly evidenced the presence of a singularity at 375 K. This is corroborated by the temperature dependence of the photoluminescence, which pointed out a first-order order-disorder phase transition at ˜375 K, with a hysteresis loop of 40 K width. Raman spectroscopy data suggest that this transition arises from a dynamic rotational disordering of the ammonium headgroups of the alkylammonium chain. In contrast, differential scanning calorimetry measurements on a pellet sample led to an entropy change value ΔS ≈0.39 J/K/mol at the transition, suggesting the existence of a residual short-range order of the NH3+ on cooling from the high temperature phase.
Bluish-white-light-emitting diodes based on two-dimensional lead halide perovskite (C6H5C 2 H 4 NH3)2PbCl2Br2NASA Astrophysics Data System (ADS) Cai, Peiqing; Wang, Xiangfu; Seo, Hyo Jin; Yan, Xiaohong updating Bluish-white-light-emitting diodes (BWLEDs) are designed based on the two-dimensional mixed halide perovskite (C6H5C2H4NH3)2PbCl2Br2 at room temperature. Bluish-white electroluminescence devices were fabricated by a spin-coating method. The BWLEDs can be turned on at 4.9 V and depict a maximum luminance of ˜70 cd/m2 at 7 V. Low and room temperature photoluminescence spectra show the coexistence of free exciton and self-trapped exciton luminescence in a deformable lattice. The strategy of achieving white electroluminescence (EL) from mixed halide perovskite reported here can be applied to other two-dimensional perovskites to increase the optoelectronic efficiency of the device in the future.
Combined valence bond-molecular mechanics potential-energy surface and direct dynamics study of rate constants and kinetic isotope effects for the H + C 2 H 6 reaction.PubMed Chakraborty, Arindam; Zhao, Yan; Lin, Hai; Truhlar, Donald G updating This article presents a multifaceted study of the reaction H+C(2)H(6)-->H(2)+C(2)H(5) and three of its deuterium-substituted isotopologs. First we present high-level electronic structure calculations by the W1, G3SX, MCG3-MPWB, CBS-APNO, and MC-QCISD/3 methods that lead to a best estimate of the barrier height of 11.8+/-0.5 kcal/mol. Then we obtain a specific reaction parameter for the MPW density functional in order that it reproduces the best estimate of the barrier height; this yields the MPW54 functional. The MPW54 functional, as well as the MPW60 functional that was previously parametrized for the H+CH(4) reaction, is used with canonical variational theory with small-curvature tunneling to calculate the rate constants for all four ethane reactions from 200 to 2000 K. The final MPW54 calculations are based on curvilinear-coordinate generalized-normal-mode analysis along the reaction path, and they include scaled frequencies and an anharmonic C-C bond torsion. They agree with experiment within 31% for 467-826 K except for a 38% deviation at 748 K; the results for the isotopologs are predictions since these rate constants have never been measured. The kinetic isotope effects (KIEs) are analyzed to reveal the contributions from subsets of vibrational partition functions and from tunneling, which conspire to yield a nonmonotonic temperature dependence for one of the KIEs. The stationary points and reaction-path potential of the MPW54 potential-energy surface are then used to parametrize a new kind of analytical potential-energy surface that combines a semiempirical valence bond formalism for the reactive part of the molecule with a standard molecular mechanics force field for the rest; this may be considered to be either an extension of molecular mechanics to treat a reactive potential-energy surface or a new kind of combined quantum-mechanical/molecular mechanical (QM/MM) method in which the QM part is semiempirical valence bond theory; that is, the new potential
Deviation from the trans -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl 3(C 2 H 4 ) - with Heavier Halides (Br –, I - )SciTech Connect Hou, Gao-Lei; Govind, Niranjan; Xantheas, Sotiris S. Four new Zeise’s family ions with mixed-halide ligands, i.e., PtCl nX 3-n(C 2H 4) - (X = Br, I; n = 1, 2), were synthesized via ligand-exchange reactions of KX salts with KPtCl 3(C 2H 4) in aqueous solutions, and were detected in vacuum via electrospray ionization mass spectrometry. Their photoelectron spectra reveal a series of well-resolved spectral peaks with their electron binding energies (EBEs) decreasing with increasing halide size, with I having a much stronger effect than Br, i.e., 4.57 (–Cl 3) > 4.56 (–Cl 2Br) > 4.53 (–ClBr 2) > 4.34 (–Cl 2I) > 4.30 eV (–ClI 2).more » Ab initio electronic structure calculations including spin-orbit coupling (SOC) predict that the cis- and trans-isomers are nearly isoenergetic with the cis-isomer for –Cl 2X, and the trans-isomer for –ClX 2 slightly favored, respectively. Excited-state spectra calculated with time-dependent density functional theory (TDDFT), and their comparison with the observed ones, suggest that for each species, both the cis- and trans-configurations coexist in the experiments and contribute to the observed spectra, a fact that clearly violates the prediction of the widely accepted trans-effect, which suggests that only one isomer would have formed.« less
S-graphite slit pore: A superior selective adsorbent for light hydrocarbonsNASA Astrophysics Data System (ADS) Xue, Qingzhong; Li, Xiaofang; Chang, Xiao; Ling, Cuicui; Zhu, Lei; Xing, Wei updating Separation of light hydrocarbons (C1-C3) is extremely significant since these are alternative energy resources and raw materials in the industrial process. In this work, we have examined the performance of S-graphite slit pore in selective separation of CH4 over C2H2, C2H4, C2H6, C3H6 and C3H8 using Grand Canonical Monte Carlo calculations. Generally, its C3/C1 selectivity is higher than C2/C1 selectivity. Exactly, at 300 K and 1 bar, the selectivity is around 13, 17 and 18 for CH4/C2H2, CH4/C2H4 and CH4/C2H6 while it is about 63 and 70 for CH4/C3H6 and CH4/C3H8, respectively. Importantly, we have found that the optimum pore size is 0.65 nm for CH4/C2H2 and CH4/C2H4, 0.75 nm for CH4/C2H6, which is smaller than that (1.0 nm) for CH4/C3H6 and CH4/C3H8. Besides, density functional theory calculations demonstrate the remarkable selective separation of CH4 over C2H2, C2H4, C2H6, C3H6 and C3H8 of S-graphite slit pore is attributed to its stronger interactions with C2H2, C2H4, C2H6, C3H6 and C3H8 molecule than CH4 molecule due to the larger polarizability of C2 and C3 molecules, which also manifests that S-graphite slit pore is an extremely promising candidate for separating light hydrocarbons.
The relative abundance of ethane to acetylene in the Jovian stratosphereNASA Technical Reports Server (NTRS) Allen, Mark; Yung, Yuk L.; Gladstone, G. R. updating The inclusion of the results of laboratory kinetics studies on the reaction of C2H3 and H2 to yield C2H4, which is suggestive of an efficient chemical mechanism for the hydrogenation of C2H2 to C2H6, can be included in a comprehensive model of the Jupiter atmosphere hydrocarbon photochemistry to explain the observed altitude variation of the C2H6/C2H2 ratio. The sensitivity of these results to uncertainties in key low-temperature rate constants is demonstrated. These key reaction-rate constants decrease with falling temperature.
ACE-FTS Observation of a Young Biomass Burning Plume: First Reported Measurements of C 2 H 4 , C3H6O, H2CO and PAN by Infrared Occultation from SpaceNASA Technical Reports Server (NTRS) Coheur, Pierre-Francois; Herbin, Herve; Clerbaux, Cathy; Hurtmans, Daniel; Wespes, Catherine; Carleer, Michel; Turquety, Solene; Rinsland, Curtis P.; Remedios, John; Hauglustaine, Didier; updating In the course of our study of the upper tropospheric composition with the infrared 35 Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE FTS), we 36 found an occultation sequence that on 8 October 2005, sampled a remarkable plume near the 37 east coast of Tanzania. Model simulations of the CO distribution in the Southern hemisphere 38 are performed for this period and they demonstrate that the emissions for this event originated 39 from a nearby forest fire, after which the plume was transported from the source region to the 40 upper troposphere. Taking advantage of the very high signal-to-noise ratio of the ACE FTS 41 spectra over a wide wavenumber range (updating cm(exp -1), we present in-depth analyses of the 42 chemical composition of this plume in the middle and upper troposphere, focusing on the 43 measurements of weakly absorbing pollutants. For this specific biomass burning event, we 44 report simultaneous observations of an unprecedented number of organic species. 45 Measurements of C2H4 (ethene), C3H4 (propyne), H2CO (formaldehyde), C3H6O (acetone) 46 and CH3COO2NO2 (perxoxyacetylnitrate, abbreviated as PAN) are the first reported 47 detections using infrared occultation spectroscopy from satellites. Based on the lifetime of the 48 emitted species, we discuss the photochemical age of the plume and also report, whenever 49 possible, the enhancement ratios relative to CO.
Thermoelectric properties of the 3C , 2 H , 4 H, and 6H polytypes of the wide-band-gap semiconductors SiC, GaN, and ZnOSciTech Connect Huang, Zheng; Lü, Tie-Yu; Wang, Hui-Qiong We have investigated the thermoelectric properties of the 3C, 2H, 4H, and 6H polytypes of the wide-band-gap(n-type) semiconductors SiC, GaN, and ZnO based on first-principles calculations and Boltzmann transport theory. Our results show that the thermoelectric performance increases from 3C to 6H, 4H, and 2H structures with an increase of hexagonality for SiC. However, for GaN and ZnO, their power factors show a very weak dependence on the polytype. Detailed analysis of the thermoelectric properties with respect to temperature and carrier concentration of 4H-SiC, 2H-GaN, and 2H-ZnO shows that the figure of merit of these three compounds increases with temperature,more » indicating the promising potential applications of these thermoelectric materials at high temperature. The significant difference of the polytype-dependent thermoelectric properties among SiC, GaN, and ZnO might be related to the competition between covalency and ionicity in these semiconductors. Our calculations may provide a new way to enhance the thermoelectric properties of wide-band-gap semiconductors through atomic structure design, especially hexagonality design for SiC.« less
Electronic structure of the alkyne-bridged dicobalt hexacarbonyl complex Co(2) micro-C (2 )H (2 ) (CO)(6): evidence for singlet diradical character and implications for metal-metal bonding.PubMed Platts, James A; Evans, Gareth J S; Coogan, Michael P; Overgaard, Jacob updating A series of ab initio calculations are presented on the alkyne-bridged dicobalt hexacarbonyl cluster Co2 micro-C2H2 (CO)6, indicating that this compound has substantial multireference character, which we interpret as evidence of singlet diradical behavior. As a result, standard theoretical methods such as restricted Hartree-Fock (RHF) or Kohn-Sham (RKS) density functional theory cannot properly describe this compound. We have therefore used complete active space (CAS) methods to explore the bonding in and spectroscopic properties of Co2 micro-C2H2 (CO)6. CAS methods identify significant population of a Co-Co antibonding orbital, along with Co-pi* back-bonding, and a relatively large singlet-triplet energy splitting. Analysis of the electron density and related quantities, such as energy densities and atomic overlaps, indicates a small but significant amount of covalent bonding between cobalt centers.
Ion-molecule reactions relevant to Titan's ionosphere.NASA Astrophysics Data System (ADS) McEwan, M. J.; Scott, G. B. I.; Anicich, V. G. updating Twenty four new ion-molecule reactions are presented for inclusion in the modeling of the ionosphere of Saturn's satellite Titan. Sixteen reactions were re-examined to reduce uncertainties in the previous literature results. In this study the authors have examined the reactions of N+ and N2+ with CH4, C2H2, C2H4, C2H6, HCN, CH2CHCN and HC3N; the reaction of N+ with CH3CN; the reactions of C3H5+ with CH4, C2H2 C2H4, C2H6, H2, HCN, HC3N and CH2CHCN; the reactions of C2N2+ with C2H2; C2H2+ and C2N2; C2H4 with C2H3+, C2H4+, CHCCNH+, and HC5N+; HCNH+ with C2H6; C3H6+ with C3H6; HCN with C2H6+, C3H6+, c-C3H6+, C2N2+ and NO+; N2 with C2H2+ and C2H5+; C2H4+ and HC3N. The ions selected for this study were derived either from nitrogen, appropriate hydrocarbons or nitriles. The reactant neutrals were selected on the basis of their known presence in Titan's atmosphere. The reaction products are consistent with the expected increase in ion size through ion-molecule reaction processing. Data are also presented for the reactions of 23 ions with molecular nitrogen. Almost all of these ions are unreactive with N2.
Effect of in situ pyrolysis of acetylene (C 2 H 2 ) gas as a carbon source on the electrochemical performance of LiFePO4 for rechargeable lithium-ion batteriesNASA Astrophysics Data System (ADS) Saroha, Rakesh; Panwar, Amrish K. updating The intention of this work is to study the effect of in situ pyrolysis of acetylene (C2H2) gas used as a carbon source on the physicochemical and electrochemical performance of pristine LiFePO4 (LFP). Acetylene gas, which decomposed to carbon and methane along with some side products when exposed to high temperature (>625 °C), is used as a carbon source for coating over the surface of LFP particles. Thermogravimetric (TGA) measurements were performed in an air atmosphere, primarily to estimate the exact amount of carbon deposited on the surface of the olivine cathode material due to the decomposition of C2H2 gas. Raman and TGA results confirm the presence of carbon as coated on the surface of the prepared compositions. Among all the synthesized samples, LFP with 10 min C2H2 treatment (LFPC10) shows the highest discharge capacity at all C-rates and exhibits excellent rate performance. LFPC10 delivers a specific discharge capacity of 144 (±5) mAh g-1 (~85% of the theoretical capacity of 170 mAh g-1) at 0.1C rate. LFPC10 demonstrates the best cycling performance as it offers an initial discharge capacity of about 117 (±5) mAh g-1 (~69% of the theoretical capacity) at 1C-rate and has 97% capacity retention even after 100 charge/discharge cycles.
Kinetics of initiation, propagation, and termination for the [rac-(C (2 )H (4 )(1-indenyl)(2))ZrMe][MeB(C(6)F(5))(3)]-catalyzed polymerization of 1-hexene.PubMed Liu, Z; Somsook, E; White, C B; Rosaaen, K A; Landis, C R updating Metallocene-catalyzed polymerization of 1-alkenes offers fine control of critical polymer attributes such as molecular weight, polydispersity, tacticity, and comonomer incorporation. Enormous effort has been expended on the synthesis and discovery of new catalysts and activators, but elementary aspects of the catalytic processes remain unclear. For example, it is unclear how the catalyst is distributed among active and dormant sites and how this distribution influences the order in monomer for the propagation rates, for which widely varying values are reported. Similarly, although empirical relationships between average molecular weights and monomer have been established for many systems, the underlying mechanisms of chain termination are unclear. Another area of intense interest concerns the role of ion-pairing in controlling the activity and termination mechanisms of metallocene-catalyzed polymerizations. Herein we report the application of quenched-flow kinetics, active site counting, polymer microstructure analysis, and molecular weight distribution analysis to the determination of fundamental rate laws for initiation, propagation, and termination for the polymerization of 1-hexene in toluene solution as catalyzed by the contact ion-pair, [rac-(C(2)H(4)(1-indenyl)(2))ZrMe][MeB(C(6)F(5))(3)] (1) over the temperature range of -10 to 50 degrees C. Highly isotactic (>99% mmmm) poly-1-hexene is produced with no apparent enchained regioerrors. Initiation and propagation processes are first order in the concentrations of 1-hexene and 1 but independent of excess borane or the addition of the contact ion-pair [PhNMe(3)][MeB(C(6)F(5))(3)]. Active site counting and the reaction kinetics provide no evidence of catalyst accumulation in dormant or inactive sites. Initiation is slower than propagation by a factor of 70. The principal termination process is the formation of unsaturates of two types: vinylidene end groups that arise from termination after a 1,2 insertion and
Comparative Shock-Tube Study of Autoignition and Plasma-Assisted Ignition of C2-HydrocarbonsNASA Astrophysics Data System (ADS) Kosarev, Ilya; Kindysheva, Svetlana; Plastinin, Eugeny; Aleksandrov, Nikolay; Starikovskiy, Andrey updating The dynamics of pulsed picosecond and nanosecond discharge development in liquid water, ethanol and hexane Using a shock tube with a discharge cell, ignition delay time was measured in a lean (φ = 0.5) C2H6:O2:Ar mixture and in lean (φ = 0.5) and stoichiometric C2H4:O2:Ar mixtures with a high-voltage nanosecond discharge and without it. The measured results were compared with the measurements made previously with the same setup for C2H6-, C2H5OH- and C2H2-containing mixtures. It was shown that the effect of plasma on ignition is almost the same for C2H6, C2H4 and C2H5OH. The reduction in time is smaller for C2H2, the fuel that is well ignited even without the discharge. Autoignition delay time was independent of the stoichiometric ratio for C2H6 and C2H4, whereas this time in stoichiometric C2H2- and C2H5OH-containing mixtures was noticeably shorter than that in the lean mixtures. Ignition after the discharge was not affected by a change in the stoichiometric ratio for C2H2 and C2H4, whereas the plasma-assisted ignition delay time for C2H6 and C2H5OH decreased as the equivalence ratio changed from 1 to 0.5. Ignition delay time was calculated in C2-hydrocarbon-containing mixtures under study by simulating separately discharge and ignition processes. Good agreement was obtained between new measurements and calculated ignition delay times.

Water-Stable In(III)-Based Metal-Organic Frameworks with Rod-Shaped Secondary Building Units: Single-Crystal to Single-Crystal Transformation and Selective Sorption of C 2 H 2 over CO2 and CH4.PubMed Guo, Zhen-Ji; Yu, Jiamei; Zhang, Yong-Zheng; Zhang, Jian; Chen, Ya; Wu, Yufeng; Xie, Lin-Hua; Li, Jian-Rong updating Three new water-stable In(III)-based metal-organic frameworks, namely, [In 3 (TTTA) 2 (OH) 3 (H 2 O)]·(DMA) 3 (BUT-70, DMA = N,N-dimethylacetamide), [In 3 (TTTA) 2 (CH 3 O) 3 ] (BUT-70A), and [In 3 (TTTA) 2 (OH) 3 ] (BUT-70B), with rod-shaped secondary building units (SBUs) and an new acrylate-based ligand, (2E,2'E,2″E)-3,3',3″-(2,4,6-trimethylbenzene-1,3,5-triyl)-triacrylate (TTTA 3- ) were obtained and structurally characterized. BUT-70A and -70B were generated in a single-crystal to single-crystal transformation fashion from BUT-70 through guest exchange followed by their removal. The solvents used for guest exchange were methanol and dichloromethane, respectively. Single-crystal structure analyses show that the guest exchange and removal process is accompanied by the substitution of coordinated water molecules of In(III) centers with uncoordinated carboxylate O atoms of TTTA 3- ligands. Moreover, hydroxyl groups bridging two In(III) centers are also replaced by methoxyl groups in the transformation from BUT-70 to -70A. Overall, three metal-organic frameworks (MOFs) are constructed by infinite chains consisting of corner-sharing InO 4 (OR) 2 (R = H or Me) octahedral entities, which are interconnected by TTTA 3- ligands to form three-dimensional frameworks. Unlike most reported MOFs with infinite chains as SBUs, such as well-known MIL-53 and M-MOF-74, which have one-dimensional channels along the chain direction, the BUT-70 series contain two-dimensional intersecting channels. The Brunauer-Emmett-Teller surface area and pore volume of BUT-70A were estimated to be 460 m 2 g -1 and 0.18 cm 3 g -1 , respectively, which are obviously lower than those of BUT-70B (695 m 2 g -1 and 0.29 cm 3 g -1 ). Gas adsorption experiments demonstrated that BUT-70A and -70B are able to selectively adsorb C 2 H 2 over CO 2 and CH 4 . At 1 atm and 298 K, BUT-70A uptakes 3.1 mmol g -1 C 2 H 2 , which is 3.6 times that of the CO 2 uptake and 7.2 times that of the CH 4 uptake
H2, He, and CO2 line-broadening coefficients, pressure shifts and temperature-dependence exponents for the HITRAN database. Part 1: SO2, NH3, HF, HCl, OCS and C 2 H 2NASA Astrophysics Data System (ADS) Wilzewski, Jonas S.; Gordon, Iouli E.; Kochanov, Roman V.; Hill, Christian; Rothman, Laurence S. updating To increase the potential for use of the HITRAN database in astronomy, experimental and theoretical line-broadening coefficients, line shifts and temperature-dependence exponents of molecules of planetary interest broadened by H2, He, and CO2 have been assembled from available peer-reviewed sources. The collected data were used to create semi-empirical models so that every HITRAN line of the studied molecules has corresponding parameters. Since H2 and He are major constituents in the atmospheres of gas giants, and CO2 predominates in atmospheres of some rocky planets with volcanic activity, these spectroscopic data are important for remote sensing studies of planetary atmospheres. In this paper we make the first step in assembling complete sets of these parameters, thereby creating datasets for SO2, NH3, HF, HCl, OCS and C2H2.
Separation of C2 hydrocarbons from methane in a microporous metal-organic frameworkNASA Astrophysics Data System (ADS) Tang, Fu-Shun; Lin, Rui-Biao; Lin, Rong-Guang; Zhao, John Cong-Gui; Chen, Banglin updating The recovery of C2 hydrocarbons including acetylene, ethylene and ethane is challenging but important for natural gas upgrading. The separation of C2 hydrocarbons over methane was demonstrated here by using a microporous metal-organic framework [Zn3(OH)2(SDB)2] (H2SDB = 4,4'-sulfonyldibenzoic acid) consisting narrow one-dimensional pore channels. Gas sorption experiments revealed that this MOF material showed considerable uptake capacity for C2H2, C2H4 and C2H6 under ambient conditions, while its capacity for CH4 was very low. High selectivity from IAST calculations for C2H2/CH4, C2H4/CH4 and C2H6/CH4 binary mixtures demonstrated that this MOF material were promising for efficiently separating important separation of C2 hydrocarbons from methane in natural gas processing.
Comparison of one-particle basis set extrapolation to explicitly correlated methods for the calculation of accurate quartic force fields, vibrational frequencies, and spectroscopic constants: Application to H2O, N2H+, NO2+, and C 2 H 2NASA Astrophysics Data System (ADS) Huang, Xinchuan; Valeev, Edward F.; Lee, Timothy J. updating One-particle basis set extrapolation is compared with one of the new R12 methods for computing highly accurate quartic force fields (QFFs) and spectroscopic data, including molecular structures, rotational constants, and vibrational frequencies for the H2O, N2H+, NO2+, and C2H2 molecules. In general, agreement between the spectroscopic data computed from the best R12 and basis set extrapolation methods is very good with the exception of a few parameters for N2H+ where it is concluded that basis set extrapolation is still preferred. The differences for H2O and NO2+ are small and it is concluded that the QFFs from both approaches are more or less equivalent in accuracy. For C2H2, however, a known one-particle basis set deficiency for C-C multiple bonds significantly degrades the quality of results obtained from basis set extrapolation and in this case the R12 approach is clearly preferred over one-particle basis set extrapolation. The R12 approach used in the present study was modified in order to obtain high precision electronic energies, which are needed when computing a QFF. We also investigated including core-correlation explicitly in the R12 calculations, but conclude that current approaches are lacking. Hence core-correlation is computed as a correction using conventional methods. Considering the results for all four molecules, it is concluded that R12 methods will soon replace basis set extrapolation approaches for high accuracy electronic structure applications such as computing QFFs and spectroscopic data for comparison to high-resolution laboratory or astronomical observations, provided one uses a robust R12 method as we have done here. The specific R12 method used in the present study, CCSD(T)R12, incorporated a reformulation of one intermediate matrix in order to attain machine precision in the electronic energies. Final QFFs for N2H+ and NO2+ were computed, including basis set extrapolation, core-correlation, scalar relativity, and higher
A Ni-Doped Carbon Nanotube Sensor for Detecting Oil-Dissolved Gases in TransformersPubMed Central Lu, Jia; Zhang, Xiaoxing; Wu, Xiaoqing; Dai, Ziqiang; Zhang, Jinbin updating C2H2, C2H4, and C2H6 are important oil-dissolved gases in power transformers. Detection of the composition and content of oil-dissolved gases in transformers is very significant in the diagnosis and assessment of the state of transformer operations. The commonly used oil-gas analysis methods have many disadvantages, so this paper proposes a Ni-doped carbon nanotube (Ni-CNT) gas sensor to effectively detect oil-dissolved gases in a transformer. The gas-sensing properties of the sensor to C2H2, C2H4, and C2H6 were studied using the test device. Based on the density functional theory (DFT) the adsorption behaviors of the three gases on intrinsic carbon nanotubes (CNTs) and Ni-CNTs were calculated. The adsorption energy, charge transfer, and molecular frontier orbital of the adsorption system were also analyzed. Results showed that the sensitivity of the CNT sensor to the three kinds of gases was in the following order: C2H2 > C2H4 > C2H6. Moreover, the doped Ni improved the sensor response, and the sensor response and gas concentration have a good linear relationship. PMID:updating
A Ni-Doped Carbon Nanotube Sensor for Detecting Oil-Dissolved Gases in Transformers.PubMed Lu, Jia; Zhang, Xiaoxing; Wu, Xiaoqing; Dai, Ziqiang; Zhang, Jinbin updating C2H2, C2H4, and C2H6 are important oil-dissolved gases in power transformers. Detection of the composition and content of oil-dissolved gases in transformers is very significant in the diagnosis and assessment of the state of transformer operations. The commonly used oil-gas analysis methods have many disadvantages, so this paper proposes a Ni-doped carbon nanotube (Ni-CNT) gas sensor to effectively detect oil-dissolved gases in a transformer. The gas-sensing properties of the sensor to C2H2, C2H4, and C2H6 were studied using the test device. Based on the density functional theory (DFT) the adsorption behaviors of the three gases on intrinsic carbon nanotubes (CNTs) and Ni-CNTs were calculated. The adsorption energy, charge transfer, and molecular frontier orbital of the adsorption system were also analyzed. Results showed that the sensitivity of the CNT sensor to the three kinds of gases was in the following order: C2H2 > C2H4 > C2H6. Moreover, the doped Ni improved the sensor response, and the sensor response and gas concentration have a good linear relationship.
The C 2 H 2 -type transcription factor, FlbC, is involved in the transcriptional regulation of Aspergillus oryzae glucoamylase and protease genes specifically expressed in solid-state culture.PubMed Tanaka, Mizuki; Yoshimura, Midori; Ogawa, Masahiro; Koyama, Yasuji; Shintani, Takahiro; Gomi, Katsuya updating Aspergillus oryzae produces a large amount of secreted proteins in solid-state culture, and some proteins such as glucoamylase (GlaB) and acid protease (PepA) are specifically produced in solid-state culture, but rarely in submerged culture. From the disruption mutant library of A. oryzae transcriptional regulators, we successfully identified a disruption mutant showing an extremely low production level of GlaB but a normal level of α-amylase production. This strain was a disruption mutant of the C2H2-type transcription factor, FlbC, which is reported to be involved in the regulation of conidiospore development. Disruption mutants of other upstream regulators comprising a conidiation regulatory network had no apparent effect on GlaB production in solid-state culture. In addition to GlaB, the production of acid protease in solid-state culture was also markedly decreased by flbC disruption. Northern blot analyses revealed that transcripts of glaB and pepA were significantly decreased in the flbC disruption strain. These results suggested that FlbC is involved in the transcriptional regulation of genes specifically expressed under solid-state cultivation conditions, possibly independent of the conidiation regulatory network.
Neutral ligand TIPA-based two 2D metal-organic frameworks: ultrahigh selectivity of C 2 H 2 /CH4 and efficient sensing and sorption of Cr(vi ).PubMed Fu, Hong-Ru; Zhao, Ying; Zhou, Zhan; Yang, Xiao-Gang; Ma, Lu-Fang updating One neutral tripodal semi-rigidity ligand tri(4-imidazolylphenyl)amine (TIPA) with excellent hole-transfer nature, was selected as a linker to construct MOFs. Two two-dimensional (2D) microporous metal-organic frameworks (MOFs) were synthesized solvothermally: [Ni(TIPA)(COO - ) 2 (H 2 O)]·2(DMF)2(H 2 O) (1) and [Cd(TIPA) 2 (ClO 4 - ) 2 ]·(DMF)3(H 2 O) (2). Compound 1 incorporated carboxylic groups into the channel and exhibited the high capacity of light hydrocarbons as well as the remarkable selectivity of C 2 H 2 /CH 4 . The value is in excess of 100 at room temperature, which is the highest value reported to date. Compound 2, as a cationic framework with high water stability, was not only applied as a sensor, displaying the ultrahigh sensitivity against Cr 2 O 7 2- with a detection limit as low as 8 ppb, but also possessed excellent Cr(vi) sorption with good repeatability in aqueous solution. This study provides an efficient strategy to design cationic MOFs for the selective separation of light hydrocarbons and the sensing and trapping of toxic chromate for the purification of water.
The C 2 H 2 Transcription Factor REGULATOR OF SYMBIOSOME DIFFERENTIATION Represses Transcription of the Secretory Pathway Gene VAMP721a and Promotes Symbiosome Development in Medicago truncatula[W][OPENPubMed Central Sinharoy, Senjuti; Torres-Jerez, Ivone; Bandyopadhyay, Kaustav; Kereszt, Attila; Pislariu, Catalina I.; Nakashima, Jin; Benedito, Vagner A.; Kondorosi, Eva; Udvardi, Michael K. updating Transcription factors (TFs) are thought to regulate many aspects of nodule and symbiosis development in legumes, although few TFs have been characterized functionally. Here, we describe REGULATOR OF SYMBIOSOME DIFFERENTIATION (RSD) of Medicago truncatula, a member of the Cysteine-2/Histidine-2 (C2H2) family of plant TFs that is required for normal symbiosome differentiation during nodule development. RSD is expressed in a nodule-specific manner, with maximal transcript levels in the bacterial invasion zone. A tobacco (Nicotiana tabacum) retrotransposon (Tnt1) insertion rsd mutant produced nodules that were unable to fix nitrogen and that contained incompletely differentiated symbiosomes and bacteroids. RSD protein was localized to the nucleus, consistent with a role of the protein in transcriptional regulation. RSD acted as a transcriptional repressor in a heterologous yeast assay. Transcriptome analysis of an rsd mutant identified 11 genes as potential targets of RSD repression. RSD interacted physically with the promoter of one of these genes, VAMP721a, which encodes vesicle-associated membrane protein 721a. Thus, RSD may influence symbiosome development in part by repressing transcription of VAMP721a and modifying vesicle trafficking in nodule cells. This establishes RSD as a TF implicated directly in symbiosome and bacteroid differentiation and a transcriptional regulator of secretory pathway genes in plants. PMID:updating
C 2 H 4 F2 1,2-DifluoroethaneNASA Astrophysics Data System (ADS) Demaison, J. This document is part of Part 1 of Subvolume D 'Asymmetric Top Molecules' of Volume 29 'Molecular Constants Mostly from Microwave, Molecular Beam, and Sub-Doppler Laser Spectroscopy' of Landolt-Börnstein - Group II 'Molecules and Radicals'.
High Color Rendering Index White-Light Emission from UV-Driven LEDs Based on Single Luminescent Materials: Two-Dimensional Perovskites (C6H5C 2 H 4 NH3)2PbBr xCl4- x.PubMed Yang, Shuming; Lin, Zhenghuan; Wang, Jingwei; Chen, Yunxiang; Liu, Zhengde; Yang, E; Zhang, Jian; Ling, Qidan updating Two-dimensional (2D) white-light-emitting hybrid perovskites (WHPs) are promising active materials for single-component white-light-emitting diodes (WLEDs) driven by UV. However, the reported WHPs exhibit low quantum yields (≤9%) and low color rendering index (CRI) values less than 85, which does not satisfy the demand of solid-state lighting applications. In this work, we report a series of mixed-halide 2D layered WHPs (C 6 H 5 C 2 H 4 NH 3 ) 2 PbBr x Cl 4- x (0 C 2 H 4 NH 3 ) 2 PbCl 4 , the mixed-halide perovskites display morphology-dependent white emission for the different extents of self-absorption. Additionally, the amount of Br has a huge influence on the photophysical properties of mixed-halide WHPs. With the increasing content of Br, the quantum yields of WHPs increase gradually from 0.2 to 16.9%, accompanied by tunable color temperatures ranging from 4000 K ("warm" white light) to 7000 K ("cold" white light). When applied to the WLEDs, the mixed-halide perovskite powders exhibit tunable white electroluminescent emission with very high CRI of 87-91.
Experimental and theoretical study of the reactions between neutral vanadium oxide clusters and ethane, ethylene, and acetylene.PubMed Dong, Feng; Heinbuch, Scott; Xie, Yan; Rocca, Jorge J; Bernstein, Elliot R; Wang, Zhe-Chen; Deng, Ke; He, Sheng-Gui updating Reactions of neutral vanadium oxide clusters with small hydrocarbons, namely C2H6, C2H4, and C2H2, are investigated by experiment and density functional theory (DFT) calculations. Single photon ionization through extreme ultraviolet (EUV, 46.9 nm, 26.5 eV) and vacuum ultraviolet (VUV, 118 nm, 10.5 eV) lasers is used to detect neutral cluster distributions and reaction products. The most stable vanadium oxide clusters VO2, V2O5, V3O7, V4O10, etc. tend to associate with C2H4 generating products V(m)O(n)C2H4. Oxygen-rich clusters VO3(V2O5)(n=0,1,2...), (e.g., VO3, V3O8, and V5O13) react with C2H4 molecules to cause a cleavage of the C=C bond of C2H4 to produce (V2O5)(n)VO2CH2 clusters. For the reactions of vanadium oxide clusters (V(m)O(n)) with C2H2 molecules, V(m)O(n)C2H2 are assigned as the major products of the association reactions. Additionally, a dehydration reaction for VO3 + C2H2 to produce VO2C2 is also identified. C2H6 molecules are quite stable toward reaction with neutral vanadium oxide clusters. Density functional theory calculations are employed to investigate association reactions for V2O5 + C2H(x). The observed relative reactivity of C2 hydrocarbons toward neutral vanadium oxide clusters is well interpreted by using the DFT calculated binding energies. DFT calculations of the pathways for VO3+C2H4 and VO3+C2H2 reaction systems indicate that the reactions VO3+C2H4 --> VO2CH2 + H2CO and VO3+C2H2 --> VO2C2 + H2O are thermodynamically favorable and overall barrierless at room temperature, in good agreement with the experimental observations.
Structure and composition of Pluto's atmosphere from the New Horizons solar ultraviolet occultationNASA Astrophysics Data System (ADS) Young, Leslie A.; Kammer, Joshua A.; Steffl, Andrew J.; Gladstone, G. Randall; Summers, Michael E.; Strobel, Darrell F.; Hinson, David P.; Stern, S. Alan; Weaver, Harold A.; Olkin, Catherine B.; Ennico, Kimberly; McComas, David J.; Cheng, Andrew F.; Gao, Peter; Lavvas, Panayotis; Linscott, Ivan R.; Wong, Michael L.; Yung, Yuk L.; Cunningham, Nathanial; Davis, Michael; Parker, Joel Wm.; Schindhelm, Eric; Siegmund, Oswald H. W.; Stone, John; Retherford, Kurt; Versteeg, Maarten updating The Alice instrument on NASA's New Horizons spacecraft observed an ultraviolet solar occultation by Pluto's atmosphere on 2015 July 14. The transmission vs. altitude was sensitive to the presence of N2, CH4, C2H2, C2H4, C2H6, and haze. We derived line-of-sight abundances and local number densities for the 5 molecular species, and line-of-sight optical depth and extinction coefficients for the haze. We found the following major conclusions: (1) We confirmed temperatures in Pluto's upper atmosphere that were colder than expected before the New Horizons flyby, with upper atmospheric temperatures near 65-68 K. The inferred enhanced Jeans escape rates were (3-7) × 1022 N2 s-1 and (4-8) × 1025 CH4 s-1 at the exobase (at a radius of ∼ 2900 km, or an altitude of ∼1710 km). (2) We measured CH4 abundances from 80 to 1200 km above the surface. A joint analysis of the Alice CH4 and Alice and REX N2 measurements implied a very stable lower atmosphere with a small eddy diffusion coefficient, most likely between 550 and 4000 cm2 s-1. Such a small eddy diffusion coefficient placed the homopause within 12 km of the surface, giving Pluto a small planetary boundary layer. The inferred CH4 surface mixing ratio was ∼ updating%. (3) The abundance profiles of the ;C2Hx hydrocarbons; (C2H2, C2H4, C2H6) were not simply exponential with altitude. We detected local maxima in line-of-sight abundance near 410 km altitude for C2H4, near 320 km for C2H2, and an inflection point or the suggestion of a local maximum at 260 km for C2H6. We also detected local minima near 200 km altitude for C2H4, near 170 km for C2H2, and an inflection point or minimum near 170-200 km for C2H6. These compared favorably with models for hydrocarbon production near 300-400 km and haze condensation near 200 km, especially for C2H2 and C2H4 (Wong et al., updating) We found haze that had an extinction coefficient approximately proportional to N2 density.
Quantitative Measurements of HO2 and other products of n-butane oxidation (H2O2, H2O, CH2O, and C 2 H 4 ) at elevated temperatures by direct coupling of a jet-stirred reactor with sampling nozzle and cavity ring-down spectroscopy (cw-CRDS).PubMed Djehiche, Mokhtar; Le Tan, Ngoc Linh; Jain, Chaithanya D; Dayma, Guillaume; Dagaut, Philippe; Chauveau, Christian; Pillier, Laure; Tomas, Alexandre updating For the first time quantitative measurements of the hydroperoxyl radical (HO2) in a jet-stirred reactor were performed thanks to a new experimental setup involving fast sampling and near-infrared cavity ring-down spectroscopy at low pressure. The experiments were performed at atmospheric pressure and over a range of temperatures (550-900 K) with n-butane, the simplest hydrocarbon fuel exhibiting cool flame oxidation chemistry which represents a key process for the auto-ignition in internal combustion engines. The same technique was also used to measure H2O2, H2O, CH2O, and C2H4 under the same conditions. This new setup brings new scientific horizons for characterizing complex reactive systems at elevated temperatures. Measuring HO2 formation from hydrocarbon oxidation is extremely important in determining the propensity of a fuel to follow chain-termination pathways from R + O2 compared to chain branching (leading to OH), helping to constrain and better validate detailed chemical kinetics models.
Hydrothermal Syntheses and Structures of Three-Dimensional Oxo-fluorovanadium Phosphates: [H 2N(C 2 H 4 ) 2NH 2] 0.5[(VO) 4V(HPO 4) 2(PO 4) 2F 2(H 2O) 4] · 2H 2O and K 2[(VO) 3(PO 4) 2F 2(H 2O)] · H 2ONASA Astrophysics Data System (ADS) Bonavia, Grant; Haushalter, R. C.; Zubieta, Jon updating The hydrothermal reactions of FPO3H2with vanadium oxides result in the incorporation of fluoride into V-P-O frameworks as a consequence of metal-mediated hydrolysis of the fluorophosphoric acid to produce F-and PO3-4. By exploiting this convenient source of F-, two 3-dimensional oxo-fluorovanadium phosphate phases were isolated, [H2N(C2H4)2NH2]0.5[(VO)4V(HOP4)2(PO4)2F2(H2O)4) · 2H2O (1 · 2H2O) and K2[(VO)3(PO4)2F2(H2O)] · H2O (2 · H2O). Both anionic frameworks contain (VIVO)-F--phosphate layers, with confacial bioctahedral {(VIVO)2FO6} units as the fundamental motif. In the case of 1, the layers are linked through {VIIIO6} octahedra, while for 2 the interlayer connectivity is provided by edge-sharing {(VIVO)2F2O6} units. Crystal data are 1 · 2H2O, CH10FN0.5O13P2V2.5, monoclinicC2/m,a= updating) Å,c= 8.954(2) Å, β = updating,V= updating) Å3,Z= 4,Dcalc= 2.423 g cm-3; 2 · H2O, H4F2K2O13P2V3, triclinicPoverline1,a= 7.298(1) Å,b= 8.929(2) Å,c = updating) Å, α = updating, β = updating, δ = updating,V= 623.8(3) Å3,Z= 2,Dcalc= 2.891 g cm-3.
Global Frequency and Intensity Analysis of the νb{10}/νb{7}/νb{4}/νb{12} Bands System of 12C _2 H _4 at 10 μm Using the D2h Top Data SystemNASA Astrophysics Data System (ADS) Alkadrou, Abdulsamee; Rotger, Maud; Boudon, Vincent; Vander Auwera, Jean updating A global frequency and intensity analysis of the infrared tetrad located in the updating cm-1 region was carried out using the tensorial formalism developed in Dijon for X_2Y_4 asymmetric-top molecules and a program suite called D2hTDS (now part of the XTDS/SPVIEW spectroscopic software). It relied on spectroscopic information available in the literature and retrieved from absorption spectra recorded in Brussels using a Bruker IFS 120 to 125 HR upgraded Fourier transform spectrometer, in the frame of either the present or previous work. In particular, 645 and 131 lines intensities have been respectively measured for the weak ν10 and ν_4 bands. Including the Coriolis interactions affecting the upper vibrational levels 10^1, 7^1, 4^1 and 12^1, a total of 10737 line positions and 1870 line intensities have been assigned and fitted with global root mean square deviations of 2.6 × 10-4 cm-1 and {2.4} %, respectively. Relying on the results of the present work and available in the literature, a list of parameters for 65420 lines in the ν10, ν7, ν4 and ν12 bands of 12C_2H_4 was generated. The present work provides an obvious improvement over HITRAN and GEISA for the ν10 band (see figure), and a marginally better modeling for the ν7 band (and for the ν4 band hidden beneath it). To the best of our knowledge, this is the first time that a global intensity analysis is carried out in this range of the ethylene spectrum. Raballand W, Rotger M, Boudon V, Loëte M. J Mol Spectrosc 2003;217:239-48. Wenger Ch, Boudon V, Rotger M, Champion JP, Sanzharov M. J Mol Spectrosc 2008;251:102-13. Rotger M, Boudon V, Vander Auwera J. J Quant Spectrosc Radiat Transf 2008;109:952-62.
Absolute Integral Cross Sections for the State-selected Ion-Molecule Reaction N2+(X2Σg+ v+ = 0-2) + C 2 H 2 in the Collision Energy Range of updating eVNASA Astrophysics Data System (ADS) Xu, Yuntao; Xiong, Bo; Chung Chang, Yih; Ng, C. Y. updating Using the vacuum ultraviolet laser pulsed field ionization-photoion source, together with the double-quadrupole-double-octopole mass spectrometer developed in our laboratory, we have investigated the state-selected ion-molecule reaction {{{{N}}}2}+({X}2{{{{Σ }}}{{g}}}+; v + = 0-2, N+ = 0-9) + C2H2, achieving high internal-state selectivity and high kinetic energy resolution for reactant {{{{N}}}2}+ ions. The charge transfer (CT) and hydrogen-atom transfer (HT) channels, which lead to the respective formation of product {{{C}}}2{{{{H}}}2}+ and N2H+ ions, are observed. The vibrationally selected absolute integral cross sections for the CT [σ CT(v +)] and HT [[σ HT(v +)] channels obtained in the center-of-mass collision energy (E cm) range of updating eV reveal opposite E cm dependences. The σ CT(v +) is found to increase as E cm is decreased, and is consistent with the long-range exothermic CT mechanism, whereas the E cm enhancement observed for the σ HT(v +) suggests effective coupling of kinetic energy to internal energy, enhancing the formation of N2H+. The σ HT(v +) curve exhibits a step at E cm = updating eV, suggesting the involvement of the excited {{{C}}}2{{{{H}}}2}+({A}2{{{{Σ }}}{{g}}}+) state in the HT reaction. Contrary to the strong E cm dependences for σ CT(v +) and σ HT(v +), the effect of vibrational excitation of {{{{N}}}2}+ on both the CT and HT channels is marginal. The branching ratios and cross sections for the CT and HT channels determined in the present study are useful for modeling the atmospheric compositions of Saturn's largest moon, Titan. These cross sections and branching ratios are also valuable for benchmarking theoretical calculations on chemical dynamics of the titled reaction.
Some problems in interpretation of the New Horizons observations of Pluto's atmosphereNASA Astrophysics Data System (ADS) Krasnopolsky, Vladimir A. updating Here I briefly discuss the following problems related to Pluto's atmosphere: (1) restrictions to LTE in the rotational lines of H2O and HCN above 700 km that affect thermal balance of the atmosphere; (2) contradictions in the estimates of H2O influx from ablation of the interplanetary dust; (3) great difference between the haze volume surface area in the LORRI and MVIC observations and that in the UV solar occultations and the models, including significant corrections to sticking coefficients of C2H2, C2H4, C2H6, and HCN in condensation, and (4) Triton's thermosphere during the Voyager 2 flyby.
A combined crossed-beam and theoretical study of the reaction dynamics of O(3P) + C2H3 → C 2 H 2 + OH: Analysis of the nascent OH products with the preferential population of the Π(A') componentNASA Astrophysics Data System (ADS) Park, Min-Jin; Jang, Su-Chan; Choi, Jong-Ho updating The gas-phase reaction dynamics of ground-state atomic oxygen [O(3P) from the photo-dissociation of NO2] with vinyl radicals [C2H3 from the supersonic flash pyrolysis of vinyl iodide, C2H3I] has been investigated using a combination of high-resolution laser-induced fluorescence spectroscopy in a crossed-beam configuration and ab initio calculations. Unlike the previous gas-phase bulk kinetic experiments by Baulch et al. [J. Phys. Chem. Ref. Data 34, updating)], 10.1063/updating, a new exothermic channel of O(3P) + C2H3 → C2H2 + OH (X 2Π: υ″ = 0) has been identified for the first time, and the population analysis shows bimodal nascent rotational distributions of OH products with low- and high-N″ components with a ratio of 2.4:1. No spin-orbit propensities were observed, and the averaged ratios of Π(A')/Π(A″) were determined to be 1.66 ± 0.27. On the basis of computations at the CBS-QB3 theory level and comparison with prior theory, the microscopic mechanisms responsible for the nascent populations can be understood in terms of two competing dynamical pathways: a direct abstraction process in the low-N″ regime as the major pathway and an addition-complex forming process in the high-N″ regime as the minor pathway. Particularly, during the bond cleavage process of the weakly bound van der Waals complex C2H2—OH, the characteristic pathway from the low dihedral-angle geometry was consistent with the observed preferential population of the Π(A') component in the nascent OH products. A molecular-level discussion of the reactivity, mechanism, and dynamical features of the title reaction are presented together with a comparison to gas-phase oxidation reactions of a series of prototypical hydrocarbon radicals.
A combined crossed-beam and theoretical study of the reaction dynamics of O(3P) + C2H3 → C 2 H 2 + OH: analysis of the nascent OH products with the preferential population of the Π(A') component.PubMed Park, Min-Jin; Jang, Su-Chan; Choi, Jong-Ho updating The gas-phase reaction dynamics of ground-state atomic oxygen [O((3)P) from the photo-dissociation of NO(2)] with vinyl radicals [C(2)H(3) from the supersonic flash pyrolysis of vinyl iodide, C(2)H(3)I] has been investigated using a combination of high-resolution laser-induced fluorescence spectroscopy in a crossed-beam configuration and ab initio calculations. Unlike the previous gas-phase bulk kinetic experiments by Baulch et al. [J. Phys. Chem. Ref. Data 34, updating)], a new exothermic channel of O((3)P) + C(2)H(3) → C(2)H(2) + OH (X (2)Π: υ" = 0) has been identified for the first time, and the population analysis shows bimodal nascent rotational distributions of OH products with low- and high-N" components with a ratio of 2.4:1. No spin-orbit propensities were observed, and the averaged ratios of Π(A('))∕Π(A") were determined to be 1.66 ± 0.27. On the basis of computations at the CBS-QB3 theory level and comparison with prior theory, the microscopic mechanisms responsible for the nascent populations can be understood in terms of two competing dynamical pathways: a direct abstraction process in the low-N" regime as the major pathway and an addition-complex forming process in the high-N" regime as the minor pathway. Particularly, during the bond cleavage process of the weakly bound van der Waals complex C(2)H(2)-OH, the characteristic pathway from the low dihedral-angle geometry was consistent with the observed preferential population of the Π(A') component in the nascent OH products. A molecular-level discussion of the reactivity, mechanism, and dynamical features of the title reaction are presented together with a comparison to gas-phase oxidation reactions of a series of prototypical hydrocarbon radicals.

Double differential cross sections of ethane moleculeNASA Astrophysics Data System (ADS) Kumar, Rajeev updating Partial and total double differential cross sections corresponding to various cations C2H6+, C2H4+, C2H5+, C2H3+, C2H2+, CH3+, H+, CH2+, C2H+, H2+, CH+, H3+, C2+ and C+ produced during the direct and dissociative electron ionization of Ethane (C2H6) molecule have been calculated at fixed impinging electron energies 200 and 500eV by using modified Jain-Khare semi empirical approach. The calculation for double differential cross sections is made as a function of energy loss suffered by primary electron and angle of incident. To the best of my knowledge no other data is available for the comparison.
Analysis Of The Different Zones Of Glow Discharge Of Ethyl Alcohol (C 2 H 6 O)NASA Astrophysics Data System (ADS) Torres, C.; Reyes, P. G.; Mulia, J.; Castillo, F.; Martínez, H. updating The aim of this work is to explore the emission spectroscopy of ethyl alcohol in some regions, also is determine the result elements of the glow discharge, the spectrums were observed in a range of 200 at 1100 nm in the different zones inside of the tube at different distances of 20 and 30 cm. The elements are: in anode region C6Hupdatingnm), CHO (519.56nm) and Hupdatingnm), in the positive column COupdating y 337.00nm), O+ (357.48nm), CH+ (380.61nm) and CO+ (399.73nm); in the cathode region we observed O+ (391.19nm), CHOCHO (428.00nm), CO+ (471.12nm) and Hupdatingnm). C6H5, CHO y H2 species occurring in all regions analyzed varying the glow discharge emission intensity.
Peroxy Radical Measurements during the IRRONIC Field Project by C 2 H 6 - NO Chemical AmplificationNASA Astrophysics Data System (ADS) Wood, E. C. D.; Kundu, S.; Deming, B.; Lew, M.; Stevens, P. S.; Sklaveniti, S.; Dusanter, S. updating We present measurements of total peroxy radicals (HO2 + RO2) during the Indiana Radical, Reactivity and Ozone Production Intercomparison (IRRONIC) field project in Bloomington, Indiana during July 2015. Peroxy radicals were measured by chemical amplification using ethane and nitric oxide in dual PFA reaction chambers, and the amplification product NO2 was quantified by cavity attenuated phase shift spectroscopy. On sunny days mid-day peroxy radical mixing ratios were typically between 20 and 70 ppt and were well correlated with "HO2*" measured by the Indiana University Laser-Induced Fluorescence with Fluorescence Assay by Gas Expansion (IU-FAGE) instrument. The ratio of total peroxy radicals (UMass) to the IU-FAGE HO2* measurements was greater than two. We also describe results from an informal intercomparison of the two instruments' calibration sources, which are based on acetone photolysis (UMass) and water photolysis (IU). In addition to sampling the IU calibration source in "amplification" mode, the UMass instrument also separately quantified the HO2 mixing ratio in the IU calibration gas by reaction with excess NO and subsequent quantification of the NO2 produced.
C 2 H 4 ArF2 1,2-Difluoroethane - argon (1/1)NASA Astrophysics Data System (ADS) Demaison, J. This document is part of Part 1 of Subvolume D 'Asymmetric Top Molecules' of Volume 29 'Molecular Constants Mostly from Microwave, Molecular Beam, and Sub-Doppler Laser Spectroscopy' of Landolt-Börnstein - Group II 'Molecules and Radicals'.
C 2 H 4 ArF2 1,1-Difluoroethane - argon (1/1)NASA Astrophysics Data System (ADS) Demaison, J. This document is part of Part 1 of Subvolume D 'Asymmetric Top Molecules' of Volume 29 'Molecular Constants Mostly from Microwave, Molecular Beam, and Sub-Doppler Laser Spectroscopy' of Landolt-Börnstein - Group II 'Molecules and Radicals'.
High-pressure copolymerization of C 2 H 4 and CONASA Astrophysics Data System (ADS) Buback, M.; Tups, H. updating Kinetics of the free radical high-pressure copolymerization of ethylene and carbon monoxide using thermal, chemical, and laser-photochemical initiation have been investigated via quantitative infrared and near infrared spectroscopy up to 2300 bar and 513 K. The slow thermal copolymerization is influenced by the formation of metal carbonyls inside the stainless steel cell. With chemical initiation, using 120 ppm oxygen, ethylene and CO polymerize to polyketone without any indication of additional products. The photo-copolymerization induced by an exciplex laser working on the KrF line at 248 nm, has been studied between 486 K and 513 K up to 2300 bar and for CO mole fractions up to 3 percent. Overall quantum yields of about 2000 copolymerizing molecules per one absorbed laser photon are observed.
Dehydrogenation involved Coulomb explosion of molecular C 2 H 4 FBr in an intense laser fieldNASA Astrophysics Data System (ADS) Pei, Minjie; Yang, Yan; Zhang, Jian; Sun, Zhenrong updating The dissociative double ionization (DDI) of molecular 1-fluo-2-bromoethane (FBE) in an intense laser field has been investigated by dc-slice imaging technology. The DDI channels involved with dehydrogenation are revealed and it's believed both the charge distribution and the bound character of real potential energy surfaces of parent ions play important roles in the dissociation process. The relationship between the potential energy surfaces of the precursor species and the photofragment ejection angles are also discussed and analyzed. Furthermore, the competition between the DDI channels has been studied and the Csbnd C bond cleavages dominate the DDI process at relative higher laser intensity.
[Application of optimized parameters SVM based on photoacoustic spectroscopy method in fault diagnosis of power transformer].PubMed Zhang, Yu-xin; Cheng, Zhi-feng; Xu, Zheng-ping; Bai, Jing updating In order to solve the problems such as complex operation, consumption for the carrier gas and long test period in traditional power transformer fault diagnosis approach based on dissolved gas analysis (DGA), this paper proposes a new method which is detecting 5 types of characteristic gas content in transformer oil such as CH4, C2H2, C2H4, C2H6 and H2 based on photoacoustic Spectroscopy and C2H2/C2H4, CH4/H2, C2H4/C2H6 three-ratios data are calculated. The support vector machine model was constructed using cross validation method under five support vector machine functions and four kernel functions, heuristic algorithms were used in parameter optimization for penalty factor c and g, which to establish the best SVM model for the highest fault diagnosis accuracy and the fast computing speed. Particles swarm optimization and genetic algorithm two types of heuristic algorithms were comparative studied in this paper for accuracy and speed in optimization. The simulation result shows that SVM model composed of C-SVC, RBF kernel functions and genetic algorithm obtain 97. 5% accuracy in test sample set and updating% accuracy in train sample set, and genetic algorithm was about two times faster than particles swarm optimization in computing speed. The methods described in this paper has many advantages such as simple operation, non-contact measurement, no consumption for the carrier gas, long test period, high stability and sensitivity, the result shows that the methods described in this paper can instead of the traditional transformer fault diagnosis by gas chromatography and meets the actual project needs in transformer fault diagnosis.
Jupiter's auroral-related thermal infrared emission from IRTF-TEXESNASA Astrophysics Data System (ADS) Sinclair, James; Orton, Glenn; Greathouse, Thomas; Fletcher, Leigh; Irwin, Patrick updating Auroral processes on Jupiter can be observed at a large range of wavelengths. Charged particles of the solar wind are deflected by Jupiter’s magnetic field and penetrate the atmosphere at high latitudes. This results in ion and/or electron precipitation, which produces emission at X-ray, UV, visible, near-infrared and even radio wavelengths. These observations indicate three distinct features of the aurora: 1) filament-like oval structures fixed at the magnetic poles (~80°W (System III) in the south, ~180°W in the north), 2) spatially-continuous but transient aurora that fill these oval regions and 3) discrete spots associated with the magnetic footprints of Io and other Galilean satellites. However, observations in the thermal infrared indicate the aurora also modify the neutral atmosphere. Enhanced emission of CH4 is observed coincident with the auroral ovals and indicates heightened stratospheric temperatures possibly as a result of joule heating by the influx of charged particles. Stronger emission is also observed of C2H2, C2H4, C2H6 and even C6H6 though previous work has struggled to determine whether this is a temperature or compositional effect. In order to quantify the auroral effects on the neutral atmosphere and to support the 2016 Juno mission (which has no thermal infrared instrument) we have performed a retrieval analysis of IRTF-TEXES (Texas Echelon Cross Echelle Spectrograph, 5- to 25-μm) spectra obtained on Dec 11th 2014 near solar maximum. The instrument slit was scanned east-west across high latitudes in each hemisphere and Jupiter’s rotation was used to obtain ~360° longitudinal coverage. Spectra of H2 S(1), CH4, C2H2, C2H4 and C2H6 emission were measured at a resolving power of R = 85000, allowing a large vertical range in the atmosphere (updating mbar) to be sounded. Preliminary retrievals of the vertical temperature profile from H2 S(1) and CH4 measurements at 60°N, 180°W (on aurora), in comparison to 60°N, 60°W (quiescent
Infrared and EPR Spectroscopic Studies of 2-C 2 H 2 F and 1-C 2 H 2 F Radicals Isolated in Solid ArgonNASA Astrophysics Data System (ADS) Goldschleger, I. U.; Akimov, A. V.; Misochko, E. Ya.; Wight, C. A. 2001-02-01 2-fluorovinyl radicals were generated in solid argon by solid-state chemical reactions of mobile F atoms with acetylene and its deuterated analogues. Highly resolved EPR spectra of the stabilized radicals CHF•CH, CDF•CD, CHF•CD, and CDF•CH were obtained for the first time. The observed spectra were assigned to cis-2-fluorovinyl radical based on excellent agreement between the measured (aF = 6.50, aβH = 3.86, aαH = 0.25 mT) hyperfine constants and those calculated using density functional (B3LYP) theory. Analogous experiments carried out using infrared spectroscopy yielded a complete assignment of the vibrational frequencies. An unusual reversible photochemical conversion is observed in which cis-2-fluorovinyl radicals can be partially converted to 1-fluorovinyl radicals by pulsed laser photolysis at 532 nm. Photolysis at 355 nm converts 1-fluorovinyl back to cis-2-fluorovinyl. High-resolution EPR and infrared spectra of 1-fluorovinyl were obtained for the first time. The measured hyperfine constants (aF = 13.71, aH1 = 4.21, aH2 = 1.16 mT) are in good agreement with calculated values.
The role of NH3 and hydrocarbon mixtures in GaN pseudo-halide CVD: a quantum chemical study.PubMed Gadzhiev, Oleg B; Sennikov, Peter G; Petrov, Alexander I; Kachel, Krzysztof; Golka, Sebastian; Gogova, Daniela; Siche, Dietmar updating The prospects of a control for a novel gallium nitride pseudo-halide vapor phase epitaxy (PHVPE) with HCN were thoroughly analyzed for hydrocarbons-NH3-Ga gas phase on the basis of quantum chemical investigation with DFT (B3LYP, B3LYP with D3 empirical correction on dispersion interaction) and ab-initio (CASSCF, coupled clusters, and multireference configuration interaction including MRCI+Q) methods. The computational screening of reactions for different hydrocarbons (CH4, C2H6, C3H8, C2H4, and C2H2) as readily available carbon precursors for HCN formation, potential chemical transport agents, and for controlled carbon doping of deposited GaN was carried out with the B3LYP method in conjunction with basis sets up to aug-cc-pVTZ. The gas phase intermediates for the reactions in the Ga-hydrocarbon systems were predicted at different theory levels. The located π-complexes Ga…C2H2 and Ga…C2H4 were studied to determine a probable catalytic activity in reactions with NH3. A limited influence of the carbon-containing atmosphere was exhibited for the carbon doping of GaN crystal in the conventional GaN chemical vapor deposition (CVD) process with hydrocarbons injected in the gas phase. Our results provide a basis for experimental studies of GaN crystal growth with C2H4 and C2H2 as auxiliary carbon reagents for the Ga-NH3 and Ga-C-NH3 CVD systems and prerequisites for reactor design to enhance and control the PHVPE process through the HCN synthesis.
Efficient purification of ethene by an ethane-trapping metal-organic frameworkPubMed Central Liao, Pei-Qin; Zhang, Wei-Xiong; Zhang, Jie-Peng; Chen, Xiao-Ming updating Separating ethene (C2H4) from ethane (C2H6) is of paramount importance and difficulty. Here we show that C2H4 can be efficiently purified by trapping the inert C2H6 in a judiciously designed metal-organic framework. Under ambient conditions, passing a typical cracked gas mixture (15:1 C2H4/C2H6) through 1 litre of this C2H6 selective adsorbent directly produces 56 litres of C2H4 with 99.95%+ purity (required by the C2H4 polymerization reactor) at the outlet, with a single breakthrough operation, while other C2H6 selective materials can only produce ca. ⩽ litre, and conventional C2H4 selective adsorbents require at least four adsorption–desorption cycles to achieve the same C2H4 purity. Single-crystal X-ray diffraction and computational simulation studies showed that the exceptional C2H6 selectivity arises from the proper positioning of multiple electronegative and electropositive functional groups on the ultramicroporous pore surface, which form multiple C–H···N hydrogen bonds with C2H6 instead of the more polar competitor C2H4. PMID:updating
Potential energy function for CH3+CH3 ⇆ C 2 H 6 : Attributes of the minimum energy pathNASA Astrophysics Data System (ADS) Robertson, S. H.; Wardlaw, D. M.; Hirst, D. M. updating The region of the potential energy surface for the title reaction in the vicinity of its minimum energy path has been predicted from the analysis of ab initio electronic energy calculations. The ab initio procedure employs a 6-31G** basis set and a configuration interaction calculation which uses the orbitals obtained in a generalized valence bond calculation. Calculated equilibrium properties of ethane and of isolated methyl radical are compared to existing theoretical and experimental results. The reaction coordinate is represented by the carbon-carbon interatomic distance. The following attributes are reported as a function of this distance and fit to functional forms which smoothly interpolate between reactant and product values of each attribute: the minimum energy path potential, the minimum energy path geometry, normal mode frequencies for vibrational motion orthogonal to the reaction coordinate, a torsional potential, and a fundamental anharmonic frequency for local mode, out-of-plane CH3 bending (umbrella motion). The best representation is provided by a three-parameter modified Morse function for the minimum energy path potential and a two-parameter hyperbolic tangent switching function for all other attributes. A poorer but simpler representation, which may be satisfactory for selected applications, is provided by a standard Morse function and a one-parameter exponential switching function. Previous applications of the exponential switching function to estimate the reaction coordinate dependence of the frequencies and geometry of this system have assumed the same value of the range parameter α for each property and have taken α to be less than or equal to the ``standard'' value of 1.0 Å-1. Based on the present analysis this is incorrect: The α values depend on the property and range from ˜1.2 to ˜1.8 Å-1.
Dissipation dynamics of field-free molecular alignment for symmetric-top molecules: Ethane (C 2 H 6 )NASA Astrophysics Data System (ADS) Zhang, H.; Billard, F.; Yu, X.; Faucher, O.; Lavorel, B. updating The field-free molecular alignment of symmetric-top molecules, ethane, induced by intense non-resonant linearly polarized femtosecond laser pulses is investigated experimentally in the presence of collisional relaxation. The dissipation dynamics of field-free molecular alignment are measured by the balanced detection of ultrafast molecular birefringence of ethane gas samples at high pressures. By separating the molecular alignment into the permanent alignment and the transient alignment, the decay time-constants of both components are quantified at the same pressure. It is observed that the permanent alignment always decays slower compared to the transient alignment within the measured pressure range. This demonstrates that the propensity of molecules to conserve the orientation of angular momentum during collisions, previously observed for linear species, is also applicable to symmetric-top molecules. The results of this work provide valuable information for further theoretical understanding of collisional relaxation within nonlinear polyatomic molecules, which are expected to present interesting and nontrivial features due to an extra rotational degree of freedom.
The atmosphere of Pluto as observed by New HorizonsNASA Astrophysics Data System (ADS) Gladstone, G. Randall; Stern, S. Alan; Ennico, Kimberly; Olkin, Catherine B.; Weaver, Harold A.; Young, Leslie A.; Summers, Michael E.; Strobel, Darrell F.; Hinson, David P.; Kammer, Joshua A.; Parker, Alex H.; Steffl, Andrew J.; Linscott, Ivan R.; Parker, Joel Wm.; Cheng, Andrew F.; Slater, David C.; Versteeg, Maarten H.; Greathouse, Thomas K.; Retherford, Kurt D.; Throop, Henry; Cunningham, Nathaniel J.; Woods, William W.; Singer, Kelsi N.; Tsang, Constantine C. C.; Schindhelm, Eric; Lisse, Carey M.; Wong, Michael L.; Yung, Yuk L.; Zhu, Xun; Curdt, Werner; Lavvas, Panayotis; Young, Eliot F.; Tyler, G. Leonard; Bagenal, F.; Grundy, W. M.; McKinnon, W. B.; Moore, J. M.; Spencer, J. R.; Andert, T.; Andrews, J.; Banks, M.; Bauer, B.; Bauman, J.; Barnouin, O. S.; Bedini, P.; Beisser, K.; Beyer, R. A.; Bhaskaran, S.; Binzel, R. P.; Birath, E.; Bird, M.; Bogan, D. J.; Bowman, A.; Bray, V. J.; Brozovic, M.; Bryan, C.; Buckley, M. R.; Buie, M. W.; Buratti, B. J.; Bushman, S. S.; Calloway, A.; Carcich, B.; Conard, S.; Conrad, C. A.; Cook, J. C.; Cruikshank, D. P.; Custodio, O. S.; Ore, C. M. Dalle; Deboy, C.; Dischner, Z. J. B.; Dumont, P.; Earle, A. M.; Elliott, H. A.; Ercol, J.; Ernst, C. M.; Finley, T.; Flanigan, S. H.; Fountain, G.; Freeze, M. J.; Green, J. L.; Guo, Y.; Hahn, M.; Hamilton, D. P.; Hamilton, S. A.; Hanley, J.; Harch, A.; Hart, H. M.; Hersman, C. B.; Hill, A.; Hill, M. E.; Holdridge, M. E.; Horanyi, M.; Howard, A. D.; Howett, C. J. A.; Jackman, C.; Jacobson, R. A.; Jennings, D. E.; Kang, H. K.; Kaufmann, D. E.; Kollmann, P.; Krimigis, S. M.; Kusnierkiewicz, D.; Lauer, T. R.; Lee, J. E.; Lindstrom, K. L.; Lunsford, A. W.; Mallder, V. A.; Martin, N.; McComas, D. J.; McNutt, R. L.; Mehoke, D.; Mehoke, T.; Melin, E. D.; Mutchler, M.; Nelson, D.; Nimmo, F.; Nunez, J. I.; Ocampo, A.; Owen, W. M.; Paetzold, M.; Page, B.; Pelletier, F.; Peterson, J.; Pinkine, N.; Piquette, M.; Porter, S. B.; Protopapa, S.; Redfern, J.; Reitsema, H. J.; Reuter, D. C.; Roberts, J. H.; Robbins, S. J.; Rogers, G.; Rose, D.; Runyon, K.; Ryschkewitsch, M. G.; Schenk, P.; Sepan, B.; Showalter, M. R.; Soluri, M.; Stanbridge, D.; Stryk, T.; Szalay, J. R.; Tapley, M.; Taylor, A.; Taylor, H.; Umurhan, O. M.; Verbiscer, A. J.; Versteeg, M. H.; Vincent, M.; Webbert, R.; Weidner, S.; Weigle, G. E.; White, O. L.; Whittenburg, K.; Williams, B. G.; Williams, K.; Williams, S.; Zangari, A. M.; Zirnstein, E. updating Observations made during the New Horizons flyby provide a detailed snapshot of the current state of Pluto's atmosphere. Whereas the lower atmosphere (at altitudes of less than 200 kilometers) is consistent with ground-based stellar occultations, the upper atmosphere is much colder and more compact than indicated by pre-encounter models. Molecular nitrogen (N2) dominates the atmosphere (at altitudes of less than 1800 kilometers or so), whereas methane (CH4), acetylene (C2H2), ethylene (C2H4), and ethane (C2H6) are abundant minor species and likely feed the production of an extensive haze that encompasses Pluto. The cold upper atmosphere shuts off the anticipated enhanced-Jeans, hydrodynamic-like escape of Pluto's atmosphere to space. It is unclear whether the current state of Pluto's atmosphere is representative of its average state - over seasonal or geologic time scales.
Rate constants of quenching and vibrational relaxation in the OH({{A}^{2}}{{ \\Sigma }^{+}},v=0,1 ), manifold with various collidersNASA Astrophysics Data System (ADS) Martini, L. M.; Gatti, N.; Dilecce, G.; Scotoni, M.; Tosi, P. updating Laser induced fluorescence is intensively used for the detection of OH in many atmospheric pressure discharge devices. At this pressure, a quantitative knowledge of the collision phenomena in the upper excited state is critical. Here we report the measurement at T = 300 K of a set of rate constants of electronic quenching and vibrational relaxation of the OH≤ft({{A}2}{{ Σ }+},{{v}\\prime}=0,1\\right) electronic state, by collision with N2, O2, H2O, CO2, CO, H2, D2, CH4, C2H2, C2H4, C2H6. These are the main gases in applications like plasma medicine, hydrocarbons reforming and CO2 conversion. Available literature data are revisited, and new data are added, mostly relevant to {{v}\\prime}=1 quenching and vibrational relaxation.
Experimentally Determined Binding Energies of Astrophysically Relevant Hydrocarbons in Pure and H2O-Layered IcesNASA Astrophysics Data System (ADS) Behmard, Aida; Graninger, Dawn; Fayolle, Edith; Oberg, Karin I. updating Small hydrocarbons represent an important organic reservoir in a variety of interstellar environments. Constraints on desorption temperatures and binding energies of hydrocarbons are thus necessary for accurate predictions of where and in which phase these molecules exist. Through a series of temperature programmed desorption experiments, we determined binding energies of 1, 2, and 3-carbon interstellar hydrocarbons (CH4, C2H2, C2H4, C2H6, C3H4, C3H6, and C3H8) in pure ices and in relation to water ice, the dominant ice constituent during star and planet formation. These empirically determined values can be used to inform observations and models of the molecular spatial distribution in protoplanetary disks, thus providing insight into planetesimal composition. In addition, knowledge of hydrocarbon binding energies will refine simulations of grain surface chemistry, allowing for better predictions of the chemical conditions that lead to the production of complex organic molecules vital for life.
Correlation of molecular valence- and K-shell photoionization resonances with bond lengthsNASA Technical Reports Server (NTRS) Sheehy, J. A.; Gil, T. J.; Winstead, C. L.; Farren, R. E.; Langhoff, P. W. updating The relationship between the interatomic distance and the positions of valence-shell and K-shell sigma(asterisk) photoionization resonances is investigated theoretically for the molecules C2, F2, N2, O2, CO, NO, C2H2, C2H4, C2H6, HCN, H2CO, N20, CO2, and C2N2. The results of molecular-orbital computations are presented in three-dimensional diagrams, which are shown to be similar to the wave functions of a particle in a cylindrical well, confirming the validity of free-electron molecular-orbital (FEMO) approximations for modeling the potential along the symmetry axis. FEMO orbital energies and resonance positions are found to be in good agreement with previous theoretical and experimental results. Also included is a Feshbach-Fano analysis of the relevance of virtual-valence orbitals to the appearance of single-channel resonances in molecular photoionization cross sections.
The atmosphere of Pluto as observed by New Horizons.PubMed Gladstone, G Randall; Stern, S Alan; Ennico, Kimberly; Olkin, Catherine B; Weaver, Harold A; Young, Leslie A; Summers, Michael E; Strobel, Darrell F; Hinson, David P; Kammer, Joshua A; Parker, Alex H; Steffl, Andrew J; Linscott, Ivan R; Parker, Joel Wm; Cheng, Andrew F; Slater, David C; Versteeg, Maarten H; Greathouse, Thomas K; Retherford, Kurt D; Throop, Henry; Cunningham, Nathaniel J; Woods, William W; Singer, Kelsi N; Tsang, Constantine C C; Schindhelm, Eric; Lisse, Carey M; Wong, Michael L; Yung, Yuk L; Zhu, Xun; Curdt, Werner; Lavvas, Panayotis; Young, Eliot F; Tyler, G Leonard updating Observations made during the New Horizons flyby provide a detailed snapshot of the current state of Pluto's atmosphere. Whereas the lower atmosphere (at altitudes of less than 200 kilometers) is consistent with ground-based stellar occultations, the upper atmosphere is much colder and more compact than indicated by pre-encounter models. Molecular nitrogen (N2) dominates the atmosphere (at altitudes of less than 1800 kilometers or so), whereas methane (CH4), acetylene (C2H2), ethylene (C2H4), and ethane (C2H6) are abundant minor species and likely feed the production of an extensive haze that encompasses Pluto. The cold upper atmosphere shuts off the anticipated enhanced-Jeans, hydrodynamic-like escape of Pluto's atmosphere to space. It is unclear whether the current state of Pluto's atmosphere is representative of its average state--over seasonal or geologic time scales. Copyright © 2016, American Association for the Advancement of Science.
Infrared Spectra and Optical Constants of Astronomical Ices: II. Ethane and EthyleneNASA Technical Reports Server (NTRS) Hudson, Reggie L.; Gerakines, Perry A.; Moore, M. H. updating Infrared spectroscopic observations have established the presence of hydrocarbon ices on Pluto and other TNOs, but the abundances of such molecules cannot be deduced without accurate optical constants (n, k) and reference spectra. In this paper we present our recent measurements of near- and mid-infrared optical constants for ethane (C2H6) and ethylene (C2H4) in multiple ice phases and at multiple temperatures. As in our recent work on acetylene (C2H2), we also report new measurements of the index of refraction of each ice at 670 nm. Comparisons are made to earlier work where possible, and electronic versions of our new results are made available.

Jupiter's auroral-related stratospheric heating and chemistry II: Analysis of IRTF-TEXES spectra measured in December 2014NASA Astrophysics Data System (ADS) Sinclair, J. A.; Orton, G. S.; Greathouse, T. K.; Fletcher, L. N.; Moses, J. I.; Hue, V.; Irwin, P. G. J. updating
Molybdenum-independent nitrogenases of Azotobacter vinelandii: a functional species of alternative nitrogenase-3 isolated from a molybdenum-tolerant strain contains an iron-molybdenum cofactor.PubMed Central Pau, R N; Eldridge, M E; Lowe, D J; Mitchenall, L A; Eady, R R updating Nitrogenase-3 of Azotobacter vinelandii is synthesized under conditions of molybdenum and vanadium deficiency. The minimal metal requirement for its synthesis, and its metal content, indicated that the only transition metal in nitrogenase-3 was iron [Chisnell, Premakumar and Bishop (1988) J. Bacteriol. 170, 27-33; Pau, Mitchenall and Robson (1989) J. Bacteriol. 171, 124-129]. A new species of nitrogenase-3 has been purified from a strain of A. vinelandii (RP306) lacking structural genes for the Mo- and V-nitrogenases and containing a mutation which enables nitrogenase-3 to be synthesized in the presence of molybdenum. SDS/PAGE showed that component 1 contained a 15 kDa polypeptide which N-terminal amino acid sequence determination showed to be encoded by anfG. This confirms that nitrogenase-3, like V-nitrogenase, comprises three subunits. Preparations of the nitrogenase-3 from strain RP306 contained 24 Fe atoms and 1 Mo atom per molecule. Characterization of the cofactor centre of the enzyme by e.p.r. spectroscopy and an enzymic cofactor assay, together with stimulation of the growth of strain RP306 by Mo, showed that nitrogenase-3 can incorporate the Mo-nitrogenase cofactor (FeMoco) to form a functional enzyme. The specific activities (nmol of product produced/min per mg of protein) determined from activity titration curves were: under N2, NH3 formation 110, with concomitant H2 evolution of 220; under argon, H2 evolution 350; under 10% acetylene (C2H2) in argon, ethylene (C2H4) 58, ethane (C2H6) 26, and concomitant H2 evolution 226. The rate of formation of C2H6 was non-linear, and the C2H6/C2H4 ratio strongly dependent on the ratio of nitrogenase components. PMID:8392330
Simulation of nanoparticle coagulation in radio-frequency C 2 H 2 /Ar microdischargesNASA Astrophysics Data System (ADS) Xiang-Mei, Liu; Qi-Nan, Li; Rui, Li updating The nanoparticle coagulation is investigated by using a couple of fluid models and aerosol dynamics model in argon with a 5% molecular acetylene admixture rf microdischarges, with the total input gas flow rate of 400 sccm. It co-exists with a homogeneous, secondary electron-dominated low temperature Î³-mode glow discharges. The heat transfer equation and flow equation for neutral gas are taken into account. We mainly focused on investigations of the nanoparticle properties in atmospheric pressure microdischarges, and discussed the influences of pressure, electrode spacing, and applied voltage on the plasma density and nanoparticle density profiles. The results show that the characteristics of microdischarges are quite different from those of low pressure radio-frequency discharges. First, the nanoparticle density in the bulk plasma in microdischarges is much larger than that of low pressure discharges. Second, the nanoparticle density of 10 nm experiences an exponential increase as soon as the applied voltage increases, especially in the presheath. Finally, as the electrode spacing increases, the nanoparticle density decreased instead of increasing. Project supported by the Natural Science Foundation of Heilongjiang Province, China (Grant Nos. A2015011 and A2015010), the Postdoctoral Scientific Research Development Fund of Heilongjiang Province, China (Grant No. LBH-Q14159), the Program for Young Teachers Scientific Research in Qiqihar University (Grant No. 2014k-Z11), the National Natural Science Foundation of China (Grant No. updating), and the University Nursing Program for Yong Scholars with Creative Talents in Heilongjiang Province, China (Grant No. UNPYSCT-2015095).
High spatial and spectral resolution measurements of Jupiter's auroral regions using Gemini-North-TEXESNASA Astrophysics Data System (ADS) Sinclair, J. A.; Orton, G. S.; Greathouse, T. K.; Lacy, J.; Giles, R.; Fletcher, L. N.; Vogt, M.; Irwin, P. G. updating Jupiter exhibits auroral emission at a multitude of wavelengths. Auroral emission at X-ray, ultraviolet and near-infrared wavelengths demonstrate the precipitation of ion and electrons in Jupiter's upper atmosphere, at altitudes exceeding 250 km above the 1-bar level. Enhanced mid-infrared emission of CH4, C2H2, C2H4 and further hydrocarbons is also observed coincident with Jupiter's auroral regions. Retrieval analyses of infrared spectra from IRTF-TEXES (Texas Echelon Cross Echelle Spectrograph on NASA's Infrared Telescope Facility) indicate strong heating at the 1-mbar level and evidence of ion-neutral chemistry, which enriches the abundances of unsaturated hydrocarbons (Sinclair et al., 2017b, doi:10.1002/2017GL073529, Sinclair et al., 2017c (under review)). The extent to which these phenomena in the stratosphere are correlated and coupled physically with the shorter-wavelength auroral emission originating from higher altitudes has been a challenge due to the limited spatial resolution available on the IRTF. Smaller-scale features observed in the near-infrared and ultraviolet emission, such as the main `oval', transient `swirls' and dusk-active regions within the main oval (e.g. Stallard et al., 2014, doi:10.1016/j/Icarus.updating, Nichols et al., 2017, doi: 10.1002/2017GL073029) are potentially being blurred in the mid-infrared by the diffraction-limited resolution (0.7") of IRTF's 3-metre primary aperture. However, on March 17-19th 2017, we obtained spectral measurements of H2 S(1), CH4, C2H2, C2H4 and C2H6 emission of Jupiter's high latitudes using TEXES on Gemini-North, which has a 8-metre primary aperture. This rare opportunity combines the superior spectral resolving power of TEXES and the high spatial resolution provided by Gemini-North's 8-metre aperture. We will perform a retrieval analyses to determine the 3D distributions of temperature, C2H2, C2H4 and C2H6. The morphology will be compared with near-contemporaneous measurements of H3+ emission from
Photochemistry of Pluto's atmosphere and ionosphere near perihelionNASA Astrophysics Data System (ADS) Krasnopolsky, Vladimir A.; Cruikshank, Dale P. updating We consider Pluto's photochemistry using a background model for a hydrodynamically escaping atmosphere by Krasnopolsky [1999]. Some adjustments are made in the basic continuity equation and in the boundary conditions to account for hydrodynamic flow in the atmosphere. We model the photochemistry for 44 neutral and 23 ion species. Because of the high methane mixing ratio, Pluto's photochemistry is more similar to that of Titan than that of Triton. Charge exchange between N2+ and CH4 significantly reduces the production of atomic nitrogen. The most abundant photochemical products are C2H2(3Ã1017), C4H2(1017), HCN(6Ã1016), H2(4Ã1016), C2H4(4Ã1016), HC3N(3.4Ã1016), C2H6(2Ã1016), C3H2(9Ã1015), and C3H4 (8Ã1015, all in cm-2). In addition to the parent N2, CH4, and CO molecules which absorb photons with Î»C2H2, C4H2, HC3N, HCN, C2H6, and C2H4 (65, 58, 23, 14, 9, and 6 g cm-2 Byr-1, respectively, reduced by a factor of 3 to account for seasonal variations). Escape of photochemical products is highest for H2, H, C2H2, C2H4, HCN, and N(2Ã1026, 1.4Ã1026, 6Ã1024, 3.6Ã1024, 2.3Ã1024, and 1.8Ã1024s-1, respectively). The electron density reaches a maximum of 800 cm-3 at 2250 km. The most abundant ions are HCNH+, C3H3+, and C3H5+. Some of the photochemical products might be detected using the technique of UV solar occultation spectroscopy from a spacecraft flyby.
High Selectivity Toward C 2 H 4 Production over Cu Particles Supported by Butterfly-Wing-Derived Carbon Frameworks.PubMed Huo, Yajiao; Peng, Xianyun; Liu, Xijun; Li, Huaiyu; Luo, Jun updating Converting carbon dioxide to useful C2 chemicals in a selective and efficient manner remains a major challenge in renewable and sustainable energy research. Herein, we adopt butterfly wings to assist the preparation of an electrocatalyst containing monodispersed Cu particles supported by nitrogen-doped carbon frameworks for an efficient reduction of CO 2 . Benefiting from structure advantages and the synergistic effect between nitrogen dopants and stepped surface-rich Cu particles, the resulting catalyst exhibited a high faradic efficiency of 63.7 Â± 1.4% for ethylene production (corresponding to an ethylene/methane products' ratio of 57.9 Â± 5.4) and an excellent durability (â¼100% retention after 24 h). This work presents some guidelines for the rational design and accurate modulation of metal heterocatalysts for high selectivity toward ethylene from CO 2 electroreduction.
Temporally Varying Ethylene Emission on JupiterNASA Technical Reports Server (NTRS) Romani, Paul N.; Jennings, Donald E.; Bjoraker, Gordon L.; Sada, Pedro V.; McCabe. Geprge; Boyle, Robert J. updating Ethylene (C2H4) emission has been measured in the poles and equator of Jupiter. The 949 cm(sup -1) spectra were recorded with a high resolution spectrometer at the McMath-Pierce telescope at Kitt Peak in October-November 1998 and at the Infrared Telescope Facility at Mauna Kea in June 2000. C2H4 is an important product of methane chemistry in the outer planets. Knowledge of its abundance can help discriminate among the various proposed sets of CH4 photolysis branching ratios at Ly-alpha, and determine the relative importance of the reaction pathways that produce C2H2 and C2H6. In the equatorial region the C2H4 emission is weak, and we were only able to detect it at high air-mass, near the limb. We derive a peak equatorial molar abundance of C2H4 of 4.5 x 10(exp -updating x 10(exp -6) near 2.2 x 10(exp -3) mbar, with a total column of 5.7 x 10(exp updating x 10(exp 15) molecules cm(exp -2) above 10 mbar depending upon choice of thermal profile. We observed enhanced C2H4 emission from the poles in the regions where auroras are seen in X-ray, UV, and near infrared images. In 2000 we measured a short-term change in the distribution of polar C2H4 emission; the emission in the north IR auroral "hot spot" decreased by a factor of three over a two-day interval. This transient its contribution peak at 5-10 microbar suggests that the polar e is primarily a thermal effect coupled with vertical transport. Comparing our observations from Kitt Peak and Mauna Kea shows that the C2H4 emission of the northern non-"hot spot" auroral regions did not change over the three-year period while that in the southern polar regions decreased.
Poster 4: Investigating the first steps of hydrocarbon condensation in the laboratory and in Titan's atmosphereNASA Astrophysics Data System (ADS) Biennier, Ludovic; Bourgalais, Jeremy; Benidar, Abdessamad; Le Picard, Sebastien updating Hydrocarbons formed in Titan's cold atmosphere, starting with ethane C2H6, ethylene C2H4, acetylene C2H2, propane C3H8,... up to benzene C6H6, play some role in aerosol production, cloud processes, rain generation and Titan's lakes formation. We have started to study in the laboratory the kinetics of the first steps of condensation of these hydrocarbons. Rate coefficients are very sensitive to the description of the potential interaction surfaces of the molecules involved. Combined theoretical and experimental studies at the molecular level of the homogenous nucleation of various small molecules should improve greatly our fundamental understanding. This knowledge will serve as a model for studying more complex nucleation processes actually taking places in planetary atmospheres. Here we present the first experimental kinetic study of the dimerization of two small hydrocarbons: ethane C2H6 and propane C3H8. We have performed experiments to identify the temperature and partial densities ranges over which small hydrocarbon clusters form in saturated uniform supersonic flows. Using our unique reactor based on a Laval nozzle expansions, the kinetics of the formation has also been investigated down to 23 K. The chemical species present in the reactor are probed by a time of flight mass spectrometer equipped with an electron gun for soft ionization of the neutral reagents and products. This work aims at putting some constraints on the role of small hydrocarbon condensation in the formation of haze particles in the dense atmosphere of Titan.
The Jovian ionospheric E regionNASA Astrophysics Data System (ADS) Kim, Y. H.; Fox, J. L. updating A model of the Jovian ionosphere was constructed, that includes direct photoionization of hydrocarbon molecules. A high-resolution solar spectrum was synthesized from Hinteregger's solar maximum spectrum (F79050N), and high-resolution cross sections for photoabsorption by H2 bands in the range 842 to 1116 A were constructed. Two strong solar lines and about 30 percent of the continuum flux between 912 and 1116 A penetrate below the methane homopause despite strong absorption by CH4 and H2. It is found that hydrocarbons (mainly C2H2 are ionized at a maximum rate of 55/cu cm per sec at 320 km above the ammonia cloud tops. The hydrocarbon ions produced are quickly converted to more complex hydrocarbon ions through reactions with CH4, C2H2, C2H6, and C2H4. It is found that a hydrocarbon ion layer is formed near 320 km that is about 50 km wide with a peak density in excess of 10,000/cu cm.
Infrared polar brightening on Jupiter. III - Spectrometry from the Voyager 1 IRIS experimentNASA Technical Reports Server (NTRS) Kim, S. J.; Caldwell, J.; Rivolo, A. R.; Wagener, R.; Orton, G. S. updating Spectra from the Voyager 1 IRIS experiment confirm the existence of enhanced infrared emission near Jupiter's north magnetic pole in March 1979. The spectral characteristics of the enhanced emission are consistent with a Planck source function. A temperature-pressure profile is derived for the region near the north magnetic pole, from which quantitative abundance estimates of minor species are made. Some species previously detected on Jupiter, including CH3D, C2H2, and C2H6, have been observed again near the pole. Newly discovered species, not previously observed on Jupiter, include C2H4, C3H4, and C6H6. All of these species except CH3D appear to have enhanced abundances at the north polar region with respect to midlatitudes. Upper limits are determined for C4H2 and C3H8. The quantitative results are compared with model calculations based on ultraviolet results from the IUE satellite. The plausibility of the C6H6 identification is discussed in terms of the literature on C2H2 polymerization. The relation of C6H6 to cuprene is also discussed.
Helium Atom Scattering from C 2 H 6 , F2HCCH3, F3CCH2F and C2F6 in Crossed Molecular BeamsNASA Astrophysics Data System (ADS) Hammer, Markus; Seidel, Wolfhart updating Rotationally unresolved differential cross sections were measured in crossed molecular beam experiments by scattering Helium atoms from Ethane, 1,1-Difluoroethane, 1,1,1,2-Tetrafluoroethane and Hexafluoroethane. The damping of observed diffraction oscillations was used to extract anisotropic interaction potentials for these scattering systems applying the infinite order sudden approximation (IOSA). Binary macroscopic parameters such as second heterogeneous virial coefficients and the coefficients of diffusion and viscosity were computed from these potentials and compared to results from macroscopic experiments.
VizieR Online Data Catalog: IR absorbance spectra of CH4, C 2 H 6 , C3H8 & C4H10 (Turner+, 2018)NASA Astrophysics Data System (ADS) Turner, A. M.; Abplanalp, M. J.; Blair, T. J.; Dayuha, R.; Kaiser, R. I. updating In situ infrared data were collected by a Nicolet 6700 Fourier Transform Infrared Spectrometer at 4cm-1 resolution throughout the irradiation and temperature programmed desorption (TPD). (2 data files).
Density function theoretical study on the complex involved in Th atom-activated C-C bond in C 2 H 6NASA Astrophysics Data System (ADS) Qing-Qing, Wang; Peng, Li; Tao, Gao; Hong-Yan, Wang; Bing-Yun, Ao updating Density functional theory (DFT) calculations are performed to investigate the reactivity of Th atom toward ethane C-C bond activation. A comprehensive description of the reaction mechanisms leading to two different reaction products is presented. We report a complete exploration of the potential energy surfaces by taking into consideration different spin states. In addition, the intermediate and transition states along the reaction paths are characterized. Total, partial, and overlap population density of state diagrams and analyses are also presented. Furthermore, the natures of the chemical bonding of intermediate and transition states are studied by using topological method combined with electron localization function (ELF) and Mayer bond order. Infrared spectrum (IR) is obtained and further discussed based on the optimized geometries. Project supported by the National Natural Science Foundation of China (Grant Nos. updating, updating, and updating).
Full-dimensional analytical potential energy surface describing the gas-phase Cl + C 2 H 6 reaction and kinetics study of rate constants and kinetic isotope effects.PubMed Rangel, Cipriano; Espinosa-Garcia, Joaquin updating Within the Born-Oppenheimer approximation a full-dimensional analytical potential energy surface, PES-2017, was developed for the gas-phase hydrogen abstraction reaction between the chlorine atom and ethane, which is a nine body system. This surface presents a valence-bond/molecular mechanics functional form dependent on 60 parameters and is fitted to high-level ab initio calculations. This reaction presents little exothermicity, -2.30 kcal mol -1 , with a low height barrier, 2.44 kcal mol -1 , and intermediate complexes in the entrance and exit channels. We found that the energetic description was strongly dependent on the ab initio level used and it presented a very flat topology in the entrance channel, which represents a theoretical challenge in the fitting process. In general, PES-2017 reproduces the ab initio information used as input, which is merely a test of self-consistency. As a first test of the quality of the PES-2017, a theoretical kinetics study was performed in the temperature range updating K using two approaches, i.e. the variational transition-state theory and quasi-classical trajectory calculations, with spin-orbit effects. The rate constants show reasonable agreement with experiments in the whole temperature range, with the largest differences at the lowest temperatures, and this behaviour agrees with previous theoretical studies, thus indicating the inherent difficulties in the theoretical simulation of the kinetics of the title reaction. Different sources of error were analysed, such as the limitations of the PES and theoretical methods, recrossing effects, and the tunnelling effect, which is negligible in this reaction, and the manner in which the spin-orbit effects were included in this non-relativistic study. We found that the variation of spin-orbit coupling along the reaction path, and the influence of the reactivity of the excited Cl( 2 P 1/2 ) state, have relative importance, but do not explain the whole discrepancy. Finally, the activation energy and the kinetics isotope effects reproduce the experimental information.
Energetic investigation of the adsorption process of CH4, C 2 H 6 and N2 on activated carbon: Numerical and statistical physics treatmentNASA Astrophysics Data System (ADS) Ben Torkia, Yosra; Ben Yahia, Manel; Khalfaoui, Mohamed; Al-Muhtaseb, Shaheen A.; Ben Lamine, Abdelmottaleb updating The adsorption energy distribution (AED) function of a commercial activated carbon (BDH-activated carbon) was investigated. For this purpose, the integral equation is derived by using a purely analytical statistical physics treatment. The description of the heterogeneity of the adsorbent is significantly clarified by defining the parameter N(E). This parameter represents the energetic density of the spatial density of the effectively occupied sites. To solve the integral equation, a numerical method was used based on an adequate algorithm. The Langmuir model was adopted as a local adsorption isotherm. This model is developed by using the grand canonical ensemble, which allows defining the physico-chemical parameters involved in the adsorption process. The AED function is estimated by a normal Gaussian function. This method is applied to the adsorption isotherms of nitrogen, methane and ethane at different temperatures. The development of the AED using a statistical physics treatment provides an explanation of the gas molecules behaviour during the adsorption process and gives new physical interpretations at microscopic levels.
Quasi-Classical Trajectory Dynamics Study of the Cl(2P) + C 2 H 6 â HCl(v,j) + C2H5 Reaction. Comparison with Experiment.PubMed Espinosa-Garcia, Joaquin; Martinez-NuÃ±ez, Emilio; Rangel, Cipriano updating To understand and simulate the dynamics behavior of the title reaction, QCT calculations were performed on a recently developed global analytical potential energy surface, PES-2017. These calculations combine the classical description of the dynamics with pseudoquantization in the reactants and products to perform a theoretical/experimental comparison on the same footing. Thus, in the products a series of constraints are included to analyze the HCl(v = 0,j) product, which is experimentally detected. At collision energies of 5.5 and 6.7 kcal mol -1 the largest fraction of available energy is deposited as translation, 67%, while the ethyl radical shows significant internal energy, 27%, and so it does not act as a spectator of the reaction, thus reproducing recent experimental evidence. The HCl(v=0, j) rotational distribution is cold, peaking at j = 2, only one unit hotter than experiment, which represents an error of 0.12 kcal mol -1 . At a collision energy of 5.5 kcal mol -1 product translational distribution is slightly hotter than experiment, but at 6.7 kcal mol -1 agreement with recent experiments is practically quantitative, suggesting that the first experiments should be revised. In addition, we observe that the HCl(v=0, j) scattering distribution shifts from isotropic at low values of j to backward at high values of j, which is in agreement with experimental data. Finally, no evidence was found for the "chattering" mechanism suggested to explain the low translational energy of the HCl product in the backward scattering region. In sum, agreement with experiments of a series of sensible dynamic properties permits us to be optimistic on the quality and accuracy of the theoretical tools used in the present work, QCT and PES-2017.
Communication: An accurate calculation of the S 1 C 2 H 2 cis-trans isomerization barrier heightDOE PAGES Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F. updating In this study, a high level ab initio calculation of the cis-trans isomerization barrier height in the first excited singlet electronic state of acetylene is found to agree very well with a recent experimental determination.
Application of the HartmannâTran profile to precise experimental data sets of 12C 2 H 2DOE PAGES Forthomme, D.; Cich, M. J.; Twagirayezu, S.; ... updating Self- and nitrogen-broadened line shape data for the P e(11) line of the Î½â + Î½â band of acetylene, recorded using a frequency comb-stabilized laser spectrometer, have been analyzed using the HartmannâTran profile (HTP) line shape model in a multispectrum fitting. In total, the data included measurements recorded at temperatures between 125 K and 296 K and at pressures between 4 and 760 Torr. New, sub-Doppler, frequency comb-referenced measurements of the positions of multiple underlying hot band lines have also been made. These underlying lines significantly affect the P e(11) line profile at temperatures above 240 K and poorly knownmoreÂ Â» frequencies previously introduced errors into the line shape analyses. Thus, the behavior of the HTP model was compared to the quadratic speed dependent Voigt profile (QSDVP) expressed in the frequency and time domains. A parameter uncertainty analysis was carried out using a Monte Carlo method based on the estimated pressure, transmittance and frequency measurement errors. From the analyses, the P e(11) line strength was estimated to be updating) Ã 10 -20 in cm.moleculesâ»Â¹ units at 296 K with the standard deviation in parenthesis. For analyzing these data, we found that a reduced form of the HTP, equivalent to the QSDVP, was most appropriate because the additional parameters included in the full HTP were not well determined. As a supplement to this work, expressions for analytic derivatives and a lineshape fitting code written in Matlab for the HTP are available.Â«Â less
Application of the Hartmann-Tran profile to precise experimental data sets of 12C 2 H 2NASA Astrophysics Data System (ADS) Forthomme, D.; Cich, M. J.; Twagirayezu, S.; Hall, G. E.; Sears, T. J. updating Self- and nitrogen-broadened line shape data for the Pe(11) line of the Î½1 +Î½3 band of acetylene, recorded using a frequency comb-stabilized laser spectrometer, have been analyzed using the Hartmann-Tran profile (HTP) line shape model in a multispectrum fitting. In total, the data included measurements recorded at temperatures between 125 K and 296 K and at pressures between 4 and 760 Torr. New, sub-Doppler, frequency comb-referenced measurements of the positions of multiple underlying hot band lines have also been made. These underlying lines significantly affect the Pe(11) line profile at temperatures above 240 K and poorly known frequencies previously introduced errors into the line shape analyses. The behavior of the HTP model was compared to the quadratic speed dependent Voigt profile (QSDVP) expressed in the frequency and time domains. A parameter uncertainty analysis was carried out using a Monte Carlo method based on the estimated pressure, transmittance and frequency measurement errors. From the analyses, the Pe(11) line strength was estimated to be updating) Ã10-20 in cmmolecule-1 units at 296 K with the standard deviation in parenthesis. For analyzing these data, we found that a reduced form of the HTP, equivalent to the QSDVP, was most appropriate because the additional parameters included in the full HTP were not well determined. As a supplement to this work, expressions for analytic derivatives and a lineshape fitting code written in Matlab for the HTP are available.
Characterization of CcSTOP1; a C 2 H 2 -type transcription factor regulates Al tolerance gene in pigeonpea.PubMed Daspute, Abhijit Arun; Kobayashi, Yuriko; Panda, Sanjib Kumar; Fakrudin, Bashasab; Kobayashi, Yasufumi; Tokizawa, Mutsutomo; Iuchi, Satoshi; Choudhary, Arbind Kumar; Yamamoto, Yoshiharu Y; Koyama, Hiroyuki updating Al-responsive citrate-transporting CcMATE1 function and its regulation by CcSTOP1 were analyzed using NtSTOP1 -KD tobacco- and pigeonpea hairy roots, respectively, CcSTOP1 binding sequence of CcMATE1 showed similarity with AtALMT1 promoter. The molecular mechanisms of Aluminum (Al) tolerance in pigeonpea (Cajanus cajan) were characterized to provide information for molecular breeding. Al-inducible citrate excretion was associated with the expression of MULTIDRUGS AND TOXIC COMPOUNDS EXCLUSION (CcMATE1), which encodes a citrate transporter. Ectopic expression of CcMATE1-conferred Al tolerance to hairy roots of transgenic tobacco with the STOP1 regulation system knocked down. This gain-of-function approach clearly showed CcMATE1 was involved in Al detoxification. The expression of CcMATE1 and another Al-tolerance gene, ALUMINUM SENSITIVE 3 (CcALS3), was regulated by SENSITIVE TO PROTON RHIZOTOXICITY1 (CcSTOP1) according to loss-of-function analysis of pigeonpea hairy roots in which CcSTOP1 was suppressed. An in vitro binding assay showed that the Al-responsive CcMATE1 promoter contained the GGNVS consensus bound by CcSTOP1. Mutation of GGNVS inactivated the Al-inducible expression of CcMATE1 in pigeonpea hairy roots. This indicated that CcSTOP1 binding to the promoter is critical for CcMATE1 expression. The STOP1 binding sites of both the CcMATE1 and AtALMT1 promoters contained GGNVS and a flanking 3' sequence. The GGNVS region was identical in both CcMATE1 and AtALMT1. By contrast, the 3' flanking sequence with binding affinity to STOP1 did not show similarity. Putative STOP1 binding sites with similar structures were also found in Al-inducible MATE and ALMT1 promoters in other plant species. The characterized Al-responsive CcSTOP1 and CcMATE1 genes will help in pigeonpea breeding in acid soil tolerance.

Molecular simulations of MOF membranes for separation of ethane/ethene and ethane/methane mixtures.PubMed Altintas, Cigdem; Keskin, Seda updating Metal organic framework (MOF) membranes have been widely investigated for gas separation applications. Several MOFs have been recently examined for selective separation of C 2 H 6 . Considering the large number of available MOFs, it is not possible to fabricate and test the C 2 H 6 separation performance of every single MOF membrane using purely experimental methods. In this study, we used molecular simulations to assess the membrane-based C 2 H 6 /C 2 H 4 and C 2 H 6 /CH 4 separation performances of 175 different MOF structures. This is the largest number of MOF membranes studied to date for C 2 H 6 separation. We computed adsorption selectivity, diffusion selectivity, membrane selectivity and gas permeability of MOFs for C 2 H 6 /C 2 H 4 and C 2 H 6 /CH 4 mixtures. Our results show that a significant number of MOF membranes are C 2 H 6 selective for C 2 H 6 /C 2 H 4 separation in contrast to traditional nanoporous materials. Selectivity and permeability of MOF membranes were compared with other membrane materials, such as polymers, zeolites, and carbon molecular sieves. Several MOFs were identified to exceed the upper bound established for polymeric membranes and many MOF membranes exhibited higher gas permeabilities than zeolites and carbon molecular sieves. Examining the structure-performance relations of MOF membranes revealed that MOFs with cavity diameters between 6 and 9 Ã, porosities lower than 0.50, and surface areas between updating m 2 g -1 have high C 2 H 6 selectivities. The results of this study will be useful to guide the experiments to the most promising MOF membranes for efficient separation of C 2 H 6 and to accelerate the development of new MOFs with high C 2 H 6 selectivities.
Reaction pathways of producing and losing particles in atmospheric pressure methane nanosecond pulsed needle-plane discharge plasmaNASA Astrophysics Data System (ADS) Zhao, Yuefeng; Wang, Chao; Li, Li; Wang, Lijuan; Pan, Jie updating In this work, a two-dimensional fluid model is built up to numerically investigate the reaction pathways of producing and losing particles in atmospheric pressure methane nanosecond pulsed needle-plane discharge plasma. The calculation results indicate that the electron collisions with CH4 are the key pathways to produce the neutral particles CH2 and CH as well as the charged particles e and CH3+. CH3, H2, H, C2H2, and C2H4 primarily result from the reactions between the neutral particles and CH4. The charge transfer reactions are the significant pathways to produce CH4+, C2H2+, and C2H4+. As to the neutral species CH and H and the charged species CH3+, the reactions between themselves and CH4 contribute to substantial losses of these particles. The ways responsible for losing CH3, H2, C2H2, and C2H4 are CH3 + H â CH4, H2 + CH â CH2 + H, CH4+ + C2H2 â C2H2+ + CH4, and CH4+ + C2H4 â C2H4+ + CH4, respectively. Both electrons and C2H4+ are consumed by the dissociative electron-ion recombination reactions. The essential reaction pathways of losing CH4+ and C2H2+ are the charge transfer reactions.
Volumetric Properties of the Mixture Pentafluoroethane C2HF5 + C 2 H 4 F2 1,1-Difluoroethane (LB1530, VMSD1541)NASA Astrophysics Data System (ADS) Cibulka, I.; HnÄdkovskÃ½, L.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V. This document is part of Subvolume A `Binary Liquid Systems of Nonelectrolytes' of Volume 23 `Volumetric Properties of Mixtures and Solutions' of Landolt-BÃ¶rnstein Group IV `Physical Chemistry'. It corresponds to the data set LB1530 of the ELBT database.
Species and temperature measurements of methane oxidation in a nanosecond repetitively pulsed dischargePubMed Central Lefkowitz, Joseph K; Guo, Peng; Rousso, Aric; Ju, Yiguang updating Speciation and temperature measurements of methane oxidation during a nanosecond repetitively pulsed discharge in a low-temperature flow reactor have been performed. Measurements of temperature and formaldehyde during a burst of pulses were made on a time-dependent basis using tunable diode laser absorption spectroscopy, and measurements of all other major stable species were made downstream of a continuously pulsed discharge using gas chromatography. The major species for a stoichiometric methane/oxygen/helium mixture with 75% dilution are H2O, CO, CO2, H2, CH2O, CH3OH, C2H6, C2H4 and C2H2. A modelling tool to simulate homogeneous plasma combustion kinetics is assembled by combining the ZDPlasKin and CHEMKIN codes. In addition, a kinetic model for plasma-assisted combustion (HP-Mech/plasma) of methane, oxygen and helium mixtures has been assembled to simulate the measurements. Predictions can accurately capture reactant consumption as well as production of the major product species. However, significant disagreement is found for minor species, particularly CH2O and CH3OH. Further analysis revealed that the plasma-activated low-temperature oxidation pathways, particularly those involving CH3O2 radical reactions and methane reactions with O(1D), are responsible for this disagreement. PMID:updating
On the truncation of the number of excited states in density functional theory sum-over-states calculations of indirect spin spin coupling constantsNASA Astrophysics Data System (ADS) Zarycz, M. Natalia C.; Provasi, Patricio F.; Sauer, Stephan P. A. updating It is investigated, whether the number of excited (pseudo)states can be truncated in the sum-over-states expression for indirect spin-spin coupling constants (SSCCs), which is used in the Contributions from Localized Orbitals within the Polarization Propagator Approach and Inner Projections of the Polarization Propagator (IPPP-CLOPPA) approach to analyzing SSCCs in terms of localized orbitals. As a test set we have studied the nine simple compounds, CH4, NH3, H2O, SiH4, PH3, SH2, C2H2, C2H4, and C2H6. The excited (pseudo)states were obtained from time-dependent density functional theory (TD-DFT) calculations with the B3LYP exchange-correlation functional and the specialized core-property basis set, aug-cc-pVTZ-J. We investigated both how the calculated coupling constants depend on the number of (pseudo)states included in the summation and whether the summation can be truncated in a systematic way at a smaller number of states and extrapolated to the total number of (pseudo)states for the given one-electron basis set. We find that this is possible and that for some of the couplings it is sufficient to include only about 30% of the excited (pseudo)states.
The New Horizons Ultraviolet Solar Occultation by Pluto's AtmosphereNASA Astrophysics Data System (ADS) Young, L. A.; Kammer, J.; Steffl, A.; Gladstone, R.; Summers, M. E.; Strobel, D. F.; Hinson, D. P.; Stern, A.; Weaver, H. A., Jr.; Olkin, C.; Ennico Smith, K.; McComas, D. J. updating The Alice instrument on NASA's New Horizons spacecraft observed an ultraviolet solar occultation by Pluto's atmosphere on 2015 July 14, as the spacecraft flew nearly diametrically though the solar shadow. The resulting dataset was a time-series of spectra from 52 to 187 nm with a spectral resolution of 0.3 nm. From these, we derived line-of-sight abundances and local number densities for the major species (N2 and CH4) and minor hydrocarbons (C2H2, C2H4, C2H6), and line-of-sight optical depth and extinction coefficients for the haze. Analysis of these data imply that (1) temperatures in Pluto's upper atmosphere were colder than expected before the New Horizons flyby, with upper atmospheric temperatures near 65-68 K, and subsequently lower escape rates, dominated by CH4 escape over N2; (2) the lower atmosphere was very stable, placing the homopause within 12 km of the surface, (3) the abundance profiles of the "C2Hx hydrocarbons" had non-exponential density profiles that compared favorably with models for hydrocarbon production near 300-400 km and haze condensation near 200 km, and (4) haze had an extinction coefficient approximately proportional to N2 density.
Pluto's Solar Occultation from New HorizonsNASA Astrophysics Data System (ADS) Young, Leslie; Kammer, Joshua; Steffl, Andrew J.; Gladstone, Randy; Summers, Michael; Strobel, Darrell F.; Hinson, David P.; Stern, S. Alan; Weaver, Harold A.; Olkin, Catherine; Ennico, Kimberly; McComas, Dave; New Horizons Atmospheres Science Theme Team updating The Alice instrument on NASAâs New Horizons spacecraft observed an ultraviolet solar occultation by Pluto's atmosphere on 2015 July 14. We derived line-of-sight abundances and local number densities for the major species (N2 and CH4) and minor hydrocarbons (C2H2, C2H4, C2H6), and line-of-sight optical depth and extinction coefficients for the haze. Our major conclusions are that (1) we confirmed temperatures in Plutoâs upper atmosphere that were colder than expected before the New Horizons flyby, with upper atmospheric temperatures near 65-68 K, and subsequently lower escape rates, (2) the lower atmosphere was very stable, placing the homopause within 12 km of the surface, (3) the abundance profiles of the âC2Hx hydrocarbonsâ had non-exponential density profiles that compare favorably with models for hydrocarbon production near 300-400 km and haze condensation near 200 km, and (4) haze had an extinction coefficient approximately proportional to N2 density.This work was supported by NASAâs New Horizons project.
Many-body calculations of molecular electric polarizabilities in asymptotically complete basis setsNASA Astrophysics Data System (ADS) Monten, Ruben; HajgatÃ³, BalÃ¡zs; Deleuze, Michael S. updating The static dipole polarizabilities of Ne, CO, N2, F2, HF, H2O, HCN, and C2H2 (acetylene) have been determined close to the Full-CI limit along with an asymptotically complete basis set (CBS), according to the principles of a Focal Point Analysis. For this purpose the results of Finite Field calculations up to the level of Coupled Cluster theory including Single, Double, Triple, Quadruple and perturbative Pentuple excitations [CCSDTQ(P)] were used, in conjunction with suited extrapolations of energies obtained using augmented and doubly-augmented Dunning's correlation consistent polarized valence basis sets of improving quality. The polarizability characteristics of C2H4 (ethylene) and C2H6 (ethane) have been determined on the same grounds at the CCSDTQ level in the CBS limit. Comparison is made with results obtained using lower levels in electronic correlation, or taking into account the relaxation of the molecular structure due to an adiabatic polarization process. Vibrational corrections to electronic polarizabilities have been empirically estimated according to Born-Oppenheimer Molecular Dynamical simulations employing Density Functional Theory. Confrontation with experiment ultimately indicates relative accuracies of the order of 1 to 2%.
Dual-resolution Raman spectroscopy for measurements of temperature and twelve species in hydrocarbonâair flamesSciTech Connect Magnotti, Gaetano; Barlow, Robert S. updating This study introduces dual-resolution Raman spectroscopy as a novel diagnostics approach for measurements of temperature and species in flames where multiple hydrocarbons are present. Simultaneous measurement of multiple hydrocarbons is challenging because their vibrational Raman spectra in the CâH stretch region are closely overlapped and are not well known over the range of temperature encountered in flames. Overlap between the hydrocarbon spectra is mitigated by adding a second spectrometer, with a higher dispersion grating, to collect the Raman spectra in the CâH stretch region. A dual-resolution Raman spectroscopy instrument has been developed and optimized for measurements of major species (NmoreÂ Â» 2, O 2, H 2O, CO 2, CO, H 2, DME) and major combustion intermediates (CH 4, CH 2O, C 2H 2, C 2H 4 and C 2H 6) in DMEâair flames. The temperature dependences of the hydrocarbon Raman spectra over fixed spectral regions have been determined through a series of measurements in laminar Bunsen-burner flames, and have been used to extend a library of previously acquired Raman spectra up to flame temperature. The paper presents the first Raman measurements of up to twelve species in hydrocarbon flames, and the first quantitative Raman measurements of formaldehyde in flames. Lastly, the accuracy and precision of the instrument are determined from measurements in laminar flames and the applicability of the instrument to turbulent DMEâair flames is discussed.Â«Â less
Clathrate hydrates in the solar systemNASA Technical Reports Server (NTRS) Miller, S. L. updating Clathrate hydrates are crystalline compounds in which an expanded ice lattice forms cages that contain gas molecules. There are two principal hydrate structures. Structure I, with a 12 A cubic unit cell, contains 46 water molecules and 8 cages of two types, giving an ideal formula (for CH4) of CH4.5.75H2O. The actual formula contains somewhat more water as the cages are not completely filled. Other examples that form Structure I hydrates are C2H6, C2H4, C2H2, CO2, SO2, OCS, Xe, H2S. Structure II, with a 17 A cubic unit cell, contains 136 water molecules, and 8 large and 16 small cages. The ideal formula for CHCl3 is CHCL3.17H2O. Other examples of Structure II hydrates include C3H8, C2H5Cl, acetone, and tetrahydrofuran. Small molecules such as Ar, Kr and probably N2 and O2 also form a Structure II hydrate. The small molecules occupy both the large and small cages, giving an ideal formula of Ar.5.67H2O. The conditions of pressure and temperature for hydrate formation are discussed.
An experimental study of the structure of laminar premixed flames of ethanol/methane/oxygen/argonPubMed Central Tran, L.S.; Glaude, P.A.; Battin-Leclerc, F. updating The structures of three laminar premixed stoichiometric flames at low pressure (6.7 kPa): a pure methane flame, a pure ethanol flame and a methane flame doped by 30% of ethanol, have been investigated and compared. The results consist of concentration profiles of methane, ethanol, O2, Ar, CO, CO2, H2O, H2, C2H6, C2H4, C2H2, C3H8, C3H6, p-C3H4, a-C3H4, CH2O, CH3HCO, measured as a function of the height above the burner by probe sampling followed by on-line gas chromatography analyses. Flame temperature profiles have been also obtained using a PtRh (6%)-PtRh (30%) type B thermocouple. The similarities and differences between the three flames were analyzed. The results show that, in these three flames, the concentration of the C2 intermediates is much larger than that of the C3 species. In general, mole fraction of all intermediate species in the pure ethanol flame is the largest, followed by the doped flame, and finally the pure methane flame. PMID:updating
Spectroscopic studies of MW plasmas containing HMDSO, O2 and N2NASA Astrophysics Data System (ADS) Nave, Andy; Roepcke, Juergen; Mitschker, Felix; Awakowicz, Peter updating The deposition of SiOx layers based on organosilicon plasmas is used to implement advantageous mechanical, electrical, and/or optical properties on various substrates. The development of such coating processes resulting in a wide range of chemical and physical film properties, using hexamethyldisiloxane (HMDSO) as a precursor, has been in the center of interest of various studies. In plasma, the dissociation of HMDSO into a large amount of fragments is a complex chemical phenomenon. The monitoring of the precursor and of formed species is very valuable to understand the plasma chemistry. Infrared absorption spectroscopy based on lead salt lasers and EC Quantum Cascade Laser have been used to monitor the concentrations of HMDSO, and of the reaction products CH4, C2H2, C2H4,C2H6, CO, CO2 and CH3 as a function of the HMDSO/O2 mixture ratio, and the power at various pressures in a MW plasma deposition reactor. Optical emission spectroscopy has been applied as complementary diagnostics to evaluate electron density and electron temperature. Supported by the German Research Foundation within SFB-TR24 and SFB-TR87.
A model study of the vertical distributions and escape fluxes of the major and minor species in Titan's thermosphere under different conditionsNASA Astrophysics Data System (ADS) Hsu, Jen-Kai; Liang, Mao-Chang; Ip, Wing-Huen updating From the measurements of the Ion Neutral Mass Spectrometer (INMS) on the Cassini spacecraft at different close encounters with Titan, it is know that the vertical temperature profile and density distributions of N2, CH4, H2 and other species could have large variations which might be driven by environmental effects such as solar radiation and magnetospheric interaction. For example, the atmospheric temperature as determined from the N2 density profiles can vary between 120 K and 175 K. Following the treatment of Li et al. (PSS, updating) by applying a non-monotonic eddy diffusivity profile, we compute the vertical distributions of different species between Titan's surface to 2000 km altitude, for a range of atmospheric temperatures. Intercomparison between the model results and observations leads to better understanding of the production mechanisms of the minor species like C2H2, C2H4, C2H6 and others, all important to the hydrocarbon budgets of Titan's atmosphere and surface, respectively. Furthermore, such detailed photochemical calculations will also yield accurate estimates of the escape fluxes of H, H2 and CH4 into the circum-planetary region.
On the Radiolysis of Ethylene Ices by Energetic Electrons and Implications to the Extraterrestrial Hydrocarbon ChemistryNASA Astrophysics Data System (ADS) Zhou, Li; Maity, Surajit; Abplanalp, Matt; Turner, Andrew; Kaiser, Ralf I. updating The chemical processing of ethylene ices (C2H4) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH4), the C2 species acetylene (C2H2), ethane (C2H6), the ethyl radical (C2H5), andâfor the very first time in ethylene irradiation experimentsâthe C4 hydrocarbons 1-butene (C4H8) and n-butane (C4H10). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.
Porous anionic indium-organic framework with enhanced gas and vapor adsorption and separation ability.PubMed Huang, Yuanbiao; Lin, Zujin; Fu, Hongru; Wang, Fei; Shen, Min; Wang, Xusheng; Cao, Rong updating A three-dimensional microporous anionic metal-organic framework (MOF) (Et4N)3[In3(TATB)4] (FJI-C1, H3TATB=4,4',4''-s-triazine-2,4,6-triyltribenzoic acid) with large unit cell volume has been synthesized. Assisted by the organic cation group Et4N in the pores of the compound, FJI-C1 not only shows high adsorption uptakes of C2 and C3 hydrocarbons, but also exhibits highly selective separation of propane, acetylene, ethane, and ethylene from methane at room temperature. Furthermore, it also exhibits high separation selectivity for propane over C2 hydrocarbons and acetylene can be readily separated from their C2 hydrocarbons mixtures at low pressure due to the high selectivity for C2H2 in comparison to C2H4 and C2H6. In addition, FJI-C1 with hydrophilic internal pores surfaces shows highly efficient adsorption separation of polar molecules from nonpolar molecules. Notably, it exhibits high separation selectivity for benzene over cyclohexane due to the Ï-Ï interactions between benzene molecules and s-triazine rings of the porous MOF. Â© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Retrievals of abundances of hydrocarbon and nitrile species in Titanâs upper atmosphereNASA Astrophysics Data System (ADS) Yung, Yuk; Fan, Siteng; Shemansky, D. E.; Li, Cheng; Gao, Peter updating We develop an innovative retrieval method for Titan occultation measurements by the Cassini UVIS experiment. The T35 occultation is analyzed to illustrate the methodology. A significant number of occultations observed using the UVIS spectrographs show loss of pointing control required for correction of the spectral vectors. Consequently, only three stellar occultations have been analyzed to date. We use the Markov Chain Monte-Carlo (MCMC) method to retrieve the abundances or upper limits of thirteen hydrocarbon and nitrile species (N2, CH4, C2H2, C2H4, C2H6, HCN, C4H2, C6N2, C6H6, tholin, HC3N, C2N2, NH3) along with the pointing error using the Cassini/UVIS simulator. These numbers are derived for the fast T35 occultation, which has never been analyzed because of large pointing errors. Uncertainty in the retrievals is determined using an intrinsic fitting probability distribution function. The Caltech/JPL photochemical and kinetics model, KINETICS, is used to calculate the atmospheric aforementioned species. Comparisons between model and observations reveal gaps in our current understanding of the chemical kinetics of hydrocarbons and nitrile species, especially for C6H6.
Surface science studies of ethene containing model interstellar icesNASA Astrophysics Data System (ADS) Puletti, F.; Whelan, M.; Brown, W. A. updating The formation of saturated hydrocarbons in the interstellar medium (ISM) is difficult to explain only by taking into account gas phase reactions. This is mostly due to the fact that carbonium ions only react with H_2 to make unsaturated hydrocarbons, and hence no viable route to saturated hydrocarbons has been postulated to date. It is therefore likely that saturation processes occur via surface reactions that take place on interstellar dust grains. One of the species of interest in this family of reactions is C_2H_4 (ethene) which is an intermediate in several molecular formation routes (e.g. C_2H_2 â C_2H_6). To help to understand some of the surface processes involving ethene, a study of ethene deposited on a dust grain analogue surface (highly oriented pyrolytic graphite) held under ultra-high vacuum at 20 K has been performed. The adsorption and desorption of ethene has been studied both in water-free and water-dominated model interstellar ices. A combination of temperature programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS) have been used to identify the adsorbed and trapped species and to determine the kinetics of the desorption processes. In all cases, ethene is found to physisorb on the carbonaceous surface. As expected water has a very strong influence on the desorption of ethene, as previously observed for other model interstellar ice systems.
From double-slit interference to structural information in simple hydrocarbonsPubMed Central Kushawaha, Rajesh Kumar; Patanen, Minna; Guillemin, Renaud; Journel, Loic; Miron, Catalin; Simon, Marc; Piancastelli, Maria Novella; Skates, C.; Decleva, Piero updating Interferences in coherent emission of photoelectrons from two equivalent atomic centers in a molecule are the microscopic analogies of the celebrated Youngâs double-slit experiment. By considering inner-valence shell ionization in the series of simple hydrocarbons C2H2, C2H4, and C2H6, we show that double-slit interference is widespread and has built-in quantitative information on geometry, orbital composition, and many-body effects. A theoretical and experimental study is presented over the photon energy range of 70â700 eV. A strong dependence of the oscillation period on the CâC distance is observed, which can be used to determine bond lengths between selected pairs of equivalent atoms with an accuracy of at least 0.01 Ã. Furthermore, we show that the observed oscillations are directly informative of the nature and atomic composition of the inner-valence molecular orbitals and that observed ratios are quantitative measures of elusive many-body effects. The technique and analysis can be immediately extended to a large class of compounds. PMID:updating
The retrieval of atmospheric constituent mixing-ratio profiles from solar absorption spectra. Ph.D. Thesis. Interim Technical ReportNASA Technical Reports Server (NTRS) Shaffer, W. A. updating Methods used to determine various atmospheric gas distributions are summarized. The experimentally determined mixing ratio profiles (the mixing ratio of a gas is the ratio of the number of gas molecules to the number of air molecules) of some atmospheric gases are shown. In most in situ experiments stratospheric gas samples are collected at several altitudes by balloon, aircraft, or rocket. These samples are then analyzed by various methods. Mixing ratio profiles of Ci, ClO, and OH were determined by laser induced fluorescence of samples. Others have analyzed gas samples by gas chromatography in order to determine the molecular abundances of CCl2F2, CCl4, CCl3F, CFCl3, CF2Cl2, CHClF2, CH3CCl3, CH4, CO, C2Cl3F3, C2Cl4, C2HCl3, C2H2, C2H4, C2H6, C3H8, C6H6, C7H8, H2, and N2O.
Modification of primordial ices by cosmic rays as simulated by cyclotron irradiationNASA Technical Reports Server (NTRS) Kaiser, R. I.; Roessler, K. updating Frozen CH4 and CH4/Ar mixtures closed into metal cuvettes and open to the vacuum were irradiated at 15 and 77 K with 10 - 20 MeV p and He-3(2+) ions in order to simulate the effect of cosmic rays on solid organic matter in space. Ices exposed to vacuum represent surfaces of icy systems whereas closed systems stand for bulk ices. The products were analyzed by MS, SEM, RBS, ERDA, H-1-NMR, HPLC, GC-MS, NEXAFS, and FT-IR. Volatile products consisted of a mixture of low molecular species, e.g., C2H2, C2H4, C2H6, and long linear aliphatic and olefinic compounds. The formation of polycyclic aromatic hydrocarbons (PAH's) and related species in solid CH4 is due to a multi-center reaction within one collision cascade and is governed by energy density effects with critical linear energy transfer values L(sub T) between 2 and 10 keV/micron. Open ices exhibit preferential hydrogen release resulting in an increased carbonization as compared to more hydrogen rich molecules protected inside large icy bodies.

Research on gas within transformer oil based on photo-spectroscopy technologyNASA Astrophysics Data System (ADS) Song, Gui-cai; Na, Yan-xiang; Zhang, Qi; Shi, Wen-zong updating Insulating oil is widely used in transformer and other large high-voltage electrical equipment.Its main functions are insulation, cooling and arc extinction. When the transformer runs, it may emit heat or discharge, which generate gas, micro water and trace metals in transformer oil. This will not only reduce the insulation capacity of insulating oil,and will greatly reduce the ability of its extinction, causing the transformers or other oil-filled electrical equipment appearing Internal latent malfunction, which would affect the operation of equipment. In this Paper, we simulate the transformer discharge effect to discharge in transformer oil. Then we use spectral theory and photo-spectroscopy technology to measure and analyse the oil sample, combining with IR absorption peaks of main fault characteristic gases, and qualitatively analyse CO, CO2, CH4, C2H6, C2H4, C2H2, H2 in gas mixture. The results show that the Fourier transform infrared spectroscopy can be very effective for analysing gases in transformer oil, which can quickly detect possible problems in the equipment.
Laboratory Studies of Low Temperature Rate Coefficients: The Atmospheric Chemistry of the Outer Planets and TitanNASA Technical Reports Server (NTRS) Bogan, Denis updating Laboratory measurements have been carried out to determine low temperature chemical rate coefficients of ethynyl radical (C2H) for the atmospheres of the outer planets and their satellites. This effort is directly related to the Cassini mission which will explore Saturn and Titan. A laser-based photolysis/infrared laser probe setup was used to measure the temperature dependence of kinetic rate coefficients from approx. equal to 150 to 350 K for C2H radicals with H2, C2H2, CH4, CD4, C2H4, C2H6, C3H8, n-C4H10, i-C4H10, neo-C5H12, C3H4 (methylacetylene and allene), HCN, and CH3CN. The results revealed discrepancies of an order of magnitude or more compared with the low temperature rate coefficients used in present models. A new Laval nozzle, low Mach number supersonic expansion kinetics apparatus has been constructed, resulting in the first measurements of neutral C2H radical kinetics at 90 K and permitting studies on condensable gases with insufficient vapor pressure at low temperatures. New studies of C 2H with acetylene have been completed.
Molybdenum Nitrogenase Catalyzes the Reduction and Coupling of CO to Form Hydrocarbons*â¦PubMed Central Yang, Zhi-Yong; Dean, Dennis R.; Seefeldt, Lance C. updating The molybdenum-dependent nitrogenase catalyzes the multi-electron reduction of protons and N2 to yield H2 and 2NH3. It also catalyzes the reduction of a number of non-physiological doubly and triply bonded small molecules (e.g. C2H2, N2O). Carbon monoxide (CO) is not reduced by the wild-type molybdenum nitrogenase but instead inhibits the reduction of all substrates catalyzed by nitrogenase except protons. Here, we report that when the nitrogenase MoFe protein Î±-Val70 residue is substituted by alanine or glycine, the resulting variant proteins will catalyze the reduction and coupling of CO to form methane (CH4), ethane (C2H6), ethylene (C2H4), propene (C3H6), and propane (C3H8). The rates and ratios of hydrocarbon production from CO can be adjusted by changing the flux of electrons through nitrogenase, by substitution of other amino acids located near the FeMo-cofactor, or by changing the partial pressure of CO. Increasing the partial pressure of CO shifted the product ratio in favor of the longer chain alkanes and alkenes. The implications of these findings in understanding the nitrogenase mechanism and the relationship to Fischer-Tropsch production of hydrocarbons from CO are discussed. PMID:updating
Titan's Atmospheric Composition from Observations by the Cassini Infrared SpectrometerNASA Technical Reports Server (NTRS) Abbas, M. M.; LeClair, A.; Flasar, F. M.; Kunde, V. G.; Conrath, B. J.; Coustenis, A.; Jennings, D. J.; Nixon, C. A.; Brasunas, J.; Achterberg, R. K. updating The Composite Infrared Spectrometer (CIRS) aboard the Cassini spacecraft has been making observations during the fly-bys of Titan since the Saturn-Orbit-Insertion in July 2004. The observations provide infrared them1 emission spectra of Titan s atmosphere in three spectral channels covering the 10/cm to 1400/cm spectral region, with variable spectral resolutions of 0.53/cm and 2.8/cm. The uniquely observed spectra exhibit rotational and vibrational-rotational spectral lines of the molecular constituents of Titan s atmosphere that may be analyzed to retrieve information about the composition, thermal structure, and physical and dynamical processes in the remotely sensed atmosphere. We present an analysis of Titan's infrared spectra observed during July 2004 (TO), December 2004 (Tb) and February 2005 (T3), for retrieval of the stratospheric thermal structure, distribution of the hydrocarbons, nitriles, and oxygen bearing constituents, such as C2H2, C2H4, C2H6, C3H8, HCN, HC3N, CO, and CO2 . Preliminary results on the distribution and opacity of haze in Titan s atmosphere are discussed.
Interstellar Aldehydes and their corresponding Reduced Alcohols: Interstellar Propanol?NASA Astrophysics Data System (ADS) Etim, Emmanuel; Chakrabarti, Sandip Kumar; Das, Ankan; Gorai, Prasanta; Arunan, Elangannan updating There is a well-defined trend of aldehydes and their corresponding reduced alcohols among the known interstellar molecules; methanal (CH_2O) and methanol (CH_3OH); ethenone (C_2H_2O) and vinyl alcohol (CH_2CHOH); ethanal (C_2H_4O) and ethanol(C_2H_5OH); glycolaldehyde (C_2H_4O_2) and ethylene glycol(C_2H_6O_2). The reduced alcohol of propanal (CH_3CH_2CHO) which is propanol (CH_3CH_2CH_2OH) has not yet been observed but its isomer; ethyl methyl ether (CH_3CH_2OCH_3) is a known interstellar molecule. In this article, different studies are carried out in investigating the trend between aldehydes and their corresponding reduced alcohols and the deviation from the trend. Kinetically and with respect to the formation route, alcohols could have been produced from their corresponding reduced aldehydes via two successive hydrogen additions. This is plausible because of (a) the unquestionable high abundance of hydrogen, (b) presence of energy sources within some of the molecular clouds and (c) the ease at which successive hydrogen addition reaction occurs. In terms of stability, the observed alcohols are thermodynamically favorable as compared to their isomers. Regarding the formation process, the hydrogen addition reactions are believed to proceed on the surface of the interstellar grains which leads to the effect of interstellar hydrogen bonding. From the studies, propanol and propan-2-ol are found to be more strongly attached to the surface of the interstellar dust grains which affects its overall gas phase abundance as compared to its isomer ethyl methyl ether which has been observed.
Shock Synthesis in the Atmosphere of JupiterNASA Astrophysics Data System (ADS) Khare, B. N.; Sagan, C.; McDonald, G. D.; de Vanssay, E.; Borucki, W. J.; McKay, C. P.; Bernstein, M. P.; Hartman, T. G.; Lech, J. updating We have previously investigated an approximate simulation of the Jupiter troposphere at the 1 bar NH_3 cloud level using Laser Induced Plasma (LIP) for shock synthesis in a 84.62:13.3:1.07:1.01 H_2:He:CH_4:NH_3 gas mixture, and found by GC/MS that HCN is the most abundant product, more abundant than all the major product hydrocarbons (C_2H_6, C_2H_2, C_3H_8, and C_4H10) combined. Using purge and trap isolation techniques on the LIP gas mixture using two absorbent traps in tandem, thermal desorption GC/MS has revealed a large array of product molecules starting from simple hydrocarbons such as C_2H_2, C_2H_4, etc., simple nitriles such as HCN, CH_3CN, etc., to molecules up to C13 (e.g. C13H23N). Here we report the results of our more accurate simulation of Jupiter at the 5 bar level using LIP with a 88:11.7:0.2:0.1 H_2:He:CH_4:NH_3 mixture, for comparison with mass spectral data from the Galileo probe. We detect in this more acurate simulation of Jupiter many of the same compounds, such as HCN, dimethylaminoacetonitrile, and dimethylcyanamide, as in the previous lower dilution experiment. We will compare the present results with those from low-pressure continuous flow plasma discharge experiments (McDonald et al. 1992, al Icarus 99, 131). We will also discuss the relevance of our data in light of the significant discrepancies between standard models of the jovian atmosphere and the compositional data returned by the Galileo entry probe.
Rate constants for the reacion C4H radical with various hydrocarbons at very low temperatures relevant to the atmospheric chemistry of Titan and other astronomical sourcesNASA Astrophysics Data System (ADS) Berteloite, Coralie; Le Picard, SÃ©bastien D.; Canosa, AndrÃ©; Sims, Ian R. H2, C2H4, C2H6 and C4H2.
Possible Sources for Methane and C2-C5 Organics in the Plume of EnceladusNASA Technical Reports Server (NTRS) McKay, Chris; Khare, Bishun N.; Amin, Ranjamin; Klasson, Martin; Kral, Timothy A. updating In this paper we consider six possible sources of CH4 and other low-mass (C2 - C5) organics in the plume of Enceladus: initial endowments of cometary organics or Titan- like tholin, in situ production by Fisher-Tropsch type reactions, water-rock reactions, or microbiology, and thermogenesis from heavier organics already present. We report on new laboratory results C2 hydrocarbons released on thermogenesis of laboratory tholin and Fisher-Tropsch type synthesis. Tholin heating produced ratios of CH4/C2H4 and CH4/C2H6 of about 2 for temperatures up to 450 C and about 6 for a temperature of 650 C. Low pressure Fisher-Tropsch type experiments produced CH4/C2H4 of approx 1.5, similar to previous results. No C2H2 was produced by either process. Tests of gas production by four strains of methanogens confirmed the absence of any detectable production of non-methane hydrocarbons. Cometary endowment, Fisher-Tropsch type synthesis, and Titan-like tholin incorporation could be primary inputs of organics and subsequent thermal processing of any of these all are possible sources of low mass organics in the plume. Biological production and water-rock reactions are an alternative source of CH4. Neither water-- ]rock reactions or thermal processing of biomass could be a source C2 . C5 organics due to the low interior pressures. The confirmed detection of CO and C2H2 in the plume of Enceladus would provide an important constraint on sources as we have identified no process . other than the initial volatile component of cometary organics which can supply these gases. Precise determination of the relative concentrations of C1 - C5 hydrocarbons may provide additional constraints on sources but a detailed isotopic analysis of C and H in these organics and a search for amino acids constitute the next important steps in resolving the sources of the organics in Enceladus' plume.
Theoretical study on the gas adsorption capacity and selectivity of CPM-200-In/Mg and CPM-200-In/Mg-X (-X = -NH2, -OH, -N, -F).PubMed Liu, Xiao-le; Chen, Guang-Hui; Wang, Xiu-Jun; Li, Peng; Song, Yi-Bing; Li, Rui-Yan updating The adsorption capacities of a heterometallic metal-organic framework (CPM-200-In/Mg) to VOCs (HCHO, C 2 H 4 , CH 4 , C 2 H 2 , C 3 H 8 , C 2 H 6 , C 2 H 3 Cl, C 2 H 2 Cl 2 , CH 2 Cl 2 and CHCl 3 ) and some inorganic gas molecules (HCN, SO 2 , NO, CO 2 , CO, H 2 S and NH 3 ), as well as its selectivity in ternary mixture systems of natural gas and post-combustion flue gas are theoretically explored at the grand canonical Monte Carlo (GCMC) and density functional theory (DFT) levels. It is shown that CPM-200-In/Mg is suitable for the adsorption of VOCs, particularly for HCHO (up to 0.39 g g -1 at 298 K and 1 bar), and the adsorption capacities of some inorganic gas molecules such as SO 2 , H 2 S and CO 2 match well with the sequence of their polarizability (SO 2 > H 2 S > CO 2 ). The large adsorption capacities of HCN and HCHO in the framework result from the strong interaction between adsorbates and metal centers, based on analyzing the radial distribution functions (RDF). Comparing C 2 H 4 and CH 4 molecules interacting with CPM-200-In/Mg by VDW interaction, we speculate that the high adsorption capacities of their chlorine derivatives in the framework could be due to the existence of halogen bonding or strong electrostatic and VDW interactions. It is found that the basic groups, including -NH 2 , -N and -OH, can effectively improve both the adsorption capacities and selectivity of CPM-200-In/Mg for harmful gases. Note that the adsorption capacity of CPM-200-In/Mg-NH 2 (site 2) (245 cm 3 g -1 ) for CO 2 exceeded that of MOF-74-Mg (228 cm 3 g -1 ) at 273 K and 1 bar and that for HCHO can reach 0.41 g g -1 , which is almost twice that of 438-MOF and nearly 45 times of that in active carbon. Moreover, for natural gas mixtures, the decarburization and desulfurization abilities of CPM-200-In/Mg-NH 2 (site 2) have exceeded those of the MOF-74 series, while for post-combustion flue gas mixtures, the desulfurization ability of CPM-200-In/Mg-NH 2 (site 2) is still
Evaluation of Data Used for Modelling the Stratosphere of SaturnNASA Astrophysics Data System (ADS) Armstrong, Eleanor Sophie; Irwin, Patrick G. J.; Moses, Julianne I. updating Planetary atmospheres are modeled through the use of a photochemical and kinetic reaction scheme constructed from experimentally and theoretically determined rate coefficients, photoabsorption cross sections and branching ratios for the molecules described within them. The KINETICS architecture has previously been developed to model planetary atmospheres and is applied here to Saturnâs stratosphere. We consider the pathways that comprise the reaction scheme of a current model, and update the reaction scheme according the to findings in a literature investigation. We evaluate contemporary photochemical literature, studying recent data sets of cross-sections and branching ratios for a number of hydrocarbons used in the photochemical scheme of Model C of KINETICS. In particular evaluation of new photodissociation branching ratios for CH4, C2H2, C2H4, C3H3, C3H5 and C4H2, and new cross-sectional data for C2H2, C2H4, C2H6, C3H3, C4H2, C6H2 and C8H2 are considered. By evaluating the techniques used and data sets obtained, a new reaction scheme selection was drawn up. These data are then used within the preferred reaction scheme of the thesis and applied to the KINETICS atmospheric model to produce a model of the stratosphere of Saturn in a steady state. A total output of the preferred reaction scheme is presented, and the data is compared both with the previous reaction scheme and with data from the Cassini spacecraft in orbit around Saturn.One of the key findings of this work is that there is significant change in the modelâs output as a result of temperature dependent data determination. Although only shown within the changes to the photochemical portion of the preferred reaction scheme, it is suggested that an equally important temperature dependence will be exhibited in the kinetic section of the reaction scheme. The photochemical model output is shown to be highly dependent on the preferred reaction scheme used within it by this thesis. The importance of correct
Changes in the geometries of CâHâ and CâHâ on coordination to CuCl revealed by broadband rotational spectroscopy and ab-initio calculations.PubMed Stephens, Susanna L; Bittner, Dror M; Mikhailov, Victor A; Mizukami, Wataru; Tew, David P; Walker, Nicholas R; Legon, Anthony C updating The molecular geometries of isolated complexes in which a single molecule of C2H4 or C2H2 is bound to CuCl have been determined through pure rotational spectroscopy and ab-initio calculations. The C2H2Â·Â·Â·CuCl and C2H4Â·Â·Â·CuCl complexes are generated through laser vaporization of a copper rod in the presence of a gas sample undergoing supersonic expansion and containing C2H2 (or C2H4), CCl4, and Ar. Results are presented for five isotopologues of C2H2Â·Â·Â·CuCl and six isotopologues of C2H4Â·Â·Â·CuCl. Both of these complexes adopt C(2v), T-shaped geometries in which the hydrocarbon binds to the copper atom through its Ï electrons such that the metal is equidistant from all H atoms. The linear and planar geometries of free C2H2 and C2H4, respectively, are observed to distort significantly on attachment to the CuCl unit, and the various changes are quantified. The â (*-C-H) parameter in C2H2 (where * indicates the midpoint of the Câ¡C bond) is measured to be 192.4(7)Â° in the r0 geometry of the complex representing a significant change from the linear geometry of the free molecule. This distortion of the linear geometry of C2H2 involves the hydrogen atoms moving away from the copper atom within the complex. Ab-initio calculations at the CCSD(T)(F12*)/AVTZ level predict a dihedral â (HCCCu) angle of 96.05Â° in C2H4Â·Â·Â·CuCl, and the experimental results are consistent with such a distortion from planarity. The bonds connecting the carbon atoms within each of C2H2 and C2H4, respectively, extend by 0.027 and 0.029 Ã relative to the bond lengths in the isolated molecules. Force constants, k(Ï), and nuclear quadrupole coupling constants, Ï(aa)(Cu), [Ï(bb)(Cu) - Ï(cc)(Cu)], Ï(aa)(Cl), and [Ï(bb)(Cl) - Ï(cc)(Cl)], are independently determined for all isotopologues of C2H2Â·Â·Â·CuCl studied and for four isotopologues of C2H4Â·Â·Â·CuCl.
The Evolution of Hydrocarbon Compounds in Saturn's Stratosphere During the 2010 Northern StormNASA Astrophysics Data System (ADS) Hesman, B. E.; Bjoraker, G. L.; Achterberg, R. K.; Sada, P. V.; Jennings, D. E.; Lunsford, A. W.; Sinclair, J.; Romani, P. N.; Boyle, R.; Fletcher, L. N.; Irwin, P. updating The massive eruption at 40N (planetographic latitude) in December 2010 has produced significant and long-lived changes in temperature and species abundances in Saturn's northern hemisphere (Hesman et al. 2012a, Fletcher et al. 2012). The northern storm region has been observed on many occasions between January 2011 and June of 2012 by Cassini's Composite Infrared Spectrometer (CIRS). In this time period, temperatures in regions referred to as 'beacons' (warm regions in the stratosphere at certain longitudes in the storm latitude) became significantly warmer than pre-storm values of 140K. In this period hydrocarbon emission greatly increased; however, this increased emission could not be attributed due to the temperature changes alone for many of these species (Hesman et al. 2012b, Bjoraker et al 2012). The unique nature of the stratospheric beacons also resulted in the detection of ethylene (C2H4) using CIRS. These beacon regions have also led to the identification of rare hydrocarbon species such as C4H2 and C3H4 in the stratosphere. These species are all expected from photochemical processes in the stratosphere, however high temperatures, unusual chemistry, or dynamics are enhancing these species. The exact cause of these enhancements is still under investigation. Ground-based observations were performed using the high-resolution spectrometer Celeste in May 2011 to confirm the CIRS detection of C2H4 and to study its spectral signatures at higher spectral resolution. In order to follow the evolution of its emission further observations were performed in July 2011 and March 2012. These observations are being used in conjunction with the CIRS observations to investigate the source of the approximately 100-fold increase of ethylene in the stratospheric beacon. The time evolution of hydrocarbon emission from C2H2, C2H4, C2H6, C3H4, and C4H2 in Saturn's Northern Storm beacon regions will be discussed. References: Bjoraker, G., B.E. Hesman, R.K. Achterberg, P.N. Romani
A C 2 H 2 -type zinc finger protein, SGR5, is involved in early events of gravitropism in Arabidopsis inflorescence stems.PubMed Morita, Miyo T; Sakaguchi, Keitaro; Kiyose, Shin-Ichiro; Taira, Kensuke; Kato, Takehide; Nakamura, Moritaka; Tasaka, Masao updating Plants can sense the direction of gravity and change the growth orientation of their organs. To elucidate the molecular mechanisms of gravity perception and the signal transduction of gravitropism, we have characterized a number of shoot gravitropism (sgr) mutants of Arabidopsis. The sgr5-1 mutant shows reduced gravitropism in the inflorescence stem but its root and hypocotyl have normal gravitropism. SGR5 encodes a zinc finger protein with a coiled-coil motif. The SGR5-GFP fusion protein is localized in the nucleus of Arabidopsis protoplasts, suggesting that SGR5 may act as a transcription factor. Analysis of GUS expression under the control of the SGR5 promoter revealed that SGR5 is mainly expressed in the endodermis, the gravity-sensing tissue in inflorescence stems. Furthermore, the observation that endodermis-specific expression of SGR5 using the SCR promoter in the sgr5-1 mutant restores shoot gravitropism indicates that it could function in the gravity-sensing endodermal cell layer. In contrast to other sgr mutants reported previously, almost all amyloplasts in the endodermal cells of the sgr5-1 mutant sedimented in the direction of gravity. Taken together, our results suggest that SGR5 may be involved in an early event in shoot gravitropism such as gravity perception and/or a signaling process subsequent to amyloplast sedimentation as a putative transcription factor in gravity-perceptive cells.
The C 2 H 2 zinc-finger protein SlZF3 regulates AsA synthesis and salt tolerance by interacting with CSN5B.PubMed Li, Ying; Chu, Zhuannan; Luo, Jinying; Zhou, Yuhong; Cai, Yujing; Lu, Yongen; Xia, Junhui; Kuang, Hanhui; Ye, Zhibiao; Ouyang, Bo updating Abiotic stresses are a major cause of crop loss. Ascorbic acid (AsA) promotes stress tolerance by scavenging reactive oxygen species (ROS), which accumulate when plants experience abiotic stress. Although the biosynthesis and metabolism of AsA are well established, the genes that regulate these pathways remain largely unexplored. Here, we report on a novel regulatory gene from tomato (Solanum lycopersicum) named SlZF3 that encodes a Cys2/His2-type zinc-finger protein with an EAR repression domain. The expression of SlZF3 was rapidly induced by NaCl treatments. The overexpression of SlZF3 significantly increased the levels of AsA in tomato and Arabidopsis. Consequently, the AsA-mediated ROS-scavenging capacity of the SlZF3-overexpressing plants was increased, which enhanced the salt tolerance of these plants. Protein-protein interaction assays demonstrated that SlZF3 directly binds CSN5B, a key component of the COP9 signalosome. This interaction inhibited the binding of CSN5B to VTC1, a GDP-mannose pyrophosphorylase that contributes to AsA biosynthesis. We found that the EAR domain promoted the stability of SlZF3 but was not required for the interaction between SlZF3 and CSN5B. Our findings indicate that SlZF3 simultaneously promotes the accumulation of AsA and enhances plant salt-stress tolerance. Â© 2017 The Authors. Plant Biotechnology Journal published by Society for Experimental Biology and The Association of Applied Biologists and John Wiley & Sons Ltd.
Is the Reaction of C3N(-) with C 2 H 2 a Possible Process for Chain Elongation in Titan's Ionosphere?PubMed LindÃ©n, Fredrik; Alcaraz, Christian; Ascenzi, Daniela; Guillemin, Jean-Claude; Koch, Leopold; Lopes, Allan; PolÃ¡Å¡ek, Miroslav; Romanzin, Claire; Å½abka, Jan; Zymak, Illia; Geppert, Wolf D updating The reaction of C3N(-) with acetylene was studied using three different experimental setups, a triple quadrupole mass spectrometer (Trento), a tandem quadrupole mass spectrometer (Prague), and the "CERISES" guided ion beam apparatus at Orsay. The process is of astrophysical interest because it can function as a chain elongation mechanism to produce larger anions that have been detected in Titan's ionosphere by the Cassini Plasma Spectrometer. Three major products of primary processes, C2H(-), CN(-), and C5N(-), have been identified, whereby the production of the cyanide anion is probably partly due to collisional induced dissociation. The formations of all these products show considerable reaction thresholds and also display comparatively small cross sections. Also, no strong signals of anionic products for collision energies lower than 1 eV have been observed. Ab initio calculations have been performed to identify possible pathways leading to the observed products of the title reaction and to elucidate the thermodynamics of these processes. Although the productions of CN(-) and C5N(-) are exoergic, all reaction pathways have considerable barriers. Overall, the results of these computations are in agreement with the observed reaction thresholds. Due to the existence of considerable reaction energy barriers and the small observed cross sections, the title reaction is not very likely to play a major role in the buildup of large anions in cold environments like the interstellar medium or planetary and satellite ionospheres.
Characterization of the Minimum Energy Paths for the Reactions of CH(X(sup 2 Pi) and (1)CH2 with C 2 H 2NASA Technical Reports Server (NTRS) Walch, Stephen P.; Langhoff, S. R. (Technical Monitor) updating The reactions of CH(sup 2 Pi) and singlet methylene (1)CH2 with acetylene lead to intermediates which may be important in soot formation. CH(sup 2 Pi) + acetylene leads to CHCHCH (C3H3), CHCCH (C3H2), and propargyl (CH2CCH). (1)CH2 + acetylene leads to cyclopropene and propargyl. All of these reaction products are formed with no barrier. Miller and Melius have previously discussed the dimerization of propargyl to give benzene. C3H3 and C3H2 can dimerize with no barrier to give benzene and para-benzyne, respectively. C3H3 and C3H2 can also add to smaller polynuclear aromatic hydrocarbons (PAH), and may be important species in forming larger PAH or fullerenes.
Saturation Dip Measurements of High-J Transitions in the v_1+v_3 Band of C _2 H _2 : Absolute Frequencies and Self-BroadeningNASA Astrophysics Data System (ADS) Sears, Trevor; Twagirayezu, Sylvestre; Hall, Gregory updating Saturation dip spectra of acetylene in the v_1 + v_3 band have been obtained for rotational lines with J = 31-37 inclusive, using a diode laser referenced to a frequency comb. The estimated accuracy and precision of the measurements is better than 10 kHz in 194 THz. Data were obtained as a function of sample pressure to investigate the broadening of the saturation features. The observed line shapes are well modeled by convolution of a fixed Gaussian transit-time and varying Lorentzian lifetime broadening, i.e. a Voigt-type profile. The lines exhibit a significantly larger collisional (lifetime) broadening than has been measured in conventional Doppler and pressure-broadened samples at ambient temperatures. The figure shows the fitted Lorentzian width versus sample pressure for P(31). The slope of this plot gives the pressure broadening coefficient, Î³_{self} = 9.35(13) MHz/mbar. For comparison, the coefficient derived from conventional Doppler and pressure broadened spectra for this transition is 2.7 MHz/mbar. The sub-Doppler broadening coefficients are all significantly larger than the conventionally measured ones, due to the increased importance of velocity-changing collisions. The measurements therefore give information on the balance between hard phase- or state-changing and large cross-section velocity-changing collisions. Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-SC0012704 with the U.S. Department of Energy, Office of Science, and supported by its Division of Chemical Sciences, Geosciences and Biosciences within the Office of Basic Energy Sciences. J. Molec. Spectrosc. 209, updating) and J. Quant. Spectrosc. Rad. Transf. 76, updating)
Resonant inelastic x-ray scattering on iso-C 2 H 2 Cl2 around the chlorine K-edge: Structural and dynamical aspectsNASA Astrophysics Data System (ADS) Kawerk, Elie; Carniato, StÃ©phane; Journel, LoÃ¯c; Marchenko, Tatiana; Piancastelli, Maria Novella; Å½itnik, MatjaÅ¾; BuÄar, Klemen; Bohnic, Rok; KavÄiÄ, MatjaÅ¾; CÃ©olin, Denis; Khoury, Antonio; Simon, Marc updating We report a theoretical and experimental study of the high resolution resonant KÎ± X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the KÎ± emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state.
A philosophical theory on human communication and modern physics: e(,2)c (,2 )H ('2 )T energy-exchange and consciousness-change toward humanism, healing, and transformationNASA Astrophysics Data System (ADS) Jenkins-Tate, Marnishia Laverne This dissertation addresses the need for a body of human communication theory that can be useful toward advancing personal and social transformation. Of the humanistic genre, it suggests that there is a need to promote humanism, healing, and personal transformation in the non-clinical settings of everyday living. Three questions guide the effort. First, it asks: what kind of human communication theory might describe some of the underlying dynamics of human interaction, while also suggesting ways to improve the quality of interactions of any related philosophical theory be grounded by some scientific discipline? Then finally, it asks: how might these proposed concepts be captured in a manner that can be useful to human beings in everyday human interaction? Extending the work of modern physics to the realm of human communication, the theory integrates conceptual aspects of quantum theory, relativity theory, communication accommodation theory, and various nonverbal communication theory. Then, it proposes the philosophical framework for a new body of theory which it calls the energy-exchange theory of human communication. Treating human beings as living forms of matter, it suggests that ``energy'' is the life-force that sustains all human beings, and that ``consciousness'' is that qualitative level of development at which energy manifests itself in the human experience. It proposes that human beings have the capacity to exchange energy and influence consciousness during the human communication process, and that these interactions can advance humanism, healing, and transformation-which it proposes are the higher states and levels of human consciousness. Thus, this research effort sought to know and to describe a phenomenon that is the interactive human being; and to suggest useful ways that this volitional being can know and transform itself through human interaction. With verisimilitude as a driving factor in describing human beings as communicators, the research is ontology- centered. It suggests that human beings are most notably creatures of feeling and soul, and that it is through interaction involving these dimensions that one can best come to know the human being. Accordingly, the research employs a hermeneutic phenomenological approach toward participative inquiry and experiential knowing. With practicality as a driving factor in suggesting ways that the human phenomenon can know and transform itself, this work utilizes a pragmatic approach to theory- building. Pragmatism suggests that all theories are approximations that ultimately should be judged on their abilities to truthfully describe phenomena and to solve human problems. Thus, having undergone an inductive progression from data to theory-building, now this work must go from theory to data, such that next steps should involve formal assessment of its verisimilitude and pragmatism based on feedback gained through field research on various persons who may apply the theory and its model to everyday living. (Abstract shortened by UMI.)
Nuclear localization of the C 2 H 2 zinc finger protein Msn2p is regulated by stress and protein kinase AâactivityPubMed Central GÃ¶rner, Wolfram; Durchschlag, Erich; Martinez-Pastor, Maria Teresa; Estruch, Francisco; Ammerer, Gustav; Hamilton, Barbara; Ruis, Helmut; SchÃ¼ller, Christoph updating Msn2p and the partially redundant factor Msn4p are key regulators of stress-responsive gene expression in Saccharomyces cerevisiae. They are required for the transcription of a number of genes coding for proteins with stress-protective functions. Both Msn2p and Msn4p are Cys2His2 zinc finger proteins and bind to the stress response element (STRE). In vivo footprinting studies show that the occupation of STREs is enhanced in stressed cells and dependent on the presence of Msn2p and Msn4p. Both factors accumulate in the nucleus under stress conditions, such as heat shock, osmotic stress, carbon-source starvation, and in the presence of ethanol or sorbate. Stress-induced nuclear localization was found to be rapid, reversible, and independent of protein synthesis. Nuclear localization of Msn2p and Msn4p was shown to be correlated inversely to cAMP levels and protein kinase A (PKA) activity. A region with significant homologies shared between Msn2p and Msn4p is sufficient to confer stress-regulated localization to a SV40âNLSâGFP fusion protein. Serine to alanine or aspartate substitutions in a conserved PKA consensus site abolished cAMP-driven nuclear export and cytoplasmic localization in unstressed cells. We propose stress and cAMP-regulated intracellular localization of Msn2p to be a key step in STRE-dependent transcription and in the general stress response. PMID:9472026

The dynamics of the Cl+C 2 H 6 âHCl(v',j')+C2H5 reaction at 0.24 eV: Is ethyl a spectator?NASA Astrophysics Data System (ADS) Bass, M. J.; Brouard, M.; Vallance, C.; Kitsopoulos, T. N.; Samartzis, P. C.; Toomes, R. L. updating The hydrogen atom abstraction reaction between Cl(2P3/2) and ethane has been studied at a mean collision energy of 0.24 eV. The experiments were performed in a coexpansion of molecular chlorine and ethane, with the atomic Cl reactants generated by laser photodissociation of Cl2 at 355 nm. HCl(v',j') products were detected quantum state selectively using (2+1) resonantly enhanced multiphoton ionization, coupled with velocity-map ion imaging. The ion images were used to determine center-of-mass angular and kinetic energy release distributions. Several analysis methods were employed and have been carefully assessed. It is shown that the single beam experiments can be used with confidence to determine both center-of-mass angular and energy release distributions. For the title reaction the angular distribution is found to be forward peaking, with on average 22% of the available energy channeled into internal excitation of the ethyl coproducts. Possible sources of this internal excitation are discussed.
State-resolved differential cross-section measurement of Cl+C 2 H 6 âHCl+C 2H 5 reaction using single-beam velocity mappingNASA Astrophysics Data System (ADS) Samartzis, Peter C.; Smith, Derek J.; Rakitzis, T. Peter; Kitsopoulos, Theofanis N. updating The bimolecular reaction of atomic chlorine with ethane at a collision energy of 0.36 eV is studied in a single-beam experiment, using velocity mapping of a state-selected reaction product. The differential cross-section for HCl( v=0, J=1) product is directly determined from its Abel-inverted velocity map image. Our results are similar to previous measurements of the differential cross-section and suggest that the HCl( v=0, J=1) scattering is broad with a side-scattered peak. This Letter demonstrates the power of velocity mapping for measuring differential cross-sections for reactions for which one of the reactants is produced photolytically.
Differential solubility of ethylene and acetylene in room-temperature ionic liquids: a theoretical study.PubMed Zhao, Xu; Xing, Huabin; Yang, Qiwei; Li, Rulong; Su, Baogen; Bao, Zongbi; Yang, Yiwen; Ren, Qilong updating The room-temperature ionic liquids (RTILs) have potential in realizing the ethylene (C(2)H(4)) and acetylene (C(2)H(2)) separation and avoiding solvent loss and environmental pollution compared with traditional solvents. The interaction mechanisms between gases and RTILs are important for the exploration of new RTILs for gas separation; thus, they were studied by quantum chemical calculation and molecular dynamics simulation in this work. The optimized geometries were obtained for the complexes of C(2)H(4)/C(2)H(2) with anions (Tf(2)N(-), BF(4)(-), and OAc(-)), cation (bmim(+)), and their ion pairs, and the analysis for geometry, interaction energy, natural bond orbital (NBO), and atoms in molecules (AIM) was performed. The quantum chemical calculation results show that the hydrogen-bonding interaction between the gas molecule and anion is the dominant factor in determining the solubility of C(2)H(2) in RTILs. However, the hydrogen-bonding interaction, the p-Ï interaction in C(2)H(4)-anion, and the Ï-Ï interaction in C(2)H(4)-cation are weak and comparable, which all affect the solubility of C(2)H(4) in RTILs with comparable contribution. The calculated results for the distance of H(gas)Â·Â·Â·X (X = O or F in anions), the BSSE-corrected interaction energy, the electron density of H(gas)Â·Â·Â·X at the bond critical point (Ï(BCP)), and the relative second-order perturbation stabilization energy (E(2)) are consistent with the experimental data that C(2)H(2) is more soluble than C(2)H(4) in the same RTILs and the solubility of C(2)H(4) in RTILs has the following order: [bmim][Tf(2)N] > [bmim][OAc] > [bmim][BF(4)]. The calculated results also agree with the order of C(2)H(2) solubility in different RTILs that [bmim][OAc] > [bmim][BF(4)] > [bmim][Tf(2)N]. Furthermore, the calculation results indicate that there is strong C(2)H(2)-RTIL interaction, which cannot be negligible compared to the RTIL-RTIL interaction; thus, the regular solution theory is probably not
Spectroscopic studies of microwave plasmas containing hexamethyldisiloxaneNASA Astrophysics Data System (ADS) Nave, A. S. C.; Mitschker, F.; Awakowicz, P.; RÃ¶pcke, J. updating Low-pressure microwave discharges containing hexamethyldisiloxane (HMDSO) with admixtures of oxygen and nitrogen, used for the deposition of silicon containing films, have been studied spectroscopically. Optical emission spectroscopy (OES) in the visible spectral range has been combined with infrared laser absorption spectroscopy (IRLAS). The experiments were carried out in order to analyze the dependence of plasma chemical phenomena on power and gas mixture at relatively low pressures, up to 50 Pa, and power values, up to 2 kW. The evolution of the concentration of the methyl radical, CH3, and of seven stable molecules, HMDSO, CH4, C2H2, C2H4, C2H6, CO and CO2, was monitored in the plasma processes by in situ IRLAS using tunable lead salt diode lasers (TDL) and external-cavity quantum cascade lasers (EC-QCL) as radiation sources. To achieve reliable values for the gas temperature inside and outside the plasma bulk as well as for the temperature in the plasma hot and colder zones, which are of great importance for calculation of species concentrations, three different methods based on emission and absorption spectroscopy data of N2, CH3 and CO have been used. In this approach line profile analysis has been combined with spectral simulation methods. The concentrations of the various species, which were found to be in the range between 1011 to 1015 cm-3, are in the focus of interest. The influence of the discharge parameters power, pressure and gas mixture on the molecular concentrations has been studied. To achieve further insight into general plasma chemical aspects the dissociation of the HMDSO precursor gas including its fragmentation and conversion to the reaction products was analyzed in detail.
Modeling the neutral gas and dust coma of Comet 1P/HalleyNASA Astrophysics Data System (ADS) Rubin, Martin; Tenishev, Valeriy M.; Combi, Michael R.; Hansen, Kenneth C.; Gombosi, Tamas I.; Altwegg, Kathrin; Balsiger, Hans updating The neutral gas environment of a comet is largely influenced by dissociation of parent molecules created at the surface of the comet and collisions of all the involved species. We compare the results from a kinetic model of the neutral cometary environment with measurements from the Neutral Mass Spectrometer (NMS) and the Dust Impact Detection System (DIDSY) onboard the Giotto spacecraft which flew-by at comet 1P/Halley in 1986. We further show that our model is in good agreement to measurements obtained by the International Ultraviolet Explorer (IUE), sounding rocket experiments, and the International Halley Watch (IHW). The model solves the Boltzmann equation with a Direct Simulation Monte Carlo technique [Tenishev et al. (2008, Astrophys. J., 685, 659-677)] by tracking trajectories of gas molecules and dust grains under the influence of the comet's weak gravity field with momentum exchange among particles modeled in a probabilistic manner. The cometary nucleus is considered to be the source of dust and the parent species (in our model: H2O, CO, H2CO, CO2, CH3OH, C2H6, C2H4, C2H2, HCN, NH3, and CH4) in the coma. Subsequently our model also tracks the corresponding dissociation products (H, H2, O, OH, C, CH, CH2, CH3, N, NH, NH2, C2, C2H, C2H5, CN, and HCO). This work has been supported by JPL subcontract 1266313 under NASA grant NMO710889, NASA planetary atmospheres program grant NNX09AB59G, grant AST-0707283 from the NSF Planetary Astronomy program, and the Swiss National Science Foundation.
The Effect of Aerosols on Pluto's C2 Hydrocarbon ChemistryNASA Astrophysics Data System (ADS) Luspay-Kuti, Adrienn; Mandt, Kathleen; Jessup, Kandis-Lea; Hue, Vincent; Kammer, Joshua; Filwett, Rachael; Hamel, Mark updating On July 14, 2015 the New Horizons spacecraft flew through the Pluto system, providing critical details about Plutoâs atmosphere. The vertical profiles of N2 and CH4, C2H2, C2H4, and C2H6 derived from New Horizons Alice transmission data allow the more accurate modeling of Plutoâs atmosphere than in the pre-New Horizons era, and help better understand the physical and photochemical processes in Plutoâs atmosphere. All the measured C2 hydrocarbon densities showed an unexpected inversion between ~100 and 400 km, which suggests that processes other than chemistry play an important role in shaping their vertical profiles. We present here a state-of-the-art Pluto Ion-Neutral-Photochemistry (Pluto INP) model that includes the condensation onto and incorporation into aerosol particles, and evaluate the dominant production and loss processes of C2 hydrocarbons with a special emphasis on the role of aerosol interaction. We found that in order to reproduce the C2 profiles measured by New Horizons, they must stick to and be permanently removed by aerosols - a process different from condensation. We determined through empirical fits to the New Horizons data that the sticking efficiency of C2 hydrocarbons and the stickiness of the aerosol particles are inversely related to the available aerosol surface area, which has been inferred from observation to increase as altitude decreases. This counterintuitive relationship between sticking efficiency and available aerosol surfaces indicates that similarly to Titan, Plutoâs aerosols must harden and become less sticky as they age. Such hardening with ageing is both necessary and sufficient to explain the vertical profiles of C2 hydrocarbons in Plutoâs atmosphere.
Soot Oxidation in Hydrocarbon/Air Diffusion Flames at Atmospheric Pressure. Appendix KNASA Technical Reports Server (NTRS) Xu, F.; El-Leathy, A. M.; Faeth, G. M.; Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor) updating Soot oxidation was studied experimentally in laminar hydrocarbon/air diffusion flames at atmospheric pressure. Measurements were carried out along the axes of round jets burning in coflowing air considering acetylene, ethylene, propylene and propane as fuels. Measurements were limited to the initial stages of soot oxidation (carbon consumption less than 70%) where soot oxidation mainly occurs at the surface of primary soot particles. The following properties were measured as a function of distance above the burner exit: soot concentrations by deconvoluted laser extinction, soot temperatures by deconvoluted multiline emission, soot structure by thermophoretic sampling and analysis using Transmission Electron Microscopy (TEM), concentrations of stable major gas species (N2, H2O, H2, O2, CO, CO2, CH4, C2H2,C2H4, C2H6, C3H6, and C3H8) by sampling and gas chromatography, concentrations of some radical species (H, OH, O) by the deconvoluted Li/LiOH atomic absorption technique and flow velocities by laser velocimetry. It was found that soot surface oxidation rates are not particularly affected by fuel type for laminar diffusion flames and are described reasonably well by the OH surface oxidation mechanism with a collision efficiency of 0.10, (standard deviation of 0.07) with no significant effect of fuel type in this behavior; these findings are in good agreement with the classical laminar premixed flame measurements of Neoh et al. Finally, direct rates of surface oxidation by O2 were small compared to OH oxidation for present conditions, based on estimated O2 oxidation rates due to Nagle and Strickland-Constable (1962), because soot oxidation was completed near the flame sheet where O2 concentrations were less than 1.2% by volume.
Canceling buoyancy of gaseous fuel flames in a gravitational environment using an ion-driven wind.PubMed Papac, M J; Dunn-Rankin, D updating Electric fields applied to combustion plasmas can be used to manipulate the thermofluid flow field to reduce buoyant forces and, hence, convection in locations near and within the flame. The resulting flow field is similar to that which is obtained in microgravity. Previous work has shown that buoyancy is modified in a non-premixed methane-air capillary flame when it burns in a capillary-to-plane configuration and an electric field is applied, and that regions of neutral or microbuoyancy exist, as indicated by the examined temperature and oxidizer profiles. The aim of this article is to examine in more detail this microbuoyancy condition and the coupling between the ion wind and resulting thermofluid flow field. To this end, the voltage-current characteristics (VCC) of CH4, C2H2, C2H4, C2H6, and C3H8 are measured and compared. Soot generated in the C2H(X) and propane flames lead to a hysteresis in the VCC curve whereby increased sooting leads to lower ion currents at constant flow rates and applied potentials. Buoyancy regimes for these flames in this configuration are determined. Methane can achieve the highest flow rate without sooting at the microbuoyant condition, and does not exhibit hysteresis in the VCC for the flow rates examined here. Furthermore, in this geometry, the microbuoyant condition for methane is found to coincide with ion current saturation when the capillary-to-plane distance is varied. These results allow for several simplifications to be made when modeling the flame at these conditions: the imposition of a spherical flame boundary with known ion current, and negligible recombination in the domain.
Photochemical formation rates of organic aerosols through time-resolved in situ laboratory measurementsNASA Astrophysics Data System (ADS) ÃdÃ¡mkovics, MÃ¡tÃ©; Boering, Kristie A. updating The fundamental kinetics of photochemical particle formation and the mechanism(s) for polymerization of hydrocarbons to form condensable species under anoxic conditions have yet to be determined experimentally. Thus these processes remain highly parameterized in models of planetary atmospheres. We have developed instrumentation for simultaneously measuring the net production rates of complex gas-phase hydrocarbons and of organic aerosols formed from irradiating mixtures of simple precursor gases through online quadrupole mass spectrometry measurements of stable gas-phase species and in situ optical scattering detection of the particulates at 633 nm. The new technique and results for the generation of hydrocarbon aerosol from the irradiation of pure, gas-phase CH4 at a pressure of 70 Torr with 8.8 +/- 0.8 Ã 1015 photons s-1 of vacuum ultraviolet light (120-300nm) are reported. The net production rates for the following gaseous species are measured: H2 = 9.9 +/- updating, C2H2 = 2.8 +/- updating, C2H4 = 5.5 +/- updating, C2H6 = 8.6 +/- updating, C3H4 = 2.5 +/- updating, C4H2 = 6.6 +/- updating, C4H10 = 1.3 +/- updating cm-3 s-1. The production of hydrocarbon particulates is detected by optical scattering, and the condensed phase C-C bond formation rate is inferred to be 7.5 +/- updating cm-3 s-1. Applications of this technique to the atmospheres of Titan and terrestrial-like planets, such as the early Earth before the rise of molecular oxygen, are discussed.
Constraints on the microphysics of Pluto's photochemical haze from New Horizons observationsNASA Astrophysics Data System (ADS) Gao, Peter; Fan, Siteng; Wong, Michael L.; Liang, Mao-Chang; Shia, Run-Lie; Kammer, Joshua A.; Yung, Yuk L.; Summers, Michael E.; Gladstone, G. Randall; Young, Leslie A.; Olkin, Catherine B.; Ennico, Kimberly; Weaver, Harold A.; Stern, S. Alan; New Horizons Science Team updating The New Horizons flyby of Pluto confirmed the existence of hazes in its atmosphere. Observations of a large high- to low- phase brightness ratio, combined with the blue color of the haze (indicative of Rayleigh scattering), suggest that the haze particles are fractal aggregates, perhaps analogous to the photochemical hazes on Titan. Therefore, studying the Pluto hazes can shed light on the similarities and differences between the Pluto and Titan atmospheres. We model the haze distribution using the Community Aerosol and Radiation Model for Atmospheres assuming that the distribution is shaped by downward transport and coagulation of particles originating from photochemistry. Hazes composed of both purely spherical and purely fractal aggregate particles are considered. General agreement between model results and solar occultation observations is obtained with aggregate particles when the downward mass flux of photochemical products is equal to the column-integrated methane destruction rate â¼1.2 Ã 10-14 g cm-2 s-1, while for spherical particles the mass flux must be 2-3 times greater. This flux is nearly identical to the haze production flux of Titan previously obtained by comparing microphysical model results to Cassini observations. The aggregate particle radius is sensitive to particle charging effects, and a particle charge to radius ratio of 30 e-/Î¼m is necessary to produce â¼0.1-0.2 Î¼m aggregates near Pluto's surface, in accordance with forward scattering measurements. Such a particle charge to radius ratio is 2-4 times higher than those previously obtained for Titan. Hazes composed of spheres with the same particle charge to radius ratio have particles that are 4 times smaller at Pluto's surface. These results further suggest that the haze particles are fractal aggregates. We also consider the effect of condensation of HCN, C2H2, C2H4, and C2H6 on the haze particles, which may play an important role in shaping their altitude and size distributions.
Hydrogen production by conversion of ethanol injected into a microwave plasmaNASA Astrophysics Data System (ADS) Czylkowski, Dariusz; Hrycak, Bartosz; JasiÅski, Mariusz; Dors, MirosÅaw; Mizeraczyk, Jerzy updating Reforming of gaseous and liquid hydrocarbon compounds into hydrogen is of high interest. In this paper we present a microwave (2.45 GHz) plasma-based method for hydrogen production by conversion of ethanol (C2H5OH) in the thermal reforming process in nitrogen plasma. In contrast to our earlier investigations, in which C2H5OH vapour was supplied into the microwave plasma region either in the form of a swirl or axial flow, in this experiment we injected C2H5OH vapour directly into the nitrogen microwave plasma flame, behind the microwave plasma generation region. The experimental results were as follows. At an absorbed microwave power of 5 kW, N2 (plasma-generating gas) swirl flow rate of 2700 NL(N2)/h and C2H5OH mass flow rate of 2.7 kg(C2H5OH)/h the hydrogen production rate was 1016 NL(H2)/h, which corresponds to the energy yield of hydrogen production 203 NL(H2)/kWh. After the C2H5OH conversion the outlet gas contained 27.6% (vol.) H2, 10.2% CO, 0.2% CO2, 4.8% CH4, 4.3% C2H2, 3.7% C2H4 and 3.7% C2H6. These results are comparable to those obtained in our earlier investigations, in which different methods of C2H5OH vapour supply to the microwave plasma generation region were employed. Contribution to the Topical Issue: "Advances in Plasma Chemistry", edited by Slobodan MiloÅ¡eviÄ, NikÅ¡a KrstuloviÄ, and Holger Kersten.
Diagnostic studies of H2 Ar N2 microwave plasmas containing methane or methanol using tunable infrared diode laser absorption spectroscopyNASA Astrophysics Data System (ADS) Hempel, F.; Davies, P. B.; Loffhagen, D.; Mechold, L.; RÃ¶pcke, J. updating Tunable infrared diode laser absorption spectroscopy has been used to detect the methyl radical and nine stable molecules, CH4, CH3OH, C2H2, C2H4, C2H6, NH3, HCN, CH2O and C2N2, in H2-Ar-N2 microwave plasmas containing up to 7% of methane or methanol, under both flowing and static conditions. The degree of dissociation of the hydrocarbon precursor molecules varied between 20% and 97%. The methyl radical concentration was found to be in the range updating molecules cm-3. By analysing the temporal development of the molecular concentrations under static conditions it was found that HCN and NH3 are the final products of plasma chemical conversion. The fragmentation rates of methane and methanol (RF(CH4) = (2-7) Ã 1015 molecules J-1, RF(CH3OH) = (6-9) Ã 1015 molecules J-1) and the respective conversion rates to methane, hydrogen cyanide and ammonia (RCmax(CH4) = 1.2 Ã 1015 molecules J-1, RCmax(HCN) = 1.3 Ã 1015 molecules J-1, RCmax(NH3) = 1 Ã 1014 molecules J-1) have been determined for different hydrogen to nitrogen concentration ratios. An extensive model of the chemical reactions involved in the H2-N2-Ar-CH4 plasma has been developed. Model calculations were performed by including 22 species, 145 chemical reactions and appropriate electron impact dissociation rate coefficients. The results of the model calculations showed satisfactory agreement between calculated and measured concentrations. The most likely main chemical pathways involved in these plasmas are discussed and an appropriate reaction scheme is proposed.
Soot Oxidation in Laminar Hydrocarbon/Air Diffusion Flames at Atmospheric Pressure. Appendix DNASA Technical Reports Server (NTRS) Xu, F.; El-Leathy, A. M.; Faeth, G. M. updating Soot oxidation was studied experimentally in laminar hydrocarbon/air diffusion flames at atmospheric pressure. Measurements were carried out along the axes of round jets burning in coflowing air considering acetylene, ethylene, proplyene and propane as fuels. Measurements were limited to the initial stages of soot oxidation (carbon consumption less than 70%) where soot oxidation mainly occurs at the surface of primary soot particles. The following properties were measured as a function of distance above the burner exit: soot concentrations by deconvoluted laser extinction, soot temperatures by deconvoluted multiline emission, soot structure by thermophoretic sampling and analysis using Transmission Electron Microscopy (TEM), concentrations of stable major gas species (N2, H2O, H2, 02, CO, CO2, CH4, C2H2, C2H4, C2H6, C3H6, and C3H8) by sampling and gas chromatography, concentrations of some radical species (H, OH, O) by the deconvoluted Li/LiOH atomic absorption technique and flow velocities by laser velocimetry. It was found that soot surface oxidation rates are not particularly affected by fuel type for laminar diffusion flames and are described reasonably well by the OH surface oxidation mechanism with a collision efficiency of 0.10, (standard deviation of 0.07) with no significant effect of fuel type in this behavior; these findings are in good agreement with the classical laminar premixed flame measurements of Neoh et al. Finally, direct rates of surface oxidation by O2 were small compared to OH oxidation for present conditions, based on estimated O2 oxidation rates due to Nagle and Strickland-Constable, because soot oxidation was completed near the flame sheet where O2 concentrations were less than 1.2% by volume.
Thermolysis of scrap tire and rubber in sub/super-critical water.PubMed Li, Qinghai; Li, Fuxin; Meng, Aihong; Tan, Zhongchao; Zhang, Yanguo updating The rapid growth of waste tires has become a serious environmental issue. Energy and material recovery is regarded as a promising use for waste tires. Thermolysis of scrap tire (ST), natural rubber (NR), and styrene-butadiene rubber (SBR) was carried out in subcritical and supercritical water using a temperature-pressure independent adjustable batch tubular reactor. As a result, oil yields increased as temperature and pressure increased, and they reached maximum values as the state of water was near the critical point. However, further increases in water temperature and pressure reduced the oil yields. The maximum oil yield of 21.21% was obtained at 420â¯Â°C and 18â¯MPa with a reaction time of 40â¯min. The relative molecular weights of the chemicals in the oil products were in the range of 70-140â¯g/mole. The oil produced from ST, NR, and SBR contained similar chemical compounds, but the oil yield of SR was between those of NR and SBR. The oil yield from thermolysis of subcritical or supercritical water should be further improved. The main gaseous products, including CH 4 , C 2 H 2 , C 2 H 4 , C 2 H 6 , and C 3 H 8 , increased with reaction time, temperature, and pressure, whereas the solid residues, including carbon black and impurities, decreased. These results provide useful information to develop a sub/super-critical water thermolysis process for energy and material regeneration from waste tires. Copyright Â© 2017 Elsevier Ltd. All rights reserved.
The effect of pressure on open-framework silicates: elastic behaviour and crystal-fluid interactionNASA Astrophysics Data System (ADS) Gatta, G. D.; Lotti, P.; Tabacchi, G. updating fluid (if mixed with other non-penetrating molecules), the rate of P-increase, the surface/volume ratio of the crystallites under investigations and the temperature at which the experiment is conducted. An overview of the intrusion phenomena of monoatomic species (e.g. He, Ar, Kr), small (e.g. H2O, CO2) and complex molecules, along with the P-induced polymerization phenomena (e.g. C2H2, C2H4, C2H6O, C2H6O2, BNH6, electrolytic MgCl2Â·21H2O solution) is provided, with a discussion of potential technological and geological implications of these experimental findings.
Interface behaviors of acetylene and ethylene molecules with 1-butyl-3-methylimidazolium acetate ionic liquid: a combined quantum chemistry calculation and molecular dynamics simulation study.PubMed Xu, Hao; Han, Zhe; Zhang, Dongju; Zhan, Jinhua updating Although imidazolium-based ionic liquids (ILs) combined with oxygen-containing anions were proposed as the potential solvents for the selective separation of acetylene (C(2)H(2)) and ethylene (C(2)H(4)), the detailed mechanism at the molecular level is still not well understood. The present work focuses on a most effective IL for removing C(2)H(2) from a C(2)H(4) stream, 1-butyl-3-methylimidazolium acetate ([BMIM][OAc]), aiming at understanding the first steps of the adsorption process of the molecules at the IL surface. We present a combined quantum mechanical (QM) calculation and molecular dynamics (MD) simulation study on the structure and property of the IL as well as its interaction with C(2)H(2) and C(2)H(4) molecules. The calculated results indicate that C(2)H(2) presents a stronger interaction with the IL than C(2)H(4) and the anion of the IL is mainly responsible for the stronger interaction. QM calculations show a stronger hydrogen-binding linkage between an acidic proton of C(2)H(2)/C(2)H(4) and the basic oxygen atom in [OAc](-) anion, in contrast to the relative weaker association via the C-HÂ·Â·Â·Ï interaction between C(2)H(2)/C(2)H(4) and the cation. From MD simulations, it is observed that in the interfacial region, the butyl chain of cations and methyl of anions point into the vapor phase. The coming molecules on the IL surface may be initially wrapped by the extensive butyl chain and then devolved to the interface or caught into the bulk by the anion of IL. The introduction of guest molecules significantly influences the anion distribution and orientation on the interface, but the cations are not disturbed because of their larger volume and relatively weaker interaction with the changes in the guest molecules. The theoretical results provide insight into the molecular mechanism of the observed selective separation of C(2)H(2) form a C(2)H(4) stream by ILs.
Insight into ethylene interactions with molybdenum suboxide cluster anions from photoelectron spectra of chemifragmentsNASA Astrophysics Data System (ADS) Schaugaard, Richard N.; Topolski, Josey E.; Ray, Manisha; Raghavachari, Krishnan; Jarrold, Caroline Chick updating Recent studies on reactions between MoxOy- cluster anions and H2O/C2H4 mixtures revealed a complex web of addition, hydrogen evolution, and chemifragmentation reactions, with chemifragments unambiguously connected to cluster reactions with C2H4. To gain insight into the molecular-scale interactions along the chemifragmentation pathways, the anion photoelectron (PE) spectra of MoC2H2-, MoC4H4-, MoOC2H2-, and MoO2C2H2- formed directly in MoxOy- + C2H4 (x > 1; y â¥ x) reactions, along with supporting CCSD(T) and density functional theory calculations, are presented and analyzed. The complexes have spectra that are all consistent with Î·2-acetylene complexes, though for all but MoC4H4-, the possibility that vinylidene complexes are also present cannot be definitively ruled out. Structures that are consistent with the PE spectrum of MoC2H2- differ from the lowest energy structure, suggesting that the fragment formation is under kinetic control. The PE spectrum of MoO2C2H2- additionally exhibits evidence that photodissociation to MoO2- + C2H2 may be occurring. The results suggest that oxidative dehydrogenation of ethylene is initiated by Lewis acid/base interactions between the Mo centers in larger clusters and the Ï orbitals in ethylene.
Photochemistry, mixing and transport in Jupiter's stratosphere constrained by CassiniNASA Astrophysics Data System (ADS) Hue, V.; Hersant, F.; CavaliÃ©, T.; Dobrijevic, M.; Sinclair, J. A. updating In this work, we aim at constraining the diffusive and advective transport processes in Jupiter's stratosphere, using Cassini/CIRS observations published by Nixon et al. (2007,2010). The Cassini-Huygens flyby of Jupiter on December 2000 provided the highest spatially resolved IR observations of Jupiter so far, with the CIRS instrument. The IR spectrum contains the fingerprints of several atmospheric constituents and allows probing the tropospheric and stratospheric composition. In particular, the abundances of C2H2 and C2H6, the main compounds produced by methane photochemistry, can be retrieved as a function of latitude in the pressure range at which CIRS is sensitive to. CIRS observations suggest a very different meridional distribution for these two species. This is difficult to reconcile with their photochemical histories, which are thought to be tightly coupled to the methane photolysis. While the overall abundance of C2H2 decreases with latitude, C2H6 becomes more abundant at high latitudes. In this work, a new 2D (latitude-altitude) seasonal photochemical model of Jupiter is developed. The model is used to investigate whether the addition of stratospheric transport processes, such as meridional diffusion and advection, are able to explain the latitudinal behavior of C2H2 and C2H6. We find that the C2H2 observations are fairly well reproduced without meridional diffusion. Adding meridional diffusion to the model provides an improved agreement with the C2H6 observations by flattening its meridional distribution, at the cost of a degradation of the fit to the C2H2 distribution. However, meridional diffusion alone cannot produce the observed increase with latitude of the C2H6 abundance. When adding 2D advective transport between roughly 30 mbar and 0.01 mbar, with upwelling winds at the equator and downwelling winds at high latitudes, we can, for the first time, reproduce the C2H6 abundance increase with latitude. In parallel, the fit to the C2H2 distribution is
HITRAN2016 Database Part II: Overview of the Spectroscopic Parameters of the Trace GasesNASA Astrophysics Data System (ADS) Tan, Yan; Gordon, Iouli E.; Rothman, Laurence S.; Kochanov, Roman V.; Hill, Christian updating The 2016 edition of HITRAN database is available now. This new edition of the database takes advantage of the new structure and can be accessed through HITRANonline (www.hitran.org). The line-by-line lists for almost all of the trace atmospheric species were updated in comparison with the previous edition HITRAN2012. These extended update covers not only updating few transitions of the certain molecules, but also complete replacements of the whole line lists, and as well as introduction of new spectroscopic parameters for non-Voigt line shape. The new line lists for NH_3, HNO_3, OCS, HCN, CH_3Cl, C_2H_2, C_2H_6, PH_3, C_2H_4, CH_3CN, CF_4, C_4H_2, and SO_3 feature substantial expansion of the spectral and dynamic ranges in addition of the improved accuracy of the parameters for already existing lines. A semi-empirical procedure was developed to update the air-broadening and self-broadening coefficients of N_2O, SO_2, NH_3, CH_3Cl, H_2S, and HO_2. We draw particular attention to flaws in the commonly used expression n_{air}=0.79n_{N_2}+0.21n_{O_2} to determine the air-broadening temperature dependence exponent in the power law from those for nitrogen and oxygen broadening. A more meaningful approach will be presented. The semi-empirical line width, pressure shifts and temperature-dependence exponents of CO, NH_3, HF, HCl, OCS, C_2H_2, SO_2 perturbed by H_2, He, and CO_2 have been added to the database based on the algorithm described in Wilzewski et al.. The new spectroscopic parameters for HT profile were implemented into the database for hydrogen molecule. The HITRAN database is supported by the NASA AURA program grant NNX14AI55G and NASA PDART grant NNX16AG51G. I. E. Gordon, L. S. Rothman, et al., J Quant Spectrosc Radiat Transf 2017; submitted. Hill C, et al., J Quant Spectrosc Radiat Transf 2013;130:51-61. Wilzewski JS,et al., J Quant Spectrosc Radiat Transf 2016;168:193-206. Wcislo P, et al., J Quant Spectrosc Radiat Transf 2016;177:75-91.
Transmission Spectra of Transiting Planet Atmospheres: Model Validation and Simulations of the Hot Neptune GJ 436b for the James Webb Space TelescopeNASA Astrophysics Data System (ADS) Shabram, Megan; Fortney, Jonathan J.; Greene, Thomas P.; Freedman, Richard S. updating We explore the transmission spectrum of the Neptune-class exoplanet GJ 436b, including the possibility that its atmospheric opacity is dominated by a variety of nonequilibrium chemical products. We also validate our transmission code by demonstrating close agreement with analytic models that use only Rayleigh scattering or water vapor opacity. We find broad disagreement with radius variations predicted by another published model. For GJ 436b, the relative coolness of the planet's atmosphere, along with its implied high metallicity, may make it dissimilar in character compared to "hot Jupiters." Some recent observational and modeling efforts suggest low relative abundances of H2O and CH4 present in GJ 436b's atmosphere, compared to calculations from equilibrium chemistry. We include these characteristics in our models and examine the effects of absorption from methane-derived higher-order hydrocarbons. To our knowledge, the effects of these nonequilibrium chemical products on the spectra of close-in giant planets have not previously been investigated. Significant absorption from HCN and C2H2 is found throughout the infrared, while C2H4 and C2H6 are less easily seen. We perform detailed simulations of James Webb Space Telescope observations, including all likely noise sources, and find that we will be able to constrain chemical abundance regimes from this planet's transmission spectrum. For instance, the width of the features at 1.5, 3.3, and 7 Î¼m indicates the amount of HCN versus C2H2 present. The NIRSpec prism mode will be useful due to its large spectral range and the relatively large number of photo-electrons recorded per spectral resolution element. However, extremely bright host stars like GJ 436 may be better observed with a higher spectroscopic resolution mode in order to avoid detector saturation. We find that observations with the MIRI low-resolution spectrograph should also have high signal-to-noise in the 5-10 Î¼m range due to the brightness of the star

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A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layerNASA Astrophysics Data System (ADS) Toyota, K.; Kanaya, Y.; Takahashi, M.; Akimoto, H. updating A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry) to investigate photochemical interactions between volatile organic compounds (VOCs) and reactive halogen species in the marine boundary layer (MBL). Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit description of oxidative degradation of up to C3-hydrocarbons (CH4, C2H6, C3H8, C2H4, C3H6, and C2H2) initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in forming halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO) and alkenes (especially C3H6) are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from a reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. The reaction between Br atoms and C2H2 is shown to be unimportant for determining the degree of bromine activation in the remote MBL. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl sulfide, NOx, and
A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layerNASA Astrophysics Data System (ADS) Toyota, K.; Kanaya, Y.; Takahashi, M.; Akimoto, H. updating A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry) to investigate photochemical interactions between volatile organic compounds (VOCs) and reactive halogen species in the marine boundary layer (MBL). Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit treatment of oxidative degradation of up to C3-hydrocarbons CH4, C2H6, C3H8, C2H4, C3H6, and C2H2) initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in the formation of halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO) and alkenes (especially C3H6) are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. On the other hand, the reaction between Br atoms and C2H2 is unimportant for determining the degree of bromine activation in the remote MBL. It is suggested that peroxyacetic acid formed via CH3CHO oxidation is one of the important chemical agents for triggering autocatalytic halogen release from sea-salt aerosols. These results imply that
Direct observation of surface ethyl to ethane interconversion upon C 2 H 4 hydrogenation over Pt/Al2O3 catalyst by time-resolved FT-IR spectroscopy.PubMed Wasylenko, Walter; Frei, Heinz updating Time-resolved FT-IR spectra of ethylene hydrogenation over alumina-supported Pt catalyst were recorded at 25 ms resolution in the temperature range of 323-473 K using various H2 concentrations (1 atm total gas pressure). Surface ethyl species (2870 and 1200 cm(-1)) were detected at all temperatures along with the gas-phase ethane product (2954 and 2893 cm(-1)). The CH3CH2Pt growth was instantaneous on the time scale of 25 ms under all experimental conditions. At 323 K, the decay time of surface ethyl (122 +/- 10 ms) coincides with the rise time of ethane (144 +/- 14 ms). This establishes direct kinetic evidence for surface ethyl as the relevant reaction intermediate. Such a direct link between the temporal behavior of an unstable surface intermediate and the final product in a heterogeneous catalytic system has not been demonstrated before. A fraction (25%) of the asymptotic ethane growth at 323 K is prompt, indicating that there are surface ethyl species that react much faster than the majority of the CH3CH2Pt intermediates. The dispersive kinetics is attributed to the varying strength of interaction of the ethyl species with the Pt surface caused by heterogeneity of the surface environment. At 473 K, the majority of ethyl intermediates are hydrogenated prior to the recording of the first time slice (24 ms), and a correspondingly large prompt growth of ethane is observed. The yield and kinetics of the surface ethylidyne are in agreement with the known spectator nature of this species.
High-dispersion infrared spectroscopic observations of comet 8P/Tuttle with VLT/CRIRESNASA Astrophysics Data System (ADS) Kobayashi, H.; BockelÃ©e-Morvan, D.; Kawakita, H.; Dello Russo, N.; Jehin, E.; Manfroid, J.; Smette, A.; HutsemÃ©kers, D.; StÃ¼we, J.; Weiler, M.; Arpigny, C.; Biver, N.; Cochran, A.; Crovisier, J.; Magain, P.; Sana, H.; Schulz, R.; Vervack, R. J.; Weaver, H.; Zucconi, J.-M. updating We report on the composition of the Halley-family comet (HFC) 8P/Tuttle investigated with high-dispersion near-infrared spectroscopic observations. The observations were carried out at the ESO VLT (Very Large Telescope) with the CRIRES instrument as part of a multi-wavelength observation campaign of 8P/Tuttle performed in late January and early February 2008. Radar observations suggested that 8P/Tuttle is a contact binary, and it was proposed that these components might be heterogeneous in chemistry. We determined mixing ratios of organic volatiles with respect to H2O and found that mixing ratios were consistent with previous near infrared spectroscopic observations obtained in late December 2007 and in late January 2008. It has been suggested that because 8P/Tuttle is a contact binary, it might be chemically heterogeneous. However, we find no evidence for chemical heterogeneity within the nucleus of 8P/Tuttle. We also compared the mixing ratios of organic molecules in 8P/Tuttle with those of both other HFCs and long period comets (LPCs) and found that HCN, C2H2, and C2H6 are depleted whereas CH4 and CH3OH have normal abundances. This may indicate that 8P/Tuttle was formed in a different region of the early solar nebula than other HFCs and LPCs. We estimated the conversion efficiency from C2H2 to C2H6 by hydrogen addition reactions on cold grains by employing the C2H6/(C2H6+C2H2) ratio. The C2H6/(C2H6+C2H2) ratio in 8P/Tuttle is consistent with the ratios found in other HFCs and LPCs within the error bars. We also discuss the source of C2 and CN based on our observations and conclude that the abundances of C2H2 and C2H6 are insufficient to explain the C2 abundances in comet 8P/Tuttle and that the abundance of HCN is insufficient to explain the CN abundances in the comet, so at least one additional parent is needed for each species, as pointed out in previous study. Based on observations collected at the European Southern Observatory, Paranal, Chile (ESO Prog. 080.C
An Ideal Molecular Sieve for Acetylene Removal from Ethylene with Record Selectivity and Productivity.PubMed Li, Bin; Cui, Xili; O'Nolan, Daniel; Wen, Hui-Min; Jiang, Mengdie; Krishna, Rajamani; Wu, Hui; Lin, Rui-Biao; Chen, Yu-Sheng; Yuan, Daqiang; Xing, Huabin; Zhou, Wei; Ren, Qilong; Qian, Guodong; Zaworotko, Michael J; Chen, Banglin updating Realization of ideal molecular sieves, in which the larger gas molecules are completely blocked without sacrificing high adsorption capacities of the preferred smaller gas molecules, can significantly reduce energy costs for gas separation and purification and thus facilitate a possible technological transformation from the traditional energy-intensive cryogenic distillation to the energy-efficient, adsorbent-based separation and purification in the future. Although extensive research endeavors are pursued to target ideal molecular sieves among diverse porous materials, over the past several decades, ideal molecular sieves for the separation and purification of light hydrocarbons are rarely realized. Herein, an ideal porous material, SIFSIX-14-Cu-i (also termed as UTSA-200), is reported with ultrafine tuning of pore size (3.4 Ã) to effectively block ethylene (C 2 H 4 ) molecules but to take up a record-high amount of acetylene (C 2 H 2 , 58 cm 3 cm -3 under 0.01 bar and 298 K). The material therefore sets up new benchmarks for both the adsorption capacity and selectivity, and thus provides a record purification capacity for the removal of trace C 2 H 2 from C 2 H 4 with 1.18 mmol g -1 C 2 H 2 uptake capacity from a 1/99 C 2 H 2 /C 2 H 4 mixture to produce 99.9999% pure C 2 H 4 (much higher than the acceptable purity of 99.996% for polymer-grade C 2 H 4 ), as demonstrated by experimental breakthrough curves. Â© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Klebsiella pneumoniae nitrogenase. Inhibition of hydrogen evolution by ethylene and the reduction of ethylene to ethane.PubMed Central Ashby, G A; Dilworth, M J; Thorneley, R N updating Ethylene (C2H4) inhibited H2 evolution by the Mo-containing nitrogenase of Klebsiella pneumoniae. The extent of inhibition depended on the electron flux determined by the ratio of Fe protein (Kp2) to MoFe protein (Kp1) with KiC2H4 = 409 kPa ([Kp2]/[Kp1] = 22:1) and KC2H4i = 88 kPa ([Kp1]/[Kp2] = 21:1) at 23 degrees C at pH 7.4. At [Kp2]/[Kp1] = 1:1, inhibition was minimal with C2H4 (101 kPa). Extrapolation of data obtained when C2H4 was varied from 60 to 290 kPa indicates that at infinite pressure of C2H4 total inhibition of H2 evolution should occur. C2H4 inhibited concomitant S2O4(2-) oxidation to the same extent that it inhibited H2 evolution. Although other inhibitors of total electron flux such as CN- and CH3NC uncouple MgATP hydrolysis from electron transfer, C2H4 did not affect the ATP/2e ratio. Inhibition of H2 evolution by C2H4 was not relieved by CO. C2H4 was reduced to C2H6 at [Kp2]/[Kp1] ratios greater than or equal to 5:1 in a reaction that accounted for no more than 1% of the total electron flux. These data are discussed in terms of the chemistry of alkyne and alkene reduction on transition-metal centres. PMID:3322266
Quantum Chemical Evaluation of the Astrochemical Significance of Reactions between S Atom and Acetylene or EthyleneNASA Technical Reports Server (NTRS) Woon, David E. updating Addition-elimination reactions of S atom in its P-3 ground state with acetylene (C2H2) and ethylene (C2H4) were characterized with both molecular orbital and density functional theory calculations employing correlation consistent basis sets in order to assess the likelihood either reaction might play a general role in astrochemistry or a specific role in the formation of S2 (X (sup 3 SIGMA (sub g) (sup -)) via a mechanism proposed by Saxena and Misra (Mon. Not. R. Astron. Soc. 1995, 272, 89). The acetylene and ethylene reactions proceed through C2H2S ((sup 3)A")) and C2H4S ((sup 3)A")) intermediates, respectively, to yield HCCS ((sup 2)II)) and C2H3S ((sup 2)A')). Substantial barriers were found in the exit channels for every combination of method and basis set considered in this work, which effectively precludes hydrogen elimination pathways for both S + C2H2 and S + C2H4 in the ultracold interstellar medium where only very modest barriers can be surmounted and processes without barriers tend to predominate. However, if one or both intermediates is formed and stabilized efficiently under cometary or dense interstellar cloud conditions, they could serve as temporary reservoirs for S atom and participate in reactions such as S + C2H2S (right arrow) S2 = C2H2 or S + C2H4S (right arrow) S2 + C2H4. For formation and stabilization to be efficient, the reaction must possess a barrier height small enough to be surmountable at low temperatures yet large enough to prevent redissociation to reactants. Barrier heights computed with B3LYP and large basis sets are very low, but more rigorous QCISD(T) and RCCSD(T) results indicate that the barrier heights are closer to 3-4 kcal/mol. The calculations therefore indicate that S + C2H2 or S + C2H4 could contribute to the formation of S2 in comets and may serve as a means to gauge coma temperature. The energetics of the ethylene reaction are more favorable.
Photochemistry of Saturn's Atmosphere. 1; Hydrocarbon Chemistry and Comparisons with ISO ObservationsNASA Technical Reports Server (NTRS) Moses, Julianne I.; Bezard, Bruno; Lellouch, Emmanuel; Gladstone, G. Randall; Feuchtgruber, Helmut; Allen, Mark updating To investigate the details of hydrocarbon photochemistry on Saturn, we have developed a one-dimensional diurnally averaged model that couples hydrocarbon and oxygen photochemistry, molecular and eddy diffusion, radiative transfer, and condensation. The model results are compared with observations from the Infrared Space Observatory (ISO) to place tighter constraints on molecular abundances, to better define Saturn's eddy diffusion coefficient profile, and to identify important chemical schemes that control the abundances of the observable hydrocarbons in Saturn's upper atmosphere. From the ISO observations, we determine that the column 12 densities of CH3, CH3C2H, and C4H2 above 10 mbar are 4 (sup +2) (sub -1.5) x 10 (exp 13) cm (sup -2), (1.1 plus or minus 0.3) x 10 (exp 15) cm (exp -2), and (1.2 plus or minus 0.3) x 10 (exp 14) cm (sup -2), respectively. The observed ISO emission features also indicate C2H2 mixing ratios of 1.2 (sup +0.9) (sub -0.6) x 10 (exp -6) at 0.3 mbar and (2.7 plus or minus 0.8) x 10 (exp -7) at 1.4 mbar, and a C2H6 mixing ratio of (9 plus or minus 2.5) x 10 (exp -6) at 0.5 mbar. Upper limits are provided for C2H4, CH2CCH2, C3H8, and C6H2 sensitivity of the model results to variations in the eddy diffusion coefficient profile, the solar flux, the CH4 photolysis branching ratios, the atomic hydrogen influx, and key reaction rates are discussed in detail. We find that C4H2 and CH3C2H are particularly good tracers of important chemical processes and physical conditions in Saturn's upper atmosphere, and C2H6 is a good tracer of the eddy diffusion coefficient in Saturn's lower stratosphere. The eddy diffusion coefficient must be smaller than approximately 3 x 10 (exp 4) sq cm s (sup -1) at pressures greater than 1 mbar in order to reproduce the C2H6 abundance inferred from ISO observations. The eddy diffusion coefficients in the upper stratosphere could be constrained by observations of CH3 radicals if the low-temperature chemistry of CH3 were
Dissociative photoionization of 1,3-butadiene: experimental and theoretical insights.PubMed Fang, Wenzheng; Gong, Lei; Zhang, Qiang; Shan, Xiaobin; Liu, Fuyi; Wang, Zhenya; Sheng, Liusi updating The vacuum-ultraviolet photoionization and dissociative photoionization of 1,3-butadiene in a region â¼8.5-17 eV have been investigated with time-of-flight photoionization mass spectrometry using tunable synchrotron radiation. The adiabatic ionization energy of 1,3-butadiene and appearance energies for its fragment ions, C(4)H(5)(+), C(4)H(4)(+), C(4)H(3)(+), C(3)H(3)(+), C(2)H(4)(+), C(2)H(3)(+), and C(2)H(2)(+), are determined to be 9.09, 11.72, 13.11, 15.20, 11.50, 12.44, 15.15, and 15.14 eV, respectively, by measurements of photoionization efficiency spectra. Ab initio molecular orbital calculations have been performed to investigate the reaction mechanism of dissociative photoionization of 1,3-butadiene. On the basis of experimental and theoretical results, seven dissociative photoionization channels are proposed: C(4)H(5)(+) + H, C(4)H(4)(+) + H(2), C(4)H(3)(+) + H(2) + H, C(3)H(3)(+) + CH(3), C(2)H(4)(+) + C(2)H(2), C(2)H(3)(+) + C(2)H(2) + H, and C(2)H(2)(+) + C(2)H(2) + H(2). Channel C(3)H(3)(+) + CH(3) is found to be the dominant one, followed by C(4)H(5)(+) + H and C(2)H(4)(+) + C(2)H(2). The majority of these channels occur via isomerization prior to dissociation. Transition structures and intermediates for those isomerization processes were also determined.
Effects of nonmethane hydrocarbons in the atmosphereNASA Technical Reports Server (NTRS) Chameides, W. L.; Cicerone, R. J. updating An investigation was conducted to determine whether nonmethane hydrocarbons (NMHC) are abundant enough to have a significant impact upon the ambient photochemistry. The vertical distribution of C2H6, C2H2, C3H8, C4H10, and C5H12 in the altitude range from 0 to 40 km was calculated in this connection. A one-dimensional steady state model with coupled photochemistry and vertical transport was employed in the investigation. The calculations imply that measurable quantities of relatively unreactive NMHC, especially C2H6 and C2H2, may be present in the upper troposphere and stratosphere. The results indicate, however, that NMHC are not likely to have a large impact on the background photochemistry of the troposphere, although local effects near source regions are probable. The findings support the current practice of many modelers who neglect NMHC in their calculations.
High-resolution 3-Î¼m spectra of Jupiter: Latitudinal spectral variations influenced by molecules, clouds, and hazeNASA Astrophysics Data System (ADS) Kim, Sang J.; Geballe, T. R.; Kim, J. H.; Jung, A.; Seo, H. J.; Minh, Y. C. updating We present latitudinally-resolved high-resolution ( R = 37,000) pole-to-pole spectra of Jupiter in various narrow longitudinal ranges, in spectral intervals covering roughly half of the spectral range updating Î¼m. We have analyzed the data with the aid of synthetic spectra generated from a model jovian atmosphere that included lines of CH 4, CH 3D, NH 3, C 2H 2, C 2H 6, PH 3, and HCN, as well as clouds and haze. Numerous spectral features of many of these molecular species are present and are individually identified for the first time, as are many lines of H3+ and a few unidentified spectral features. In both polar regions the updating-Î¼m continuum is more than 10 times weaker than in spectra at lower latitudes, implying that in this wavelength range the single-scattering albedos of polar haze particles are very low. In contrast, the updating Î¼m the weak polar and equatorial continua are of comparable intensity. We derive vertical distributions of NH 3, C 2H 2 and C 2H 6, and find that the mixing ratios of NH 3 and C 2H 6 show little variation between equatorial and polar regions. However, the mixing ratios of C 2H 2 in the northern and southern polar regions are Ë6 and Ë3 times, respectively, less than those in the equatorial regions. The derived mixing ratio curves of C 2H 2 and C 2H 6 extend up to the 10 -6 bar level, a significantly higher altitude than most previous results in the literature. Further ground-based observations covering other longitudes are needed to test if these mixing ratios are representative values for the equatorial and polar regions.
Fluid inclusion volatile analysis by gas chromatography with photoionization micro-thermal conductivity detectors: Applications to magmatic MoS 2 and other H 2O-CO 2 and H 2O-CH 4 fluidsNASA Astrophysics Data System (ADS) Bray, C. J.; Spooner, E. T. C. updating Eighteen fluid inclusion volatile peaks have been detected and identified from 1-2 g samples (quartz) by gas chromatography using heated (~105Â°C) on-line crushing, helium carrier gas, a single porous polymer column (HayeSep R; 10' Ã 1/8â³: 100/120#; Ni alloy tubing), two temperature programme conditions for separate sample aliquots, micro-thermal conductivity (TCD) and photoionization detectors (PID; 11.7 eV lamp), and off-line digital peak processing. In order of retention time these volatile peaks are: N 2, Ar, CO, CH 4, CO 2, C 2H 4, C 2H 6, C 2H 2, COS, C 3H 6, C 3H 8, C 3H 4 (propyne), H 2O (22.7 min at 80Â°C), SO 2, Â± iso- C4H10 Â± C4H8 (1-butene) Â± CH3SH, C 4H 8 (iso-butylene), (?) C 4H 6 (1,3 butadiene) and Â± n- C4H10 Â± C4H8 (trans-2-butene) (80 and -70Â°C temperature programme conditions combined). H 2O is analysed directly. O 2 can be analysed cryogenically between N 2 and Ar, but has not been detected in natural samples to date in this study. H 2S, SO 2, NH 3, HCl, HCN, and H 2 ca nnot be analysed at present. Blanks determined by crushing heat-treated Brazilian quartz (800-900Â°C/4 h) are zero for 80Â°C temperature programme conditions, except for a large, unidentified peak at ~64 min, but contain H 2O, CO 2, and some low molecular weight hydrocarbons at -70Â°C temperature conditions due to cryogenic accumulation from the carrier gas and subsequent elution. TCD detection limits are ~30 ppm molar in inclusions; PID detection limits are ~ 1 ppm molar in inclusions and lower for unsaturated hydrocarbons (e.g., ~0.2 ppm for C 2H 4; ~ 1 ppb for C 2H 2; ~0.3 ppb for C 3H 6). Precisions (1Ï) are ~ Â±1-2% and ~ Â± 13% for H 2O in terms of total moles detected; the latter value is equivalent to Â±0.6 mol% at the 95 mol% H 2O level. Major fluid inclusion volatile species have been successfully analysed on a ~50 mg fluid inclusion section chip (~7 mm Ã ~10 mm Ã ~100 Î¼m). Initial inclusion volatile analyses of fluids of interpreted magmatic origin from
Low temperature rate coefficients for the reactions of 1CH2 with reactive and non-reactive species, and the implications for Titan's atmosphereNASA Astrophysics Data System (ADS) Douglas, Kevin; Slater, Eloise; Blitz, Mark; Plane, John; Heard, Dwayne; Seakins, Paul updating The Cassini-Huygens mission to Titan revealed unexpectedly large amounts of benzene in the troposphere, and confirmed the absence of a global ethane ocean as predicted by photochemical models of methane conversion over the lifetime of the solar system. An important chemical intermediate in both the production and loss of benzene and ethane is the first electronically excited state of methylene, 1CH2. For example, at room temperature an important reaction of 1CH2 is with acetylene (R1a), leading to the formation of propargyl (C3H3)[1]. The subsequent recombination of propargyl radicals is the major suggested route to benzene in Titan's atmosphere (R2)[2]. In addition to reaction of 1CH2 leading to products, there is also competition between inelastic electronic relaxation to form the ground triplet state 3CH2 (R1b). This ground state 3CH2 has a markedly different reactivity to the singlet, reacting primarily with methyl radicals (CH3) to form ethene (R3). As methyl radical recombination is the primary route to ethane (R4)[3], reactions of 1CH2 will also heavily influence the ethane budget on Titan. 1CH2 + C2H2 â C3H3 + H (R1a) 1CH2 + C2H2 â 3CH2 + C2H2 (R1b) C3H3 + C3H3 â C6H6 (R2) 3CH2 + CH3 â C2H4 + H (R3) CH3 + CH3 (+ M) â C2H6 (R4) Thus this competition between chemical reaction and electronic relaxation in the reactions of 1CH2 with H2, CH4, C2H4, and C2H6 will play an important role in determining the benzene and ethane budgets on Titan. Despite this there are no measurements of any rate constants for 1CH2 at temperatures relevant to Titan's atmosphere (updating K). Using a pulsed Laval nozzle apparatus coupled with pulsed laser photolysis laser-induced fluorescence, the low temperature reaction kinetics for the removal of 1CH2 with nitrogen, hydrogen, methane, ethane, ethene, acetylene, and oxygen, have been studied. The results revealed an increase in the removal rate of 1CH2 at temperatures below 200 K, with a sharp increase of around a factor of
Detections and Sensitive Upper Limits for Methane and Related Trace Gases on Mars during updating, and planned extensions in 2016NASA Astrophysics Data System (ADS) Mumma, Michael J.; Villanueva, Geronimo L.; Novak, Robert E. updating Five groups report methane detections on Mars; all results suggest local release and high temporal variability [1-7]. Our team searched for CH4 on many dates and seasons and detected it on several dates [1, 9, 10]. TLS (Curiosity rover) reported methane upper limits [6], and then detections [7] that were consistent in size with earlier reports and that also showed rapid modulation of CH4 abundance.[8] argued that absorption features assigned to Mars 12CH4 by [1] might instead be weak lines of terrestrial 13CH4. If not properly removed, terrestrial 13CH4 signatures would appear on the blue wing of terrestrial 12CH4 even when Mars is red-shifted - but they do not (Fig. S6 of [1]), demonstrating that terrestrial signatures were correctly removed. [9] demonstrated that including the dependence of Î´13CH4 with altitude did not affect the residual features, nor did taking Î´13CH4 as zero. Were Î´13CH4 important, its omission would have overemphasized the depth of 13CH4 terrestrial absorption, introducing emission features in the residual spectra [1]. However, the residual features are seen in absorption, establishing their origin as non-terrestrial - [8] now agrees with this view.We later reported results for multiple organic gases (CH4, CH3OH, H2CO, C2H6, C2H2, C2H4), hydroperoxyl (HO2), three nitriles (N2O, NH3, HCN) and two chlorinated species (HCl, CH3Cl) [9]. Most of these species cannot be detected with current space assets, owing to instrumental limitations (e.g., spectral resolving power). However, the high resolution infrared spectrometers (NOMAD, ACS) on ExoMars 2016 (Trace Gas Orbiter) will begin measurements in late 2016. In solar occultation, TGO sensitivities will far exceed prior capabilities.We published detailed hemispheric maps of H2O and HDO on Mars, inferring the size of a lost early ocean [10]. In 2016, we plan to acquire 3-D spatial maps of HDO and H2O with ALMA, and improved maps of organics with iSHELL/NASA-IRTF.References: [1] Mumma et al. Sci09
Simultaneous determination of dissolved gases and moisture in mineral insulating oils by static headspace gas chromatography with helium photoionization pulsed discharge detection.PubMed Jalbert, J; Gilbert, R; TÃ©treault, P updating This paper presents the development of a static headspace capillary gas chromatographic method (HS-GC) for simultaneously determining dissolved gases (H2, O2, N2, CO, CO2, CH4, C2H6, C2H4, C2H2, C3H8) and moisture from a unique 15-mL mineral oil sample. A headspace sampler device is used to equilibrate the sample species in a two-phase system under controlled temperature and agitation conditions. A portion of the equilibrated species is then automatically split-injected into two chromatographic channels mounted on the same GC for their separation. The hydrocarbons and the lighter gases are separated on the first channel by a GS-Q column coupled with a MolSieve 5-A column via a bypass valve, while the moisture is separated on the second channel using a Stabilwax column. The analytes are detected by using two universal pulsed-discharge helium ionization detectors (PDHID). The performance of the method was established using equilibrated vials containing known amounts of gas mixture, water, and blank oil. The signal is linear over the concentration ranges normally found for samples collected from open-breathing power transformers. Determination sensitivity varies with the nature of the species considered with values as high as 21 500 A x 10(-9) s (microg/ g)(-1) for H2O, 46-216 A x 10(-9) s (microL/L)(-1) for the hydrocarbons and carbon oxides, and as low as 8-21 A x 10(-9) s (microL/L)(-1) for the O2 and N2 permanent gases. The detection limit of the method is between 0.08 and 6 microL/L for the dissolved gases, except for O2, N2, and CO2, where higher values are observed due to air intrusion during sampler operations, and 0.1 microg/g for the dissolved water. Ten consecutive measurements in the low and high levels of the calibration curves have shown a precision better than 12% and 6%, respectively, in all cases. A comparison study between the HS-GC method and the ASTM standard procedures on 31 field samples showed a very good agreement of the results. The advantages
How fast do hydrocarbons condense in Titan's atmosphere? Insights from the laboratoryNASA Astrophysics Data System (ADS) Biennier, L.; Bourgalais, J.; Capron, M.; Roussel, V.; Le Picard, S. D. updating Titan's dense atmosphere shows a complex photochemistry initiated by the dissociation of its two most abundant components, nitrogen N2 and methane CH4. This cold chemistry generates a plethora of hydrocarbons and nitriles and takes part in the production of a thick haze. According to a recent scenario constructed from Cassini-Huygens measurements, the chemical reactions and physical processes occurring at high altitudes near 1000 km could be the haze source [1]. This haze material could act as a nucleus for the condensation of organic vapors in Titan's stratosphere and troposphere. However, the pathways leading to the formation and growth of haze aerosols remain far to be well understood. Hydrocarbons, which are formed in Titan's cold atmosphere, starting with ethane C2H6, ethylene C2H4, acetylene C2H2, propane C3H8â¦ up to benzene C6H6, play also some active role in aerosol production, cloud processes, rain generation and Titan's lakes formation. Our goal is to study in the laboratory the kinetics of the first steps of condensation of these hydrocarbon molecules. Several studies have investigated the phase of e.g. ethane and propane and their spectral signatures. At the exception of our recent studies on the dimerization of pyrene C16H10 [2] and anthracene C14H10 [3] performed over the 50-300 K temperature range, there is however no other work on the first elementary steps of the kinetics of nucleation for hydrocarbons. Here we present the first experimental kinetics study of the dimerization of a small hydrocarbon: propane C3H8. We have performed experiments to identify the temperature range over which small propane clusters form in saturated uniform supersonic flows. Using our unique reactor based on a Laval nozzle [4], the kinetics of the formation has also been investigated over the 15-300 K temperature range. The chemical species present in the reactor are probed by a time of flight mass spectrometer equipped with an electron gun for soft ionization of the
Are Makemake and Eris Sputnik Planets?NASA Astrophysics Data System (ADS) Grundy, William M.; Umurhan, Orkan M. updating happens when plausible additional contaminants, such as CO, Ar, C2H2, C2H4, C2H6, etc. are added, but bounding cases for N2-dominated and CH4-dominated ice compositions can be calculated.
Primary Volatile Abundances in Comets from Infrared Spectroscopy: Implications for Reactions on Grain Surfaces in the Interstellar/Nebular EnvironmentNASA Technical Reports Server (NTRS) DiSanti, M. A.; Bonev, B. P.; Vilanueva, G. L.; Paganini, L.; Radeva, Y. L.; Mumma, M. J.; Gibb, E.; Magee-Sauer, K. updating Comets retain relatively primitive icy material remaining from the epoch of Solar System formation, however the extent to which they are modified from their initial state remains a key question in cometary science. High-resolution lR spectroscopy has emerged as a powerful tool for measuring vibrational emissions from primary volatiles (i.e., those contained in the nuclei of comets). With modern instrumentation, most notably NIRSPEC at the Keck II 10-m telescope, we can quantify species of astrobiological importance (e.g., H20, C2H2, CH4, C2H6, CO, H2CO, CH30H, HCN, NH3). In space environments, compounds of keen interest to astrobiology could originate from HCN and NH3 (leading to amino acids), H2CO (leading to sugars), or C2H6 and CH4 (suggested precursors of ethyl- and methylamine). Measuring the abundances of these precursor molecules (and their variability among comets) is a feasible task that contributes to understanding their delivery to Earth's early biosphere and to the synthesis of more complex pre biotic compounds. Over 20 comets have now been measured with IR spectroscopy, and this sample reveals significant diversity in primary volatile compositions. From this, a taxonomic classification scheme is emerging, presumably reflecting the diverse conditions experienced by pre-cometary grains in interstellar and subsequent nebular environs. The importance of H-atom addition to C2H2 on the surfaces of interstellar grains to produce C2H6 was validated by the discovery of abundant ethane in comet C/1996 B2 (Hyakutake) with C2H6/CH4 well above that achievable by gas-phase chemistry , and then in irradiation experiments on laboratory ices at 10 - 50 K. The large abundance ratios C2H6/CH4 observed universally in comets establish H-atom addition as an important and likely ubiquitous process, and comparing C2H6/C2H2 among comets can provide information on its efficiency. The IR is uniquely capable since symmetric hydrocarbons (e.g., C2H2, CH4, C2H6) have no electric
Experimental and theoretical simulations of Titan's VUV photochemistryNASA Astrophysics Data System (ADS) Peng, Z.; Carrasco, N.; Pernot, P. updating A new reactor, named APSIS (Atmospheric Photochemistry SImulated by Synchrotron), has been designed to simulate planetary atmospheric photochemistry [Peng et al. JGR-E. 2013, 118, 778]. We report here a study focusing on Titan's upper atmosphere. A nitrogen-methane gas flow was irradiated by a continuous 60-350 nm VUV beam provided by the DISCO line at SOLEIL synchrotron radiation facility. The production of C2-C4 hydrocarbons as well as several nitriles (HCN, CH3 CN and C2N2) was detected by in situ mass spectrometry, in agreement with Cassini's INMS observations at Titan, and ex situ GC-MS of a cryogenic experiment. We compared the mass spectra with those obtained by a plasma experiment [Carrasco et al. Icarus. 2012, 219, 230] and with another synchrotron-based experiment [Imanaka and Smith. PNAS. 2010, 107, 12423], and with the in situ measurements of the INMS instrument onboard Cassini probing the neutral content of Titan's upper atmosphere. In spite of lower photochemical production efficiency and different environmental conditions, the APSIS reactor seems to simulate Titan's neutral composition rather well. To interpret these experimental data, we developed a fully coupled ion-neutral photochemical model of the reactor, with uncertainty management, based on the neutral model of HÃ©brard et al. [J. Photochem. Photobiol. A. 2006, 7, 211], the model of ion chemistry of Plessis et al. [J. Chem. Phys. 2010, 133, 134110], and a new representation of photolysis cross-sections and branching ratios [Gans et al. Icarus. 2013, 223, 330]. Compared to the measurements, the production in Cn blocks is in good agreement. Ion chemistry and the full dissociative recombination scheme have been demonstrated to be important features of the model. The photolysis was confirmed to be globally influential by sensivity analysis. We observed the importance of the addition of small (C1 or C2) units in molecular growth, as well as 3 growth families, promoted by C2H2, C2H4 and C2H5/C2H6
Evaluation of advanced bladder technologyNASA Technical Reports Server (NTRS) Christensen, M. V.; Pasternak, R. A. updating Research conducted during this period is reported. Studies presented include: (1) diffusion and permeation of CO2, O2, N2, and NO2 through polytetra fluoroethylene; (2) diffusion, permeation and solubility of simple gases (CO2, O2, N2, CH4, C2H6, C3H8, and C2H4) through a copolymer of hexafluoro propylene and tetrafluoro ethylene (FEP); (3) viscous flow and diffusion of gases throug small apertures; (4) diffusion and permeation of O2, N2, CO2, CH4, C2H6, and C3H8 through nitroso rubber; and (5) results of gas transport studies with carborane siloxane, nitroso rubber, silicone membrane, krytox coating on teflon, and FEP coated glass cloth. Publications generated under this program are listed.

A theoretical study of the reaction of Ti+ with ethaneNASA Astrophysics Data System (ADS) Moc, Jerzy; Fedorov, Dmitri G.; Gordon, Mark S. updating The doublet and quartet potential energy surfaces for the Ti++C2H6âTiC2H4++H2 and Ti++C2H6âTiCH2++CH4 reactions are studied using density functional theory (DFT) with the B3LYP functional and ab initio coupled cluster CCSD(T) methods with high quality basis sets. Structures have been optimized at the DFT level and the minima connected to each transition state (TS) by following the intrinsic reaction coordinate (IRC). Relative energies are calculated both at the DFT and coupled-cluster levels of theory. The relevant parts of the potential energy surface, especially key transition states, are also studied using multireference wave functions with the final energetics obtained with multireference second-order perturbation theory.
The Composition of Comet C 2012 K1 (PanSTARRS) and the Distribution of Primary Volatile Abundances Among CometsNASA Technical Reports Server (NTRS) Roth, Nathan X.; Gibb, Erika; Bonev, Boncho P.; Disanti, Michael A.; Mumma, Michael J.; Villanueva, Geronimo L.; Paganini, Lucas updating On 2014 May 22 and 24 we characterized the volatile composition of the dynamically new Oort cloud comet C2012 K1 (PanSTARRS) using the long-slit, high resolution ( lambda/delta lambda is approximately or equal to 25,000) near-infrared echelle spectrograph (NIRSPEC) at the 10 m Keck II telescope on Maunakea, Hawaii. We detected fluorescent emission from six primary volatiles (H2O, HCN, CH4, C2H6, CH3OH, and CO). Upper limits were derived for C2H2, NH3, and H2CO. We report rotational temperatures, production rates, and mixing ratios (relative to water). Compared with median abundance ratios for primary volatiles in other sampled Oort cloud comets, trace gas abundance ratios in C2012 K1 (PanSTARRS) for CO and HCN are consistent, but CH3OH and C2H6 are enriched while H2CO, CH4, and possibly C2H2 are depleted. When placed in context with comets observed in the near- infrared to date, the data suggest a continuous distribution of abundances of some organic volatiles (HCN, C2H6, CH3OH, CH4) among the comet population. The level of enrichment or depletion in a given comet does not necessarily correlate across all molecules sampled, suggesting that chemical diversity among comets may be more complex than the simple organics-enriched, organics-normal, and organics-depleted framework.
Dissolved gases in the DOSECC Cajon Pass well: first year resultsUSGS Publications Warehouse Evans, William C.; White, L.D.; Kharaka, Y.K. updating Fluid sampled from granitic rock near the 2 km depth in the DOSECC Cajon Pass well contained He, H2, CH4, C2H6, and C2 H4 in concentrations much greater than in air-saturated water. Measured pCO2 values were very low, about 10-5 atm., and the carbon isotopes (??13C = -18.9 per mil) point to an organic source such as plant root respiration for the dissolved carbonate species. No evidence of mantle volatiles was found despite proximity of the well to the San Andreas fault. -from Authors
The Acetylene-Ethylene Assay for N2 Fixation: Laboratory and Field Evaluation 1PubMed Central Hardy, R. W. F.; Holsten, R. D.; Jackson, E. K.; Burns, R. C. updating The methodology, characteristics and application of the sensitive C2H2-C2H4 assay for N2 fixation by nitrogenase preparations and bacterial cultures in the laboratory and by legumes and free-living bacteria in situ is presented in this comprehensive report. This assay is based on the N2ase-catalyzed reduction of C2H2 to C2H4, gas chromatographic isolation of C2H2 and C2H4, and quantitative measurement with a H2-flame analyzer. As little as 1 Î¼Î¼mole C2H4 can be detected, providing a sensitivity 103-fold greater than is possible with 15N analysis. A simple, rapid and effective procedure utilizing syringe-type assay chambers is described for the analysis of C2H2-reducing activity in the field. Applications to field samples included an evaluation of N2 fixation by commercially grown soybeans based on over 2000 analyses made during the course of the growing season. Assay values reflected the degree of nodulation of soybean plants and indicated a calculated seasonal N2 fixation rate of 30 to 33 kg N2 fixed per acre, in good agreement with literature estimates based on Kjeldahl analyses. The assay was successfully applied to measurements of N2 fixation by other symbionts and by free living soil microorganisms, and was also used to assess the effects of light and temperature on the N2 fixing activity of soybeans. The validity of measuring N2 fixation in terms of C2H2 reduction was established through extensive comparisons of these activities using defined systems, including purified N2ase preparations and pure cultures of N2-fixing bacteria. With this assay it now becomes possible and practicable to conduct comprehensive surveys of N2 fixation, to make detailed comparisons among different N2-fixing symbionts, and to rapidly evaluate the effects of cultural practices and environmental factors on N2 fixation. The knowledge obtained through extensive application of this assay should provide the basis for efforts leading to the maximum agricultural exploitation of the N2
Infrared study of matrix-isolated ethyl cyanide: simulation of the photochemistry in the atmosphere of Titan.PubMed Toumi, A; PiÃ©tri, N; Couturier-Tamburelli, I updating Low-temperature Ar matrix isolation has been carried out to investigate the infrared spectrum of ethyl cyanide (CH3CH2CN), a molecule present in the atmosphere of Titan. The Î» > 120 nm and Î» > 230 nm photolysis reactions of ethyl cyanide in an Ar matrix were also performed in order to compare the behaviour of this compound when it is submitted to high and low energetic radiations. These different wavelengths have been used with the aim to reproduce the radiation reaching the various parts of the atmosphere. Several photoproducts have been identified during photolysis such as vinyl cyanide (CH2[double bond, length as m-dash]CHCN), cyanoacetylene (HC3N), and ethylene/hydrogen cyanide (C2H4/HCN), ethylene/hydrogen isocyanide (C2H4/HNC), acetylene/hydrogen cyanide (C2H2/HCN), acetylene/hydrogen isocyanide (C2H2/HNC), and acetylene:methylenimine (C2H2:HNCH2) complexes. Ethyl isocyanide (CH3CH2NC) and a ketenimine form (CH3CH[double bond, length as m-dash]C[double bond, length as m-dash]NH) have been identified as well. Photoproduct identification and spectral assignments were done using previous studies and density functional theory (DFT) calculations with the B3LYP/cc-pVTZ basis set.
Corrigendum to "Global frequency and intensity analysis of the Î½10 /Î½7 /Î½4 /Î½12 band system of 12C 2 H 4 at 10 Î¼m using the D2 h top data system" [J. Quant. Spectrosc. Radiat. Transf. updatingNASA Astrophysics Data System (ADS) Alkadrou, A.; Bourgeois, M.-T.; Rotger, M.; Boudon, V.; Vander Auwera, J. updating This corrigendum provides a new version of one of the 3 supplementary data files associated with the article A. Alkadrou et al., J. Quant. Spectrosc. Radiat. Transf. updating, namely the HITRAN-formatted linelist generated as described in section 5 of the article. Indeed, the Ka and Kc labels of the upper levels of a number of transitions belonging to the Î½10, Î½7 and Î½4 bands listed in this supplementary data file were found to be incorrect. The linelist provided with this corrigendum corrects these erroneous assignments, and provides Ka and Kc labels for all the upper levels.
Atlas of Absorption Lines from 0 to 17900 cm-1DTIC Science & Technology updating Hampton, Virginia H. M. Pickett Jet Propulsion Laboratory Pasadena, California D. J. Richardson and J. S. Namkung ST Systems Corporation (STX...2 NH3 HN03 OH HF HCi HBr HI CIO OCS H2CO H0C1 N2 HCN CH3C! H202 C2H2 C2H6 PH3 Oj(JPL) +- 0(3P)(JPL) H02(JPL) Solor CO...Hanscom AFB, Massachusetts. H. M. Pickett: Jet Propulsion Laboratory, Pasadena, California. D. J. Richardson and J. S. Namkung: ST Systems Corporation
Remote sensing of the troposphere by infrared emission spectroscopyNASA Technical Reports Server (NTRS) Beer, Reinhard; Glavich, Thomas A. updating This paper describes the concept of a cryogenic IR imaging Fourier transform spectrometer, called the Tropospheric Emission Spectrometer (TES), designed for observations of the troposphere and lower stratosphere from a near-earth orbit, using natural thermal emission and reflected sunlight. The principal molecular species to be measured by TES are O3, CO, CO2, N2O, H2O, H2O2, NO, NO2, HNO3, NH3, CH4, C2H6, C2H2, SO2, COS, CFCl3, and CF2Cl2. The TES is scheduled for a launch on the second polar platform of the Earth Observing System in 1998.
Abundances of Jupiter's Trace Hydrocarbons from Voyager and Cassini. Data Tables: Cassini CIRS Observations Planetary and Space Science, Forthcoming 2010NASA Technical Reports Server (NTRS) Nixon, C. A.; Achterberg, R. K.; Romani, P. N.; Allen, M.; Zhang, X.; Teanby, N. A.; Irwin, P. G. J.; Flasar, F. M. updating The following six tables give the retrieved temperatures and volume mixing ratios of C2H2 and C2H6 and the formal errors on these results from the retrieval, as described in the manuscript. These are in the form of two-dimensional tables, specified on a latitudinal and vertical grid. The first column is the pressure in bar, and the second column gives the altitude in kilometers calculated from hydrostatic equilibrium, and applies to the equatorial profile only. The top row of the table specifies the planetographic latitude.
Abundances of Jupiter's Trace Hydrocarbons from Voyager and Cassini. Data Tables: Voyager IRIS Observations Planetary and Space Science, Forthcoming 2010NASA Technical Reports Server (NTRS) Nixon, C. A.; Achterberg, R. K.; Romani, P. N.; Allen, M.; Zhang, X.; Irwin, P. G. J.; Flasar, F. M. updating The following six tables give the retrieved temperatures and volume mixing ratios of C2H2 and C2H6 and the formal errors on these results from the retrieval, as described in the manuscript. These are in the form of two-dimensional tables, specified on a latitudinal and vertical grid. The first column is the pressure in bar, and the second column gives the altitude in kilometers calculated from hydrostatic equilibrium, and applies to the equatorial profile only. The top row of the table specifies the planetographic latitude.
ANN-based calibration model of FTIR used in transformer online monitoringNASA Astrophysics Data System (ADS) Li, Honglei; Liu, Xian-yong; Zhou, Fangjie; Tan, Kexiong updating Recently, chromatography column and gas sensor have been used in online monitoring device of dissolved gases in transformer oil. But some disadvantages still exist in these devices: consumption of carrier gas, requirement of calibration, etc. Since FTIR has high accuracy, consume no carrier gas and require no calibration, the researcher studied the application of FTIR in such monitoring device. Experiments of "Flow gas method" were designed, and spectrum of mixture composed of different gases was collected with A BOMEM MB104 FTIR Spectrometer. A key question in the application of FTIR is that: the absorbance spectrum of 3 fault key gases, including C2H4, CH4 and C2H6, are overlapped seriously at 2700~3400cm-1. Because Absorbance Law is no longer appropriate, a nonlinear calibration model based on BP ANN was setup to in the quantitative analysis. The height absorbance of C2H4, CH4 and C2H6 were adopted as quantitative feature, and all the data were normalized before training the ANN. Computing results show that the calibration model can effectively eliminate the cross disturbance to measurement.
Pluto's Far Ultraviolet Spectrum and Airglow EmissionsNASA Astrophysics Data System (ADS) Steffl, A.; Schindhelm, E.; Kammer, J.; Gladstone, R.; Greathouse, T. K.; Parker, J. W.; Strobel, D. F.; Summers, M. E.; Versteeg, M. H.; Ennico Smith, K.; Hinson, D. P.; Linscott, I.; Olkin, C.; Parker, A. H.; Retherford, K. D.; Singer, K. N.; Tsang, C.; Tyler, G. L.; Weaver, H. A., Jr.; Woods, W. W.; Young, L. A.; Stern, A. updating The Alice far ultraviolet spectrograph on the New Horizons spacecraft is the second in a family of six instruments in flight on, or under development for, NASA and ESA missions. Here, we present initial results from the Alice observations of Pluto during the historic flyby. Pluto's far ultraviolet spectrum is dominated by sunlight reflected from the surface with absorption by atmospehric constituents. We tentatively identify C2H2 and C2H4 in Pluto's atmosphere. We also present evidence for weak airglow emissions.
Enhanced Oxidative Dehydrogenation of Ethane with Facilitated Transport Membranes for Low Cost Production of EthyleneSciTech Connect Nemser, Stuart; Shangguan, Ning; Pennisi, Kenneth This SBIR program has been extremely successful. We have met or exceeded all of the key objectives. We have successfully demonstrated the product and process feasibility. Compact Membrane Systems proposed a membrane separation technology which can efficiently separate ethylene from ethane in the presence of H 2O and CO 2. The CMS ethylene/ethane separation will significantly improve the economics of the Oxidative Dehydrogenation (ODH) process. We have developed membranes with high ethylene flux and high ethylene/ethane selectivity. These membranes have also shown good resistance to high concentration CO 2 and CO. Economic analysis shows at least **% cost savings comparedmoreÂ Â» with conventional distillation used for ethylene/ethane separation. Given our success to date, we have been able to establish key direct partnerships with other collaborators. The primary objective of the Phase I program was to develop a stable membrane that is capable of providing very efficient and cost effective production of ethylene from ethane. The CMS fluorinated membrane developed during this program was found to be able to provide very good C 2H 4/C 2H 6 selectivity and outstanding C 2H 4 permeance. With the development of the fast and highly selective ethylene CMS membrane, we have achieved all our Phase I program objectives. This is especially true of the estimated cost of ethylene production that is projected to be over **% less than the conventional method (distillation) at scale applications (** Nm3/h). The final result is better than the Phase I goal of 30% less. In summary, during the Phase I, we developed a CMS membrane with a high C 2H 4 permeance good C 2H 4/C 2H 6 selectivity. The stability and anti-fouling ability of the CMS membrane was demonstrated by exposing the membrane to a C 2H 4/C 2H 6 mixture gas for 7 weeks. A membrane based ODH production and separation system was designed and the economic and engineering evaluation using the VMGSim models predicted a cost of
Photoinduced ethane formation from reaction of ethene with matrix-isolated Ti, V, or Nb atoms.PubMed Thompson, Matthew G K; Parnis, J Mark updating The reactions of matrix-isolated Ti, V, or Nb atoms with ethene (C(2)H(4)) have been studied by FTIR absorption spectroscopy. Under conditions where the ethene dimer forms, metal atoms react with the ethene dimer to yield matrix-isolated ethane (C(2)H(6)) and methane. Under lower ethene concentration conditions ( approximately 1:70 ethene/Ar), hydridic intermediates of the types HMC(2)H(3) and H(2)MC(2)H(2) are also observed, and the relative yield of hydrocarbons is diminished. Reactions of these metals with perdeuterioethene, and equimolar mixtures of C(2)H(4) and C(2)D(4), yield products that are consistent with the production of ethane via a metal atom reaction involving at least two C(2)H(4) molecules. The absence of any other observed products suggests the mechanism also involves production of small, highly symmetric species such as molecular hydrogen and metal carbides. Evidence is presented suggesting that ethane production from the ethene dimer is a general photochemical process for the reaction of excited-state transition-metal atoms with ethene at high concentrations of ethene.
Polymeric membrane materials: new aspects of empirical approaches to prediction of gas permeability parameters in relation to permanent gases, linear lower hydrocarbons and some toxic gases.PubMed Malykh, O V; Golub, A Yu; Teplyakov, V V updating ), C(2)H(6), C(3)H(8), C(4)H(10), C(2)H(4), C(3)H(6), C(4)H(8) - 1, C(2)H(2), C(3)H(4)-m (methylacetylene) and C(3)H(4)-a (allen) is determined by using two above mentioned approaches. All of this allows calculating preliminary the permeability parameters of above mentioned gases for most part of known polymers based on limited experimental data. The new correlations suggested demonstrate that the available free volume of polymeric matrix plays an important role in providing of rate and selectivity of gas diffusion for glassy-like polymers; the rate and selectivity of gas diffusion in rubbers is affected mainly by cohesion energy density (CED) the both polymer parameters being calculated by traditional additive group contributions technique. Results of present study are demonstrated by calculation of expected permeability parameters in relation to lower hydrocarbons and some toxic gases for polynorbornene based polymers, PIM and PTMSP outlining potential of practical application for new membrane polymers. Copyright Â© 2010 Elsevier B.V. All rights reserved.
Photochemistry of Triton's atmosphere and ionosphere.PubMed Krasnopolsky, V A; Cruikshank, D P updating The photochemistry of 32 neutral and 21 ion species in Triton's atmosphere is considered. Parent species N2, CH4, and CO (with a mixing ratio of 3 x 10(-4) in our basic model) sublime from the ice with rates of 40, 208, and 0.3 g/cm2/b.y., respectively. Chemistry below 50 km is driven mostly by photolysis of methane by the solar and interstellar medium Lyman-alpha photons, producing hydrocarbons C2H4, C2H6, and C2H2 which form haze particles with precipitation rates of 135, 28, and 1.3 g/cm2/b.y., respectively. Some processes are discussed which increase the production of HCN (by an order of magnitude to a value of 29 g/cm2/b.y.) and involve indirect photolysis of N2 by neutrals. Reanalysis of the measured methane profiles gives an eddy diffusion coefficient K = 4 x 10(3) cm2/s above the tropopause and a more accurate methane number density near the surface, (3.1 +/- 0.8) x 10(11) cm-3. Chemistry above 200 km is driven by the solar EUV radiation (lambda
Photochemistry of Triton's Atmosphere and IonosphereNASA Technical Reports Server (NTRS) Krasnopolsky, Vladimir A.; Cruikshank, Dale P. updating The photochemistry of 32 neutral and 21 ion species in Triton's atmosphere is considered. Parent species N2, CH4, and CO (with a mixing ratio of 3 x 10(exp -4) in our basic model) sublime from the ice with rates of 40, 208, and 0.3 g/sq cm/b.y., respectively. Chemistry below 50 km is driven mostly by photolysis of methane by the solar and interstellar medium Lyman-alpha photons, producing hydrocarbons C2H4, C2H6, and C2H2 which form haze particles with precipitation rates of 135, 28, and 1.3 g/sq cm/b.y., respectively. Some processes are discussed which increase the production of HCN (by an order of magnitude to a value of 29 g/sq cm/b.y.) and involve indirect photolysis of N2 by neutrals. Reanalysis of the measured methane profiles gives an eddy diffusion coefficient K = 4 x 10(exp 3)sq cm/s above the tropopause and a more accurate methane number density near the surface, (3.1 +/- 0.8)x IO(exp 11)/cu cm. Chemistry above 200 km is driven by the solar EUV radiation (lambda less than 1000 A) and by precipitation of magnetospheric electrons with a total energy input of 10(exp 8) W (based on thermal balance calculations). The most abundant photochemical species are N, H2, H, 0, and C. They escape with the total rates of 7.7 x 10(exp 24)/ s, 4.5 x 10(exp 25)/s, 2.4 x 10(exp 25)/s, 4.4 x 10(exp 22)/s, and 1.1 x 10(exp 24), respectively. Atomic species are transported to a region of 50-200 km and drive the chemistry there. Ionospheric chemistry explains the formation of an E region at 150-240 km with HCO(+) as a major ion, and of an F region above 240 km with a peak at 320 km and C(+) as a major ion. The ionosphere above 500 km consists of almost equal densities of C(+) and N(+) ions. The model profiles agree with the measured atomic nitrogen and electron density profiles. A number of other models with varying rate coefficients of some reactions, differing properties of the haze particles (chemically passive or active), etc., were developed. These models show that there
Abundances of Jupiter's trace hydrocarbons from Voyager and CassiniNASA Astrophysics Data System (ADS) Nixon, C. A.; Achterberg, R. K.; Romani, P. N.; Allen, M.; Zhang, X.; Teanby, N. A.; Irwin, P. G. J.; Flasar, F. M. updating The flybys of Jupiter by the Voyager spacecraft in 1979, and over two decades later by Cassini in 2000, have provided us with unique datasets from two different epochs, allowing the investigation of seasonal change in the atmosphere. In this paper we model zonal averages of thermal infrared spectra from the two instruments, Voyager 1 IRIS and Cassini CIRS, to retrieve the vertical and meridional profiles of temperature, and the abundances of the two minor hydrocarbons, acetylene (C 2H 2) and ethane (C 2H 6). The spatial variation of these gases is controlled by both chemistry and dynamics, and therefore their observed distribution gives us an insight into both processes. We find that the two gases paint quite different pictures of seasonal change. Whilst the 2-D cross-section of C 2H 6 abundance is slightly increased and more symmetric in 2000 (northern summer solstice) compared to 1979 (northern fall equinox), the major trend of equator to pole increase remains. For C 2H 2 on the other hand, the Voyager epoch exhibits almost no latitudinal variation, whilst the Cassini era shows a marked decrease polewards in both hemispheres. At the present time, these experimental findings are in advance of interpretation, as there are no published models of 2-D Jovian seasonal chemical variation available for comparison.
Abundances of Jupiter's Trace Hydrocarbons from Voyager and CassiniNASA Technical Reports Server (NTRS) Nixon, C. A.; Achterberg, R. K.; Romani, P. N.; Allen, M.; Zhang, X.; Teanby, N. A.; Irwin, P. G. J.; Flasar, F. M. updating The flybys of Jupiter by the Voyager spacecraft in 1979, and over two decades later by Cassini in 2000, have provided us with unique datasets from two different epochs, allowing the investigation of seasonal change in the atmosphere. In this paper we model zonal averages of thermal infrared spectra from the two instruments, Voyager 1 IRIS and Cassini CIRS, to retrieve the vertical and meridional profiles of temperature, and the abundances of the two minor hydrocarbons, acetylene (C2H2) and ethane (C2H6). The spatial variation of these gases is controlled by both chemistry and dynamics, and therefore their observed distribution gives us an insight into both processes, We find that the two gases paint quite different pictures of seasonal change. Whilst the 2-D cross-section of C2H6 abundance is slightly increased and more symmetric in 2000 (northern summer solstice) compared to 1979 (northern fall equinox), the major trend of equator to pole increase remains. For C2H2 on tile other hand, the Voyager epoch exhibits almost no latitudinal variation, whilst the Cassini era shows a marked decrease polewards in both hemispheres. At the present time, these experimental findings are in advance of interpretation, as there are no published models of 2-D Jovian seasonal chemical variation available for comparison.
Non-LTE models of Titan's upper atmosphereNASA Technical Reports Server (NTRS) Yelle, Roger V. updating Models for the thermal structure of Titan's upper atmosphere, between 0.1 mbar and 0.01 nbar are presented. The calculations include non-LTE heating/cooling in the rotation-vibration bands of CH4, C2H2, and C2H6, absorption of solar IR radiation in the near-IR bands of CH4 and subsequent cascading to the nu-4 band of CH4, absorption of solar EUV and UV radiation, thermal conduction and cooling by HCN rotational lines. Unlike earlier models, the calculated exospheric temperature agrees well with observations, because of the importance of HCN cooling. The calculations predict a well-developed mesopause with a temperature of 135-140 K at an altitude of approximately 600 km and pressure of about 0.1 microbar. The mesopause is at a higher pressure than predicted by earlier calculations because non-LTE radiative transfer in the rotation-vibration bands of CH4, C2H2, and C2H6 is treated in an accurate manner. The accuracy of the LTE approximation for source functions and heating rates is discussed.

Plasma CVD of hydrogenated boron-carbon thin films from triethylboronNASA Astrophysics Data System (ADS) Imam, Mewlude; HÃ¶glund, Carina; Schmidt, Susann; Hall-Wilton, Richard; Birch, Jens; Pedersen, Henrik updating Low-temperature chemical vapor deposition (CVD) of BâC thin films is of importance for neutron voltaics and semiconductor technology. The highly reactive trialkylboranes, with alkyl groups of 1-4 carbon atoms, are a class of precursors that have been less explored for low-temperature CVD of BâC films. Herein, we demonstrate plasma CVD of BâC thin films using triethylboron (TEB) as a single source precursor in an Ar plasma. We show that the film density and B/C ratio increases with increasing plasma power, reaching a density of 2.20 g/cm3 and B/C = 1.7. This is attributed to a more intense energetic bombardment during deposition and more complete dissociation of the TEB molecule in the plasma at higher plasma power. The hydrogen content in the films ranges between 14 and 20 at. %. Optical emission spectroscopy of the plasma shows that BH, CH, C2, and H are the optically active plasma species from TEB. We suggest a plasma chemical model based on Î²-hydrogen elimination of C2H4 to form BH3, in which BH3 and C2H4 are then dehydrogenated to form BH and C2H2. Furthermore, C2H2 decomposes in the plasma to produce C2 and CH, which together with BH and possibly BH3-x(C2H5)x are the film forming species.
Increase in Dry Weight and Total Nitrogen Content in Zea mays and Setaria italica Associated with Nitrogen-fixing Azospirillum spp. 1PubMed Central Cohen, Efraim; Okon, Yaacov; Kigel, Jaime; Nur, Israel; Henis, Yigal updating The association between nitrogen-fixing bacteria from the genus Azospirillum and the grasses Zea mays and Setaria italica was investigated in sterilized Leonard-jar assemblies. Nitrogen-fixing bacteria isolated from Cynodon dactylon roots in Israel and Azospirillum brasilense (Sp-7, Sp-80, and Cd) were examined. C2H2 reduction activity was detected in systems containing 0.0 to 0.08 but not in those containing 0.16 gram per liter NH4NO3. The organisms tested significantly increased plant dry weight (50-100%), total N content of leaves (50-100%) and C2H4 production (updating nanomoles C2H4 per plant per hour). Highest C2H2 reduction activities were obtained above 30 C and with high light intensities. Significant increases in S. italica dry weight (DW) and nitrogen (N) content were observed in sand (DW = 80%, N = 150%), sandy loam soil (DW = 80%, N = 75%) and loess (DW = 37%, N = 25%). The results obtained in this work clearly demonstrate the potential benefit of inoculating grasses with Azospirillum. PMID:updating
Al or Si decorated graphene-oxide: A promising material for capture and activation of ethylene and acetyleneNASA Astrophysics Data System (ADS) Esrafili, Mehdi D.; Dinparast, Leila updating In this work, quantum chemical calculations are performed to compare adsorption behavior of ethylene and acetylene molecules over Al- or Si-decorated graphene oxide (Al/Si-GO). The corresponding adsorption energies, geometrical parameters and net charge-transfer values are calculated using the dispersion-corrected DFT calculations. The obtained large adsorption energies of the Al and Si atoms over GO suggest that both Al-GO and Si-GO are stable enough to be used as a stable substrate to capture and activate ethylene or acetylene. The results show that the adsorption of C2H4 or C2H2 on Al-GO is more favorable than over Si-GO surface, mainly due to the orbital interactions between the adsorbate and surface. Also, the DFT calculations reveal that the interaction of C2H2 with both surfaces is stronger than that of C2H4. Our findings are applicable for future theoretical and experimental studies about the interaction of hydrocarbons with light metal decorated graphene-based materials as well as heterogeneous catalysis.
Mechanism of cyanoacetylene photochemistry at 185 and 254 nmNASA Technical Reports Server (NTRS) Clarke, D. W.; Ferris, J. P. updating The role of cyanoacetylene (HC3N) in the atmospheric photochemistry of Titan and its relevance to polymer formation are discussed. Investigation of the relative light absorption of HC3N, acetylene (C2H2), and diacetylene (C4H2) revealed that HC3N is an important absorber of UV light in the 205- to 225-nanometer wavelength region in Titan's polar regions. Laboratory studies established that photolysis of C2H2 initiates the polymerization of HC3N even though the HC3N is not absorbing the UV light. Quantum yield measurements establish that HC3N is 2-5 times as reactive as C2H2 for polymer formation. Photolysis of HC3N with 185-nanometer light in the presence of N2, H2, Ar, or CF4 results in a decrease in the yield of 1,3,5-tricyanobenzene (1,3,5-tcb), while photolysis in the presence of CH4, C2H6, or n-C4H10 results in an increase in 1,3,5-tcb. The rate of loss of HC3N is increased by all gases except H2, where it is unchanged. It was not possible to detect 1,3,5-tcb as a photoproduct when the partial pressure of HC3N was decreased to 1 torr. Photolysis of HC3N with 254-nanometer light in the presence of H2 or N2 results in the formation of 1,2,4-tcb, while photolysis in the presence of CH4, C2H6, or n-C4H10 results in the formation of increasing amounts of 1,3,5-tcb. Mechanisms for the formation of polymers are presented.
Size and Site Dependence of the Catalytic Activity of Iridium Clusters toward Ethane Dehydrogenation.PubMed Ge, Yingbin; Jiang, Hao; Kato, Russell; Gummagatta, Prasuna updating This research focuses on optimizing transition metal nanocatalyst immobilization and activity to enhance ethane dehydrogenation. Ethane dehydrogenation, catalyzed by thermally stable Ir n (n = 8, 12, 18) atomic clusters that exhibit a cuboid structure, was studied using the B3LYP method with triple-Î¶ basis sets. Relativistic effects and dispersion corrections were included in the calculations. In the dehydrogenation reaction Ir n + C 2 H 6 â H-Ir n -C 2 H 5 â (H) 2 -Ir n -C 2 H 4 , the first H-elimination is the rate-limiting step, primarily because the reaction releases sufficient heat to facilitate the second H-elimination. The catalytic activity of the Ir clusters strongly depends on the Ir cluster size and the specific catalytic site. Cubic Ir 8 is the least reactive toward H-elimination in ethane: Ir 8 + C 2 H 6 â H-Ir 8 -C 2 H 5 has a large (65 kJ/mol) energy barrier, whereas Ir 12 (3 Ã 2 Ã 2 cuboid) and Ir 18 (3 Ã 3 Ã 2 cuboid) lower this energy barrier to 22 and 3 kJ/mol, respectively. The site dependence is as prominent as the size effect. For example, the energy barrier for the Ir 18 + C 2 H 6 â H-Ir 18 -C 2 H 5 reaction is 3, 48, and 71 kJ/mol at the corner, edge, or face-center sites of the Ir 18 cuboid, respectively. Energy release due to Ir cluster insertion into an ethane C-H bond facilitates hydrogen migration on the Ir cluster surface, and the second H-elimination of ethane. In an oxygen-rich environment, oxygen molecules may be absorbed on the Ir cluster surface. The oxygen atoms bonded to the Ir cluster surface may slightly increase the energy barrier for H-elimination in ethane. However, the adsorption of oxygen and its reaction with H atoms on the Ir cluster releases sufficient heat to yield an overall thermodynamically favored reaction: Ir n + C 2 H 6 + 1 / 2 O 2 â Ir n + C 2 H 4 + H 2 O. These results will be useful toward reducing the energy cost of ethane dehydrogenation in industry.
On the chemistry of Jupiter's upper atmosphereUSGS Publications Warehouse Saslaw, W.C.; Wildey, R.L. updating We conduct a first investigation into the ion-molecule chemistry of the upper Jovian atmosphere. Experimental results show that intense ultraviolet radiation reacts with the constituents of the Jovian atmosphere to produce C2H4, C2H6, C3H8, and higher polymers. The general procedure for calculating both equilibrium and nonequilibrium abundances of these products is formulated and applied to the case of the surface passage of a satellite shadow. A specific example is made of ethylene, for which an analytical approximation gives 1010 molecules in an atmospheric column of 1 cm2 cross section after a very rapid rise to equilibrium. Such a concentration of ethylene does not substantially affect the infrared radiation in the shadow. ?? 1967.
Reforming of glucose and wood at the critical conditions of waterNASA Technical Reports Server (NTRS) Modell, M. updating Reforming of organics in aqueous solutions is being investigated as a potential waste treatment process. Earlier studies showed that glucose in water reacts to form a gaseous mixture of CO, H2, CH4, CO2, C2H6, and C2H4 in the vicinity of the critical conditions of water (374 C, 22 MPa). The earlier work has been extended to determine the effect of variations in temperature and feed concentration on the extent of gasification. The percent gasification decreases with increasing feed concentration, indicating an overall kinetic order less than unity. Surprisingly, the percent gasification decreases with increasing temperature. A number of preliminary experiments were conducted with maple sawdust feed, which was thought to be representative of complex organic wastes from paper and vegetable matter. Once again, no solid products were found under the critical conditions; the percent gasification ranged from 16 to 88 percent, depending on the feed composition and residence time.
Numerical investigation of combustion phenomena in pulse detonation engine with different fuelsNASA Astrophysics Data System (ADS) Alam, Noor; Sharma, K. K.; Pandey, K. M. updating The effects of different fuel-air mixture on the cyclic operation of pulse detonation engine (PDE) are numerically investigated. The present simulation is to be consider 1200 mm long straight tube combustor channel and 60 mm internal diameter, and filled with stoichiometric ethane-air and ethylene-air (C2H6-air & C2H4) fuel mixture at atmospheric pressure and temperature of 0.1 MPa and 300 K respectively. The obstacles of blockage ratio (BR) 0.5 and having 60 mm spacing among them are allocated inside the combustor tube. There are realizable k-É turbulence model used to analyze characteristic of combustion flame. The objective of present simulation is to analyze the variation in combustion mechanism for two different fuels with one-step reduced chemical reaction model. The obstacles were creating perturbation inside the PDE tube. Therefore, flame surface area increases and reduces deflagration-to-detonation transition (DDT) run-up length.
The in vivo hydrocarbon formation by vanadium nitrogenase follows a secondary metabolic pathwayDOE PAGES Rebelein, Johannes G.; Lee, Chi Chung; Hu, Yilin; ... updating The vanadium (V)-nitrogenase of Azotobacter vinelandii catalyses the in vitro conversion of carbon monoxide (CO) to hydrocarbons. Here we show that an A. vinelandii strain expressing the V-nitrogenase is capable of in vivo reduction of CO to ethylene (C 2H 4), ethane (C 2H 6) and propane (C 3H 8). Moreover, we demonstrate that CO is not used as a carbon source for cell growth, being instead reduced to hydrocarbons in a secondary metabolic pathway. These findings suggest a possible role of the ancient nitrogenase as an evolutionary link between the carbon and nitrogen cycles on Earth and establish amoreÂ Â» solid foundation for biotechnological adaptation of a whole-cell approach to recycling carbon wastes into hydrocarbon products. Furthermore, this study has several repercussions for evolution-, environment- and energy-related areas.Â«Â less
Partially Interpenetrated NbO Topology MetalâOrganic Framework Exhibiting Selective Gas AdsorptionSciTech Connect Verma, Gaurav; Kumar, Sanjay; Pham, Tony updating We report on the first partially interpenetrated metalâorganic framework (MOF) with NbO topology for its ability to separate methane from carbon dioxide and permanently sequester the greenhouse gas CO2. The MOF, Cu2(pbpta) (H4pbpta = 4,4',4'',4'''-(1,4-phenylenbis(pyridine-4,2-6-triyl))-tetrabenzoic acid), crystallizes in the monoclinic C2/m space group and has a 2537 m2/g Brunauer, Emmett and Teller surface area with an 1.06 cm3/g pore volume. The MOF exhibits selective adsorption of CO2 over CH4 as well as that of C2H6 and C2H4 over CH4. Cu2(pbpta) additionally shows excellent catalytic efficacy for the cycloaddition reaction of CO2 with epoxides to produce industrially important cyclic carbonates usingmoreÂ Â» solvent-free conditions.Â«Â less
Identifying fire plumes in the Arctic with tropospheric FTIR measurements and transport modelsNASA Astrophysics Data System (ADS) Viatte, C.; Strong, K.; Hannigan, J.; Nussbaumer, E.; Emmons, L.; Conway, S.; Paton-Walsh, C.; Hartley, J.; Benmergui, J.; Lin, J. updating We investigate Arctic tropospheric composition using ground-based Fourier Transform Infrared (FTIR) solar absorption spectra, recorded at the Polar Environment Atmospheric Research Laboratory (PEARL, Eureka, Nunavut, Canada, 80Â°5' N, 86Â°42' W) and at Thule (Greenland, 76Â°53' N, -68Â°74' W) from 2008 to 2012. The target species: carbon monoxide (CO), hydrogen cyanide (HCN), ethane (C2H6), acetylene (C2H2), formic acid (HCOOH), and formaldehyde (H2CO) are emitted by biomass burning and can be transported from mid-latitudes to the Arctic. By detecting simultaneous enhancements of three biomass burning tracers (HCN, CO, and C2H6), ten and eight fire events are identified at Eureka and Thule, respectively, within the five-year FTIR timeseries. Analyses of Hybrid Single Particle Lagrangian Integrated Trajectory Model (HYSPLIT) back-trajectories coupled with Moderate Resolution Imaging Spectroradiometer (MODIS) fire hot spot data, Stochastic Time-Inverted Lagrangian Transport model (STILT) footprints, and Ozone Monitoring Instrument (OMI) UV aerosol index maps are used to attribute burning source regions and travel time durations of the plumes. By taking into account the effect of aging of the smoke plumes, measured FTIR enhancement ratios were corrected to obtain emission ratios and equivalent emission factors. The means of emission factors for extratropical forest estimated with the two FTIR datasets are 0.39 Â± 0.15 g kg-1 for HCN, 1.23 Â± 0.49 g kg-1 for C2H6, 0.34 Â± 0.16 g kg-1 for C2H2, 2.13 Â± 0.92 g kg-1 for HCOOH, and 3.14 Â± 1.28 g kg-1 for CH3OH. To improve our knowledge concerning the dynamical and chemical processes associated with Arctic pollution from fires, the two sets of FTIR measurements were compared to the Model for Ozone and Related chemical Tracers, version 4 (MOZART-4). Seasonal cycles and day-to-day variabilities were compared to assess the ability of the model to reproduce emissions from fires and their transport. Good agreement in winter
Identifying fire plumes in the Arctic with tropospheric FTIR measurements and transport modelsNASA Astrophysics Data System (ADS) Viatte, C.; Strong, K.; Hannigan, J.; Nussbaumer, E.; Emmons, L. K.; Conway, S.; Paton-Walsh, C.; Hartley, J.; Benmergui, J.; Lin, J. updating We investigate Arctic tropospheric composition using ground-based Fourier transform infrared (FTIR) solar absorption spectra, recorded at the Polar Environment Atmospheric Research Laboratory (PEARL, Eureka, Nunavut, Canada, 80Â°05' N, 86Â°42' W) and at Thule (Greenland, 76Â°53' N, -68Â°74' W) from 2008 to 2012. The target species, carbon monoxide (CO), hydrogen cyanide (HCN), ethane (C2H6), acetylene (C2H2), formic acid (HCOOH), and formaldehyde (H2CO) are emitted by biomass burning and can be transported from mid-latitudes to the Arctic. By detecting simultaneous enhancements of three biomass burning tracers (HCN, CO, and C2H6), ten and eight fire events are identified at Eureka and Thule, respectively, within the 5-year FTIR time series. Analyses of Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model back-trajectories coupled with Moderate Resolution Imaging Spectroradiometer (MODIS) fire hotspot data, Stochastic Time-Inverted Lagrangian Transport (STILT) model footprints, and Ozone Monitoring Instrument (OMI) UV aerosol index maps, are used to attribute burning source regions and travel time durations of the plumes. By taking into account the effect of aging of the smoke plumes, measured FTIR enhancement ratios were corrected to obtain emission ratios and equivalent emission factors. The means of emission factors for extratropical forest estimated with the two FTIR data sets are 0.40 Â± 0.21 g kg-1 for HCN, 1.24 Â± 0.71 g kg-1 for C2H6, 0.34 Â± 0.21 g kg-1 for C2H2, and 2.92 Â± 1.30 g kg-1 for HCOOH. The emission factor for CH3OH estimated at Eureka is 3.44 Â± 1.68 g kg-1. To improve our knowledge concerning the dynamical and chemical processes associated with Arctic pollution from fires, the two sets of FTIR measurements were compared to the Model for OZone And Related chemical Tracers, version 4 (MOZART-4). Seasonal cycles and day-to-day variabilities were compared to assess the ability of the model to reproduce emissions from fires and
Chemical Characteristics of Continental Outflow from Asia to the Troposphere over the Western Pacific Ocean during September - October 1991: Results from PEM-West ANASA Technical Reports Server (NTRS) Talbot, R. W.; Dibb, J. E.; Klemm, K. I.; Bradshaw, J. D.; Sandholm, S. T.; Blake, D. R.; Sachse, G. W.; Collins, J.; Heikes, B. G.; Gregory, G. L.; updating An important objective of the Pacific Exploratory Mission-West A (PEM-West A) was the chemical characterization of the outflow of tropospheric trace gases and aerosol particles from the Asian continent over the western Pacific Ocean. This paper summarizes the chemistry of this outflow during the period September - October 1991. The vertical distributions of CO, C2H6, and NO(x), showed regions of outflow at altitudes below 2 km and from 8 to 12 km. Mixing ratios of CO were approx. equals 130 parts per billion by volume (ppbv), approx. equals 1OOO parts per trillion by volume (pptv) for C2H6, and approx. equals 100 pptv for NO(x) in both of these regions. Direct outflow of Asian industrial materials was clearly evident at altitudes below 2 km, where halocarbon tracer compounds such as CH3CCl3 and C2Cl4 were enhanced about threefold compared to aged Pacific air. The source attribution of species outflowing from Asia to the Pacific at 8-12 km altitude was not straightforward. Above 10 km altitude there were substantial enhancements of NO(y), O3, CO, CH4, SO2, C2H6, C3H8, C2H2, and aerosol Pb-210 but not halocarbon industrial tracers. These air masses were rich in nitrogen relative to sulfur and contained ratios of C2H2/CO and C3H8/C2H6 (approx. equals l.5 and 0.1 respectively) indicative of several- day-old combustion emissions. It is unclear if these emissions were of Asian origin, or if they were rapidly transported to this region from Europe by the high wind speeds in this tropospheric region (60 - 70 m/s). The significant cyclonic activity over Asia at this time could have transported to the upper troposphere emissions from biomass burning in Southeast Asia or emissions from the extensive use of various biomass materials for cooking and space heating. Apparently, the emissions in the upper troposphere were brought there by wet convective systems since water-soluble gases and aerosols were depleted in these air masses. Near 9 km altitude there was a distinct [external_link offset=2]
Nanoporous Boron Nitride as Exceptionally Thermally Stable Adsorbent: Role in Efficient Separation of Light Hydrocarbons.PubMed Saha, Dipendu; Orkoulas, Gerassimos; Yohannan, Samuel; Ho, Hoi Chun; Cakmak, Ercan; Chen, Jihua; Ozcan, Soydan updating In this work, nanoporous boron nitride sample was synthesized with a Brunauer-Emmett-Teller (BET) surface area of 1360 m 2 /g and particle size 5-7 Î¼m. The boron nitride was characterized with X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electron microscopy (TEM and SEM). Thermogravimetric analysis (TGA) under nitrogen and air and subsequent analysis with XPS and XRD suggested that its structure is stable in air up to 800 Â°C and in nitrogen up to 1050 Â°C, which is higher than most of the common adsorbents reported so far. Nitrogen and hydrocarbon adsorption at 298 K and pressure up to 1 bar suggested that all hydrocarbon adsorption amounts were higher than that of nitrogen and the adsorbed amount of hydrocarbon increases with an increase in its molecular weight. The kinetics of adsorption data suggested that adsorption becomes slower with the increase in molecular weight of hydrocarbons. The equilibrium data suggested that that boron nitride is selective to paraffins in a paraffin-olefin mixture and hence may act as an "olefin generator". The ideal adsorbed solution theory (IAST)-based selectivity for CH 4 /N 2 , C 2 H 6 /CH 4 , and C 3 H 8 /C 3 H 6 was very high and probably higher than the majority of adsorbents reported in the literature. IAST-based calculations were also employed to simulate the binary mixture adsorption data for the gas pairs of CH 4 /N 2 , C 2 H 6 /CH 4 , C 2 H 6 /C 2 H 4 , and C 3 H 8 /C 3 H 6 . Finally, a simple mathematical model was employed to simulate the breakthrough behavior of the above-mentioned four gas pairs in a dynamic column experiment. The overall results suggest that nanoporous boron nitride can be used as a potential adsorbent for light hydrocarbon separation.
Molecular frame photoelectron angular distributions for core ionization of ethane, carbon tetrafluoride and 1,1-difluoroethyleneDOE PAGES Menssen, A.; Trevisan, C. S.; SchÃ¶ffler, M. S.; ... updating Molecular frame photoelectron angular distributions (MFPADs) are measured in this paper in electronâion momentum imaging experiments and compared with complex Kohn variational calculations for carbon K-shell ionization of carbon tetrafluoride (CF 4), ethane (C 2H 6) and 1,1-difluoroethylene (C 2H 2F 2). While in ethane the polarization averaged MFPADs show a tendency at low energies for the photoelectron to be emitted in the directions of the bonds, the opposite effect is seen in CF 4. A combination of these behaviors is seen in difluoroethylene where ionization from the two carbons can be distinguished experimentally because of their different K-shell ionizationmoreÂ Â» potentials. Excellent agreement is found between experiment and simple static-exchange or coupled two-channel theoretical calculations. Finally, however, simple electrostatics do not provide an adequate explanation of the suggestively simple angular distributions at low electron ejection energies.Â«Â less
Molecular Detectability in Exoplanetary Emission SpectraNASA Astrophysics Data System (ADS) Tessenyi, M.; Tinetti, G.; Savini, G.; Pascale, E. updating Of the many recently discovered worlds orbiting distant stars, very little is yet known of their chemical composition. With the arrival of new transit spectroscopy and direct imaging facilities, the question of molecular detectability as a function of signal-to-noise (SNR), spectral resolving power and type of planets has become critical. We study the detectability of key molecules in the atmospheres of a range of planet types, and report on the minimum detectable abundances at fixed spectral resolving power and SNR. The planet types considered â hot Jupiters, hot super-Earths, warm Neptunes, temperate Jupiters and temperate super-Earths â cover most of the exoplanets characterisable today or in the near future. We focus on key atmospheric molecules, such as CH4, CO, CO2, NH3, H2O, C2H2, C2H6, HCN, H2S and PH.
Ethane ocean on TitanNASA Technical Reports Server (NTRS) Lunine, J. I.; Stevenson, D. J.; Yung, Y.L. updating Voyager I radio occultation data is employed to develop a qualitative model of an ethane ocean on Titan. It is suggested that the ocean contains 25 percent CH4 and that the ocean is in dynamic equilibrium with an N2 atmosphere. Previous models of a CH4 ocean are discounted due to photolysis rates of CH4 gas. Tidal damping of Titan's orbital eccentricity is taken as evidence for an ocean layer approximately 1 km deep, with the ocean floor being covered with a solid C2H2 layer 100 to 200 m thick. The photolytic process disrupting the CH4, if the estimates of the oceanic content of CH4 are correct, could continue for at least one billion years. Verification of the model is dependent on detecting CH4 clouds in the lower atmosphere, finding C2H6 saturation in the lower troposphere, or obtaining evidence of a global ocean.
Preliminary JIRAM results from Juno polar observations: 3. Evidence of diffuse methane presence in the Jupiter auroral regionsNASA Astrophysics Data System (ADS) Moriconi, M. L.; Adriani, A.; Dinelli, B. M.; Fabiano, F.; Altieri, F.; Tosi, F.; Filacchione, G.; Migliorini, A.; GÃ©rard, J. C.; Mura, A.; Grassi, D.; Sindoni, G.; Piccioni, G.; Noschese, R.; Cicchetti, A.; Bolton, S. J.; Connerney, J. E. P.; Atreya, S. K.; Bagenal, F.; Gladstone, G. R.; Hansen, C.; Kurth, W. S.; Levin, S. M.; Mauk, B. H.; McComas, D. J.; Turrini, D.; Stefani, S.; Olivieri, A.; Amoroso, M. updating Throughout the first orbit of the NASA Juno mission around Jupiter, the Jupiter InfraRed Auroral Mapper (JIRAM) targeted the northern and southern polar regions several times. The analyses of the acquired images and spectra confirmed a significant presence of methane (CH4) near both poles through its 3.3 Î¼m emission overlapping the H3+ auroral feature at 3.31 Î¼m. Neither acetylene (C2H2) nor ethane (C2H6) have been observed so far. The analysis method, developed for the retrieval of H3+ temperature and abundances and applied to the JIRAM-measured spectra, has enabled an estimate of the effective temperature for methane peak emission and the distribution of its spectral contribution in the polar regions. The enhanced methane inside the auroral oval regions in the two hemispheres at different longitude suggests an excitation mechanism driven by energized particle precipitation from the magnetosphere.
Parent volatiles in comet 9P/Tempel 1: before and after impactNASA Technical Reports Server (NTRS) Mumma, Michael J.; DiSanti, Michael A.; Magee-Sauer, Karen; Bonev, Boncho P.; Villanueva, Geronimo L.; Kawakita, Hideyo; Dello Russo, Neil; Gibb, Erika L.; Blake, Geoffrey A.; Lyke, James E.; updating We quantified eight parent volatiles (H2O, C2H6, HCN, CO, CH3OH, H2CO, C2H2, and CH4) in the Jupiter-family comet Tempel 1 using high-dispersion infrared spectroscopy in the wavelength range 2.8 to 5.0 micrometers. The abundance ratio for ethane was significantly higher after impact, whereas those for methanol and hydrogen cyanide were unchanged. The abundance ratios in the ejecta are similar to those for most Oort cloud comets, but methanol and acetylene are lower in Tempel 1 by a factor of about 2. These results suggest that the volatile ices in Tempel 1 and in most Oort cloud comets originated in a common region of the protoplanetary disk.
Development of Primary Volatile Production in COMET C/20O9 Pl (GARRADD) During its 2011-2O12 ApparitionNASA Technical Reports Server (NTRS) Mumma, M. J.; {agamomo. :/; Vo; DiSanti, M. A.; Bonev, B. P.; Lippi, M.; Boehnhardt, H.; Keane, J. V.; Meech, K. J.; Blake, G. A. updating We quantified primary volatiles in comet C/2009 Pl (Garradd) through pre- and post-perihelion observations acquired during its apparition in 2011-12 [1,2,3]. Detected volatiles include H2O, CO, CH4, C2H2, C2H6, HCN, NH3, H2CO, and CH3OH. We present production rates and chemical abundance ratios (relative to water) for all species, and I-D spatial profiles for multiple primary volatiles. We discuss these findings in the context of an emerging taxonomy based on primary volatiles in comets [4]. We used three spectrometer/telescope combinations. On UT 20ll August 7 (Rh 2.4 AU) and September 17-21 (Rh 2.0 AU), we used CRIRES at ESO's Very Large Telescope (VLT) [1]. On September 8 and 9 (Rh 2.1 AU), we used NIRSPEC at Keck-2 and CSHELL at IRTF [2]. Using NIRSPEC on October 13 and 2012 January 08 (Rh 1.83 and 1.57 AU, respectively), we detected nine primary volatiles pre-perihelion, and six post-perihelion [3]. CO was enriched in Garradd while C2H2 was strongly depleted. C2H6 and CH3OH displayed abundances close to those measured for the majority of Oort cloud comets observed to date. The high fractional abundance of CO identifies comet C12009 P1 as a CO-rich comet. Spatial profiles revealed notable differences among individual primary species. Given the relatively large heliocentric distance of C/2009 Pl, we explored the effect of water not being fully sublimated within our field of view and we identi$, the "missing" water fraction needed to reconcile the retrieved abundance ratios with the mean values found for "organics-normal" comets.

En Route to Destruction: the Evolution in Composition of Ices in Comet D 2012 S1 (ISON) Between 1.2 and 0.34 Au from the Sun as Revealed at Infrared WavelengthsNASA Technical Reports Server (NTRS) Disanti, M. A.; Bonev, B. P.; Gibb, L. E.; Paganini, L.; Villanueva, G.; Mumma, M. J.; Keane, J. V.; Blake, G. A.; Dello Russo, N.; Meech, K. J.; updating We report production rates for H2O and eight trace molecules (CO, C2H6, CH4, CH3OH, NH3, H2CO, HCN, C2H2) in the dynamically new, Sun-grazing Comet C2012 S1 (ISON), using high-resolution spectroscopy at Keck II and the NASA IRTF on 10pre-perihelion dates encompassing heliocentric distances Rhupdating AU. Measured water production rates spanned two orders of magnitude, consistent with a long-term heliocentric power law Q(H2O) Rh-3.10.1). Abundance ratios for CO, C2H6, and CH4 with respect to H2O remained constant with Rh and below their corresponding mean values measured among a dominant sample of Oort Cloud comets. CH3OH was also depleted for Rh 0.5 AU, but was closer to its mean value for Rh0.5 AU. The remaining four molecules exhibited higher abundance ratios within 0.5 AU: for Rh 0.8 AU, NH3 and C2H2 were consistent with their mean values while H2CO and HCN were depleted. For Rh 0.5 AU, all four were enriched, with NH3, H2CO, and HCN increasing most. Spatial profiles of gas emission in ISON consistently peaked sunward of the dust continuum, which was asymmetric antisunward and remained singly peaked for all observations. NH3 within 0.5 AU showed a broad spatial distribution, possibly indicating its release in the coma provided that optical depth effects were unimportant. The column abundance ratio NH2H2O at 0.83 AU was close to the typical NHOH from optical wavelengths, but was higher within 0.5 AU. Establishing its production rate and testing its parentage (e.g., NH3) require modeling of coma outflow.
Constraining the Volatile Composition and Coma Photochemistry in Jupiter Family Comet 41P/Tuttle-Giacobini-Kresak with High Resolution IR and Optical SpectroscopyNASA Astrophysics Data System (ADS) McKay, Adam; DiSanti, Michael A.; Cochran, Anita L.; Dello Russo, Neil; Bonev, Boncho P.; Vervack, Ronald J.; Gibb, Erika L.; Roth, Nathan X.; Kawakita, Hideyo updating Over the past 20 years optical and IR spectroscopy of cometary comae has expanded our understanding both of cometary volatile composition and coma photochemistry. However, these observations tend to be biased towards Nearly Isotropic Comets (NIC's) from the Oort Cloud, rather than the generally fainter and less active Jupiter Family Comets (JFC's) that are thought to originate from the Scattered Disk. However, early 2017 provided a rare opportunity to study several JFC's. We present preliminary results from IR and optical spectroscopy of JFC 41P/Tuttle-Giacobini-Kresak obtained during its 2017 apparition. IR spectra were obtained with the NIRSPEC instrument on Keck II and the new iSHELL spectrograph on NASA IRTF. High spectral resolution optical spectra were obtained with the Tull Coude spectrograph on the 2.7-meter Harlan J. Smith Telescope at McDonald Observatory. We will discuss mixing ratios of HCN, NH3, C2H6, C2H2, H2CO, and CH3OH compared to H2O and compare these to previous observations of comets. Preliminary results from the NIRSPEC observations indicate that 41P has typical C2H2 and HCN abundances compared to other JFC's, while the C2H6 abundance is similar to that of NIC's, but is enriched compared to other JFC's. H2CO appears to be heavily depleted in 41P. Analysis of the iSHELL spectra is underway and we will include results from these observations, which complement those from NIRSPEC and extend the scope or our compositional study by measuring additional molecules. We will also present abundances for CN, C2, NH2, C3, and CH obtained from the optical spectra and discuss the implications for the coma photochemistry.This work is supported by the NASA Postdoctoral Program, administered by the Universities Space Research Association, with additional funding from the NSF and NASA PAST.
Constraining the Volatile Composition and Coma Photochemistry in Jupiter Family Comet 41P/Tuttle-Giacobini-Kresak with High Resolution IR and Optical SpectroscopyNASA Astrophysics Data System (ADS) McKay, Adam; DiSanti, Michael; Cochran, Anita; Dello Russo, Neil; Bonev, Boncho; Vervack, Ronald; Gibb, Erika; Roth, Nathan; Kawakita, Hideyo updating Over the past 20 years optical and IR spectroscopy of cometary comae has expanded our understanding both of cometary volatile composition and coma photochemistry. However, these observations tend to be biased towards Nearly Isotropic Comets (NIC'S) from the Oort Cloud, rather than the generally fainter and less active Jupiter Family Comets (JFC's) that are thought to originate from the Scattered Disk. However, early 2017 provided a rare opportunity to study several JFC's. We present preliminary results from IR and optical spectroscopy of JFC 41P/Tuttle-Giacobini-Kresak obtained during its 2017 apparition. IR spectra were obtained with the NIRSPEC instrument on Keck II and the new iSHELL spectrograph on NASA IRTF. High spectral resolution optical spectra were obtained with the Tull Coude spectrograph on the 2.7-meter Harlan J. Smith Telescope at McDonald Observatory. We will discuss mixing ratios of HCN, NH3, C2H6, C2H2, H2CO, and CH3OH compared to H2O and compare these to previous observations of comets. Preliminary results from the NIRSPEC observations indicate that 41P has typical C2H2 and HCN abundances compared to other JFC's, while the C2H6 abundance is similar to that of NIC's, but is enriched compared to other JFC's. H2CO appears to be heavily depleted in 41P. Analysis of the iSHELL spectra is underway and we will include results from these observations, which complement those from NIRSPEC and extend the scope or our compositional study by measuring additional molecules. We will also present abundances for CN, C2, NH2, C3, and CH obtained from the optical spectra and discuss the implications for the coma photochemistry.This work is supported by the NASA Postdoctoral Program, administered by the Universities Space Research Association, with additional funding from the NSF and NASA PAST.
The Composition of Comet C/2009 PI (Garradd) from Infrared Spectroscopy: Evidence for an Oxygen-Rich Heritage?NASA Technical Reports Server (NTRS) DiSanti, M. A.; Bonev, B. P.; Villanueva, G. L.; Paganini, L.; Mumma, M. J.; Charnley, S. B.; Keane, J. V.; Meech, K. J.; Blake, G. A.; Boehnhardt, H.; updating Comets retain relatively primitive icy material remaining from the epoch of Solar System for111ation, however the extent to which their ices are modified remains a key question in cometary science. One way to address this is to measure the relative abundances of primary (parent) volatiles in comets (i.e., those ices native to the nucleus). High-resolution (lambda/delta lambda greater than 10(exp 4)) infrared spectroscopy is a powerful tool for measuring parent volatiles in comets through their vibrational emissions in the 3-5 micrometer region. With modern instrumentation on worldclass telescopes, we can quantify a multitude of species (e.g., H2O, C2H2, CH4, C2H6 CO, H2CO, CH3OH, HCN, NH3), even in comets with modest gas production. In space environments, compounds of keen interest to astrobiology could originate from HCN and NH3 (leading to amino acids), H2CO (leading to sugars), or C2H6 and CH4 (suggested precursors of ethyl- and methylamine). Measuring the abundances of these precursor molecules and their variability among comets contributes to understanding the synthesis of the more complex prebiotic compounds.
The Composition of Comet C/2009 P1 (Garradd) from Infrared Spectroscopy: Evidence for an Oxygen-Rich Heritage?NASA Technical Reports Server (NTRS) DiSanti, M. A.; Bonev, B. P.; Villaneueva, G. L.; Paganini, L.; Mumma, M. J.; Charnley, S. B.; Keane, J. V.; Blake, G. A.; Boehnhardt, H.; Lippi, M. updating Comets retain relatively primitive icy material remaining from the epoch of Solar System formation, however the extent to which their ices are modified remains a key question in cometary science. One way to address this is to measure the relative abundances of primary (parent) volatiles in comets (i.e., those ices native to the nucleus). High-resolution (lambda/delta lambda greater than 10(exp 4)) infrared spectroscopy is a powerful tool for measuring parent volatiles in comets through their vibrational emissions in the approximately 3-5 micrometer region. With modern instrumentation on world-class telescopes, we can quantify a multitude of species (e.g., H2O, C2H2, CH4, C2H6, CO, H2CO, CH3OH, HCN, NH3), even in comets with modest gas production. In space environments, compounds of keen interest to astrobiology could originate from HCN and NH3 (leading to amino acids), H2CO (leading to sugars), or C2H6, and CH4 (suggested precursors of ethyl- and methylamine). Measuring the abundances of these precursor molecules and their variability among comets contributes to understanding the synthesis of the more complex prebiotic compounds.
Fiber optic gas detection system for health monitoring of oil-filled transformerNASA Astrophysics Data System (ADS) Ho, H. L.; Ju, J.; Jin, W. updating This paper reports the development of a fiber-optic gas detection system capable of detecting three types of dissolved fault gases in oil-filled power transformers or equipment. The system is based on absorption spectroscopy and the target gases include acetylene (C2H2), methane (CH4) and ethylene (C2H4). Low-cost multi-pass sensor heads using fiber coupled micro-optic cells are employed for which the interaction length is up to 4m. Also, reference gas cells made of photonic bandgap (PBG) fiber are implemented. The minimum detectable gas concentrations for methane, acetylene and ethylene are 5ppm, 2ppm and 50ppm respectively.
Ab initio calculations, structure, NBO and NCI analyses of Xsbnd H&ctdot;Ï interactionsNASA Astrophysics Data System (ADS) Wu, Qiyang; Su, He; Wang, Hongyan; Wang, Hui updating The performance of ab initio methods (MP2, DFT/B3LYP, random-phase approximation (RPA), CCSD(T) and QCISD(T)) in predicting interaction energy of Xsbnd H&ctdot;Ï (Xsbnd H = HCCH, HCl, HF; Ï = C2H2, C2H4, C6H6) hydrogen complexes are assessed systematically. The CCSD(T)/CBS benchmarks of interaction energy are reported. It is found that RPA agrees well with CCSD(T)/CBS benchmarks and experimental results. CCSD(T) and QCISD(T) perform the best only when compared with CCSD(T)/CBS benchmarks, MP2 performs well only for experimental data. B3LYP provides the worst accuracy. Additionally, the equilibrium structure, interaction type of Xsbnd H&ctdot;Ï hydrogen complexes are investigated by the natural bond orbital (NBO) and the non-covalent interaction index (NCI).
Characterization of diamond thin films and related materialsNASA Astrophysics Data System (ADS) McKindra, Travis Kyle Thin carbon films including sputtered deposited graphite and CO 2 laser-assisted combustion-flame deposited graphite and diamond thin films were characterized using optical and electron microscopy, X-ray diffraction and micro-Raman spectroscopy. Amorphous carbon thin films were deposited by DC magnetron sputtering using Ar/O2 gases. The film morphology changed with the oxygen content. The deposition rate decreased as the amount of oxygen increased due to oxygen reacting with the growing film. The use of oxygen in the working gas enhanced the crystalline nature of the films. Graphite was deposited on WC substrates by a CO2 laser-assisted O2/C2H2 combustion-flame method. Two distinct microstructural areas were observed; an inner core of dense material surrounded by an outer shell of lamellar-like material. The deposits were crystalline regardless of the laser power and deposition times of a few minutes. Diamond films were deposited by a CO2 laser-assisted O 2/C2H2/C2H4 combustion-flame method with the laser focused parallel to the substrate surface. The laser enhanced diamond growth was most pronounced when deposited with a 10.532 microm CO2 laser wavelength tuned to the CH2-wagging vibrational mode of the C2H4 molecule. Nucleation of diamond thin films deposited with and without using a CO 2 laser-assisted combustion-flame process was investigated. With no laser there was nucleation of a sub-layer of grains followed by irregular grain growth. An untuned laser wavelength yielded nucleation of a sub-layer then columnar grain growth. The 10.532 microm tuned laser wavelength caused growth of columnar grains.
Interactions between Nitrogen Fixation and Methane Cycling in Northern Minnesota Peat BogsNASA Astrophysics Data System (ADS) Warren, M. J.; Gaby, J. C.; Lin, X.; Morton, P. L.; Kostka, J. E.; Glass, J. B. updating Peatlands cover only 3% of the Earth's surface, yet store a third of soil carbon. Increasing global temperatures have the potential to change peatlands from a net sink to a net source of atmospheric carbon. N is a limiting nutrient in oligotrophic Sphagnum-dominated peatlands and biological N2 fixation likely supplies a significant but unknown fraction of N inputs. Moreover, environmental controls on diazotrophic community composition in N-limited peatlands are poorly constrained. Thus, improved understanding of feedbacks between the CH4 and N cycles is critical for predicting future changes to CH4 flux from peat bogs. We coupled measurements of N2 fixation activity measured by the acetylene (C2H2) reduction assay (ARA) with molecular analyses of expression and diversity of nifH genes encoding the molybdenum (Mo)-containing nitrogenase from two peat bogs in the Marcell Experimental Forest, Minnesota, USA. The top 10 cm of peat was sampled from the high CH4 flux S1 bog and the low CH4 flux Zim bog in April and June 2014. Despite similar N concentrations in the top 10 cm of both bogs (0.5-1.0 Î¼M NO2-+NO3- and 2-3 Î¼M NH4+), the S1 bog displayed variable ARA activity (1-100 nmol C2H4 h-1 g-1) whereas the Zim bog had consistently low ARA activity (C2H4 h-1 g-1). Highest ARA activity was measured in June from S1 bog hollows with higher moisture content incubated without O2 in the light (20-100 nmol C2H4 h-1 g-1). Dissolved Fe (1-25 Î¼M) was higher in hollow vs. hummock samples, and at S1 vs. Zim bog, while dissolved V (4-14 nM) was consistently higher than Mo (1-4 nM), suggesting that alternative V or Fe-containing nitrogenases might be present in these bogs. In contrast, Cu, an essential micronutrient for aerobic methanotrophs, was higher in hummocks (25-48 nM) than hollows (6-17 nM). The facultative methanotroph Methylocella was the dominant diazotroph in the S1 bog based on high throughput next generation sequencing of nifH cDNA amplicons. Given previous
Titan haze: structure and properties of cyanoacetylene and cyanoacetylene-acetylene photopolymersNASA Technical Reports Server (NTRS) Clarke, D. W.; Ferris, J. P. updating The structure and morphological properties of polymers produced photochemically from the UV irradiation of cyanoacetylene and cyanoacetylene mixtures have been examined to evaluate their possible contribution to the haze layers found on Titan. A structural analysis of these polymers may contribute to our understanding of the data returned from the Huygens probe of the Cassini mission that will pass through the atmosphere of Titan in the year 2004. Infrared analysis, elemental analysis, and thermal methods (thermogravimetric analysis, thermolysis, pyrolysis) were used to examine structures of polycyanoacetylenes produced by irradiation of the gas phase HC3N at 185 and 254 nm. The resulting brown to black polymer, which exists as small particles, is believed to be a branched chain of conjugated carbon-carbon double bonds, which, on exposure to heat, cyclizes to form a graphitic structure. Similar methods of analysis were used to show that when HC3N is photolyzed in the presence of Titan's other atmospheric constituents (CH4, C2H6, C2H2, and CO), a copolymer is formed in which the added gases are incorporated as substituents on the polymer chain. Of special significance is the copolymer of HC3N and acetylene (C2H2). Even in experiments where C2H2 was absorbing nearly all of the incident photons, the ratio of C2H2 to HC3N found in the resulting polymer was only 2:1. Scanning electron microscopy was used to visually examine the polymer particles. While pure polyacetylene particles are amorphous spheres roughly 1 micrometer in diameter, polycyanoacetylenes appear to be strands of rough, solid particles slightly smaller in size. The copolymer of HC3N and C2H2 exhibits characteristics of both pure polymers. This is particularly important as pure polyacetylenes do not match the optical constants measured for Titan's atmospheric hazes. The copolymers produced by the incorporation of other minor atmospheric constituents, like HC3N, into the polyacetylenes are expected to have
Pre- and Post-Perihelion Observations of C/2009 P1 (Garradd): Evidence for an Oxygen-Rich Heritage?NASA Astrophysics Data System (ADS) DiSanti, Michael A.; Villanueva, G. L.; Paganini, L.; Bonev, B. P.; Keane, J. V.; Meech, K. J.; Mumma, M. J. updating We present pre- and post-perihelion observations of Comet C/2009 P1 (Garradd), on UT 2011 October 13 (heliocentric distance Rh = 1.83 AU) and 2012 January 8 (Rh = 1.57 AU), respectively, using the high-resolution infrared spectrometer (NIRSPEC) on the Keck II 10-m telescope on Mauna Kea, HI. On October 13, we obtained production rates for nine primary volatiles (native ices): H2O, CO, CH3OH, CH4, C2H6, HCN, C2H2, H2CO, and NH3. On January 8, we obtained production rates for three of these (H2O, CH4, and HCN) and sensitive upper limits for three others (C2H2, H2CO, and NH3). CO was enriched and C2H2 was depleted, yet C2H6 and CH3OH were close to their current mean values as measured in a dominant group of Oort cloud comets. We compare the composition of Garradd with other CO-rich comets C/1999 T1 (McNaught-Hartley), C/1996 B2 (Hyakutake), and C/1995 O1 (Hale-Bopp), and with other comets in our database. We discuss possible implications regarding the processing history of its pre-cometary ices. Our measurements of C/2009 P1 indicate consistent pre- and post-perihelion abundance ratios for trace species relative to H2O, suggesting we were measuring a homogeneous composition to the depths sampled in the nucleus. The overall gas production was lower post-perihelion despite its smaller heliocentric distance on January 8. This is qualitatively consistent with other studies of C/2009 P1. On October 13, the water profile showed a pronounced excess towards the Sun-facing hemisphere that was not seen in other molecules nor in the dust continuum. Inter-comparison of profiles from October 13 permitted us to estimate the fraction of all H2O released in the coma and contained within our slit. We attribute this excess H2O to release from relatively pure, water-rich icy grains. Similar evidence for extended release was not observed on January 8 and this, together with its overall lower gas production post-perihelion, suggests loss of one or more active regions on the nucleus
Pre- and Post-perihelion Observations of C/2009 P1 (Garradd): Evidence for an Oxygen-rich Heritage?NASA Technical Reports Server (NTRS) Disanti, Michael Antonio; Villanueva, Geronimo Luis; Paganini, Lucas; Bonev, Boncho P.; Keane, Jacqueline V.; Meech, Karen J.; Mumma, Michael Jon updating We conducted pre- and post-perihelion observations of Comet C/2009 P1 (Garradd) on UT 2011 October 13 and 2012 January 8, at heliocentric distances of 1.83 and 1.57 AU, respectively, using the high-resolution infrared spectrometer (NIRSPEC) at the Keck II 10-m telescope on Mauna Kea, HI. Pre-perihelion, we obtained production rates for nine primary volatiles (native ices): H2O, CO, CH3OH, CH4, C2H6, HCN, C2H2, H2CO, and NH3. Post-perihelion, we obtained production rates for three of these (H2O, CH4, and HCN) and sensitive upper limits for three others (C2H2, H2CO, and NH3). CO was enriched and C2H2 was depleted, yet C2H6 and CH3OH were close to their currentmean values asmeasured in a dominant group of Oort cloud comets. This may indicate processing of its pre-cometary ices in a relatively oxygen-rich environment. Our measurements indicate consistent pre- and post-perihelion abundance ratios relative to H2O, suggesting we were measuring compositional homogeneity among measured species to the depths in the nucleus sampled. However, the overall gas production was lower post-perihelion despite its smaller heliocentric distance on January 8. This is qualitatively consistent with other studies of C/2009 P1, perhaps due to seasonal differences in the heating of one or more active regions on the nucleus. On October 13, the water profile showed a pronounced excess towards the Sun-facing hemisphere that was not seen in other molecules, including H2O on January 8, nor in the dust continuum. Inter-comparison of profiles from October 13 permitted us to quantify contributions due to release of H2O from the nucleus, and fromits release in the coma. This resulted in the latter source contributing 25-30% of the total observed water within our slit, which covered roughly +/-300 km by +/-4500 km from the nucleus. We attribute this excess H2O, which peaked at a mean projected distance of updating km from the nucleus, to release from water-rich, relatively pure icy grains
Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethyleneNASA Technical Reports Server (NTRS) Bosco, S. R.; Nava, D. F.; Brobst, W. D.; Stief, L. J. updating The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.
Laboratory studies of molecular growth in the Titan ionosphere.PubMed Thissen, Roland; Vuitton, Veronique; Lavvas, Panayotis; Lemaire, Joel; Dehon, Christophe; Dutuit, Odile; Smith, Mark A; Turchini, Stefano; Catone, Daniele; Yelle, Roger V; Pernot, Pascal; Somogyi, Arpad; Coreno, Marcello updating Experimental simulations of the initial steps of the ion-molecule reactions occurring in the ionosphere of Titan were performed at the synchrotron source Elettra in Italy. The measurements consisted of irradiating gas mixtures with a monochromatic photon beam, from the methane ionization threshold at 12.6 eV, up to and beyond the molecular nitrogen dissociative ionization threshold at 24.3 eV. Three gas mixtures of increasing complexity were used: N(2)/CH(updating/0.04), N(2)/CH(4)/C(2)H(2) (0.96/0.04/0.001), and N(2)/CH(4)/C(2)H(2)/C(2)H(4) (0.96/0.04/0.001/0.001). The resulting ions were detected with a high-resolution (1 T) FT-ICR mass spectrometer as a function of time and VUV photon energy. In order to interpret the experimental results, a Titan ionospheric model was adapted to the laboratory conditions. This model had previously allowed the identification of the ions detected in the Titan upper atmosphere by the ion neutral mass spectrometer (INMS) onboard the Cassini spacecraft. Comparison between observed and modeled ion densities validates the kinetic model (reactions, rate constants, product branching ratios) for the primary steps of molecular growth. It also reveals differences that we attribute to an intense surface chemistry. This result implies that heterogeneous chemistry on aerosols might efficiently produce HCN and NH(3) in the Titan upper atmosphere.
Triel Bonds, Ï-Hole-Ï-Electrons Interactions in Complexes of Boron and Aluminium Trihalides and Trihydrides with Acetylene and Ethylene.PubMed Grabowski, SÅawomir J updating MP2/aug-cc-pVTZ calculations were performed on complexes of aluminium and boron trihydrides and trihalides with acetylene and ethylene. These complexes are linked through triel bonds where the triel center (B or Al) is characterized by the Lewis acid properties through its Ï-hole region while Ï-electrons of C2H2 or C2H4 molecule play the role of the Lewis base. Some of these interactions possess characteristics of covalent bonds, i.e., the Al-Ï-electrons links as well as the interaction in the BH3-C2H2 complex. The triel-Ï-electrons interactions are classified sometimes as the 3c-2e bonds. In the case of boron trihydrides, these interactions are often the preliminary stages of the hydroboration reaction. The Quantum Theory of "Atoms in Molecules" as well as the Natural Bond Orbitals approach are applied here to characterize the Ï-hole-Ï-electrons interactions.
The Compositional Evolution of C/2012 S1 (ISON) from Ground-Based High-Resolution Infrared Spectroscopy as Part of a Worldwide Observing CampaignNASA Technical Reports Server (NTRS) Russo, N. Dello; Vervack, R. J., Jr.; Kawakita, H.; Cochran, A.; McKay, A. J.; Harris, W. M.; Weaver, H.A.; Lisse, C. M.; DiSanti, M. A.; Kobayashi, H. updating Volatile production rates, relative abundances, rotational temperatures, and spatial distributions in the coma were measured in C/2012 S1 (ISON) using long-slit high-dispersion (lambda/delta lambda approximately 2.5 times 10 (sup 4)) infrared spectroscopy as part of a worldwide observing campaign. Spectra were obtained on Universal Time 2013 October 26 and 28 with NIRSPEC (Near Infrared Spectrometer) at the W.M. Keck Observatory, and Universal Time 2013 November 19 and 20 with CSHELL (Cryogenic Echelle Spectrograph) at the NASA IRTF (Infrared Telescope Facility). H2O was detected on all dates, with production rates increasing markedly from (8.7 plus or minus 1.5) times 10 (sup 27) molecules per second on October 26 (Heliocentric Distance = 1.12 Astronomical Units) to (3.7 plus or minus 0.4) times 10 (sup 29) molecules per second on November 20 (Heliocentric Distance = 0.43 Astronomical Units). Short-term variability of H2O production is also seen as observations on November 19 show an increase in H2O production rate of nearly a factor of two over a period of about 6 hours. C2H6, CH3OH and CH4 abundances in ISON (International Scientific Optical Network) are slightly depleted relative to H2O when compared to mean values for comets measured at infrared wavelengths. On the November dates, C2H2, HCN and OCS abundances relative to H2O appear to be within the range of mean values, whereas H2CO and NH3 were significantly enhanced. There is evidence that the abundances with respect to H2O increased for some species but not others between October 28 (Heliocentric Distance = 1.07 Astronomical Units) and November 19 (Heliocentric Distance = 0.46 Astronomical Units). The high mixing ratios of H2CO to CH3OH and C2H2 to C2H6 on November 19, and changes in the mixing ratios of some species with respect to H2O between October 28 to November 19, indicates compositional changes that may be the result of a transition from sampling radiation-processed outer layers in this dynamically
Chemical Characteristics of Continental Outflow from Asia to the Troposphere Over the Western Pacific Ocean during February - March 1994: Results from PEM-West BNASA Technical Reports Server (NTRS) Talbot, R. W.; Dibb, J. E.; Lefer, B. L.; Bradshaw, J. D.; Sandholm, S. T.; Blake, D. R.; Blake, N. J.; Sachse, G. W.; Sachse, G. W.; Heikes, B. G.; updating We present here the chemical composition of outflow from the Asian continent to the atmosphere over the western Pacific basin during the Pacific Exploratory Mission-West (PEM-West B) in February-March 1994. Comprehensive measurements of important tropospheric trace gases and aerosol particulate matter were performed from the NASA DC-8 airborne laboratory. Backward 5 day isentropic trajectories were used to partition the outflow from two major source regions- continental north (greater than 20 deg N) and continental south (less than 20 deg N). Air parcels that had not passed over continental areas for the previous 5 days were classified as originating from an aged marine source. The trajectories and the chemistry together indicated that there was extensive rapid outflow of air parcels at altitudes below 5 km, while aged marine air was rarely encountered and only at less than 20 deg N latitude. The outflow at low altitudes had enhancements in common industrial solvent vapors such as C2Cl4, CH3CCl3, and C6H6, intermixed with the combustion emission products C2H2, C2H6, CO, and NO. The mixing ratios of all species were up to tenfold greater in outflow from the continental north compared to the continental south source region, with Pb-210 concentrations reaching 38 fCi (10(exp -15) curies) per standard cubic meter. In the upper troposphere we again observed significant enhancements in combustion-derived species in the 8-10 km altitude range, but water-soluble trace gases and aerosol species were depleted. These observations suggest that ground level emissions were lofted to the upper troposphere by wet convective systems which stripped water-soluble components from these air parcels. There were good correlations between C2H2 and CO and C2H6 (r(sup 2) = updating) in these air parcels and much weaker ones between C2H2 and H2O2 or CH3OOH (r(sup 2) = 0.50). These correlations were the strongest in the continental north outflow where combustion inputs appeared to be
Experimental investigation and computational modeling of hot filament diamond chemical vapor depositionNASA Astrophysics Data System (ADS) Zumbach, Volker; SchÃ¤fer, JÃ¶rg; Tobai, Jens; Ridder, Michael; Dreier, Thomas; Schaich, Thomas; Wolfrum, JÃ¼rgen; Ruf, Bernhard; Behrendt, Frank; Deutschman, Olaf; Warnatz, JÃ¼rgen updating A joint investigation has been undertaken of the gas-phase chemistry taking place in a hot-filament chemical vapor-deposition (HFCVD) process for diamond synthesis on silica surfaces by a detailed comparison of numerical modeling and experimental results. Molecular beam sampling using quadrupole mass spectroscopy and resonance-enhanced multiphoton ionization time of flight mass spectroscopy (REMPI-TOF-MS) has been used to determine absolute concentrations of stable hydrocarbons and radicals. Resulting species of a CH4/H2, a CH4/D2 (both 0.5%/99.5%) and a C2H2/H2 (0.25%/99.75%) feedgas mixture were investigated for varying filament and substrate temperatures. Spatially resolved temperature profiles at various substrate temperatures, obtained from coherent anti-Stokes Raman spectroscopy (CARS) of hydrogen, are used as input parameters for the numerical code to reproduce hydrogen atom, methyl radical, methane, acetylene, and ethylene concentration profiles in the boundary layer of the substrate. In addition, the concentration of vibrationally excited hydrogen is determined by CARS. Results reveal only qualitative agreement between measured data and simulations, concerning concentrations of stable species and radicals probed near the surface, on filament and substrate temperature dependence, respectively. Hydrogen and deuterium experiments show similar behaviour for all species. In the case of CH4 as feedgas the model describes measured concentration profiles of CH3, CH4, and C2H2 qualitatively well. Large differences between model and experiment occur for hydrogen atoms (factor of 2) and C2H4 (factor of 3). For acetylene as feedgas the model is not able to give any predictions because no conversion of C2H2 is seen in the model in contrast to the experiment.
Summary of Research/PublicationsNASA Technical Reports Server (NTRS) updating Summary of research/publications include:(1) Comment on broadening of water microwave lines by collisions with helium atoms; (2) Calculations of ion-molecule deuterium fractionation reactions involving HD; (3) Ab initio predictions on the rotational spectra of carbon-chain carbene molecules; (4) Theoretical IR spectra of ionized naphthalene; (5) Improved collisional excitation rates for interstellar water; (6) Calculations on the competition between association and reaction for C3H+ + H2; (7) Theoretical infrared spectra of some model polycyclic aromatic hydrocarbons: effect of ionization; (8) Calculations concerning interstellar isomeric abundance ratios for C3H and C3H2; (9) New calculations on the ion-molecule processes C2H2+ + H2 C2H3+ + H and C2H2+ + H2 C2H4+; (10) Anisotropic rigid rotor potential energy function for H2O-H2; (11) A correlated ab initio study of linear carbon-chain radicals CnH (n=2-7); (12) Ab initio characterization of MgCCH, MgCCH+, and MgC2 and pathways to their formation in the interstellar medium; (13) Why HOC+ is detectable in interstellar clouds: The rate of the reaction between HOC+ and H2; (14) A correlated ab initio study of the X 2A 1 and A 2E states of MgCH3; (15) On the stability of interstellar carbon clusters: The rate of the reaction between C3 and O; and (16) The rate of the reaction between CN and C2H2 at interstellar temperatures.
Numerical and experimental studies of ethanol flames and autoignition theory for higher alkanesNASA Astrophysics Data System (ADS) Saxena, Priyank elementary steps and the addition and deletion of a few key steps relevant to these tests. A mechanism developed in such a hierarchical way starting with simpler fuels such as hydrogen and carbon monoxide to the fuels with one and two carbon atoms has reduced uncertainties in the combustion chemistry of a fuel. This reaction mechanism, consisting of 137 reactions among 30 species, provides a robust building block upon which an ethanol mechanism is developed. The San Diego Mech is extended for ethanol combustion by adding 55 new reactions and 6 new species. Specifically, 33 reactions are added that involve C 2H5OH or one of the three isomers produced by abstraction of an H atom from it, CH3CHOH, CH2CH2OH and CH3CH2O, and 22 reactions are added that involve acetaldehyde or one of the two isomers produced by abstraction of H from it, CH2CHO and CH3CO. Ethanol combustion is investigated on the basis of a new reaction mechanism, thus developed, consisting of 192 elementary steps among 36 species, augmented by 53 additional steps and 14 additional species to address the formation of the oxides of nitrogen and 43 steps and 7 species to address formation of compounds involving three carbon atoms. The mechanism is tested against shock-tube autoignition-delay data, laminar burning velocities, counterflow diffusion-flame extinction and measurements of structures of counterflow partially premixed and diffusion flames. Measurements on ethanol-air flames at a strain rate of 100 s-1, employing prevaporized ethanol with a mole fraction of 0.3 in a nitrogen carrier stream, were made for the pure diffusion flame and for a partially premixed flame with a fuel-side equivalence ratio of 2.3 and involved thermocouple measurements of temperature profiles and determination of concentration profiles of C2H5OH, CO, CO2, H2, H2O, O2, N2, CH4, C2H6 and C2H2+C 2H4 by gas chromatographic analysis of samples withdrawn through fine quartz probes. Computational investigations also were made of profiles of

Analysis of Titan's neutral upper atmosphere from Cassini Ion Neutral Mass Spectrometer measurements in the Closed Source Neutral modeNASA Astrophysics Data System (ADS) Cui, Jun In this thesis I present an in-depth study of the distribution of various neutral species in Titan's upper atmosphere, at altitudes between 950 and 1,500 km for abundant species (N 2 , CH 4 as well as their isotopes) and between 950 and 1,200 km for most minor species. However, the study of the H 2 distribution on Titan is extended to an altitude as high as 6,000 km in the exosphere. The analysis is based on a large sample of Cassini/INMS (Ion Neutral Mass Spectrometer) measurements in the CSN (Closed Source Neutral) mode, obtained during 15 close flybys of Titan. The densities of abundant species including N 2 , CH 4 and H 2 are determined directly from their main channels. However, to untangle the overlapping cracking patterns of minor species, the technique of Singular Value Decomposition (SVD) is used to determine simultaneously the densities of various hydrocarbons, nitriles and oxygen compounds. All minor species except for 40 Ar present density enhancements measured during the outbound legs. This can be interpreted as a result of wall effects, which could be either adsorption/desorption or heterogeneous surface chemistry on the chamber walls. In the thesis, I use a simple model to describe the observed time behavior of minor species. Results on their atmospheric abundances are provided both in terms of direct inbound measurements assuming ram pressure enhancement and values corrected for wall adsorption/desorption. Among all minor species of photochemical interest, the INMS data provide direct observational evidences for C 2 H 2 , C 2 H 4 , C 2 H 6 , CH 3 C 2 H, C 4 H 2 , C 6 H 6 , HC 3 N and C 2 N 2 in Titan's upper atmosphere. Upper limits are put for other minor species. The globally averaged distribution of N 2 , CH 4 and H 2 are each modeled with the diffusion approximation. The N 2 profile suggests an average thermospheric temperature of 154 K. The CH 4 and H 2 distribution constrains their fluxes to be 3.0 Ã 10 9 cm -2 s -1 and 1.3 Ã 10 10 cm -2 s
Cassini results on Titan's atmospheric and surface properties changes since the northern equinoxNASA Astrophysics Data System (ADS) Coustenis, Athena; Drossart, Pierre; Flasar, F. Michael; Achterberg, Richard K.; Rodriguez, Sebastien; Nixon, Conor; Bampasidis, Georgios; Solomonidou, Anezina; Jennings, Donald; Lavvas, Panayiotis updating Since 2010, we observe the set in and enhancement at Titan's south pole of several trace species, such as HC3N and C6H6, observed only at high northern latitudes before equinox. We will present an analysis of spectra acquired by Cassini/CIRS at high resolution from 2012 in nadir mode. We investigated here several latitudes of 70Â°S to 70Â°N since 2010 (after the Southern Autumnal Equinox) until end of 2014 [1]. For some of the most abundant and longest-lived hydrocarbons (C2H2, C2H6 and C3H8) and CO2, the evolution in the past 4 years at a given latitude is not very significant within error bars especially until mid-2013 [1]. In more recent dates, these molecules show a dramatic trend for increase in the south. The 70Â°S and 50Â°S or mid-latitudes show different behavior demonstrating that they are subject to different dynamical processes in and out of the polar vortex region. For most species, we find higher abundances at 50Â°N compared to 50Â°S, with the exception of C3H8, CO2, C6H6 and HC3N, which arrive at similar mixing ratios after mid-2013 [1]. While the 70Â°N data show generally no change with a trend rather to a small decrease for most species within 2014, the 70Â°S results indicate a strong enhancement in trace stratospheric gases after 2012. In particular, HC3N, HCN and C6H6 have increased by 3 orders of magnitude over the past 3-4 years while other molecules, including C2H4, C3H4 and C4H2, have increased less sharply (by 1-2 orders of magnitude). This is a strong indication of the rapid and sudden buildup of the gaseous inventory in the southern stratosphere during updating, as expected as the pole moves deeper into winter shadow. Subsidence gases that accumulate in the absence of ultraviolet sunlight, evidently increased quickly since 2012 and some of them may be responsible also for the reported haze decrease in the north and its appearance in the south at the same time [2]. Clearly Titan is a dynamic system with indications of short and long
Mechanisms for the dehydrogenation of alkanes on platinum: insights gained from the reactivity of gaseous cluster cations, Ptn + n=1-21.PubMed Adlhart, Christian; Uggerud, Einar updating Rates for the dihydrogen elimination of methane, ethane, and propane with cationic platinum clusters, Pt(n) (+) (1C2H6)C2H6 in the presence of D(2) demonstrates exchange of all hydrogen atoms in [PtnC2H4]+ with deuterium atoms. A potential energy diagram with a high barrier for the second H2 elimination summarizes these observations. For propane twofold dihydrogen elimination is dominating, and for these reactions a far less regiospecific and more random loss of the hydrogens can be inferred, as was demonstrated by the reactions with [D6]-1,1,1,3,3,3-propane.
Acetylene fuels reductive dechlorination of TCE by Dehalococcoides/Pelobacter-containing microbial consortiaNASA Astrophysics Data System (ADS) Oremland, R. S.; Mao, X.; Mahandra, C.; Baesman, S. M.; Gushgari, S.; Alvarez-Cohen, L.; Liu, T. updating Groundwater contamination by trichloroethene (TCE) poses a threat to health and leads to the generation of vinyl chloride (VC), a carcinogen. Dehalococcoides mccartyi is the only bacterium that can completely dechlorinate TCE to ethene (C2H4). Acetylene (C2H2) occurs in TCE-contaminated sites as a consequence of chemical degradation of TCE. Yet acetylene inhibits a variety of microbial processes including methanogesis and reductive dechlorination. Pelobacter acetylenicus and related species can metabolize acetylene via acetylene hydratase and acetaldehyde dismutatse thereby generating acetate and H2 as endproducts, which could serve as electron donor and carbon source for growth of D. mccartyi. We found that 1mM acetylene (aqueous) inhibits growth of D. mccartyi strain 195 on 0.3 mM TCE, but that the inhibition was removed after 12 days with the addition of an acetylene-utilizing isolate from San Francisco Bay, Pelobacter strain SFB93. TCE did not inhibit the growth of this Pelobacter at the concentrations tested (0.1-0.5 mM) and TCE was not consumed by strain SFB93. Co-cultures of strain 195 with strain SFB93 at 5% inoculation were established in 120 mL serum bottles containing 40 mL defined medium. TCE was supplied at a liquid concentration of 0.1 mM, with 0.1 mM acetylene and N2/CO2 (90:10 v/v) headspace at 34 Â°C. Co-cultures were subsequently transferred (5% vol/vol inoculation) to generate subcultures after 20 Î¼mol TCE was reduced to VC and 36 Î¼mol acetylene was depleted. Aqueous H2 ranged from 114 to 217 nM during TCE-dechlorination, and the cell yield of strain 195 was 3.7 Â±0.3 Ã 107 cells Î¼mol-1 Cl- released. In a D. mccartyi-containing enrichment culture (ANAS) under the same conditions as above, it was found that inhibition of dechlorination by acetylene was reversed after 19 days by adding SFB93. Thus we showed that a co-culture of Pelobacter SFB93 and D. mccartyi 195 could be maintained with C2H2 as the electron donor and carbon source while TCE
The Coupled Photochemistry of Ammonia and Acetylene: Applications to the Atmospheric Chemistry on JupiterNASA Astrophysics Data System (ADS) Keane, Thomas Christopher updating Jovian reaction conditions (H_2: NH_3 : C_2H_2 = 600: 7.5: 5 torr, 180 K) the following products and their quantum yields for formation were obtained: C_2H_4 (0.129), CH_3 CH=NN=CHCH_updating), CH _3CH=NNH_updating), C_2H_5NH_updating), CH_3NH_updating), CH_3CN (0.002), HCN (0.001) and CH_3CH=NC _2H_updating).
Large-scale Distribution of CH4 in the Western North Pacific: Sources and Transport from the Asian ContinentNASA Technical Reports Server (NTRS) Bartlett, Karen B.; Sachse, Glen W.; Slate, Thomas; Harward, Charles; Blake, Donald R. updating Methane (CH4) mixing ratios in the northern Pacific Basin were sampled from two aircraft during the TRACE-P mission (Transport and Chemical Evolution over the Pacific) from late February through early April 2001 using a tunable diode laser system. Described in more detail by Jacob et al., the mission was designed to characterize Asian outflow to the Pacific, determine its chemical evolution, and assess changes to the atmosphere resulting from the rapid industrialization and increased energy usage on the Asian continent. The high-resolution, high-precision data set of roughly 13,800 CH4 measurements ranged between 1602 ppbv in stratospherically influenced air and 2149 ppbv in highly polluted air. Overall, CH4 mixing ratios were highly correlated with a variety of other trace gases characteristic of a mix of anthropogenic industrial and combustion sources and were strikingly correlated with ethane (C2H6) in particular. Averages with latitude in the near-surface (0-2 km) show that CH4 was elevated well above background levels north of 15 deg N close to the Asian continent. In the central and eastern Pacific, levels of CH4 were lower as continental inputs were mixed horizontally and vertically during transport. Overall, the correlation between CH4 and other hydrocarbons such as ethane (C2H6), ethyne (C2H2), and propane (C3H8) as well as the urban/industrial tracer perchloroethene (C2Cl4), suggests that for CH4 colocated sources such as landfills, wastewater treatment, and fossil fuel use associated with urban areas dominate regional inputs at this time. Comparisons between measurements made during TRACE-P and those of PEM-West B, flown during roughly the same time of year and under a similar meteorological setting 7 years earlier, suggest that although the TRACE-P CH4 observations are higher, the changes are not significantly greater than the increases seen in background air over this time interval.
Huygens Gas Chromatograph Mass Spectrometer Results from TitanNASA Technical Reports Server (NTRS) Niemann, Hasso updating The Huygens Probe executed a successful entry, descent and impact on the Saturnian moon of Titan on January 14, 2005. Gas Chromatograph Mass Spectrometer (GCMS) instrument conducted isotopic and compositional measurements throughout the two and one half hour descent from 146 km altitude, and on the surface for 69 minutes until loss of signal from the orbiting Cassini spacecraft. The GCMS incorporated a quadrupole mass filter with a secondary electron multiplier detection system. The gas sampling system provided continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact. Data products from the GCMS included altitude profiles of the major atmospheric constituents dinitrogen (N2) and methane (CH4), isotope ratios of N-14/N-15, C-12/C-13, and D/H, mole fractions of radiogenic argon (Ar-40)and primordial argon Ar-36), and upper limits on the mole fractions of neon, krypton and xenon, which were found to be below the detection limit of the instrument or absent. Surface measurements confirmed the presence of ethane (C2H6) and cyanogen (C2N2). Later data products include the instrument response to surface outgassing of C2N2, C2H6, acetylene (C2H2),and carbon dioxide (CO2). More recent results include the detection of benzene (C6H6) and height profiles of molecular hydrogen (H2). Numerous other trace species evaporating from the surface were also identified using the GCMS data.
Huygens GCMS Results from TitanNASA Technical Reports Server (NTRS) Niemann, Hasso B.; Demick, Jaime; Kasprzak, Wayne; Atreya, Sushil; Owen, Tobias updating The Huygens Probe executed a successful entry, descent and impact on the Saturnian moon of Titan on January 14, 2005. The Gas Chromatograph Mass Spectrometer (GCMS) instrument conducted isotopic and compositional measurements throughout the two and one half hour descent from 146 km altitude, and on the surface for 69 minutes until loss of signal from the orbiting Cassini spacecraft. The GCMS incorporated a quadrupole mass filter with a secondary electron multiplier detection system. The gas sampling system provided continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact. Data products from the GCMS included altitude profiles of the major atmospheric constituents dinitrogen (N2) and methane (CH4), isotope ratios of 14N/15N, 12C/13C, and D/H, mole fractions of radiogenic argon (40Ar) and primordial argon (36Ar), and upper limits on the mole fractions of neon, krypton and xenon, which were found to be absent. Surface measurements confirmed the presence of ethane (C2H6) and cyanogen (C2N2). Later data products expanded atmospheric profiles to include the surface response of C2N2. C2H6, acetylene (C2H2), and carbon dioxide (CO2). More recent results include the profiles of benzene (C6H6) and molecular hydrogen (H2). The GCMS data are being further analyzed to obtain higher precision results and to identify other trace species ion the atmosphere and evaporating from the surface.
Development of the Non-Hydrostatic Jupiter Global Ionosphere Thermosphere Model (J-GITM): Status and Current SimulationsNASA Astrophysics Data System (ADS) Bougher, Stephen; Ridley, Aaron; Majeed, Tariq; Waite, J. Hunter; Gladstone, Randy; Bell, Jared updating The primary objectives for development and validation of a new 3-D non-hydrostatic model of Jupiter's upper atmosphere is to improve our understanding of Jupiter's thermosphere-ionosphere-magnetosphere system and to provide a global context within which to analyze the data retrieved from the new JUNO mission. The new J-GITM model presently incorporates the progress made on the previous Jupiter-TGCM code (i.e. key parameterizations, ion-neutral chemistry, IR cooling) while also employing the non-hydrostatic numerical core of the Earth Global Ionosphere-Thermosphere Model (GITM). The GITM numerical framework has been successfully applied to Earth, Mars, and Titan (see Ridley et al. [2006], Bougher et al. [2015], Bell [2008, 2010]). Moreover, it has been shown to simulate the effects of strong, localized heat sources (such as joule heating and auroral heating) more accurately than strictly hydrostatic GCMs (Deng et al. [2007, 2008]). Thus far, in the J-GITM model development and testing, model capability has been progressively augmented to capture the neutral composition (e.g. H, H2, He major species), 3-component neutral winds, and thermal structure, as well as the ion composition (H3+, H2+, and H+ among others) above 250 km. Presently, J-GITM: (a) provides an interactive calculation for auroral particle precipitation (i.e. heating, ionization), an improvement over the static formulation used previously in the J-TGCM (Bougher et al., 2005; Majeed et al., 2005, 2009, 2015); (b) self-consistently calculates an ionosphere using updated ion-neutral chemistry, ion dynamics, and electron transport; (c) simulates the chemistry that forms key hydrocarbons at the base of the thermosphere, focusing on CH4, C2H2, and C2H6; (d) allows the production of H3+, CH4, C2H2, and C2H6 to modify the global thermal balance of Jupiter through their non-LTE radiative cooling; (e) provides a calculation of H2 vibrational chemistry to regulate H+ densities; and (f) uses the improved
The 12C/ 13C isotopic ratio in Titan hydrocarbons from Cassini/CIRS infrared spectraNASA Astrophysics Data System (ADS) Nixon, C. A.; Achterberg, R. K.; Vinatier, S.; BÃ©zard, B.; Coustenis, A.; Irwin, P. G. J.; Teanby, N. A.; de Kok, R.; Romani, P. N.; Jennings, D. E.; Bjoraker, G. L.; Flasar, F. M. updating We have analyzed infrared spectra of Titan recorded by the Cassini Composite Infrared Spectrometer (CIRS) to measure the isotopic ratio 12C/ 13C in each of three chemical species in Titan's stratosphere: CH 4, C 2H 2 and C 2H 6. This is the first measurement of 12C/ 13C in any C 2 molecule on Titan, and the first measurement of 12CH 4/ 13CH 4 (non-deuterated) on Titan by remote sensing. Our spectra cover five widely-spaced latitudes, 65Â° S to 71Â° N and we have searched for both latitude variability of 12C/ 13C within a given species, and also for differences between the 12C/ 13C in the three gases. For CH 4 alone, we find C12/C13=76.6Â±2.7 (1- Ï), essentially in agreement with the 12CH 4/ 13CH 4 measured by the Huygens Gas Chromatograph/Mass Spectrometer instrument (GCMS) [Niemann, H.B., and 17 colleagues, 2005. Nature 438, 779-784]: 82.3Â±1.0, and also with measured values in H 13CN and 13CH 3D by CIRS at lower precision [BÃ©zard, B., Nixon, C., Kleiner, I., Jennings, D., 2007. Icarus 191, 397-400; Vinatier, S., BÃ©zard, B., Nixon, C., 2007. Icarus 191, 712-721]. For the C 2 species, we find C12/C13=84.8Â±3.2 in C 2H 2 and 89.8Â±7.3 in C 2H 6, a possible trend of increasingly value with molecular mass, although these values are both compatible with the Huygens GCMS value to within error bars. There are no convincing trends in latitude. Combining all fifteen measurements, we obtain a value of C12/C13=80.8Â±2.0, also compatible with GCMS. Therefore, the evidence is mounting that 12C/ 13C is some 8% lower on Titan than on the Earth (88.9, inorganic standard), and lower than typical for the outer planets ( 88Â±7 [Sada, P.V., McCabe, G.H., Bjoraker, G.L., Jennings, D.E., Reuter, D.C., 1996. Astrophys. J. 472, 903-907]). There is no current model for this enrichment, and we discuss several mechanisms that may be at work.
High-Resolution Infrared Spectroscopic Measurements of Comet 2PlEncke: Unusual Organic Composition and Low Rotational TemperaturesNASA Technical Reports Server (NTRS) Radeva, Yana L.; Mumma, Michael J.; Villanueva, Geronimo L.; Bonev, Boncho P.; DiSanti, Michael A.; A'Hearn, Michael F.; Dello Russo, Neil updating We present high-resolution infrared spectroscopic measurements of the ecliptic comet 2P/Encke, observed on 4-6 Nov. 2003 during its close approach to the Earth, using the Near Infrared Echelle Spectrograph on the Keck II telescope. We present flux-calibrated spectra, production rates, and mixing ratios for H2O, CH3OH, HCN, H2CO, C2H2, C2H6, CH4 and CO. Comet 2P/Encke is a dynamical end-member among comets because of its short period of 3.3 years. Relative to "organics-normal" comets, we determined that 2PlEncke is depleted in HCN, H2CO, C2H2, C2H6, CH4 and CO, but it is enriched in CH3OH. We compared mixing ratios of these organic species measured on separate dates, and we see no evidence of macroscopic chemical heterogeneity in the nucleus of 2P/Encke, however, this conclusion is limited by sparse temporal sampling. The depleted abundances of most measured species suggest that 2P/Encke may have formed closer to the young Sun, before its insertion to the Kuiper belt, compared with "organics-normal" comets - as was previously suggested for other depleted comets (e.g. C/1999 S4 (LINEAR)). We measured very low rotational temperatures of 20 - 30 K for H2O, CH3OH and HCN in the near nucleus region of 2P/Encke, which correlate with one of the lowest cometary gas production rates (approx. 2.6 x 10(exp 27) molecules/s) measured thus far in the infrared. This suggests that we are seeing the effects of more efficient radiative cooling, insufficient collisional excitation, and/or inefficient heating by fast H-atoms (and icy grains) in the observed region of the coma. Its extremely short orbital period, very low gas production rate, and classification as an ecliptic comet, make 2PlEncke an important addition to our growing database, and contribute significantly to the establishment of a chemical taxonomy of comets.
Simulation Protocol for Prediction of a Solid-Electrolyte Interphase on the Silicon-based Anodes of a Lithium-Ion Battery: ReaxFF Reactive Force Field.PubMed Yun, Kang-Seop; Pai, Sung Jin; Yeo, Byung Chul; Lee, Kwang-Ryeol; Kim, Sun-Jae; Han, Sang Soo updating We propose the ReaxFF reactive force field as a simulation protocol for predicting the evolution of solid-electrolyte interphase (SEI) components such as gases (C 2 H 4 , CO, CO 2 , CH 4 , and C 2 H 6 ), and inorganic (Li 2 CO 3 , Li 2 O, and LiF) and organic (ROLi and ROCO 2 Li: R = -CH 3 or -C 2 H 5 ) products that are generated by the chemical reactions between the anodes and liquid electrolytes. ReaxFF was developed from ab initio results, and a molecular dynamics simulation with ReaxFF realized the prediction of SEI formation under real experimental conditions and with a reasonable computational cost. We report the effects on SEI formation of different kinds of Si anodes (pristine Si and SiO x ), of the different types and compositions of various carbonate electrolytes, and of the additives. From the results, we expect that ReaxFF will be very useful for the development of novel electrolytes or additives and for further advances in Li-ion battery technology.
The geochemical and genetic role of organic substances in postmagmatic derivatives of alkaline plutonsNASA Astrophysics Data System (ADS) Ermolaeva, V. N.; Chukanov, N. V.; Pekov, I. V.; Kogarko, L. N. updating Solid bituminous substances (SBS) are common components of the late hydrothermal mineral assemblages of peralkaline pegmatites. SBS are formed in a reductive setting as a result of progressive sorption of minor carbon-bearing molecules (CO, CO2, CH4, C2H6, C2H4, etc.), their polymerization, transformation into aromatic compounds (reformation), and selective oxidation on microporous zeolite-like Ti-, Nb-, and Zrsilicates serving as sorbents and catalysts. The oxygen-bearing aromatic compounds with hydrophile functional groups (-OH, -C=O, -COOH, -COO) act as complexing agents with respect to Th, REE, U, Zr, Ti, Nb, Ba, Sr, Ca, resulting in transfer of these bitumenophile elements under low-temperature hydrothermal conditions in the form of water-soluble macroassociates of the micelle type. Th, REE, and to a lesser extent, U, Zr, Ti, and Nb concentrate at the late stage of the hydrothermal process as microphases impregnating SBS or macroscopic segregations of Th and REE minerals. At the final stage, homogeneous SBS break down into organic (partly together with Ca, Sr, Ba, and Pb) and mineral (with Th, Ln, Y, Ti, Nb, Ca, Na, K, Si) microphases.
Diagnostic examination of thermally abused high-power lithium-ion cellsNASA Astrophysics Data System (ADS) Abraham, D. P.; Roth, E. P.; Kostecki, R.; McCarthy, K.; MacLaren, S.; Doughty, D. H. The inherent thermal instability of lithium-ion cells is a significant impediment to their widespread commercialization for hybrid-electric vehicle applications. Cells containing conventional organic electrolyte-based chemistries are prone to thermal runaway at temperatures around 180 Â°C. We conducted accelerating rate calorimetry measurements on high-power 18650-type lithium-ion cells in an effort to decipher the sequence of events leading to thermal runaway. In addition, electrode and separator samples harvested from a cell that was heated to 150 Â°C then air-quenched to room temperature were examined by microscopy, spectroscopy, and diffraction techniques. Self-heating of the cell began at 84 Â°C. The gases generated in the cell included CO 2 and CO, and smaller quantities of H 2, C 2H 4, CH 4, and C 2H 6. The main changes on cell heating to 150 Â°C were observed on the anode surface, which was covered by a thick layer of surface deposits that included LiF and inorganic and organo-phosphate compounds. The sources of gas generation and the mechanisms leading to the formation of compounds observed on the electrode surfaces are discussed.
[Quantitative spectrum analysis of characteristic gases of spontaneous combustion coal].PubMed Liang, Yun-Tao; Tang, Xiao-Jun; Luo, Hai-Zhu; Sun, Yong updating Aimed at the characteristics of spontaneous combustion gas such as a variety of gases, lou limit of detection, and critical requirement of safety, Fourier transform infrared (FTIR) spectral analysis is presented to analyze characteristic gases of spontaneous combustion In this paper, analysis method is introduced at first by combing characteristics of absorption spectra of analyte and analysis requirement. Parameter setting method, sample preparation, feature variable abstract and analysis model building are taken into consideration. The methods of sample preparation, feature abstraction and analysis model are introduced in detail. And then, eleven kinds of gases were tested with Tensor 27 spectrometer. CH4, C2H6, C3H8, iC4H10, nC4H10, C2 H4, C3 H6, C3 H2, SF6, CO and CO2 were included. The optical path length was 10 cm while the spectra resolution was set as 1 cm(-1). The testing results show that the detection limit of all analytes is less than 2 x 10(-6). All the detection limits fit the measurement requirement of spontaneous combustion gas, which means that FTIR may be an ideal instrument and the analysis method used in this paper is competent for spontaneous combustion gas measurement on line.
Thermal processing of paper sludge and characterisation of its pyrolysis products.PubMed Strezov, Vladimir; Evans, Tim J updating Paper sludge is a waste product from the paper and pulp manufacturing industry that is generally disposed of in landfills. Pyrolysis of paper sludge can potentially provide an option for managing this waste by thermal conversion to higher calorific value fuels, bio-gas, bio-oils and charcoal. This work investigates the properties of paper sludge during pyrolysis and energy required to perform thermal conversion. The products of paper sludge pyrolysis were also investigated to determine their properties and potential energy value. The dominant volatile species of paper sludge pyrolysis at 10 degrees C/min were found to be CO and CO(2), contributing to almost 25% of the paper sludge dry weight loss at 500 degrees C. The hydrocarbons (CH(4), C(2)H(4), C(2)H(6)) and hydrogen contributed to only 1% of the total weight loss. The bio-oils collected at 500 degrees C were primarily comprised of organic acids with the major contribution being linoleic acid, 2,4-decadienal acid and oleic acid. The high acidic content indicates that in order to convert the paper sludge bio-oil to bio-diesel or petrochemicals, further upgrading would be necessary. The charcoal produced at 500 degrees C had a calorific value of 13.3MJ/kg.
Substrate dependence of electron-stimulated O - yields from dissociative electron attachment to physisorbed O2NASA Astrophysics Data System (ADS) Huels, M. A.; Parenteau, L.; Sanche, L. updating We present measurements of O- electron stimulated desorption yields obtained under identical experimental conditions from 0.15 monolayers (ML) of O2 deposited onto disordered substrates consisting of 4 ML of either Kr, Xe, C2H6, C2H4, N2O, CH3Cl, or H2O, all condensed on Pt (polycrystalline). The resulting O- yield functions, for incident electron energies below 20 eV, are compared to that obtained from the O2/Kr solid; this allows us to assess the order of magnitude effects of the local substrate environment on dissociative electron attachment (DEA) via the 2Î u and gas phase forbidden 2Î£+g,u resonances of O-2. We note that, in addition to electron energy losses in the substrate prior to DEA to O2 and post-dissociation interactions of the O- with the substrate molecules, charge or energy transfer from the O-2 transient anion to a substrate molecule, and capture of the incident electron into a dissociative anion resonance of the substrate molecule may contribute to a reduced O- yield from the physisorbed O2. In the case of O2 deposited on amorphous ice, we find that the O- signal from DEA to O2 is completely absent for electron energies below 14 eV; we attribute this to a complete quenching of the dissociative O-2(2Î u, 2Î£+) resonances by the adjacent water molecules.
Kinetics of the Thermal Decomposition of Tetramethylsilane behind the Reflected Shock Waves in a Single Pulse Shock Tube (SPST) and Modeling StudyNASA Astrophysics Data System (ADS) Parandaman, A.; Sudhakar, G.; Rajakumar, B. Thermal reactions of Tetramethylsilane (TMS) diluted in argon were studied behind the reflected shock waves in a single-pulse shock tube (SPST) over the temperature range of updating K and pressures varied between 10.6 and 22.8 atm. The stable products resulting from the decomposition of TMS were identified and quantified using gas chromatography and also verified with Fourier Transform Infrared (FTIR) spectrometer. The major reaction products are methane (CH4) and ethylene (C2H4). The minor reaction products are ethane (C2H6) and propylene (C3H6). The initiation of mechanism in the decomposition of TMS takes plays via the Si-C bond scission by ejecting the methyl radicals (CH3) and trimethylsilyl radicals ((CH3)3Si). The measured temperature dependent rate coefficient for the total decomposition of TMS was to be ktotal = 1.66 Ã1015 exp (-64.46/RT) s-1 and for the formation of CH4 reaction channel was to be k = 2.20 Ã 1014 exp (-60.15/RT) s-1, where the activation energies are given in kcal mol-1. A kinetic scheme containing 17 species and 28 elementary reactions was used for the simulation using chemical kinetic simulator over the temperature range of updating K. The agreement between the experimental and simulated results was satisfactory.
Hydrogen evolution from aqueous-phase photocatalytic reforming of ethylene glycol over Pt/TiO2 catalysts: Role of Pt and product distributionNASA Astrophysics Data System (ADS) Li, Fuying; Gu, Quan; Niu, Yu; Wang, Renzhang; Tong, Yuecong; Zhu, Shuying; Zhang, Hualei; Zhang, Zizhong; Wang, Xuxu updating Pt nanoparticles were loaded on anatase TiO2 by the photodeposition method to investigate their photocatalytic activity for H2 evolution in an aqueous solution containing a certain amount of ethylene glycol (EG) as the sacrificial agent. The surface properties and chemical states of the Pt/TiO2 sample were characterized by X-ray powder diffraction analysis, Brunauer-Emmett-Teller surface area analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance, and electrochemical resistance. The aqueous-phase photocatalytic EG reforming using Pt/TiO2 and anatase TiO2 generated not only H2 and CO2, but also CO, CH4, C2H6, and C2H4. Moreover, the amount of formate and acetate complexes in the solution increased gradually. The EG adsorption and gas-phase intermediates during photocatalytic reaction processes were investigated by the in situ FTIR spectrum. Finally, the photocatalytic EG reforming reaction mechanism was elucidated. This helped to better understand the role of a sacrificial agent in a photocatalytic hydrogen production.
Laser Ionization Studies of Hydrocarbon Flames.NASA Astrophysics Data System (ADS) Bernstein, Jeffrey Scott Resonance-enhanced multiphoton ionization (REMPI) and laser induced fluorescence (LIF) are applied as laser based flame diagnostics for studies of hydrocarbon combustion chemistry. rm CH_4/O_2, C _2H_4/O_2, and rm C_2H_6/O_2 low pressure ( ~20 Torr), stoichiometric burner stabilized flat flames are studied. Density profiles of intermediate flame species, existing at ppm concentrations, are mapped out as a function of distance from the burner head. Profiles resulting from REMPI and LIF detection are obtained for HCO, CH_3, H, O, OH, CH, and CO flame radicals. The above flame systems are computer modeled against currently accepted combustion mechanisms using the Chemkin and Premix flame codes developed at Sandia National Laboratories. The modeled profile densities show good agreement with the experimental results of the CH_4/O_2 flame system, thus confirming the current C1 kinetic flame mechanism. Discrepancies between experimental and modeled results are found with the C2 flames. These discrepancies are partially amended by modifying the rate constant of the rm C_2H_3+rm O_2 to H_2CO + HCO reaction. The modeled results computed with the modified rate constant strongly suggest that the kinetics of several or possibly many reactions in the C2 mechanism need refinement.

Destruction of decabromodiphenyl ether (BDE-209) in a ternary carbonate molten salt reactor.PubMed Yao, Zhi-tong; Li, Jin-hui; Zhao, Xiang-yang updating Soil contamination by PBDEs has become a significant environmental concern and requires appropriate remediation technologies. In this study, the destruction of decabromodiphenyl ether (BDE-209) in a ternary molten salt (Li, Na, K)2 CO3 reactor was evaluated. The effects of reaction temperature, additive amount of BDE-209 and salt mixture, on off-gas species, were investigated. The salt mixture after reaction was characterized by XRD analysis and a reaction pathway proposed. The results showed that the amounts of C2H6, C2H4, C4H8 and CH4 in the off-gas decreased with increases in temperature, while the CO2 level increased. When the reaction temperature reached 750Â Â°C, incomplete combustion products (PICs) were no longer detected. Increasing BDE-209 loading was not helpful for the reaction, as more PICs were produced. Larger amounts of salt mixture were helpful for the reaction and PICs were not observed with the mole ratio 1: 2000 of BDE-209 to carbonate melt. XRD analysis confirmed the capture of bromine in BDE-209 by the molten salt. Copyright Â© 2013 Elsevier Ltd. All rights reserved.
Temporal and Spatial Aspects of Gas Release During the 2010 Apparition of Comet 103P/Hartley-2NASA Technical Reports Server (NTRS) Mumma, M. J.; Bonev, B. P.; Villanueva, G. L.; Paganini, L.; DiSanti, M. A.; Gibb, E. L.; Keane, J. V.; Meech, K. J.; Blake, G. A.; Ellis, R. S.; updating We report measurements of eight primary volatiles (H2O, HCN, CH4, C2H6, CH3OH, C2H2, H2CO, and NH3) and two product species (OH and NH2) in comet lO3P/Hartley-2 using high dispersion infrared spectroscopy. We quantified the long- and short-term behavior of volatile release over a three-month interval that encompassed the comet's close approach to Earth, its perihelion passage, and flyby of the comet by the Deep Impact spacecraft during the EPOXI mission. We present production rates for individual species, their mixing ratios relative to water, and their spatial distributions in the coma on multiple dates. The production rates for water, ethane, HCN, and methanol vary in a manner consistent with independent measures of nucleus rotation, but mixing ratios for HCN, C2H6, & CH3OH are independent of rotational phase. Our results demonstrate that the ensemble average composition of gas released from the nucleus is well defined, and relatively constant over the three-month interval (September 18 through December 1,7). If individual vents vary in composition, enough diverse vents must be active simultaneously to approximate (in sum) the bulk composition of the nucleus. The released primary volatiles exhibit diverse spatial properties which favor the presence of separate polar and apolar ice phases in the nucleus, establish dust and gas release from icy clumps, and from the nucleus, and provide insights into the driver for the cyanogen (CN) polar jet. The spatial distributions of C2H6 & HCN along the near-polar jet (UT 19.5 October) and nearly orthogonal to it (UT 22.5 October) are discussed relative to the origin of CN. The ortho-para ratio (OPR) of water was 2.85 +/- 0.20; the lower bound (2.65) defines T(sub spin) > 32 K. These values are consistent with results returned from ISO in 1997 .
Cross sections for electron collision with difluoroacetyleneNASA Astrophysics Data System (ADS) Gupta, Dhanoj; Choi, Heechol; Kwon, Deuk-Chul; Yoon, Jung-Sik; Antony, Bobby; Song, Mi-Young updating We report a detailed calculation of total elastic, differential elastic, momentum transfer and electronic excitation for electron impact on difluoroacetylene (C2F2) molecules using the R-matrix method at low energies. After testing many target models, the final results are reported for the target model that gave the best target properties and predicted the lowest value of the shape resonance. The shape resonance is detected at 5.86 eV and 6.49 eV with the close-coupling and static exchange models due to 2Î g (2B2g, 2B3g) states. We observed that the effect of polarization becomes prominent at low energies below 4 eV, decreasing the magnitude of the elastic cross section systematically as it increases for C2F2. We have also computed elastic cross sections for C2H2, C2F4 and C2H4 with a similar model and compared with the experimental data for these molecules along with C2F2. General agreement is found in terms of the shape and nature of the cross section. Such a comparison shows the reliability of the present method for obtaining the cross section for C2F2. The calculation of elastic scattering cross section is extended to higher energies up to 5 keV using the spherical complex optical potential method. The two methods are found to be consistent, merging at around 12 eV for the elastic scattering cross section. Finally we report the total ionization cross section using the binary encounter Bethe method for C2F2. The perfluorination effect in the shape and magnitude of the elastic, momentum transfer and ionization cross sections when compared with C2H2 showed a similar trend to that in the C2H4-C2F4 and C6H6-C6F6 systems. The cross-section data reported in this article could be an important input for the development of a C2F2 plasma model for selective etching of Si/SiO2 in the semiconductor industry.
Influence of regional-scale anthropogenic emissions on CO2 distributions over the western North PacificNASA Astrophysics Data System (ADS) Vay, S. A.; Woo, J.-H.; Anderson, B. E.; Thornhill, K. L.; Blake, D. R.; Westberg, D. J.; Kiley, C. M.; Avery, M. A.; Sachse, G. W.; Streets, D. G.; Tsutsumi, Y.; Nolf, S. R. updating We report here airborne measurements of atmospheric CO2 over the western North Pacific during the March-April 2001 Transport and Chemical Evolution over the Pacific (TRACE-P) mission. The CO2 spatial distributions were notably influenced by cyclogenesis-triggered transport of regionally polluted continental air masses. Examination of the CO2 to C2H2/CO ratio indicated rapid outflow of combustion-related emissions in the free troposphere below 8 km. Although the highest CO2 mixing ratios were measured within the Pacific Rim region, enhancements were also observed further east over the open ocean at locations far removed from surface sources. Near the Asian continent, discrete plumes encountered within the planetary boundary layer contained up to 393 ppmv of CO2. Coincident enhancements in the mixing ratios of C2Cl4, C2H2, and C2H4 measured concurrently revealed combustion and industrial sources. To elucidate the source distributions of CO2, an emissions database for Asia was examined in conjunction with the chemistry and 5-day backward trajectories that revealed the WNW/W sector of northeast Asia was a major contributor to these pollution events. Comparisons of NOAA/CMDL and JMA surface data with measurements obtained aloft showed a strong latitudinal gradient that peaked between 35Â° and 40Â°N. We estimated a net CO2 flux from the Asian continent of approximately 13.93 Tg C day-1 for late winter/early spring with the majority of the export (79%) occurring in the lower free troposphere (2-8 km). The apportionment of the flux between anthropogenic and biospheric sources was estimated at 6.37 Tg C day-1 and 7.56 Tg C day-1, respectively.
Combined Experimental and Computational Study on the Unimolecular Decomposition of JP-8 Jet Fuel Surrogates. I. n-Decane (n-C10H22).PubMed Zhao, Long; Yang, Tao; Kaiser, Ralf I; Troy, Tyler P; Ahmed, Musahid; Belisario-Lara, Daniel; Ribeiro, Joao Marcelo; Mebel, Alexander M updating Exploiting a high temperature chemical reactor, we explored the pyrolysis of helium-seeded n-decane as a surrogate of the n-alkane fraction of Jet Propellant-8 (JP-8) over a temperature range of updating K at a pressure of 600 Torr. The nascent products were identified in situ in a supersonic molecular beam via single photon vacuum ultraviolet (VUV) photoionization coupled with a mass spectroscopic analysis of the ions in a reflectron time-of-flight mass spectrometer (ReTOF). Our studies probe, for the first time, the initial reaction products formed in the decomposition of n-decane-including radicals and thermally labile closed-shell species effectively excluding mass growth processes. The present study identified 18 products: molecular hydrogen (H 2 ), C2 to C7 1-alkenes [ethylene (C 2 H 4 ) to 1-heptene (C 7 H 14 )], C1-C3 radicals [methyl (CH 3 ), vinyl (C 2 H 3 ), ethyl (C 2 H 5 ), propargyl (C 3 H 3 ), allyl (C 3 H 5 )], small C1-C3 hydrocarbons [methane (CH 4 ), acetylene (C 2 H 2 ), allene (C 3 H 4 ), methylacetylene (C 3 H 4 )], along with higher-order reaction products [1,3-butadiene (C 4 H 6 ), 2-butene (C 4 H 8 )]. On the basis of electronic structure calculations, n-decane decomposes initially by C-C bond cleavage (excluding the terminal C-C bonds) producing a mixture of alkyl radicals from ethyl to octyl. These alkyl radicals are unstable under the experimental conditions and rapidly dissociate by C-C bond Î²-scission to split ethylene (C 2 H 4 ) plus a 1-alkyl radical with the number of carbon atoms reduced by two and 1,4-, 1,5-, 1,6-, or 1,7-H shifts followed by C-C Î²-scission producing alkenes from propene to 1-octene in combination with smaller 1-alkyl radicals. The higher alkenes become increasingly unstable with rising temperature. When the C-C Î²-scission continues all the way to the propyl radical (C 3 H 7 ), it dissociates producing methyl (CH 3 ) plus ethylene (C 2 H 4 ). Also, at higher temperatures, hydrogen atoms can abstract hydrogen
New Radiative Transfer Capability in the EPIC Atmospheric Model with Application to Saturn and UranusNASA Astrophysics Data System (ADS) Dowling, Timothy Edward; Greathouse, T. K.; Sussman, M. G.; Chanover, N. J. updating We have adapted radiative transfer (RT) schemes from the gas-giant seasonal models of Greathouse et al. (EGU 2010) and Sussman et al. (AGU 2009) into the EPIC atmospheric model, and applied them to Saturn and Uranus. These additions give EPIC a hierarchy of RT options to account for solar heating via CH4 absorption from 5 microns to the UV, and radiative cooling due to thermal emission of CH4, C2H2, C2H6, and collision-induced opacity between 0 and 1600 cm-1. We have written an IDL tool to calculate radiative-equilibrium T(p) profiles for model initialization. We have ported the versatile DISORT RT model (Stamnes et al. 1988) from Fortran to C, and are incorporating it into an IDL post-processing tool to allow us to create synthetic spectra from EPIC output that accounts for thermal emission, reflected solar light, and aerosol and Rayleigh scattering. We give an update of applications to simulations of middle-atmosphere temperatures for Saturn and zonal-wind spin-up experiments for Uranus. This research is supported by NASA Planetary Atmospheres grant NNX08AE64G and NSF Planetary Astronomy grant AST-0807989.
Seasonal Variations in Titan's Stratosphere Observed with Cassini/CIRS: Temperature, Trace Molecular Gas and Aerosol Mixing Ratio ProfilesNASA Technical Reports Server (NTRS) Vinatier, S.; Bezard, B.; Anderson, C. M.; Coustenis, A.; Teanby, N. updating Titan's northern spring equinox occurred in August 2009. General Circulation Models (e.g. Lebonnois et al., 2012) predict strong modifications of the global circulation in this period, with formation of two circulation cells instead of the pole-to-pole cell that occurred during northern winter. This winter single cell, which had its descending branch at the north pole, was at the origin of the enrichment of molecular abundances and high stratopause temperatures observed by Cassini/CIRS at high northern latitudes (e.g. Achterberg et al., 2011, Coustenis et al., 2010, Teanby et al., 2008, Vinatier et al., 2010). The predicted dynamical seasonal variations after the equinox have strong impact on the spatial distributions of trace gas, temperature and aerosol abundances. We will present here an analysis of CIRS limb-geometry datasets acquired in 2010 and 2011 that we used to monitor the seasonal evolution of the vertical profiles of temperature, molecular (C2H2, C2H6, HCN, ..) and aerosol abundances.
Measuring ethane and acetylene in Antarctic ice cores to quantify long-term hydrocarbon emissions from tropical firesNASA Astrophysics Data System (ADS) Nicewonger, M. R.; Aydin, M.; Prather, M. J.; Saltzman, E. S. updating This study examines ethane (C2H6) and acetylene (C2H2) in polar ice cores in order to reconstruct variations in the atmospheric levels of these trace gases over the past 2,000 years. Both of these non-methane hydrocarbons are released from fossil fuel, biofuel, and biomass burning. Ethane, but not acetylene, is also emitted from natural geologic outgassing of hydrocarbons. In an earlier study, we reported ethane levels in Greenland and Antarctic ice cores showing roughly equal contributions from biomass burning and geologic emissions to preindustrial atmospheric ethane levels (Nicewonger et al., 2016). Here we introduce acetylene as an additional constraint to better quantify preindustrial variations in the emissions from these natural hydrocarbon sources. Here we present 30 new measurements of ethane and acetylene from the WDC-06A ice core from WAIS Divide and the newly drilled South Pole ice core (SPICECORE). Ethane results display a gradual decline from peak levels of 110 ppt at 1400 CE to a minimum of 60-80 ppt during updating CE. Acetylene correlates with ethane (r2 > 0.4), dropping from peak levels of 35 ppt at 1400 CE to 15-20 ppt at 1875 CE. The covariance between the two trace gases implies that the observed changes are likely caused by decreasing emissions from low latitude biomass burning. We will discuss results from chemical transport modeling and sensitivity tests and the implications for the preindustrial ethane and acetylene budgets.
Atmos/Atlas 3 Infrared Profile Measurements of Trace Gases in The November 1994 Tropical and Subtropical Upper TroposphereNASA Technical Reports Server (NTRS) Rinsland, C. P.; Gunson, M. R.; Wang, P.-H.; Arduini, R. F.; Baum, B. A.; Minnis, P.; Minnis, P.; Goldman, A.; Abrams, M. C.; Zander, R.; updating Vertical mixing ratio profiles of four relatively long-lives gases, HCN, C2H2, CO, and C2H6, have been retrieved from 0.01/cm resolution infrared solar occultation spectra recorded between latitudes of 5.3degN and 31.4degN. The observations were obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer during the Atmospheric Laboratory for Applications and Science (ATLAS) 3 shuttle flight, 3-12 November 1994. Elevated mixing ratios below the tropopause were measured for these gases during several of the occultations. The positive correlations obtained between the simultaneously measured mixing ratios suggest that the enhancements are likely the result of surface emissions, most likely biomass burning and/or urban industrial activities, followed by common injection via deep convective transport of the gases to the upper troposphere. The elevated levels of HCN may account for at least part of the "missing NO," in the upper troposphere. Comparisons of the observations with values measured during a recent aircraft campaign are presented.
Studying the internal ballistics of a combustion-driven potato cannon using high-speed videoNASA Astrophysics Data System (ADS) Courtney, E. D. S.; Courtney, M. W. updating A potato cannon was designed to accommodate several different experimental propellants and have a transparent barrel so the movement of the projectile could be recorded on high-speed video (at 2000 frames per second). Five experimental propellants were tested: propane (C3H8), acetylene (C2H2), ethanol (C2H6O), methanol (CH4O) and butane (C4H10). The quantity of each experimental propellant was calculated to approximate a stoichometric mixture and considering the upper and lower flammability limits, which in turn were affected by the volume of the combustion chamber. Cylindrical projectiles were cut from raw potatoes so that there was an airtight fit, and each weighed 50 (Â± 0.5) g. For each trial, position as a function of time was determined via frame-by-frame analysis. Five trials were made for each experimental propellant and the results analyzed to compute velocity and acceleration as functions of time. Additional quantities, including force on the potato and the pressure applied to the potato, were also computed. For each experimental propellant average velocity versus barrel position curves were plotted. The most effective experimental propellant was defined as that which accelerated the potato to the highest muzzle velocity. The experimental propellant acetylene performed the best on average (138.1 m s-1), followed by methanol (48.2 m s-1), butane (34.6 m s-1), ethanol (33.3 m s-1) and propane (27.9 m s-1), respectively.
Production of organic compounds in plasmas: A comparison among electric sparks, laser-induced plasmas and UV lightNASA Technical Reports Server (NTRS) Scattergood, T. W.; Mckay, C. P.; Borucki, W. J.; Giver, L. P.; Vanghyseghem, H.; Parris, J. E.; Miller, S. L. updating In order to study the production of organic compounds in plasmas (and shocks), various mixtures of N2, CH4, and H2, modeling the atmosphere of Titan, were exposed to discrete sparks, laser-induced plasmas (LIP) and ultraviolet light. The yields of HCN and simple hydrocarbons were measured and compared to those calculated from a simple quenched thermodynamic equilibrium model. The agreement between experiment and theory was fair for HCN and C2H2. However, the yields of C2H6 and other hydrocarbons were much higher than those predicted by the model. Our experiments suggest that photolysis by ultraviolet light from the plasma is an important process in the synthesis. This was confirmed by the photolysis of gas samples exposed to the light, but not to the plasma or shock waves. The results of these experiments demonstrate that, in addition to the well-known efficient synthesis of organic compounds in plasmas, the yields of saturated species, e.g., ethane, may be higher than predicted by theory and that LIP provide a convenient and clean way of simulating planetary lightning and impact plasmas in the laboratory.
Influence of Haze on Molecular Lines Formed in the Atmosphere of TitanNASA Astrophysics Data System (ADS) Kim, Sang J. updating Radiative transfer calculations for the ro-vibrational lines of CH4, C2H2, C2H6, and HCN in atmosphere of Titan have been carried out without consideration of haze opacities (e.g., Yelle and Griffith, 2003), or only for very high (z > 500 km) atmospheric layers where haze influence is assumed to be negligible (e.g., Adriani et al. 2011; and GarcÃa-Comas et al. 2011). Haze particles are found to exist in the high-altitude atmosphere of Titan, where the absorption lines of these molecules are modified by the haze opacities (Bellucci et al. 2009; Kim et al. 2011). We will present a discussion on the influence of the haze opacities on these molecular lines based on a preliminary result from updated radiative transfer calculations. References Adriani, A. et al. 2011. Icarus 214, 584-595. Bellucci, A. et al. 2009. Icarus 201, 198-216. GarcÃa-Comas, M. et al. 2011. Icarus 214, 571-583. Kim, et al. updating. Planetary and Space Science 59, 699-704. Yelle, R.V., Griffith, C.A., 2003. Icarus 166, 107-115.
Search for low-latitude atmospheric hydrocarbon variations on Jupiter from Juno-UVS measurementsNASA Astrophysics Data System (ADS) Hue, V.; Gladstone, R.; Greathouse, T.; Versteeg, M.; Davis, M. W.; Gerard, J. C. M. C.; Grodent, D. C.; Bonfond, B.; Bolton, S. J.; Levin, S.; Connerney, J. E. P. updating The Juno mission offers the opportunity to study Jupiter, from its inner structure, up to its magnetospheric environment. Juno was launched on August 2011 and its Jupiter orbit insertion (JOI) occurred on July 4th 2016. The nominal Juno mission involves 35 science polar-orbits of 14-days period, with perijove and apojove distances located at 0.06 Rj and 45 Rj, respectively. Juno-UVS is a UV spectrograph with a bandpass of 70C2H2 and C2H6 are known to absorb significantly in the 150-180 nm regions, and these absorption features can be used to determine their abundances. We will present our search for the spectroscopic features seen in Jupiter's reflected sunlight during the first perijove.
Chemistry and spectroscopy of the Jovian atmosphereNASA Technical Reports Server (NTRS) Prinn, R. G.; Owen, T. updating A comprehensive review is given of the chemistry and spectroscopic studies of the Jovian atmosphere. Thermochemical equilibrium models for determining atmospheric composition are considered along with possible disequilibrating processes, and studies of the photochemistry of H2, CH4, NH3, H2S, and PH3 using the modeling methods are summarized. It is shown that photodissociation and advection are the major disequilibrating processes in Jupiter's atmosphere, that lightning and charged-particle bombardment are relatively minor factors in the planet's bulk chemistry, and that the existence of living organisms on the planet is highly improbable. Spectroscopic investigations of Jupiter are discussed, emphasizing recent observations of absorption bands due to CH4, NH3, H2, He, and D. Spectroscopic abundance determinations are examined for H2, HD, CH4, CH3D, NH3, C2H6, C2H2, and PH3. Upper limits are given for the abundances of several unobserved gases in the visible atmosphere, including H2S, HCl, SiH4, benzene, purines, pyrimidines, and their derivatives.
Organic Volatiles in Comet 73P-B/Schwassmann-Wachmann 3 Observed during Its Outburst: A Clue to the Formation Region of the Jupiter-Family CometsNASA Astrophysics Data System (ADS) Kobayashi, Hitomi; Kawakita, Hideyo; Mumma, Michael J.; Bonev, Boncho P.; Watanabe, Jun-ichi; Fuse, Tetsuharu updating We report the chemical composition of organic molecules in fragment B of comet 73P/Schwassmann-Wachmann 3 (SW3). Comet SW3 is a Jupiter-family comet that split into three fragments during its 1995 apparition and later into additional components. It was expected that fresh ices from deep within the presplit nucleus were exposed on the surface of each fragment. We observed SW3 with the Subaru telescope in 2006 early May when component B was disintegrating rapidly. If this exposed fresh ices from deeper layers of the original nucleus, mixing ratios obtained from our observations may reflect the pristine nature of the comet. Based on our results, comet SW3-B was depleted in C2H6 and C2H 2 with respect to most comets from the Oort Cloud reservoir, suggesting its formation region might have differed from that of the dominant Oort Cloud comets. Furthermore, the chemical composition of SW3-B was similar to that of SW3-C, suggesting that the presplit nucleus was almost homogeneous in volatile composition. The combined results demonstrate that depleted-organics comets from a common formation zone entered both reservoirs, of Jupiter-family comets and and Oort Cloud comets, but likely in different fractions. This Letter is based on data collected at Subaru Telescope, which is operated by the National Astronomical Observatory of Japan. This work was financially supported by the Ministry of Education, Science, and Culture, Grant-in-Aid for Young Scientists updating (H. K.).
Chemical Composition of Asian Continental Outflow over the Western Pacific: Results from Transport and Chemical Evolution over the Pacific (TRACE-P)NASA Technical Reports Server (NTRS) Russo, R. S.; Talbot, R. W.; Dibb, J. E.; Scheuer, E.; Seid, G.; Jordan, C. E.; Fuelberg, H. E.; Sachse, G. W.; Avery, M. A.; Vay, S. A. updating We characterize the chemical composition of Asian continental outflow observed during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) mission during February-April 2001 in the western Pacific using data collected on the NASA DC-8 aircraft. A significant anthropogenic impact was present in the free troposphere and as far east as 150degE longitude reflecting rapid uplift and transport of continental emissions. Five-day backward trajectories were utilized to identify five principal Asian source regions of outflow: central, coastal, north-northwest(NNW), southeast (SE), and west-southwest (WSW). The maximum mixing ratios for several species, such as CO, C2Cl4, CH3Cl, and hydrocarbons, were more than a factor of 2 larger in the boundary layer of the central and coastal regions due to industrial activity in East Asia. CO was well correlated with C2H2, C2H6, C2Cl4, and CH3Cl at low altitudes in these two regions (r(sup 2) approx. updating). The NNW, WSW, and SE regions were impacted by anthropogenic sources above the boundary layer presumably due to the longer transport distances of air masses to the western Pacific. Frontal and convective lifting of continental emissions was most likely responsible for the high altitude outflow in these three regions. Photochemical processing was influential in each source region resulting in enhanced mixing ratios of O3, PAN, HNO3, H2O2, and CH3OOH. The air masses encountered in all five regions were composed of a complex mixture of photcrchemically aged air with more recent emissions mixed into the outflow as indicated by enhanced hydrocarbon ratios (C2H2/CO greater than or equal to 3 and C3H8/C2H6 greater than or equal to 0.2). Combustion, industrial activities, and the burning of biofuels and biomass all contributed to the chemical composition of air masses from each source region as demonstrated by the H6, SO2, and C2Cl4 were compared for the TRACE-P and PEM-West B missions. In the more northern regions, O3, CO
Cluster size selectivity in the product distribution of ethene dehydrogenation on niobium clusters.PubMed Parnis, J Mark; Escobar-Cabrera, Eric; Thompson, Matthew G K; Jacula, J Paul; Lafleur, Rick D; Guevara-GarcÃa, Alfredo; MartÃnez, Ana; Rayner, David M updating Ethene reactions with niobium atoms and clusters containing up to 25 constituent atoms have been studied in a fast-flow metal cluster reactor. The clusters react with ethene at about the gas-kinetic collision rate, indicating a barrierless association process as the cluster removal step. Exceptions are Nb8 and Nb10, for which a significantly diminished rate is observed, reflecting some cluster size selectivity. Analysis of the experimental primary product masses indicates dehydrogenation of ethene for all clusters save Nb10, yielding either Nb(n)C2H2 or Nb(n)C2. Over the range Nb-Nb6, the extent of dehydrogenation increases with cluster size, then decreases for larger clusters. For many clusters, secondary and tertiary product masses are also observed, showing varying degrees of dehydrogenation corresponding to net addition of C2H4, C2H2, or C2. With Nb atoms and several small clusters, formal addition of at least six ethene molecules is observed, suggesting a polymerization process may be active. Kinetic analysis of the Nb atom and several Nb(n) cluster reactions with ethene shows that the process is consistent with sequential addition of ethene units at rates corresponding approximately to the gas-kinetic collision frequency for several consecutive reacting ethene molecules. Some variation in the rate of ethene pick up is found, which likely reflects small energy barriers or steric constraints associated with individual mechanistic steps. Density functional calculations of structures of Nb clusters up to Nb(6), and the reaction products Nb(n)C2H2 and Nb(n)C2 (n = 1...6) are presented. Investigation of the thermochemistry for the dehydrogenation of ethene to form molecular hydrogen, for the Nb atom and clusters up to Nb6, demonstrates that the exergonicity of the formation of Nb(n)C2 species increases with cluster size over this range, which supports the proposal that the extent of dehydrogenation is determined primarily by thermodynamic constraints. Analysis of
Nitrogen Fixation (Acetylene Reduction) Associated with Duckweed (Lemnaceae) MatsPubMed Central Zuberer, D. A. updating Duckweed (Lemnaceae) mats in Texas and Florida were investigated, using the acetylene reduction assay, to determine whether nitrogen fixation occurred in these floating aquatic macrophyte communities. N2-fixing microorganisms were enumerated by plating or most-probable-number techniques, using appropriate N-free media. Results of the investigations indicated that substantial N2-fixation (C2H2) was associated with duckweed mats in Texas and Florida. Acetylene reduction values ranged from 1 to 18 Î¼mol of C2H4 g (dry weight)â1 dayâ1 for samples incubated aerobically in light. Dark N2 fixation was always two- to fivefold lower. 3-(3,4-Dichlorophenyl)-1,1-dimethylurea (7 to 10 Î¼M) reduced acetylene reduction to levels intermediate between light and dark incubation. Acetylene reduction was generally greatest for samples incubated anaerobically in the light. It was estimated that 15 to 20% of the N requirement of the duckweed could be supplied through biological nitrogen fixation. N2-fixing heterotrophic bacteria (105 cells g [wet weight]â1 and cyanobacteria (105 propagules g [wet weight]â1 were associated with the duckweed mats. Azotobacter sp. was not detected in these investigations. One diazotrophic isolate was classified as Klebsiella. PMID:updating
Photochemistry, Ion Chemistry, and Haze Formation in Plutoâs AtmosphereNASA Astrophysics Data System (ADS) Summers, Michael E.; Stern, S. A.; Gladstone, G. Randal; Young, Leslie A.; Olkin, C. B.; Weaver, H. A.; Cheng, A. F.; Strobel, D. F.; Ennico, K. A.; Kammer, J. A.; Parker, A. H.; Retherford, K. D.; Schindhelm, E.; Singer, K. N.; Steffl, A. J.; Tsang, C. C.; Versteeg, M. H.; Greathouse, T. K.; Linscott, I. R.; Tyler, L. G.; Woods, W. W.; Hinson, D. P.; Parker, J. W.; Renaud, J. P.; Ewell, M.; Lisse, Cary M. updating The detection of ethylene (C2H4) and acetylene (C2H2) in Plutoâs atmosphere provides important ground-truth observations for validating photochemical models of Plutoâs atmosphere. Their detection also confirms the production of precursor chemical compounds involved in the formation of tholins, which are thought to give Plutoâs surface its reddish color. Photochemical models predict many other hydrocarbon and nitrile products, currently undetected, which may also be participants in tholin production on Plutoâs surface or on atmospheric haze particles. The observed atmospheric haze layer extending to altitudes of ~140 km above Plutoâs surface, suggests a global and very robust process of atmospheric particle nucleation, growth, and sedimentation onto Plutoâs surface. The high altitude extent of the haze layer suggests that the nucleation process begins above the expected altitude range where hydrocarbons become supersaturated (below ~30 km altitude). This situation may be analogous to that in Titanâs atmosphere, wherein nucleation and aerosol growth is directly related to large negative ion production. In the case of Pluto, this means that nucleation may occur at altitudes as high as 1200 km altitude where ionization in Plutoâs atmosphere peaks. In this paper we discuss these processes and their implications for haze formation in Plutoâs atmosphere and its deposition onto Plutoâs surface. This work was supported by NASA's New Horizons project.
Azolla filiculoides Nitrogenase Activity Decrease Induced by Inoculation with Chlamydomonas sp. âPubMed Central Habte, Mitiku updating Experiments were conducted to determine the influence of Chlamydomonas sp. on nitrogen fixation (C2H2 â C2H4) in Azolla filiculoides and on the nitrogen fixation and growth of free-living Anabaena azollae 2B organisms. Inoculation of azolla medium with Chlamydomonas sp. was associated with decreased nitrogenase activity in A. filiculoides and with increases in the density of a fungal population identified as Acremonium sp. Subsequent inoculation of azolla medium with this fungus was also accompanied by a significant decrease in nitrogenase activity of A. filiculoides. However, the extent of depression of nitrogenase activity was significantly higher when azolla medium was inoculated with Chlamydomonas sp. than when it was inoculated with Acremonium sp. Inoculation of nitrogen-free Stanier medium with either Acremonium sp. or Chlamydomonas sp. did not adversely affect the growth or nitrogenase activity of free-living A. azollae. Decreased nitrogenase activity in A. filiculoides is apparently related to the adverse influence of the green alga and the fungus on the macrosymbiont. The mechanisms that might be involved are discussed. PMID:updating

READ Ba + 2 H2O → Ba(OH)2 + H2 – Balanced equation

Investigation of lithium sulfur dioxide (Li/SO2) battery safety hazards: Chemical studiesNASA Astrophysics Data System (ADS) Abraham, K. M.; Rupich, M. W.; Pitts, L. updating The chemistry associated with the discharge and forced overdischarge of the Li/SO2 cell was investigated in detail. A procedure for the quantitative determination of Li2S2O4 in discharged Li/SO2 cells is described. The amount of Li2S2O4 found in cells discharged to potentials down to zero volt was in very good agreement with the discharge stoichiometry, 2Li + 2SO2 yields Li2S2O4. The Li2S2O4 formed in the carbon cathode was also characterized by infrared, ESCA, and X-ray analyses. A number of organic compounds including CH4 and 3,5-diamino-2,4-hexenenitrile have been identified in forced overdischarged cells. Products identified in cells which vented during forced overdischarge include: CO2, CS2, COS, H2S, CH4, C2H4, C2H2, Li2S, and Li2SO3.
Hidden Hydride Transfer as a Decisive Mechanistic Step in the Reactions of the Unligated Gold Carbide [AuC]+ with Methane under Ambient Conditions.PubMed Li, Jilai; Zhou, Shaodong; Schlangen, Maria; Weiske, Thomas; Schwarz, Helmut updating The reactivity of the cationic gold carbide [AuC] + (bearing an electrophilic carbon atom) towards methane has been studied using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The product pairs generated, that is, Au + /C 2 H 4 , [Au(C 2 H 2 )] + /H 2 , and [C 2 H 3 ] + /AuH, point to the breaking and making of C-H, C-C, and H-H bonds under single-collision conditions. The mechanisms of these rather efficient reactions have been elucidated by high-level quantum-chemical calculations. As a major result, based on molecular orbital and NBO-based charge analysis, an unprecedented hydride transfer from methane to the carbon atom of [AuC] + has been identified as a key step. Also, the origin of this novel mechanistic scenario has been addressed. The mechanistic insights derived from this study may provide guidance for the rational design of carbon-based catalysts. Â© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Nucleation of Hydrogen Deficient Carbon Clusters in Circumstellar Envelopes of Carbon StarsNASA Astrophysics Data System (ADS) Chiong, C. C.; Asvany, O.; Balucani, N.; Lee, Y. T.; Kaiser, R. I. updating Hydrogen deficient carbon clusters HCn and H2Cn are thought to resemble the crucial link between naked carbon clusters such as C2/C3, polycyclic aromatic hydrocarbons, and carbon rich interstellar/circumstellar grains. To fully understand the astrophysical significance of these grain nuclei condensation processes, it is of paramount significance to elucidate first detailed mechanism how these simple precursors are formed in outflow of carbon rich stars. Due to this importance, we initiated in our laboratory a systematic research program to investigate reactions of C2 and C3 clusters in their singlet X1Î£g+ ground state with unsaturated hydrocarbons C2H2 and C2H4 employing the crossed molecular beam technique. These experiments yield the first doubly differential reactive cross section on the cluster versus H/H2 exchange and supply valuable information on the stepwise growth of carbon rich structures in extraterrestrial environments. Preliminary data analyses identify the CCCCH, CCCCH, and CCCCH2 isomers which were identified in the circumstellar shell of IRC+10216 together with hitherto unobserved interstellar n-C4H3, n-C5H3, and CCCCCH2 radicals.
Investigating the Chemical Pathways to PAH- and PANH-Based Aerosols in Titan's Atmospheric chemistryNASA Technical Reports Server (NTRS) Sciamma-O'Brien, Ella Marion; Contreras, Cesar; Ricketts, Claire Louise; Salama, Farid updating A complex organic chemistry between Titan's two main constituents, N2 and CH4, leads to the production of more complex molecules and subsequently to solid organic aerosols. These aerosols are at the origin of the haze layers giving Titan its characteristic orange color. In situ measurements by the Ion Neutral Mass Spectrometer (INMS) and Cassini Plasma Spectrometer (CAPS) instruments onboard Cassini have revealed the presence of large amounts of neutral, positively and negatively charged heavy molecules in the ionosphere of Titan. In particular, benzene (C6H6) and toluene (C6H5CH3), which are critical precursors of polycyclic aromatic hydrocarbon (PAH) compounds, have been detected, suggesting that PAHs might play a role in the production of Titan s aerosols. Moreover, results from numerical models as well as laboratory simulations of Titan s atmospheric chemistry are also suggesting chemical pathways that link the simple precursor molecules resulting from the first steps of the N2-CH4 chemistry (C2H2, C2H4, HCN ...) to benzene, and to PAHs and nitrogen-containing PAHs (or PANHs) as precursors to the production of solid aerosols.
Organic Molecules in Oxygen-Rich Circumstellar Envelopes: Methanol and HydrocarbonsNASA Technical Reports Server (NTRS) Charnley, S. B.; Tielens, A. G. G. M.; Kress, M. E. updating The existence of anomalously high abundances of gaseous CH4 has been invoked to explain the unexpectedly high abundances of the carbon-bearing molecules HCN and H2CO in the outflows from O-rich red giants. We have modelled the chemistry that proceeds in the outer envelope when CH4 is injected from the inner envelope. We find that photolysis by the interstellar radiation field drives an ion-neutral chemistry which produces several organic molecules. The calculated abundances of CH3OH, C2H and C2 can be comparable to those calculated for H2CO and HCN. Species such as C2H4, C2H2 and CH3CN can also be abundant. A search for CH3OH and C2H in several O-rich outflows known to exhibit strong HCN emission is needed. As it derives entirely from the CH4 photochain, is insensitive to the envelope temperature distribution, and has accessible transitions at millimetre wavelengths, the detection of the C2H radical would provide further indirect support for the presence of the hypothesized methane.
Differentiation of three pairs of aconite alkaloid isomers from Aconitum nagarum var. lasiandrum by electrospray ionization tandem mass spectrometry.PubMed Li, Rui; Wu, Zhijun; Zhang, Fan; Ding, Lisheng updating Three pairs of isomers of aconite alkaloids from Aconitum nagarum var. lasiandrum have been investigated by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS) employing ion-trap and quadrupole time-of-flight mass spectrometers in positive mode. Based on the differences of their fragmentation pathways and special fragment ions, three pairs of isomers of aconite alkaloids were differentiated. In addition, fragmentation laws of some veatchines and the discrepancy of fragmentation mechanisms between veatchine-type and aconitine-type alkaloid were also concluded. In the case of veatchines, a radical would be formed by homolysis of C18--C4 or C18--H bonds, followed by elimination of a series of C(2)H(2) and C(2)H(4). Moreover, the retro-Diels-Alder (RDA) reaction occurred in the E-ring and double-electron transfer triggered by the positive charge on C1 led to the formation of diagnostic ions at m/z 216. With regard to aconitine-type alkaloids, the N-substituent is not eliminated easily. Although there is no carbonyl group on some aconitine-type alkaloids, with hydroxyl and methoxyl on C15 and C16 respectively, CO was readily eliminated through tautomerization.
Communication: Correct charge transfer in CT complexes from the Becke'05 density functionalNASA Astrophysics Data System (ADS) Becke, Axel D.; Dale, Stephen G.; Johnson, Erin R. updating It has been known for over twenty years that density functionals of the generalized-gradient approximation (GGA) type and exact-exchange-GGA hybrids with low exact-exchange mixing fraction yield enormous errors in the properties of charge-transfer (CT) complexes. Manifestations of this error have also plagued computations of CT excitation energies. GGAs transfer far too much charge in CT complexes. This error has therefore come to be called "delocalization" error. It remains, to this day, a vexing unsolved problem in density-functional theory (DFT). Here we report that a 100% exact-exchange-based density functional known as Becke'05 or "B05" [A. D. Becke, J. Chem. Phys. 119, updating); 122, updating)] predicts excellent charge transfers in classic CT complexes involving the electron donors NH3, C2H4, HCN, and C2H2 and electron acceptors F2 and Cl2. Our approach is variational, as in our recent "B05min" dipole moments paper [Dale et al., J. Chem. Phys. 147, updating)]. Therefore B05 is not only an accurate DFT for thermochemistry but is promising as a solution to the delocalization problem as well.
A Model of Titan-like Chemistry to Connect Experiments and Cassini ObservationsNASA Astrophysics Data System (ADS) Raymond, Alexander W.; Sciamma-OâBrien, Ella; Salama, Farid; Mazur, Eric updating A numerical model is presented for interpreting the chemical pathways that lead to the experimental mass spectra acquired in the Titan Haze Simulation (THS) laboratory experiments and for comparing the electron density and temperature of the THS plasma to observations made at Titan by the Cassini spacecraft. The THS plasma is a pulsed glow-discharge experiment designed to simulate the reaction of N2/CH4-dominated gas in Titan's upper atmosphere. The transient, one-dimensional model of THS chemistry tracks the evolution of more than 120 species in the direction of the plasma flow. As the minor species C2H2 and C2H4 are added to the N2/CH4-based mixture, the model correctly predicts the emergence of reaction products with up to five carbon atoms in relative abundances that agree well with measured mass spectra. Chemical growth in Titan's upper atmosphere transpires through ionâneutral and neutralâneutral chemistry, and the main reactions involving a series of known atmospheric species are retrieved from the calculation. The model indicates that the electron density and chemistry are steady during more than 99% of the 300 Î¼s long discharge pulse. The model also suggests that the THS ionization fraction and electron temperature are comparable to those measured in Titan's upper atmosphere. These findings reaffirm that the THS plasma is a controlled analog environment for studying the first and intermediate steps of chemistry in Titan's upper atmosphere.
Monitoring gas concentrations in environmental and atmospheric applications using tunable diode lasersNASA Astrophysics Data System (ADS) Awtry, Andrew R. Two atmospheric chemistry processes that contribute to environmental concerns have been explored using mid-infrared, lead-salt diode lasers. Tunable diode laser absorption spectroscopy was used to determine concentrations of both NF3 and NH3. The focus of the NF3 research was to determine the magnitude of the nu1 absorption band in order to determine the effects of this molecule on global warming. Deposition velocity is a proportionality constant between concentration and vertical flux to a surface. The magnitude of this constant for NH 3 depositing onto water is experimentally determined using both a small cell (425 mL) and a large chamber (335 L). The results from the chamber are then incorporated into a model in an attempt to better understand the atmospheric contribution to aqueous concentrations. Near-infrared diode lasers were used in both integrated cavity output spectroscopy and cavity ringdown spectroscopy in an attempt to develop an air monitoring sensor. The following experiments were then performed determine the sensitivity, durability and dynamic range of these two techniques: flame characterization of HCN and C2H2 in a flame from a Wolfhard-Parker burner, obtaining isolated absorption features of CO, CO2, H 2O, HCN, NH3, CH4, and C2H4 in order to create calibration curves and determine detection limits, CO 2 classroom measurements, and CO2 isotope ratio measurements.
Detection methods for atoms and radicals in the gas phaseNASA Astrophysics Data System (ADS) Hack, W. This report lists atoms and free radicals in the gas phase which are of interest for environmental and flame chemistry and have been detected directly. The detection methods which have been used are discussed with respect to their range of application, specificity and sensitivity. In table 1, detection methods for the five atoms of group IV (C, Si, Ge, Sn, Pb) and about 60 radicals containing at least one atom of group IV are summarized (CH, Cd, Cf, CC1, CBr, Cn, Cs, CSe, CH2, CD2, Chf, Cdf, CHC1, CHBr, CF2, CC12, CBr2, CFC1, CFBr, CH3, CD3, CF3, CH2F, CH2C1, CH2Br, CHF2, CHC12, CHBr2, Hco, Fco, CH30, CD30, CH2OH, CH3S, Nco, CH4N, CH302, CF302; C2, C2N, C2H, C20, C2HO, C2H3, C2F3, C2H5, C2HsO, C2H4OH, CH3CO, CD3CO, C2H3O, C2H502, CH3COO2, C2H4N, C2H6N, C3; Si, SiF, SiF2, SiO, SiC, Si2; Ge, GeC, GeO, GeF, GeF2, GeCl2, Sn, SnF, SnO, SnF2, Pb, PbF, PbF2, PbO, PbS). In table 2 detection methods for about 25 other atoms and 60 radicals are listed: (H, D, O, O2, Oh, Od, HO2, DO2, F, Ci, Br, I, Fo, Cio, BrO, Io, FO2, C1O2, Li, Na, K, Rb, Cs, N, N3, Nh, Nd, Nf, Nci, NBr, NH2, ND2, Nhd, Nhf, NF2, NC12, N2H3, No, NO2, NO3, Hno, Dno, P, Ph, Pd, Pf, Pci, PH2, PD2, PF2, Po, As, AsO, AsS, Sb, Bi, S, S2, Sh, Sd, Sf, SF2, So, Hso, Dso, Sn, Se, Te, Se2, SeH, SeD, SeF, SeO, SeS, SeN, TeH, TeO, Bh, BH2, Bo, Bn, B02, Cd, Hg, UF5). The tables also cite some recent kinetic applications of the various methods.
A Deep Search for Biomarker Gases on Mars in updating: The Campaign and a Few Preliminary ResultsNASA Astrophysics Data System (ADS) Mumma, M. J.; Villanueva, G. L.; Novak, R.; Radeva, Y. L.; Kaufl, H.; Smette, A.; Hartogh, P.; Encrenaz, T. updating We searched for possible biomarker gases on Mars in the updating observing season, emphasizing nine molecules (H2_O, CH_4_, C2_H_6_, C2_H_4_, CH3_OH, H_2_CO, H2_S, and N_2_O) of fundamental astrobiological importance along with HDO and CO2_. Our search utilized Earthâs most advanced ground-based infrared spectroscopic facilities in a campaign of several dozen observing runs spanning the period 19 August 2009 to 10 June 2010. Over this interval (L_s_ = updating degrees), the season in Marsâ Northern hemisphere progressed from mid-winter, through vernal equinox and spring, and into early summer. We used long-slit high-resolution infrared spectrometers at the Keck and NASA-IRTF observatories in Hawaii, and the European Southern Observatory in Chile (VLT, Paranal). The spectral resolving powers ranged from ~ 35,000 (NIRSPEC/Keck and CSHELL/IRTF) to ~ 90,000 (CRIRES, VLT). At the sub-Earth point, the spatial resolution in non-AO mode ranged from ~600 km (FWHM) to ~ 400 km at Keck and IRTF. Using the adaptive optics (AO) mode at Keck and at VLT, we achieved an improved resolution of ~250 km (FWHM). We mapped the planet over the Earth-facing hemisphere by orienting the slit North-South in longitude and stepping it East-West across the planet, and we acquired deep searches over restricted longitude ranges by holding the slit fixed in position and taking sequential spectra as Mars rotated under it. Spectral lines of CO2_, H_2_O, HDO, and O2_ (a^1^Îg_) are obvious, even in the raw data. In the methane region near 3.3Âµm, removal of terrestrial and solar spectral lines revealed multiple lines of Mars H_2_O and CO2_, from which we extracted 2-D (lat-long) maps of Martian water vapor, atmospheric surface pressure and temperature. Subtraction of these features provided highly sensitive searches for trace gases. Preliminary results of searches for CH_4_, C2_H_4_, and C2_H_6_ will be presented in this paper. Radeva et al. (this meeting) will present preliminary results for
The Chemical Composition of Comet C/2012 S1 (ISON) between 1.2 and 0.35 AU of the SunNASA Astrophysics Data System (ADS) DiSanti, Michael A.; Bonev, Boncho P.; Gibb, Erika L.; Villanueva, Geronimo L.; Paganini, Lucas; Mumma, Michael J.; Keane, Jacqueline V.; Meech, Karen J.; Blake, Geoff A.; McKay, Adam J. updating The apparition of dynamically new, sun-grazing C/2012 S1 (ISON) [1] generated considerable ground- and space-based interest, and provided the rare opportunity to conduct compositional studies to heliocentric distances (Rh) well within 1 AU. We report gas production rates and molecular abundances from high-resolution (Î»/ÎÎ» ~ 25,000) spectra on four dates (UT 2013 Oct 22, 24, 25, and Nov 7) using NIRSPEC [2] at Keck 2, and on six dates (Nov 15 through 19, and Nov 22) using CSHELL [3] at the NASA-IRTF. This permitted measuring volatile abundances over a wide range in Rh.NIRSPEC is cross-dispersed and so allows simultaneous measure of trace species together with H2O, thereby avoiding most sources of systematic uncertainty, for example those associated with differences in slit losses and flux calibration among echelle orders. CSHELL has limited spectral coverage per setting, however the IRTF is unique among ground-based IR observatories in allowing daytime observations. This permitted compositional measurements of ISON to a minimum solar elongation angle of 20 degrees.A suite of molecules (H2O, CO, H2CO, CH3OH, C2H6, C2H2, CH4, HCN, NH3) and radicals (OH, NH2) were targeted and detected. Our serial measurements allowed a search for potential changes in molecular abundances relative to H2O. Those of some species (CO, C2H6, CH3OH, CH4) remained relatively constant with Rh, while others (e.g., H2CO, HCN) increased in abundance with decreasing Rh, for example as could result from potential compositional heterogeneity in the nucleus and/or release from increasingly heated grains in the coma. Results from our serial measurements of ISON will be presented and discussed.References: [1] Nevski V. and Novichonok A. (2012) CBET 3238. [2] McLean, I. S., et al. (1998) Proc. SPIE 3354, 566-578. [3] Tokunaga A, et al. (1990) Proc. SPIE, 1235, 131-143. This work is supported through the NASA Planetary Astronomy, Planetary Atmospheres, and Astrobiology Programs, and the National
The chemical composition of comet C/2012 S1 (ISON) between 1.2 au and 0.35 au from the SunNASA Astrophysics Data System (ADS) DiSanti, M.; Bonev, B.; Gibb, E.; Villanueva, G.; Paganini, L.; Mumma, M.; Keane, J.; Meech, K.; Blake, G.; McKay, A. updating Introduction: By virtue of their small size and prolonged storage at large heliocentric distances (R_h), comets remain largely preserved. As a result, their ices encode a record of physical and chemical conditions in the early Solar System [1,2]. The recent apparition of C/2012 S1 (ISON) [3], a dynamically new sun-grazing comet, provided a rare opportunity to both prepare for and subsequently conduct compositional studies to well within 1 au from the Sun. Observations: We obtained high-resolution spectra (Resolving Power approximately 25,000) of Comet ISON on four dates (UT 2013 Oct. 22, 24, 25, and Nov. 7) using NIRSPEC [4] at Keck 2, and on six dates (Nov. 15 through 19, and Nov. 22) using CSHELL [5] at the NASA InfraRed Telescope Facility (IRTF). Our observations provided a measure of volatile production rates and abundance ratios (relative to H_2O) over a wide range of heliocentric distances (R_h = updating au). NIRSPEC is cross-dispersed and so allows for simultaneous measure of multiple trace species together with H_2O, thereby avoiding most sources of systematic uncertainty, for example those associated with differences in slit losses and with flux calibration among settings. CSHELL has limited spectral coverage per setting, requiring judicious targeting of specific molecular emissions that (when possible) simultaneously encompass lines of H_2O and/or OH prompt emission, which serves as a proxy for water production provided equivalent OH line g-factors are known [6]. Despite this limitation, the IRTF is unique among ground-based IR observatories in its ability to conduct observations during daytime. This permitted obtaining compositional measurements of Comet ISON to a minimum solar elongation angle of 20 degrees. These will be discussed, and comparisons will be made with previously-reported results from observations with NIRSPEC [7] and HST [8]. Results: A suite of molecules (H_2O, CO, H_2CO, CH_3OH, C_2H_6, C_2H_2, CH_4, HCN, and NH_3) and radicals (OH
Photochemistry, mixing and transport in Jupiterâs stratosphere constrained by CassiniNASA Astrophysics Data System (ADS) Hue, Vincent; Hersant, Franck; CavaliÃ©, Thibault; Dobrijevic, Michel updating Jupiterâs obliquity and eccentricity drive the seasonal forcing on its atmosphere. The seasonal variations on its stratospheric temperature through radiative heating and composition through photochemistry are smaller than for Saturn, due to a lower obliquity and eccentricity. Although the physical conditions in these two planets are different, the stratospheric photochemistry is initiated and controlled by the methane photolysis [1]. We adapted a 2D (altitude-latitude) seasonal photochemical model of Saturn [2] to Jupiter. We compare the seasonal effects on the atmospheric composition between these two planets. We use previous 1D photochemical models for the vertical mixing efficiency [1,3] and recent Cassini observations to constrain the meridional mixing efficiency and transport processes [4,5,6].Cassiniâs flyby of Jupiter has allowed mapping its stratospheric temperature as a function of latitude [7]. It has also revealed the meridional distribution of hydrocarbons [8,9], which were suggested by earlier studies [10,4]. Previous models suggest that vertical mixing alone is not sufficient to reproduce the observations of C2H2 and C2H6 [5,6], and that meridional mixing is needed. We show that, in addition to meridional mixing, advective circulation is required to reproduce Cassini observations of C2H6. Preliminary results from our model suggest an equator-to-pole circulation cell in Jupiterâs stratosphere, around 30-0.01 mbar.References[1] Moses et al., 2005. JGR 110, 8001.[2] Hue et al., 2015. Icarus 257, 163-184.[3] Gladstone et al., 1996. Icarus 119, 1-52.[4] Kunde et al., 2004. Science 305, updating.[5] Liang et al., 2005. ApJ Lett. 635, L177-L180.[6] Lellouch et al., 2006. Icarus 184 (2), 478-497.[7] Simon-Miller et al., 2006. Icarus 180 (1), 98-112.[8] Nixon et al., 2007. Icarus 188, 47-71.[9] Nixon et al., 2010. PSS 58, updating.[10] Maguire et al., 1984. Bulletin of the AAS 16, 647-647.
Photo-induced CO2 reduction by CH4/H2O to fuels over Cu-modified g-C3N4 nanorods under simulated solar energyNASA Astrophysics Data System (ADS) Tahir, Beenish; Tahir, Muhammad; Amin, Nor Aishah Saidina updating Copper modified polymeric graphitic carbon nitride (Cu/g-C3N4) nanorods for photo-induced CO2 conversion with methane (CH4) and water (H2O) as reducing system under simulated solar energy has been investigated. The nanocatalysts, synthesized by pyrolysis and sonication, were characterized by XRD, FTIR, Raman analysis, XPS, SEM, N2 adsorption-desorption and PL spectroscopy. The presence of Cu2+ ions over the g-C3N4 structure inhibited charge carriers recombination process. The results indicated that photo-activity and selectivity of Cu/g-C3N4 photo-catalyst for CO2 reduction greatly dependent on the type of CO2-reduction system. CO2 was efficiently converted to CH4 and CH3OH with traces of C2H4 and C2H6 hydrocarbons in the CO2-water system. The yield of the main product, CH4 over 3 wt.% Cu/g-C3N4 was 109 Î¼mole g-cata.-1 h-1 under visible light irradiation, significantly higher than the pure g-C3N4 catalyst (60 Î¼mole/g.cat). In photo-induced CO2-CH4 reaction, CO and H2 were detected as the main products with smaller amount of hydrocarbons. The highest efficiency was detected over 3 wt.%Cu-loading of g-C3N4 and at optimal CH4/CO2 feed ratio of 1.0. The maximum yield of CO and H2 detected were 142 and 76 Î¼mole g-catal.-1 h-1, respectively at selectivity 66.6% and 32.5%, respectively. Significantly enhanced CO2/CH4 reduction over Cu/g-C3N4 was attributed to its polymeric structure with efficient charge transfer property and inhibited charges recombination rate. A proposed photo-induced reaction mechanism, corroborated with the experimental data, was also deliberated.
Identification of amines in wintertime ambient particulate material using high resolution aerosol mass spectrometryNASA Astrophysics Data System (ADS) Bottenus, Courtney L. H.; Massoli, Paola; Sueper, Donna; Canagaratna, Manjula R.; VanderSchelden, Graham; Jobson, B. Thomas; VanReken, Timothy M. updating Significant amounts of amines were detected in fine particulate matter (PM) during ambient wintertime conditions in Yakima, WA, using a high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Positive matrix factorization (PMF) of the organic aerosol (OA) signal resulted in a six-factor solution that included two previously unreported amine OA factors. The contributions of the amine factors were strongly episodic, but the concentration of the combined amine factors was as high as 10-15 Î¼g m-3 (2-min average) during those episodes. In one occasion, the Amine-II component was 45% of total OA signal. The Amine-I factor was dominated by spectral peaks at m/z 86 (C5H12N+) and m/z 100 (C6H14N+), while the Amine-II factor was dominated by spectral peaks at m/z 58 (C3H8N+ and C2H6N2+) and m/z 72 (C4H10N+ and C3H8N2+). The ions dominating each amine factor showed distinct time traces, suggesting different sources or formation processes. Investigation into the chemistry of the amine factors suggests a correlation with inorganic anions for Amine-I, but no evidence that the Amine-II was being neutralized by the same inorganic ions. We also excluded the presence of organonitrates (ON) in the OA. The presence of C2H4O2+ at m/z 60 (a levoglucosan fragment) in the Amine-I spectrum suggests some influence of biomass burning emissions (more specifically residential wood combustion) in this PMF factor, but wind direction suggested that the most likely sources of these amines were agricultural activities and feedlots to the S-SW of the site.
Characteristics of Pyrolytic Topping in Fluidized Bed for Different Volatile CoalsNASA Astrophysics Data System (ADS) Xiong, R.; Dong, L.; Xu, G. W. Coal is generally combusted or gasified directly to destroy completely the chemical structures, such as aromatic rings containing in volatile coals including bituminite and lignite. Coal topping refers to a process that extracts chemicals with aromatic rings from such volatile coals in advance of combustion or gasification and thereby takes advantage of the value of coal as a kind of chemical structure resource. CFB boiler is the coal utilization facility that can be easily retrofitted to implement coal topping. A critical issue for performing coal topping is the choice of the pyrolytic reactor that can be different types. The present study concerns fluidized bed reactor that has rarely been tested for use in coal topping. Two different types of coals, one being Xiaolongtan (XLT) lignite and the other Shanxi (SX) bituminous, were tested to clarify the yield and composition of pyrolysis liquid and gas under conditions simulating actual operations. The results showed that XLT lignite coals had the maximum tar yield in 823-873K and SX bituminite realized its highest tar yield in 873-923K. Overall, lignite produced lower tar yield than bituminous coal. The pyrolysis gas from lignite coals contained more CO and CO2 and less CH4, H2 and C2+C3 (C2H4, C2H6, C3H6, C3H8) components comparing to that from bituminous coal. TG-FTIR analysis of tars demonstrated that for different coals there are different amounts of typical chemical species. Using coal ash of CFB boiler, instead of quartz sand, as the fluidized particles decreased the yields of both tar and gas for all the tested coals. Besides, pyrolysis in a reaction atmosphere simulating the pyrolysis gas (instead of N2) resulted also in higher production of pyrolysis liquid.
Vacuum pyrolysis of waste tires with basic additives.PubMed Zhang, Xinghua; Wang, Tiejun; Ma, Longlong; Chang, Jie updating Granules of waste tires were pyrolyzed under vacuum (3.5-10 kPa) conditions, and the effects of temperature and basic additives (Na2CO3, NaOH) on the properties of pyrolysis were thoroughly investigated. It was obvious that with or without basic additives, pyrolysis oil yield increased gradually to a maximum and subsequently decreased with a temperature increase from 450 degrees C to 600 degrees C, irrespective of the addition of basic additives to the reactor. The addition of NaOH facilitated pyrolysis dramatically, as a maximal pyrolysis oil yield of about 48 wt% was achieved at 550 degrees C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50 wt% was achieved at 480 degrees C by adding 3 wt% (w/w, powder/waste tire granules) of NaOH powder. The composition analysis of pyrolytic naphtha (i.b.p. (initial boiling point) approximately 205 degrees C) distilled from pyrolysis oil showed that more dl-limonene was obtained with basic additives and the maximal content of dl-limonene in pyrolysis oil was 12.39 wt%, which is a valuable and widely-used fine chemical. However, no improvement in pyrolysis was observed with Na2CO3 addition. Pyrolysis gas was mainly composed of H2, CO, CH4, CO2, C2H4 and C2H6. Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5 wt%) was much higher.
Low Temperature Studies of the Removal Reactions of 1CH2 with Relevance to the Atmosphere of TitanNASA Astrophysics Data System (ADS) Douglas, Kevin; Slater, Eloise; Feng, Wuhu; Blitz, Mark; Plane, John; Heard, Dwayne; Seakins, Paul updating The photolysis of methane by UV photons is the primary source of hydrocarbon radicals in the atmosphere of Titan and the giant planets. Although there is still significant uncertainty in the branching ratios of products, the production of the first singlet excited state of methylene, 1CH2, is thought to be a significant channel. Reactions of 1CH2 with methane (R1a) and hydrogen (R2a) are a significant source of methyl radicals, the recombination of which is the primary route to ethane on Titan (R3). The reaction of 1CH2 with acetylene is also a source of propargyl, C3H3, the recombination of which is the primary route to benzene on Titan. However, in addition to these reactions of 1CH2 leading to chemical products, there is also competition between inelastic electronic relaxation to form ground triplet state methylene, 3CH2 (R1b and R2b). Triplet methylene is much less reactive, and cannot undergo the complex insertion elimination reactions of singlet methylene. The main reaction of 3CH2 occurs with other radical species such as H (R4). 1CH2 + CH4 â CH3 + H2 (R1a) 1CH2 + CH4 â 3CH2 + CH4 (R1b) 1CH2 + H2 â CH3 + H (R2a) 1CH2 + H2 â 3CH2 + H2 (R2a) CH3 + CH3 (+M) â C2H6 (R3) 3CH2 + H â CH + H2 (R4) Using pulsed laser photolysis laser-induced fluorescence, we have studied the reaction kinetics for the removal of 1CH2 with N2, H2, CH4, C2H6, C2H4, C2H6, and O2 as a function of temperature. Low temperatures between 43 and 135 K were obtained using a pulsed Laval nozzle apparatus, while data at 160 K was obtained using a low flow reaction cell with cryogenic cooling. In addition to measuring total removal rates, the fraction of 1CH2 removed via electronic relaxation versus chemical reaction to products has also been investigated for H2 and CH4 at 160 and 73 K. Results show that that removal of 1CH2 by electronic relaxation increases with decreasing temperature. These experimental results indicate that the majority of 1CH2 formed in Titan's atmosphere will be
Variability of Atmospheric CO2 over the western North Pacific: Influence of Asian outflow during March-April 2001NASA Astrophysics Data System (ADS) Vay, S. A.; Woo, J.; Anderson, B. E.; Thornhill, K. L.; Kiley, C.; Avery, M. A.; Sachse, G. W.; Blake, D. R.; Streets, D. G.; Nolf, S. R. updating We report here tropospheric CO2 measurements made as part of the airborne component of NASA's Transport and Chemical Evolution over the Pacific (TRACE-P) Mission during March and April in 2001. CO2 mixing ratios, sampled in the subtropics (updatingÂ° N) west of 150Â° E, exhibited a decreasing trend with height (0.5-12 km), were highly correlated with latitude showing a distinct north to south gradient, and peaked between 35-40Â° N within the planetary boundary layer. Near the Asian continent, discrete plumes encountered below 4 km contained up to 393.6 ppmv CO2 and were augmented with the combustion and industrial tracers CO, C2H6, C3H8, CH3Cl, C2Cl4, and C6H6. A chemically based air mass classification scheme using the combustion products CO and C2H2 as tracers of continental source emissions was employed in this analysis. Results show an excellent positive correlation for CO2 (r2=0.98) with respect to this ratio in the lower to mid free troposphere (4-8 km) providing evidence of continental outflow. South of the Tropic of Cancer, mean and median CO2 values derived from samples obtained below 8 km are less than those calculated for the subtropics. However, within the upper troposphere (UT) of both regions, similar values were determined and enhancements in combustion-derived species in the 8-12 km altitude range were observed. The relationship revealed between CO2 and the C2H2/CO ratio, particularly for the tropics, suggests recent inputs from the surface to the UT. In order to elucidate the processes determining the variations of CO2 in the Asian Pacific rim region during TRACE-P, a CO2 emissions data base developed for Asia was examined in conjunction with the chemistry and 5 day backward trajectories in an attempt to link CO2 enhancements observed in pollution plumes to source regions. From these data acquired downwind of the Asian continent when CO2 concentrations at the surface were approaching their seasonal maximum, we estimate a net export flux on the

Crossed beam studies of elementary reactions of N and C atoms and CN radicals of importance in combustion.PubMed Casavecchia, P; Balucani, N; Cartechini, L; Capozza, G; Bergeat, A; Volpi, G G updating The dynamics of some elementary reactions of N(2D), C(3P,1D) and CN(X2 sigma +) of importance in combustion have been investigated by using the crossed molecular beam scattering method with mass spectrometric detection. The novel capability of producing intense, continuous beams of the radical reagents by a radio-frequency discharge beam source was exploited. From angular and velocity distribution measurements obtained in the laboratory frame, primary reaction products have been identified and their angular and translational energy distributions in the center-of-mass system, as well as branching ratios, have been derived. The dominant N/H exchange channel has been examined in the reaction N(2D) + CH4, which is found to lead to H + CH2NH (methylenimine) and H + CH3N (methylnitrene); no H2 elimination is observed. In the reaction N(2D) + H2O the N/H exchange channel has been found to occur via two competing pathways leading to HNO + H and HON + H, while formation of NO + H2 is negligible. Formation of H + H2CCCH (propargyl) is the dominant pathway, at low collision energy (Ec), of the C(3P) + C2H4 reaction, while at high Ec formation of the less stable C3H3 isomers (cyclopropenyl and/or propyn-1-yl) also occurs; the H2 elimination channel is negligible. The H elimination channel has also been found to be the dominant pathway in the C(3P,1D) + CH3CCH reaction leading to C4H3 isomers and, again, no H2 elimination has been observed to occur. In contrast, both H and H2 elimination, leading in comparable ratio to C3H + H and C3(X1 sigma g+) + H2(X1 sigma g+), respectively, have been observed in the reaction C(3P) + C2H2(X1 sigma g+). The occurrence of the spin-forbidden molecular pathway in this reaction, never detected before, has been rationalized by invoking the occurrence of intersystem crossing between triplet and singlet manifolds of the C3H2 potential energy surfaces. The reaction CN(X2 sigma +) + C2H2 has been found to lead to internally excited HCCCN
Mechanism for the Coupled Photochemistry of Ammonia and Acetylene: Implications for Giant Planets, Comets and Interstellar Organic SynthesisNASA Astrophysics Data System (ADS) Keane, Thomas C. updating Laboratory studies provide a fundamental understanding of photochemical processes in planetary atmospheres. Photochemical reactions taking place on giant planets like Jupiter and possibly comets and the interstellar medium are the subject of this research. Reaction pathways are proposed for the coupled photochemistry of NH3 (ammonia) and C2H2 (acetylene) within the context Jupiter's atmosphere. We then extend the discussion to the Great Red Spot, Extra-Solar Giant Planets, Comets and Interstellar Organic Synthesis. Reaction rates in the form of quantum yields were measured for the decomposition of reactants and the formation of products and stable intermediates: HCN (hydrogen cyanide), CH3CN (acetonitrile), CH3CH = N-N = CHCH3 (acetaldazine), CH3CH = N-NH2 (acetaldehyde hydrazone), C2H5NH2 (ethylamine), CH3NH2 (methylamine) and C2H4 (ethene) in the photolysis of NH3/C2H2 mixtures. Some of these compounds, formed in our investigation of pathways for HCN synthesis, were not encountered previously in observational, theoretical or laboratory photochemical studies. The quantum yields obtained allowed for the formulation of a reaction mechanism that attempts to explain the observed results under varying experimental conditions. In general, the results of this work are consistent with the initial observations of Ferris and Ishikawa (1988). However, their proposed reaction pathway which centers on the photolysis of CH3CH = N-N = CHCH3 does not explain all of the results obtained in this study. The formation of CH3CH = N-N = CHCH3 by a radical combination reaction of CH3CH = Nâ¢ was shown in this work to be inconsistent with other experiments where the CH3CH = Nâ¢ radical is thought to form but where no CH3CH = N-N = CHCH3 was detected. The importance of the role of H atom abstraction reactions was demonstrated and an alternative pathway for CH3CH = N-N = CHCH3 formation involving nucleophilic reaction between N2H4 and CH3CH = NH is advanced.
Mechanism for the Coupled Photochemistry of Ammonia and Acetylene: Implications for Giant Planets, Comets and Interstellar Organic Synthesis.PubMed Keane, Thomas C updating Laboratory studies provide a fundamental understanding of photochemical processes in planetary atmospheres. Photochemical reactions taking place on giant planets like Jupiter and possibly comets and the interstellar medium are the subject of this research. Reaction pathways are proposed for the coupled photochemistry of NH 3 (ammonia) and C 2 H 2 (acetylene) within the context Jupiter's atmosphere. We then extend the discussion to the Great Red Spot, Extra-Solar Giant Planets, Comets and Interstellar Organic Synthesis. Reaction rates in the form of quantum yields were measured for the decomposition of reactants and the formation of products and stable intermediates: HCN (hydrogen cyanide), CH 3 CN (acetonitrile), CH 3 CHÂ =Â N-NÂ =Â CHCH 3 (acetaldazine), CH 3 CHÂ =Â N-NH 2 (acetaldehyde hydrazone), C 2 H 5 NH 2 (ethylamine), CH 3 NH 2 (methylamine) and C 2 H 4 (ethene) in the photolysis of NH 3 /C 2 H 2 mixtures. Some of these compounds, formed in our investigation of pathways for HCN synthesis, were not encountered previously in observational, theoretical or laboratory photochemical studies. The quantum yields obtained allowed for the formulation of a reaction mechanism that attempts to explain the observed results under varying experimental conditions. In general, the results of this work are consistent with the initial observations of Ferris and Ishikawa (1988). However, their proposed reaction pathway which centers on the photolysis of CH 3 CHÂ =Â N-NÂ =Â CHCH 3 does not explain all of the results obtained in this study. The formation of CH 3 CHÂ =Â N-NÂ =Â CHCH 3 by a radical combination reaction of CH 3 CHÂ =Â Nâ¢ was shown in this work to be inconsistent with other experiments where the CH 3 CHÂ =Â Nâ¢ radical is thought to form but where no CH 3 CHÂ =Â N-NÂ =Â CHCH 3 was detected. The importance of the role of H atom abstraction reactions was demonstrated and an alternative pathway for CH 3 CHÂ =Â N-NÂ =Â CHCH 3 formation involving nucleophilic reaction
Seasonal stratospheric photochemistry on Uranus and NeptuneNASA Astrophysics Data System (ADS) Moses, Julianne I.; Fletcher, Leigh N.; Greathouse, Thomas K.; Orton, Glenn S.; Hue, Vincent updating A time-variable 1D photochemical model is used to study the distribution of stratospheric hydrocarbons as a function of altitude, latitude, and season on Uranus and Neptune. The results for Neptune indicate that in the absence of stratospheric circulation or other meridional transport processes, the hydrocarbon abundances exhibit strong seasonal and meridional variations in the upper stratosphere, but that these variations become increasingly damped with depth due to increasing dynamical and chemical time scales. At high altitudes, hydrocarbon mixing ratios are typically largest where the solar insolation is the greatest, leading to strong hemispheric dichotomies between the summer-to-fall hemisphere and winter-to-spring hemisphere. At mbar pressures and deeper, slower chemistry and diffusion lead to latitude variations that become more symmetric about the equator. On Uranus, the stagnant, poorly mixed stratosphere confines methane and its photochemical products to higher pressures, where chemistry and diffusion time scales remain large. Seasonal variations in hydrocarbons are therefore predicted to be more muted on Uranus, despite the planet's very large obliquity. Radiative-transfer simulations demonstrate that latitude variations in hydrocarbons on both planets are potentially observable with future JWST mid-infrared spectral imaging. Our seasonal model predictions for Neptune compare well with retrieved C2H2 and C2H6 abundances from spatially resolved ground-based observations (no such observations currently exist for Uranus), suggesting that stratospheric circulation - which was not included in these models - may have little influence on the large-scale meridional hydrocarbon distributions on Neptune, unlike the situation on Jupiter and Saturn.
Cookstove Emissions Quantified with the Aerodyne Mobile Laboratory During the Short Lived Climate Forcing (SLCF) 2013 Campaign in PÃ¡tzcuaro MexicoNASA Astrophysics Data System (ADS) Gonzalez Abraham, R.; Zavala, M.; Molina, L. T.; Fortner, E.; Wormhoudt, J.; Knighton, B.; Herndon, S.; Roscioli, J. R.; Onasch, T. B.; Jayne, J. T.; Worsnop, D. R.; Kolb, C. E.; Masera, O.; Berrueta, V. updating Black carbon emissions are a major contributor to climate change, with cookstoves being one of the top sources. The SLCF cookstove study was conducted in March 2013 at the Interdisciplinary Group for Appropriate Rural Technology (GIRA) in PÃ¡tzcuaro, Mexico. Seven different types of wood-burning cookstoves were measured giving insight to the effects of different designs and operating conditions on particle and gas phase emissions. High-time resolution measurements of emissions were made. For most of the cookstoves, measurements were made throughout a standard water boiling test. The Aerodyne Mobile Laboratory conducted these emission measurements utilizing extractive sampling from the stove exhaust. Sample flow to the gas phase instruments was extracted directly from the stovepipe and then quickly diluted with nitrogen. Sample flows for the particulate instruments were taken at points under a meter from the exit of the stovepipe, after dilution with ambient air. The key particulate instrument was the Aerodyne soot particle aerosol mass spectrometer (SP-AMS), which provided measurements of black carbon, divided into several sub-components, along with other classes of particulate matter classified by chemical composition. Gas phase measurements conducted included CO, CO2, NO, NOx, SO2, CH4, C2H2, C2H6, and a variety of VOCs (including benzene, methanol, acetaldehyde, toluene, acetone, acetonitrile, and terpene) measured with a PTR-MS instrument. All of these measurements will be examined to construct emission ratios evaluating how these vary with different cookstove types and different stove operating conditions. Comparisons will be made to previous measurements of cookstove emissions in the literature, with a focus on the variety of particulate measurements reported.
Soot Surface Oxidation in Laminar Hydrocarbon/Air Diffusion Flames at Atmospheric Pressure. Appendix INASA Technical Reports Server (NTRS) Xu, F.; El-Leathy, A. M.; Kim, C. H.; Faeth, G. M.; Yuan, Z.-G. (Technical Monitor); Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor) updating Soot surface oxidation was studied experimentally in laminar hydrocarbon/air diffusion flames at atmospheric pressure. Measurements were carried out along the axes of round fuel jets burning in coflowing dry air considering acetylene-nitrogen, ethylene, propyiene-nitrogen, propane and acetylene-benzene-nitrogen in the fuel stream. Measurements were limited to the initial stages of soot oxidation (carbon consumption less than 70%) where soot oxidation occurs at the surface of primary soot particles. The following properties were measured as a function of distance above the burner exit: soot concentrations by deconvoluted laser extinction, soot temperatures by deconvoluted multiline emission, soot structure by thermophoretic sampling and analysis using Transmission Electron Microscopy (TEM), concentrations of major stable gas species (N2, H2O, H2, O2, CO, CO2, CH4, C2H2, C2H6, C3H6, C3H8, and C6H6) by sampling and gas chromatography, concentrations of some radical species (H, OH, O) by deconvoluted Li/LiOH atomic absorption and flow velocities by laser velocimetry. For present test conditions, it was found that soot surface oxidation rates were not affected by fuel type, that direct rates of soot surface oxidation by O2 estimated from Nagle and Strickland-Constable (1962) were small compared to observed soot surface oxidation rates because soot surface oxidation was completed near the flame sheet where O2 concentrations were less than 3% by volume, and that soot surface oxidation rates were described by the OH soot surface oxidation mechanism with a collision efficiency of 0.14 and an uncertainty (95% confidence) of +/- 0.04 when allowing for direct soot surface oxidation by O2, which is in reasonably good agreement with earlier observations of soot surface oxidation rates in both premixed and diffusion flames at atmospheric pressure.
Models for Temperature and Composition in Uranus from Spitzer, Herschel and Ground-Based Infrared through Millimeter ObservationsNASA Astrophysics Data System (ADS) Orton, Glenn; Fletcher, Leigh; Feuchtgruber, Helmut; Lellouch, Emmanuel; Moreno, Raphael; Hartogh, Paul; Jarchow, Christopher; Swinyard, Bruce; Moses, Julianne; Burgdorf, Martin; Hammel, Heidi; Line, Michael; Mainzer, Amy; Hofstadter, Mark; Sandell, Goran; Dowell, Charles updating Photometric and spectroscopic observations of Uranus were combined to create self-consistent models of its global-mean temperature profile, bulk composition, and vertical distribution of gases. These were derived from a suite of spacecraft and ground-based observations that includes the Spitzer IRS, and the Herschel HIFI, PACS and SPIRE instruments, together with ground-based observations from UKIRT and CSO. Observations of the collision-induced absorption of H2 have constrained the temperature structure in the troposphere; this was possible up to atmospheric pressures of ~2 bars. Temperatures in the stratosphere were constrained by H2 quadrupole line emission. We coupled the vertical distribution of CH4 in the stratosphere of Uranus with models for the vertical mixing in a way that is consistent with the mixing ratios of hydrocarbons whose abundances are influenced primarily by mixing rather than chemistry. Spitzer and Herschel data constrain the abundances of CH3, CH4, C2H2, C2H6, C3H4, C4H2, H2O and CO2. The Spitzer IRS data, in concert with photochemical models, show that the atmosphere the homopause is much higher pressures than for the other outer planets, with the predominant trace constituents for pressures lower than 10 Î¼bar being H2O and CO2. At millimeter wavelengths, there is evidence that an additional opacity source is required besides the H2 collision-induced absorption and the NH3 absorption needed to match the microwave spectrum; this can reasonably (but not uniquely) be attributed to H2S. These models will be made more mature by consideration of spatial variability from Voyager IRIS and more recent spatially resolved imaging and mapping from ground-based observatories. The model is of 'programmatic' interest because it serves as a calibration source for Herschel instruments, and it provides a starting point for planning future spacecraft investigations of the atmosphere of Uranus.
Models for Temperature and Composition in Uranus from Spitzer, Herschel and Ground-Based Infrared through Millimeter ObservationsNASA Astrophysics Data System (ADS) Orton, G. S.; Fletcher, L. N.; Feuchtgruber, H.; Lellouch, E.; Moreno, R.; Encrenaz, T.; Hartogh, P.; Jarchow, C.; Swinyard, B.; Moses, J. I.; Burgdorf, M. J.; Hammel, H. B.; Line, M. R.; Sandell, G.; Dowell, C. D. updating Photometric and spectroscopic observations of Uranus were combined to create self-consistent models of its global-mean temperature profile, bulk composition, and vertical distribution of gases. These were derived from a suite of spacecraft and ground-based observations that includes the Spitzer IRS, and the Herschel HIFI, PACS and SPIRE instruments, together with ground-based observations from UKIRT and CSO. Observations of the collision-induced absorption of H2 have constrained the temperature structure in the troposphere; this was possible up to atmospheric pressures of ~2 bars. Temperatures in the stratosphere were constrained by H2 quadrupole line emission. We coupled the vertical distribution of CH4 in the stratosphere of Uranus with models for the vertical mixing in a way that is consistent with the mixing ratios of hydrocarbons whose abundances are influenced primarily by mixing rather than chemistry. Spitzer and Herschel data constrain the abundances of CH3, CH4, C2H2, C2H6, C3H4, C4H2, H2O and CO2. At millimeter wavelengths, there is evidence that an additional opacity source is required besides the H2 collision-induced absorption and the NH3 absorption needed to match the microwave spectrum; this can reasonably (but not uniquely) be attributed to H2S. These models will be made more mature by consideration of spatial variability from Voyager IRIS and more recent spatially resolved imaging and mapping from ground-based observatories. The model is of ';programmatic' interest because it serves as a calibration source for Herschel instruments, and it provides a starting point for planning future spacecraft investigations of the atmosphere of Uranus.
Energy recovery from waste glycerol by utilizing thermal water vapor plasma.PubMed TamoÅ¡iÅ«nas, Andrius; ValatkeviÄius, Pranas; GimÅ¾auskaitÄ, DovilÄ; Jeguirim, Mejdi; MÄÄius, Vladas; Aikas, Mindaugas updating Glycerol, considered as a waste feedstock resulting from biodiesel production, has received much attention in recent years due to its properties, which offer to recover energy. The aim of this study was to investigate the use of a thermal water vapor plasma for waste (crude) glycerol conversion to synthesis gas, or syngas (H 2 Â +Â CO). In parallel of crude glycerol, a pure glycerol (99.5%) was used as a reference material in order to compare the concentrations of the formed product gas. A direct current (DC) arc plasma torch stabilized by a mixture of argon/water vapor was utilized for the effective glycerol conversion to hydrogen-rich synthesis gas. It was found that after waste glycerol treatment, the main reaction products were gases with corresponding concentrations of H 2 50.7%, CO 23.53%, CO 2 11.45%, and CH 4 3.82%, and traces of C 2 H 2 and C 2 H 6 , which concentrations were below 0.5%. The comparable concentrations of the formed gas products were obtained after pure glycerol conversion-H 2 46.4%, CO 26.25%, CO 2 11.3%, and CH 4 4.7%. The use of thermal water vapor plasma producing synthesis gas is an effective method to recover energy from both crude and pure glycerol. The performance of the glycerol conversion system was defined in terms of the produced gas yield, the carbon conversion efficiency, the cold gas efficiency, and the specific energy requirements.
Characteristics of the atmospheric CO2 signal as observed over the conterminous United States during INTEX-NANASA Astrophysics Data System (ADS) Choi, Yonghoon; Vay, Stephanie A.; Vadrevu, Krishna P.; Soja, Amber J.; Woo, Jung-Hun; Nolf, Scott R.; Sachse, Glen W.; Diskin, Glenn S.; Blake, Donald R.; Blake, Nicola J.; Singh, Hanwant B.; Avery, Melody A.; Fried, Alan; Pfister, Leonhard; Fuelberg, Henry E. updating High resolution in situ measurements of atmospheric CO2 were made from the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment-North America (INTEX-NA) campaign, part of the wider International Consortium for Atmospheric Research on Transport and Transformation (ICARTT). During the summer of 2004, eighteen flights comprising 160 h of measurements were conducted within a region bounded by 27 to 53Â°N and 36 to 139Â°W over an altitude range of 0.15 to 12 km. These large-scale surveys provided the opportunity to examine the characteristics of the atmospheric CO2 signal over sparsely sampled areas of North America and adjacent ocean basins. The observations showed a high degree of variability (â¤18%) due to the myriad source and sink processes influencing the air masses intercepted over the INTEX-NA sampling domain. Surface fluxes had strong effects on continental scale concentration gradients. Clear signatures of CO2 uptake were seen east of the Mississippi River, notably a persistent CO2 deficit in the lowest 2-3 km. When combining the airborne CO2 measurements with LANDSAT and MODIS data products, the lowest CO2 mixing ratios observed during the campaign (337 ppm) were tied to mid-continental agricultural fields planted in corn and soybeans. We used simultaneous measurements of CO, O3, C2Cl4, C2H6, C2H2 and other unique chemical tracers to differentiate air mass types. Coupling these distinct air mass chemical signatures with transport history permitted identification of convection, stratosphere-troposphere exchange, long-range transport from Eastern Asia, boreal wildfires, and continental outflow as competing processes at multiple scales influencing the observed concentrations. Our results suggest these are important factors contributing to the large-scale distribution in CO2 mixing ratios thus these observations offer new constraints in the computation of the North American carbon budget.
The Evolution and Fate of Saturn's Stratospheric Vortex: Infrared Spectroscopy from CassiniNASA Technical Reports Server (NTRS) Fletcher, Leigh N.; Hesman, B. E.; Arhterberg, R. K.; Bjoraker, G.; Irwin, P. G. J.; Hurley, J.; Sinclair, J.; Gorius, N.; Orton, G. S.; Read, P. L.; updating The planet-encircling springtime storm in Saturn's troposphere (December 2010-July 2011) produced dramatic perturbations to stratospheric temperatures, winds and composition at mbar pressures that persisted long after the tropospheric disturbance had abated. Observations from the Cassini Composite Infrared Spectrometer (CIRS), supported by ground-based imaging from the VISIR instrument on the Very Large Telescope,is used to track the evolution of a large, hot stratospheric anticyclone between January 2011 and the present day. The evolutionary sequence can be divided into three phases: (I) the formation and intensification of two distinct warm airmasses near 0.5 mbar between 25 and 35N (one residing directly above the convective storm head) between January-April 2011, moving westward with different zonal velocities; (II) the merging of the warm airmasses to form the large single 'stratospheric beacon' near 40N between April and June 2011, dissociated from the storm head and at a higher pressure (2 mbar) than the original beacons; and (III) the mature phase characterized by slow cooling and longitudinal shrinkage of the anticyclone since July 2011, moving west with a near-constant velocity of 2.70+/-0.04 deg/day (-24.5+/-0.4 m/s at 40N). Peak temperatures of 220 K at 2 mbar were measured on May 5th 2011 immediately after the merger, some 80 K warmer than the quiescent surroundings. Thermal winds hear calculations in August 2011 suggest clockwise peripheral velocities of 200400 mls at 2 mbar, defining a peripheral collar with a width of 65 degrees longitude (50,000 km in diameter) and 25 degrees latitude. Stratospheric acetylene (C2H2) was uniformly enhanced by a factor of three within the vortex, whereas ethane (C2H6) remained unaffected. We will discuss the thermal and chemical characteristics of Saturn's beacon in its mature phase, and implications for stratospheric vortices on other giant planets.
Biomass Burning Influences on the Composition of the Remote South Pacific Troposphere: Analysis Based on Observations from PEM Tropics-ANASA Technical Reports Server (NTRS) Singh, H. B.; Viezee, W.; Chen, Y.; Bradshaw, J.; Sandholm, S.; Blake, D.; Blake, N.; Heikes, B.; Snow, J.; Talbot, R.; updating Airborne, in-situ measurements from PEM-Tropics-A (September/October 1996) are analyzed to show the presence of distinct pollution plumes in the middle-tropical troposphere of the remote South Pacific (10-30degS). These elevated plumes cause a relative maximum at about 5-7km attitude in the vertical distribution of primary and secondary species characteristic of fuel combustion and biomass burning (CO, C2H2, C2H6, CH3Cl, PAN, O3). Similar plumes were also observed at mid-latitudes in the middle troposphere during three flights east of New Zealand (40-45degS). In all, pollution plumes with CO larger than 100 ppb were observed 24 times on 7 separate flight days south of the equator. The observed plumes were generally embedded in very dry air. Ten-day back trajectory analysis supports the view that these originated from the biomass burning regions of South Africa (and South America) and were transported to the South Pacific along long-distance subsiding trajectories. The chemical composition of the southern Pacific troposphere analyzed from the PEM-Tropics-A data is compared with data from the tropical regions of the northern Pacific (PEM-West-A) and southern Atlantic (TRACE-A) during the same Sept/Oct time period. Sizable perturbations in the abundance of ozone and its key precursors, resulting from the transport of pollution originating from biomass burning sources, are observed in much of the Southern Hemispheric troposphere.
Chemistry of the outer planetsNASA Technical Reports Server (NTRS) Scattergood, Thomas W. updating Various aspects were studied of past or present chemistry in the atmospheres of the outer planets and their satellites using lab simulations. Three areas were studied: (1) organic chemistry induced by kinetically hot hydrogen atoms in the region of Jupiter's atmosphere containing the ammonia cirrus clouds; (2) the conversion of NH3 into N2 by plasmas associated with entry of meteors and other objects into the atmosphere of early Titan; and (3) the synthesis of simple hydrocarbons and HCN by lightning in mixtures containing N2, CH4, and NH3 representing the atmospheres of Titan and the outer planets. The results showed that: (1) hot H2 atoms formed from the photodissociation of NH3 in Jupiter's atmosphere could account for some of the atmospheric chemistry in the ammonia cirrus cloud region; (2) the thermalization of hot H2 atoms in atmospheres predominated by molecular H is not as rapid as predicted by elastic collision theory; (3) the net quantum loss of NH3 in the presence of a 200 fold excess of H2 is 0.02, much higher than was expected from the amount of H2 present; (4) the conversion of NH3 into N2 in plasmas associated with infalling meteors is very efficient and rapid, and could account for most of the N2 present on Titan; (5) the yields of C2H2 and HCN from lightning induced chemistry in mixtures of CH4 and N2 is consistent with quenched thermodynamic models of the discharge core; and (6) photolysis induced by the UV light emitted by the gases in the hot plasmas may account for some, if not most, of the excess production of C2H6 and the more complex hydrocarbons.
High sensitivity stand-off detection and quantification of chemical mixtures using an active coherent laser spectrometer (ACLaS)NASA Astrophysics Data System (ADS) MacLeod, Neil A.; Weidmann, Damien updating High sensitivity detection, identification and quantification of chemicals in a stand-off configuration is a highly sought after capability across the security and defense sector. Specific applications include assessing the presence of explosive related materials, poisonous or toxic chemical agents, and narcotics. Real world field deployment of an operational stand-off system is challenging due to stringent requirements: high detection sensitivity, stand-off ranges from centimeters to hundreds of meters, eye-safe invisible light, near real-time response and a wide chemical versatility encompassing both vapor and condensed phase chemicals. Additionally, field deployment requires a compact, rugged, power efficient, and cost-effective design. To address these demanding requirements, we have developed the concept of Active Coherent Laser Spectrometer (ACLaS), which can be also described as a middle infrared hyperspectral coherent lidar. Combined with robust spectral unmixing algorithms, inherited from retrievals of information from high-resolution spectral data generated by satellitebased spectrometers, ACLaS has been demonstrated to fulfil the above-mentioned needs. ACLaS prototypes have been so far developed using quantum cascade lasers (QCL) and interband cascade lasers (ICL) to exploit the fast frequency tuning capability of these solid state sources. Using distributed feedback (DFB) QCL, demonstration and performance analysis were carried out on narrow-band absorbing chemicals (N2O, H2O, H2O2, CH4, C2H2 and C2H6) at stand-off distances up to 50 m using realistic non cooperative targets such as wood, painted metal, and bricks. Using more widely tunable external cavity QCL, ACLaS has also been demonstrated on broadband absorbing chemicals (dichloroethane, HFC134a, ethylene glycol dinitrate and 4-nitroacetanilide solid) and on complex samples mixing narrow-band and broadband absorbers together in a realistic atmospheric background.
Hypervolatiles in a Jupiter-family Comet: Observations of 45P/Honda-Mrkos-PajduÅ¡Ã¡kovÃ¡ Using iSHELL at the NASA-IRTFNASA Astrophysics Data System (ADS) DiSanti, Michael A.; Bonev, Boncho P.; Dello Russo, Neil; Vervack, Ronald J., Jr.; Gibb, Erika L.; Roth, Nathan X.; McKay, Adam J.; Kawakita, Hideyo; Feaga, Lori M.; Weaver, Harold A. updating We used the new high spectral resolution cross-dispersed facility spectrograph, iSHELL, at the NASA Infrared Telescope Facility on Maunakea, HI, to observe Jupiter-family comet (JFC) 45P/Honda-Mrkos-PajduÅ¡Ã¡kovÃ¡. We report water production rates, as well as production rates and abundance ratios relative to H2O, for eight trace parent molecules (native ices), CO, CH4, H2CO, CH3OH, HCN, NH3, C2H2, and C2H6, on 2 days spanning UT 2017 January 6/7 and 7/8, shortly following perihelion. Trace species were measured simultaneously with H2O and/or OH prompt emission, a proxy for H2O production, thereby providing a robust and consistent means of establishing the native ice composition of 45P. Its favorable geocentric radial velocity (approximately -35 km s-1) permitted sensitive measures of the âhypervolatilesâ CO and CH4, which are substantially undercharacterized in JFCs. Our results represent the most precise ground-based measures of CO and CH4 to date in a JFC, providing a foundation for building meaningful statistics regarding their abundances. The abundance ratio for CH4 in 45P (0.79% Â± 0.06% relative to H2O) was consistent with its median value as measured among Oort Cloud comets, whereas CO (0.60% Â± 0.04%) was strongly depleted. Compared with all measured comets, HCN (0.049% Â± 0.012%) was strongly depleted, CH3OH (3.6% Â± 0.3%) was enriched, and the remaining species were consistent with their respective median abundances. The volatile composition measured for 45P could indicate processing of ices prior to their incorporation into its nucleus. Spatial analysis of emissions suggests enhanced release of more volatile species into the sunward-facing hemisphere of the coma.
Synthesis of complex organic molecules in simulated methane rich astrophysical icesNASA Astrophysics Data System (ADS) Esmaili, Sasan; Bass, Andrew D.; Cloutier, Pierre; Sanche, LÃ©on; Huels, Michael A. updating It has been proposed that organic molecules required for life on earth may be formed by the radiation processing of molecular ices in space environments, e.g., within our solar system. Such processes can be studied in the laboratory with surface science analytical techniques and by using low-energy electron (LEE) irradiation to simulate the effects of the secondary electrons that are generated in great abundance whenever ionizing radiation interacts with matter. Here we present new measurements of 70 eV LEE irradiation of multilayer films of CH4, 18O2, and CH4/18O2 mixtures (3:1 ratio) at 22 K. The electron stimulated desorption (ESD) yields of cations and anions have been recorded as a function of electron fluence. At low fluence, the prompt desorption of more massive multi-carbon or CâO containing cationic fragments agrees with our earlier measurements. However, new anion ESD signals of C2-, C2H-, and C2H2- from CH4/18O2 mixtures increase with fluence, indicating the gradual synthesis (and subsequent electron-induced fragmentation) of new, more complex species containing several C and possibly O atoms. Comparisons between the temperature programed desorption (TPD) mass spectra of irradiated and unirradiated films show the electron-induced formation of new chemical species, the identities of which are confirmed by reference to the NIST database of electron impact mass spectra and by TPD measurements of films composed of the proposed products. New species observed in the TPD of irradiated mixture films include C3H6, C2H5OH, and C2H6. Furthermore, X-ray photoelectron spectroscopy of irradiated films confirms the formation of CâO, C=O, and O=CâOâ bonds of newly formed molecules. Our experiments support the view that secondary LEEs produced by ionizing radiation drive the chemistry in irradiated ices in space, irrespective of the radiation type.
The Composition of Titan's Lower Atmosphere and Simple Surface Volatiles as Measured by the Cassini-Huygens Probe Gas Chromatograph Mass Spectrometer ExperimentNASA Technical Reports Server (NTRS) Niemann, H. B.; Atreya, S. K.; Demick, J. E.; Gautier, D.; Haberman, J. A.; Harpold, D. N.; Kasprzak, W. T.; Lunine, J. I.; Owen, T. C.; Raulin, F. updating The Cassini-Huygens Probe Gas Chromatograph Mass Spectrometer (GCMS) determined the composition of the Titan atmosphere from 140km altitude to the surface. After landing, it returned composition data of gases evaporated from the surface. Height profiles of molecular nitrogen (N2), methane (CH4) and molecular hydrogen (H2) were determined. Traces were detected on the surface of evaporating methane, ethane (C2H6), acetylene (C2H2), cyanogen (C2N2) and carbon dioxide (CO2). The methane data showed evidence that methane precipitation occurred recently. The methane mole fraction was (1.48+/-0.09) x 10(exp -2) in the lower stratosphere (139.8 km to 75.5 km) and (5.65+/-0.18) x 10(exp -2) near the surface (6.7 km to the surface). The molecular hydrogen mole fraction was (1.01+/-0.16) x 10(exp -3) in the atmosphere and (9.90+/-0.17) x 10(exp -4) on the surface. Isotope ratios were 167.7+/-0.6 for N-14/N-15 in molecular nitrogen, 91.1+/-1.4 for C-12/C-13 in methane and (1.35+/-0.30) x 10(exp -4) for D/H in molecular hydrogen. The mole fractions of Ar-36 and radiogenic Ar-40 are (2.1+/-0.8) x 10(exp -7) and (3.39 +/-0.12) x 10(exp -5) respectively. Ne-22 has been tentatively identified at a mole fraction of (2.8+/-2.1) x 10(exp -7) Krypton and xenon were below the detection threshold of 1 x 10(exp -8) mole fraction. Science data were not retrieved from the gas chromatograph subsystem as the abundance of the organic trace gases in the atmosphere and on the ground did not reach the detection threshold. Results previously published from the GCMS experiment are superseded by this publication.
Composition and Cosmogonic Parameters of the Chemically Distinct Comet C/2007 N3 (Lulin)NASA Astrophysics Data System (ADS) Gibb, Erika L.; Villanueva, G. L.; Bonev, B. P.; DiSanti, M. A.; Mumma, M. J.; Radeva, Y. L. updating Comets are remnants from the early solar system that retain the volatiles (ices) from the cold outer proto-planetary disk (beyond 5 AU) where they formed. Comet nuclei were among the first objects to accrete in the early solar nebula and many of them were subsequently incorporated into the growing giant planets. Gravitational scattering redistributed the remaining comet population by either sending them to the inner solar system, where they may have enriched the early biosphere, or scattering them into their present-day dynamical reservoirs. Since this early time, comets have been orbiting the Sun relatively untouched by processing mechanisms, until their orbits are perturbed towards the inner solar system. As such, they are believed to be among the most primitive objects in the solar system and may be representative of the material from which the solar system formed. Of particular interest is their icy volatile composition since other solar system objects have either lost or have had significant modifications to their volatile compositions since their formation. Many of the volatiles observed in comets are also important prebiotic species. For example, H2CO is a chemical precursor to sugars and HCN and NH3 are precursors of amino acids. Studying comets is therefore a vital link to understanding the origin and evolution of our planetary system and life on Earth. We obtained high-resolution, near-infrared spectroscopic observations of Comet C/2007 N3 (Lulin) on 30 January - 1 February 2009 with NIRSPEC on Keck II. Lulin is an Oort Cloud comet with a very large aphelion distance, suggesting that it may have been dynamically new. We report production rates of H2O, C2H6, HCN, C2H2, CH4, NH3, H2CO, CH3OH, and CO. We also report two cosmogonic parameters: D/H ratio in H2O and CH4, and isomeric spin temperatures. The implications for comet formations scenarios are discussed.
The Unexpectedly Bright Comet C-2012 F6 (Lemmon) Unveiled at Near-Infrared WavelengthsNASA Technical Reports Server (NTRS) Paganini, Lucas; Disanti, Michael A.; Mumma, Michael J.; Villanueva, Geronimo L.; Bonev, Boncho P.; Keane, Jacqueline V.; Gibb, Erika L.; Boehnhardt, Hermann; Meech, Karen J. updating We acquired near-infrared spectra of the Oort cloud comet C/2012 F6 (Lemmon) at three different heliocentric distances (R h) during the comet's 2013 perihelion passage, providing a comprehensive measure of the outgassing behavior of parent volatiles and cosmogonic indicators. Our observations were performed pre-perihelion at R h = 1.2 AU with CRIRES (on 2013 February 2 and 4), and post-perihelion at R h = 0.75 AU with CSHELL (on March 31 and April 1) and R h = 1.74 AU with NIRSPEC (on June 20). We detected 10 volatile species (H2O, OH* prompt emission, C2H6, CH3OH, H2CO, HCN, CO, CH4, NH3, and NH2), and obtained upper limits for two others (C2H2 and HDO). One-dimensional spatial profiles displayed different distributions for some volatiles, confirming either the existence of polar and apolar ices, or of chemically distinct active vents in the nucleus. The ortho-para ratio for water was 3.31 +/- 0.33 (weighted mean of CRIRES and NIRSPEC results), implying a spin temperature >37 K at the 95% confidence limit. Our (3s) upper limit for HDO corresponds to D/H C2H6 and CH3OH, while HCN, CH4, and CO displayed abundances close to their median values found among comets. H2CO was the only volatile showing a relative enhancement. The relative paucity of C2H6 and CH3OH (with respect to H2O) suggests formation within warm regions of the nebula. However, the normal abundance of HCN and hypervolatiles CH4 and CO, and the enhancement of H2CO, may
Multiplexed photoionization mass spectrometry investigation of the O( 3P) + propyne reactionDOE PAGES Savee, John D.; Borkar, Sampada; Welz, Oliver; ... updating Here, the reaction of O( 3P) + propyne (C 3H 4) was investigated at 298 K and 4 Torr using time-resolved multiplexed photoionization mass spectrometry and a synchrotron-generated tunable vacuum ultraviolet light source. The time-resolved mass spectra of the observed products suggest five major channels under our conditions: C 2H 3 + HCO, CH 3 + HCCO, H + CH 3CCO, C 2H 4 + CO, and C 2H 2 + H 2 + CO. The relative branching ratios for these channels were found to be 1.00, (0.35 Â± 0.11), (0.18 Â± 0.10), (0.73 Â± 0.27), and (1.31 Â± 0.62).moreÂ Â» In addition, we observed signals consistent with minor production of C 3H 3 + OH and H 2 + CH 2CCO, although we cannot conclusively assign them as direct product channels from O( 3P) + propyne. The direct abstraction mechanism plays only a minor role (â¤1%), and we estimate that O( 3P) addition to the central carbon of propyne accounts for 10% of products, with addition to the terminal carbon accounting for the remaining 89%. The isotopologues observed in experiments using d1-propyne (CH 3CCD) and analysis of product branching in light of previously computed stationary points on the singlet and triplet potential energy surfaces (PESs) relevant to O( 3P) + propyne suggest that, under our conditions, (84 Â± 14)% of the observed product channels from O( 3P) + propyne result from intersystem crossing from the initial triplet PES to the lower-lying singlet PES.Â«Â less

Laboratory Measurements of Gas Phase Pyrolysis Products from Southern Wildland Fuels using Infrared SpectroscopyNASA Astrophysics Data System (ADS) Scharko, N.; Safdari, S.; Danby, T. O.; Howarth, J.; Beiswenger, T. N.; Weise, D.; Myers, T. L.; Fletcher, T. H.; Johnson, T. J. updating Combustion is an oxidation reaction that occurs when there is less fuel available than oxidizers, while pyrolysis is a thermal decomposition process that occurs under "fuel rich" conditions where all of the available oxidizers are consumed leaving some fuel(s) either unreacted or partially reacted. Gas-phase combustion products from biomass burning experiments have been studied extensively; less is known, however, about pyrolysis processes and products. Pyrolysis is the initial reaction occurring in the burning process and generates products that are subsequently oxidized during combustion, yielding highly-oxidized chemicals. This laboratory study investigates the pyrolysis processes by using an FTIR spectrometer to detect and quantify the gas-phase products from thermal decomposition of intact understory fuels from forests in the southeastern United States. In particular, a laboratory flat-flame burner operating under fuel rich conditions (no oxygen) was used to heat individual leaves to cause decomposition. The gas-phase products were introduced to an 8 meter gas cell coupled to an infrared spectrometer were used to monitor the products. Trace gas emissions along with emission ratios, which are calculated by dividing the change in the amount of the trace gas by the change in the amount of CO, for the plant species, gallberry (Ilex glabra) and swampbay (Persea palustris) were determined. Preliminary measurements observed species such as CO2, CO, C2H2, C2H4, HCHO, CH3OH, isoprene, 1,3-butadiene, phenol and NH3 being produced as part of the thermal decomposition process. It is important to note that FTIR will not detect H2.
Intermolecular interactions of trifluorohalomethanes with Lewis bases in the gas phase: an ab initio study.PubMed Wang, Yi-Siang; Yin, Chih-Chien; Chao, Sheng D updating We perform an ab initio computational study of molecular complexes with the general formula CF3X-B that involve one trifluorohalomethane CF3X (X = Cl or Br) and one of a series of Lewis bases B in the gas phase. The Lewis bases are so chosen that they provide a range of electron-donating abilities for comparison. Based on the characteristics of their electron pairs, we consider the Lewis bases with a single n-pair (NH3 and PH3), two n-pairs (H2O and H2S), two n-pairs with an unsaturated bond (H2CO and H2CS), and a single Ï-pair (C2H4) and two Ï-pairs (C2H2). The aim is to systematically investigate the influence of the electron pair characteristics and the central atom substitution effects on the geometries and energetics of the formed complexes. The counterpoise-corrected supermolecule MP2 and coupled-cluster single double with perturbative triple [CCSD(T)] levels of theory have been employed, together with a series of basis sets up to aug-cc-pVTZ. The angular and radial configurations, the binding energies, and the electrostatic potentials of the stable complexes have been compared and discussed as the Lewis base varies. For those complexes where halogen bonding plays a significant role, the calculated geometries and energetics are consistent with the Ï-hole model. Upon formation of stable complexes, the C-X bond lengths shorten, while the C-X vibrational frequencies increase, thus rendering blueshifting halogen bonds. The central atom substitution usually enlarges the intermolecular bond distances while it reduces the net charge transfers, thus weakening the bond strengths. The analysis based on the Ï-hole model is grossly reliable but requires suitable modifications incorporating the central atom substitution effects, in particular, when interaction components other than electrostatic contributions are involved.
Reactions of gas phase H atoms with ethylene, acetylene and ethane adsorbed on Ni( 1 1 1 )NASA Astrophysics Data System (ADS) BÃ¼rgi, T.; Trautman, T. R.; Gostein, M.; Lahr, D. L.; Haug, K. L.; Ceyer, S. T. updating The products of the reaction of the most energetic form of hydrogen, gas phase H atoms, with ethylene, acetylene and ethane adsorbed on a Ni(1 1 1) surface at 60 K are probed. Adsorbed ethylidyne (CCH 3) is identified by high resolution electron energy loss spectroscopy to be the major product (30% yield) in all three cases. Adsorbed acetylene is a minor product (3% yield) and arises as a consequence of a dynamic equilibrium between CCH 3 and C 2H 2 in the presence of gas phase H atoms. The observation of the same product for the reaction of H atoms with all three hydrocarbons implies that CCH 3 is the most stable C 2 species in the presence of coadsorbed hydrogen. The rates of CCH 3 production are measured as a function of the time of exposure of H atoms to each hydrocarbon. A simple kinetic model treating each reaction as a pseudo-first order reaction in the hydrocarbon coverage is fit to these data. A mechanism for the formation of CCH 3 via a CHCH 2 intermediate common to all three reactants is proposed to describe this model. The observed instability of the CH 2CH 3 species relative to C 2H 4 plays a role in the formulation of this mechanism as does the observed stability of CHCH 2 species in the presence of coadsorbed hydrogen. The CH 2CH 3 and the CHCH 2 species are produced by the translational activation of ethane and the dissociative ionization of ethane and ethylene, respectively. In addition, the binding energy and the vibrational spectrum of ethane adsorbed on Ni(1 1 1) are determined and exceptionally high resolution vibrational spectra of adsorbed ethylene and acetylene are presented.
Reduced combustion mechanism for C1-C4 hydrocarbons and its application in computational fluid dynamics flare modeling.PubMed Damodara, Vijaya; Chen, Daniel H; Lou, Helen H; Rasel, Kader M A; Richmond, Peyton; Wang, Anan; Li, Xianchang updating Emissions from flares constitute unburned hydrocarbons, carbon monoxide (CO), soot, and other partially burned and altered hydrocarbons along with carbon dioxide (CO 2 ) and water. Soot or visible smoke is of particular concern for flare operators/regulatory agencies. The goal of the study is to develop a computational fluid dynamics (CFD) model capable of predicting flare combustion efficiency (CE) and soot emission. Since detailed combustion mechanisms are too complicated for (CFD) application, a 50-species reduced mechanism, LU 3.0.1, was developed. LU 3.0.1 is capable of handling C 4 hydrocarbons and soot precursor species (C 2 H 2 , C 2 H 4 , C 6 H 6 ). The new reduced mechanism LU 3.0.1 was first validated against experimental performance indicators: laminar flame speed, adiabatic flame temperature, and ignition delay. Further, CFD simulations using LU 3.0.1 were run to predict soot emission and CE of air-assisted flare tests conducted in 2010 in Tulsa, Oklahoma, using ANSYS Fluent software. Results of non-premixed probability density function (PDF) model and eddy dissipation concept (EDC) model are discussed. It is also noteworthy that when used in conjunction with the EDC turbulence-chemistry model, LU 3.0.1 can reasonably predict volatile organic compound (VOC) emissions as well. A reduced combustion mechanism containing 50 C 1 -C 4 species and soot precursors has been developed and validated against experimental data. The combustion mechanism is then employed in the computational fluid dynamics (CFD) of modeling of soot emission and combustion efficiency (CE) of controlled flares for which experimental soot and CE data are available. The validated CFD modeling tools are useful for oil, gas, and chemical industries to comply with U.S. Environmental Protection Agency's (EPA) mandate to achieve smokeless flaring with a high CE.
Laboratory measurements of trace gas emissions from biomass burning of fuel types from the southeastern and southwestern United StatesNASA Astrophysics Data System (ADS) Burling, I. R.; Yokelson, R. J.; Griffith, D. W. T.; Johnson, T. J.; Veres, P.; Roberts, J. M.; Warneke, C.; Urbanski, S. P.; Reardon, J.; Weise, D. R.; Hao, W. M.; de Gouw, J. updating Vegetation commonly managed by prescribed burning was collected from five southeastern and southwestern US military bases and burned under controlled conditions at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The smoke emissions were measured with a large suite of state-of-the-art instrumentation including an open-path Fourier transform infrared (OP-FTIR) spectrometer for measurement of gas-phase species. The OP-FTIR detected and quantified 19 gas-phase species in these fires: CO2, CO, CH4, C2H2, C2H4, C3H6, HCHO, HCOOH, CH3OH, CH3COOH, furan, H2O, NO, NO2, HONO, NH3, HCN, HCl, and SO2. Emission factors for these species are presented for each vegetation type burned. Gas-phase nitrous acid (HONO), an important OH precursor, was detected in the smoke from all fires. The HONO emission factors ranged from 0.15 to 0.60 g kg-1 and were higher for the southeastern fuels. The fire-integrated molar emission ratios of HONO (relative to NOx) ranged from approximately 0.03 to 0.20, with higher values also observed for the southeastern fuels. The majority of non-methane organic compound (NMOC) emissions detected by OP-FTIR were oxygenated volatile organic compounds (OVOCs) with the total identified OVOC emissions constituting 61 Â± 12% of the total measured NMOC on a molar basis. These OVOC may undergo photolysis or further oxidation contributing to ozone formation. Elevated amounts of gas-phase HCl and SO2 were also detected during flaming combustion, with the amounts varying greatly depending on location and vegetation type. The fuels with the highest HCl emission factors were all located in the coastal regions, although HCl was also observed from fuels farther inland. Emission factors for HCl were generally higher for the southwestern fuels, particularly those found in the chaparral biome in the coastal regions of California.
Laboratory measurements of trace gas emissions from biomass burning of fuel types from the Southeastern and Southwestern United StatesNASA Astrophysics Data System (ADS) Burling, I. R.; Yokelson, R. J.; Griffith, D. W. T.; Johnson, T. J.; Veres, P.; Roberts, J. M.; Warneke, C.; Urbanski, S. P.; Reardon, J.; Weise, D. R.; Hao, W. M.; de Gouw, J. updating Vegetation commonly managed by prescribed burning was collected from five southeastern and southwestern US military bases and burned under controlled conditions at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The smoke emissions were measured with a large suite of state-of-the-art instrumentation including an open-path Fourier transform infrared (OP-FTIR) spectrometer for measurement of gas-phase species. The OP-FTIR detected and quantified 19 gas-phase species in these fires: CO2, CO, CH4, C2H2, C2H4, C3H6, HCHO, HCOOH, CH3OH, CH3COOH, furan, H2O, NO, NO2, HONO, NH3, HCN, HCl, and SO2. Emission factors for these species are presented for each vegetation type burned. Gas-phase nitrous acid (HONO), an important OH precursor, was detected in the smoke from all fires. The HONO emission factors ranged from 0.15 to 0.60 g kg-1 and were higher for the southeastern fuels. The fire-integrated molar emission ratios of HONO (relative to NOx) ranged from approximately 0.03 to 0.20, with higher values also observed for the southeastern fuels. The majority of non-methane organic compound (NMOC) emissions detected by OP-FTIR were oxygenated volatile organic compounds (OVOCs) with the total identified OVOC emissions constituting 61Â±12% of the total measured NMOC on a molar basis. These OVOC may undergo photolysis or further oxidation contributing to ozone formation. Elevated amounts of gas-phase HCl and SO2 were also detected during flaming combustion, with the amounts varying greatly depending on location and vegetation type. The fuels with the highest HCl emission factors were all located in the coastal regions, although HCl was also observed from fuels farther inland. Emission factors for HCl were generally higher for the southwestern fuels, particularly those found in the chaparral biome in the coastal regions of California.
Laboratory Investigation of Trace Gas Emissions from Biomass Burning on DoD BasesNASA Astrophysics Data System (ADS) Burling, I. R.; Yokelson, R. J.; Griffith, D. W.; Roberts, J. M.; Veres, P. R.; Warneke, C.; Johnson, T. J. updating Vegetation representing fuels commonly managed with prescribed fires was collected from five DoD bases and burned under controlled conditions at the USFS Firelab in Missoula, MT. The smoke emissions were measured with a large suite of state-of-the-art instrumentation. Seventy-seven fires were conducted and the smoke composition data will improve DoD land managersâ ability to assess the impact of prescribed fires on local air quality. A key instrument used in the measurement of the gas phase species in smoke was an open-path FTIR (OP-FTIR) spectrometer, built and operated by the Universities of Montana and Wollongong. The OP-FTIR has to date detected and quantified 20 gas phase species - CO2, CO, H2O, N2O, NO2, NO, HONO, NH3, HCl, SO2, CH4, CH3OH, HCHO, HCOOH, C2H2, C2H4, CH3COOH, HCN, propylene and furan. The spectra were analyzed using a non-linear least squares fitting routine that included reference spectra recently acquired at the Pacific Northwest National Laboratories. Preliminary results from the OP-FTIR analysis are reported here. Of particular interest, gas-phase nitrous acid (HONO) was detected simultaneously by the OP-FTIR and negative-ion proton-transfer chemical ionization spectrometer (NI-PT-CIMS), with preliminary fire-integrated molar emission ratios (relative to NOx) ranging from approximately 0.03 to 0.20, depending on the vegetation type. HONO is an important precursor in the production of OH, the primary oxidizing species in the atmosphere. There existed little previous data documenting HONO emissions from either wild or prescribed fires. The non-methane organic emissions were dominated by oxygenated species, which can be further oxidized and thus involved in secondary aerosol formation. Elevated amounts of gas-phase HCl were also detected in the smoke, with the amounts varying depending on location and vegetation type.
Investigating Titan's Atmospheric Chemistry at Low Temperature in Support of the NASA Cassini MissionNASA Technical Reports Server (NTRS) Sciamma-O'Brien, Ella; Salama, Farid updating Titan's atmosphere, composed mainly of N2 and CH4, is the siege of a complex chemistry induced by solar UV radiation and electron bombardment from Saturn's magnetosphere. This organic chemistry occurs at temperatures lower than 200 K and leads to the production of heavy molecules and subsequently solid aerosols that form the orange haze surrounding Titan. The Titan Haze Simulation (THS) experiment has been developed on the COSMIC simulation chamber at NASA Ames in order to study the different steps of Titan's atmospheric chemistry at low temperature and to provide laboratory data in support for Cassini data analysis. The chemistry is simulated by plasma in the stream of a supersonic expansion. With this unique design, the gas mixture is adiabatically cooled to Titan-like temperature (approx. 150 K) before inducing the chemistry by plasma discharge. Different gas mixtures containing N2, CH4, and the first products of the N2,-CH4 chemistry (C2H2, C2H4, C6H6...) but also heavier molecules such as PAHs or nitrogen containing PAHs can be injected. Both the gas phase and solid phase products resulting from the plasma-induced chemistry can be monitored and analyzed. Here we present the results of recent gas phase and solid phase studies that highlight the chemical growth evolution when injecting heavier hydrocarbon trace elements in the initial N2-CH4 mixture. Due to the short residence time of the gas in the plasma discharge, only the first steps of the chemistry have time to occur in a N2-CH4 discharge. However by adding acetylene and benzene to the initial N2-CH4 mixture, we can study the intermediate steps of Titan's atmospheric chemistry as well as specific chemical pathways. These results show the uniqueness of the THS experiment to help understand the first and intermediate steps of Titan fs atmospheric chemistry as well as specific chemical pathways leading to Titan fs haze formation.
High-sensitivity interference-free diagnostic for measurement of methane in shock tubesNASA Astrophysics Data System (ADS) Sur, Ritobrata; Wang, Shengkai; Sun, Kai; Davidson, David F.; Jeffries, Jay B.; Hanson, Ronald K. updating A sensitive CW laser absorption diagnostic for in-situ measurement of methane mole fraction at high temperatures is developed. The selected transitions for the diagnostic are a cluster of lines near 3148.8 cm-1 from the R-branch of the Î½3 band of the CH4 absorption spectrum. The selected transitions have 2-3 times more sensitivity to CH4 concentration than the P-branch in the 3.3 Î¼m region, lower interference from major interfering intermediate species in most hydrocarbon reactions, and applicability over a wide range of pressures and temperatures. Absorption cross-sections for a broad collection of hydrocarbons were simulated to evaluate interference absorption, and were generally found to be negligible near 3148.8 cm-1. However, minor interference from hot bands of C2H2 and C2H4 was observed and was characterized experimentally, revealing a weak dependence on wavelength. To eliminate such interferences, a two-color on-line and off-line measurement scheme is proposed to determine CH4 concentration. The colors selected, i.e., for on-line (3148.81 cm-1) and off-line (3148.66 cm-1), are characterized between 0.2-4 atm and 500 K-2100 K by absorption coefficient measurements in a shock tube. Minimum detectable levels of CH4 in shock tube experiments are reported for this range of temperatures and pressures. An example measurement is shown for sensitive detection of CH4 in a shock tube chemical kinetics experiment.
Combined Experimental and Computational Study on the Unimolecular Decomposition of JP-8 Jet Fuel Surrogates. II: n-Dodecane (n-C12H26).PubMed Zhao, Long; Yang, Tao; Kaiser, Ralf I; Troy, Tyler P; Ahmed, Musahid; Ribeiro, Joao Marcelo; Belisario-Lara, Daniel; Mebel, Alexander M updating We investigated temperature-dependent products in the pyrolysis of helium-seeded n-dodecane, which represents a surrogate of the n-alkane fraction of Jet Propellant-8 (JP-8) aviation fuel. The experiments were performed in a high temperature chemical reactor over a temperature range of 1200 K to 1600 K at a pressure of 600 Torr, with in situ identification of the nascent products in a supersonic molecular beam using single photon vacuum ultraviolet (VUV) photoionization coupled with the analysis of the ions in a reflectron time-of-flight mass spectrometer (ReTOF). For the first time, the initial decomposition products of n-dodecane-including radicals and thermally labile closed-shell species-were probed in experiments, which effectively exclude mass growth processes. A total of 15 different products were identified, such as molecular hydrogen (H 2 ), C2 to C7 1-alkenes [ethylene (C 2 H 4 ) to 1-heptene (C 7 H 14 )], C1-C3 radicals [methyl (CH 3 ), ethyl (C 2 H 5 ), allyl (C 3 H 5 )], small C1-C3 hydrocarbons [acetylene (C 2 H 2 ), allene (C 3 H 4 ), methylacetylene (C 3 H 4 )], as well as the reaction products [1,3-butadiene (C 4 H 6 ), 2-butene (C 4 H 8 )] attributed to higher-order processes. Electronic structure calculations carried out at the G3(CCSD,MP2)//B3LYP/6-311G(d,p) level of theory combined with RRKM/master equation of rate constants for relevant reaction steps showed that n-dodecane decomposes initially by a nonterminal C-C bond cleavage and producing a mixture of alkyl radicals from ethyl to decyl with approximately equal branching ratios. The alkyl radicals appear to be unstable under the experimental conditions and to rapidly dissociate either directly by C-C bond Î²-scission to produce ethylene (C 2 H 4 ) plus a smaller 1-alkyl radical with the number of carbon atoms diminished by two or via 1,5-, 1,6-, or 1,7- 1,4-, 1,9-, or 1,8-H shifts followed by C-C Î²-scission producing alkenes from propene to 1-nonene together with smaller 1-alkyl radicals
Formation of C3 and C2 in Cometary ComaeNASA Astrophysics Data System (ADS) HÃ¶lscher, Alexander updating allow to better constrain which parent molecules are responsible for the observational C3 and C2 column densities. Based on observations of the four sample comets C/2001 Q4 (NEAT), C/2002 T7 (LINEAR), 9P (Tempel 1) and C/1995 O1 (Hale-Bopp), this work investigates which combination of the following proposed parent molecules C4H2 (diacetylene), CH2C2H2 (allene), CH3C2H (propyne), C2H4 (ethene) and observed parent molecules C2H2 and HC3N (cyanoacetylene) can best reproduce the observational C3 and C2 column densities in cometary comae, taking into account the uncertainties in photodissociation rate coefficients. It was found that the investigated photodissociation rate coefficients have large uncertainties and also a significant effect on the C3 and C2 model column densities. The responsible key reactions were determined with the sensitivity analysis. The important result of this thesis is that one can reasonably well reproduce the observations of comets with the improved model at rh = 1.00 AU (NEAT) and rh = 3.78 AU (Hale-Bopp), within the photodissociation uncertainties using realistic parent molecule production rate ratios and by various combinations of the investigated parent molecules. To confirm the agreement (NEAT, Hale-Bopp) and to clearify remaining discrepancies (LINEAR, Tempel 1) between model and observations requires additional observations of parent and daughter molecules in the coma of comets as well as in situ measurements of cometary ices (Rosetta).zeige weniger
Revisiting global fossil fuel and biofuel emissions of ethaneNASA Astrophysics Data System (ADS) Tzompa-Sosa, Z. A.; Mahieu, E.; Franco, B.; Keller, C. A.; Turner, A. J.; Helmig, D.; Fried, A.; Richter, D.; Weibring, P.; Walega, J.; Yacovitch, T. I.; Herndon, S. C.; Blake, D. R.; Hase, F.; Hannigan, J. W.; Conway, S.; Strong, K.; Schneider, M.; Fischer, E. V. updating Recent measurements over the Northern Hemisphere indicate that the long-term decline in the atmospheric burden of ethane (C2H6) has ended and the abundance increased dramatically between 2010 and 2014. The rise in C2H6 atmospheric abundances has been attributed to oil and natural gas extraction in North America. Existing global C2H6 emission inventories are based on outdated activity maps that do not account for current oil and natural gas exploitation regions. We present an updated global C2H6 emission inventory based on 2010 satellite-derived CH4 fluxes with adjusted C2H6 emissions over the U.S. from the National Emission Inventory (NEI 2011). We contrast our global 2010 C2H6 emission inventory with one developed for 2001. The C2H6 difference between global anthropogenic emissions is subtle (7.9 versus 7.2 Tg yr-1), but the spatial distribution of the emissions is distinct. In the 2010 C2H6 inventory, fossil fuel sources in the Northern Hemisphere represent half of global C2H6 emissions and 95% of global fossil fuel emissions. Over the U.S., unadjusted NEI 2011 C2H6 emissions produce mixing ratios that are 14-50% of those observed by aircraft observations (updating). When the NEI 2011 C2H6 emission totals are scaled by a factor of 1.4, the Goddard Earth Observing System Chem model largely reproduces a regional suite of observations, with the exception of the central U.S., where it continues to underpredict observed mixing ratios in the lower troposphere. We estimate monthly mean contributions of fossil fuel C2H6 emissions to ozone and peroxyacetyl nitrate surface mixing ratios over North America of 1% and 8%, respectively.
Storage and recovery of methane-ethane mixtures in single shale poresNASA Astrophysics Data System (ADS) Wu, Haiyi; Qiao, Rui updating Natural gas production from shale formations has received extensive attention recently. While great progress has been made in understanding the adsorption and transport of single-component gas inside shales' nanopores, the adsorption and transport of multicomponent shale gas under reservoir conditions (CH4 and C2H6 mixture) has only begun to be studied. In this work, we use molecular simulations to compute the storage of CH4 and C2H6 mixtures in single nanopores and their subsequent recovery. We show that surface adsorption contributes greatly to the storage of CH4 and C2H6 inside the pores and C2H6 is enriched over CH4. The enrichment of C2H6 is enhanced as the pore is narrowed, but is weakened as the pressure increases. We show that the recovery of gas mixtures from the nanopores approximately follows the diffusive scaling law. The ratio of the production rates of C2H6 and CH4 is close to their initial mole ratio inside the pore despite that the mobility of pure C2H6 is much smaller than that of pure CH4 inside the pores. By using scale analysis, we show that the strong coupling between the transport of CH4 and C2H6 is responsible for the effective recovery of C2H6 from the nanopores.
Ion-molecule condensation reactions: a mechanism for organic synthesis in ionized reducing atmospheres.PubMed Meot-Ner, M updating The CH3+ ion, formed in ionized methane, undergoes consecutive eliminative condensation reactions with methane to form the carbonium ions C2H5+, i-C3H7+ and t-C4H9+. At T smaller than 500 degrees K, NCH4 greater than 10(16) cm-3 these ions react with NH3 in competitive condensation -- H+ transfer reactions, e.g. C2H5 + NH3 M leads to C2H5NH3+ leads to NH4+ + C2H4 At particle densities of NCH4 smaller than 10(16) cm-3 proton transfer is the only significant reaction channel. At NCH4 greater than 10(17) cm-3 condensation constitutes 5--20% of the overall reactions. The product of the condensation reaction further associates with CO2 to form C2H5NH3+ . CO2; the atomic composition of this cluster ion is identical with the protonated amino acid alanine. The carbonium ions i-C3H7+ and t-C4H9+ condense also with HCN to yield protonated isocyanides. HCNH% also appears to condense with HCN at T greater than 570 degrees K, and form cluster ions with HCN at lower temperatures. The rate constants of the condensation reactions vary with temperature and pressure in a complex manner. Under conditions similar to those on Titan at an altitude of 100 km (T = updating degrees K, NCH4 approximately 10(18) cm-3), with a methane atmosphere containing 1% H2 and traces of NH3 and H2O, ion-molecule condensation reactions followed by H+ transfer are expected to lead to the atmospheric synthesis of C2H6, C3H8, CH3OH, C2H5OH and the terminal ions NH4+, CH3NH3+ and C2H5NH3+. At higher temperatures (250 degrees K smaller than T smaller than 400 degrees K), the synthesis of i-C4H10, i-C3H7OH and t-C4H9OH and of the ions i-C3H7NH3+ and t-C4H9NH3+ is also expected. Electron recombination of the terminal ions may yield amines, imines and nitriles. Cycles of protonation and dissociative recombination of the alkanes and alcohols produced in condensation reactions will also produce unsaturated hydrocarbons, ketones and aldehydes in the ionized atmosphere.
Derivation of greenhouse gas emission factors for peatlands managed for extraction in the Republic of Ireland and the United KingdomNASA Astrophysics Data System (ADS) Wilson, D.; Dixon, S. D.; Artz, R. R. E.; Smith, T. E. L.; Evans, C. D.; Owen, H. J. F.; Archer, E.; Renou-Wilson, F. updating Drained peatlands are significant hotspots of carbon dioxide (CO2) emissions and may also be more vulnerable to fire with its associated gaseous emissions. Under the United Nations Framework Convention on Climate Change (UNFCCC) and the Kyoto Protocol, greenhouse gas (GHG) emissions from peatlands managed for extraction are reported on an annual basis. However, the Tier 1 (default) emission factors (EFs) provided in the IPCC 2013 Wetlands Supplement for this land use category may not be representative in all cases and countries are encouraged to move to higher-tier reporting levels with reduced uncertainty levels based on country- or regional-specific data. In this study, we quantified (1) CO2-C emissions from nine peat extraction sites in the Republic of Ireland and the United Kingdom, which were initially disaggregated by land use type (industrial versus domestic peat extraction), and (2) a range of GHGs that are released to the atmosphere with the burning of peat. Drainage-related methane (CH4) and nitrous oxide (N2O) emissions as well as CO2-C emissions associated with the off-site decomposition of horticultural peat were not included here. Our results show that net CO2-C emissions were strongly controlled by soil temperature at the industrial sites (bare peat) and by soil temperature and leaf area index at the vegetated domestic sites. Our derived EFs of 1.70 (Â±0.47) and 1.64 (Â±0.44) t CO2-C ha-1 yr-1 for the industrial and domestic sites respectively are considerably lower than the Tier 1 EF (2.8 Â± 1.7 t CO2-C ha-1 yr-1) provided in the Wetlands Supplement. We propose that the difference between our derived values and the Wetlands Supplement value is due to differences in peat quality and, consequently, decomposition rates. Emissions from burning of the peat (g kg-1 dry fuel burned) were estimated to be approximately 1346 CO2, 8.35 methane (CH4), 218 carbon monoxide (CO), 1.53 ethane (C2H6), 1.74 ethylene (C2H4), 0.60 methanol (CH3OH), 2.21 hydrogen
Ethylene: Indicator but Not Inducer of Phytoalexin Synthesis in Soybean 1PubMed Central Paradies, Inge; Konze, JÃ¶rg R.; Elstner, Erich F.; Paxton, Jack updating Cell wall preparations (elicitors) from Phytophthora megasperma var. sojae increase C2H4 formation, phenylalanine ammonia lyase activity, and glyceollin accumulation in soybean cotyledons within about 1.5, 3, and 6 hours after treatment, respectively. The immediate precursor of C2H4, 1-aminocyclopropane-1-carboxylic acid, stimulates C2H4 formation like the elicitor within 1.5 hours after administration, whereas phenylalanine ammonia lyase activity and glyceollin concentration remain unchanged. Aminoethoxyvinylglycine, a specific inhibitor of C2H4 formation in higher plants, inhibits elicitor-induced C2H4 formation by about 95% but has no effects on phenylalanine ammonia lyase or glyceollin accumulation. It was concluded that C2H4 is a signal accompanying the specific recognition process which finally leads to the induction of phytoalexin formation, but it is not functioning as a link or messenger in the induction sequence of glyceollin accumulation. Images PMID:updating
Dynamic Weakening (Extinction) of Simple Hydrocarbon-air Counterflow Diffusion Flames by Oscillatory InflowsNASA Technical Reports Server (NTRS) Pellett, G.; Kabaria, A.; Panigrahi, B.; Sammons, K.; Convery, J.; Wilson, L. updating insensitive (DFW approximately 0) at approximately 300 Hz, which continued to 1600 Hz. The DFW of CH4-air flames followed a similar pattern, but showed much greater weakening than C2H4/N2-air flames; i.e., the quasi-steady DFW (8 to approximately 15 Hz) was 44.3 %/Pa, or approximately 5x larger, even though the 0 Hz (SS) FS was only 3.0 x smaller. The quasi-steady DFW's of C3H8-air and C2H6-air were intermediate at 34.8 and 20.9 %Pa, respectively. The DFW profiles of all four fuels, at various frequencies, correlated well but non-linearly with respective SS FS's. Notably, the DFW profile for C3H8 air fell more rapidly in the range greater than 15 to 60 Hz, compared with the 1- and 2-carbon fuels. This may indicate a shift in chemical kinetics, and/or O2 transport to a flame that moved closer to the fuel-side. In conclusion, Dynamic Flame Weakening limits appear significant and unique for each fuel, and correlate closely, but non-linearly, with Steady-State Flame Strengths at any given frequency. For reasons unknown, the dynamic flames didn't weaken more at intermediate frequencies (e.g., at 20-50 Hz) than they did at low frequencies (less than 15 Hz), where quasi-steady weakening appears to dominate. Quasi-steady flame weakening ostensibly represents a transient input strain rate maximum that just exceeds the steady-state strain-rate-limited extinction limit for a few cycles. Clearly, further detailed mechanistic understanding is needed in the fall-off region.
ACE-FTS observations of pyrogenic trace species in boreal biomass burning plumes during BORTASNASA Astrophysics Data System (ADS) Tereszchuk, K. A.; GonzÃ¡lez Abad, G.; Clerbaux, C.; Hadji-Lazaro, J.; Hurtmans, D.; Coheur, P.-F.; Bernath, P. F. updating To further our understanding of the effects of biomass burning emissions on atmospheric composition, the BORTAS campaign (BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites) was conducted on 12 July to 3 August 2011 during the boreal forest fire season in Canada. The simultaneous aerial, ground and satellite measurement campaign sought to record instances of boreal biomass burning to measure the tropospheric volume mixing ratios (VMRs) of short- and long-lived trace molecular species from biomass burning emissions. The goal was to investigate the connection between the composition and the distribution of these pyrogenic outflows and their resulting perturbation to atmospheric chemistry, with particular focus on oxidant species to determine the overall impact on the oxidizing capacity of the free troposphere. Measurements of pyrogenic trace species in boreal biomass burning plumes were made by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) onboard the Canadian Space Agency (CSA) SCISAT-1 satellite during the BORTAS campaign. Even though biomass burning emissions are typically confined to the boundary layer, outflows are often injected into the upper troposphere by isolated convection and fire-related convective processes, thus allowing space-borne instruments to measure these pyrogenic outflows. An extensive set of 14 molecules - CH3OH, C2H2, C2H6, C3H6O, CO, HCN, HCOOH, HNO3, H2CO, NO, NO2, OCS, O3, and PAN - have been analysed. Included in this analysis is the calculation of age-dependent sets of enhancement ratios for each of the species originating from fires in North America (Canada, Alaska) and Siberia for a period of up to 7 days. Ratio values for the shorter lived primary pyrogenic species decrease over time primarily due to oxidation by the OH radical as the plume ages and values for longer lived species such as HCN and C2H6 remain relatively unchanged. Increasing negative values are
Airborne Ethane Observations in the Barnett Shale: Quantification of Ethane Flux and Attribution of Methane Emissions.PubMed Smith, Mackenzie L; Kort, Eric A; Karion, Anna; Sweeney, Colm; Herndon, Scott C; Yacovitch, Tara I updating We present high time resolution airborne ethane (C2H6) and methane (CH4) measurements made in March and October 2013 as part of the Barnett Coordinated Campaign over the Barnett Shale formation in Texas. Ethane fluxes are quantified using a downwind flight strategy, a first demonstration of this approach for C2H6. Additionally, ethane-to-methane emissions ratios (C2H6:CH4) of point sources were observationally determined from simultaneous airborne C2H6 and CH4 measurements during a survey flight over the source region. Distinct C2H6:CH4 Ã 100% molar ratios of 0.0%, 1.8%, and 9.6%, indicative of microbial, low-C2H6 fossil, and high-C2H6 fossil sources, respectively, emerged in observations over the emissions source region of the Barnett Shale. Ethane-to-methane correlations were used in conjunction with C2H6 and CH4 fluxes to quantify the fraction of CH4 emissions derived from fossil and microbial sources. On the basis of two analyses, we find 71-85% of the observed methane emissions quantified in the Barnett Shale are derived from fossil sources. The average ethane flux observed from the studied region of the Barnett Shale was 6.6 Â± 0.2 Ã 10(3) kg hr(-1) and consistent across six days in spring and fall of 2013.
Expectations for Particulate Contamination Relevant to in Situ Atmospheric Sampling for Compositional Analysis at UranusNASA Astrophysics Data System (ADS) Wong, M. H. updating NASA and ESA are considering options for in situ science with atmospheric entry probes to the ice giants Uranus and Neptune. Nominal probe entry mass is in the 300-kg range, although a miniaturized secondary probe option is being studied in the 30-kg range. In all cases, compositional sampling would commence near the 100-mbar level at Uranus, after ejection of the heat shield and deployment of the descent parachute. In this presentation, I review existing literature on the composition, mass loading, and vertical distribution of condensed material that the probe may encounter. Sample inlets for measurement of the gas composition should be heated to avoid potential buildup of condensate, which would block the flow of atmospheric gas into composition sensors. Heating rate and temperature values -- sufficient to keep sample inlets clean under various assumptions -- will be presented. Three main types of condensed material will be considered: Stratospheric hydrocarbon ices: Solar UV photolyzes CH4, leading to the production of volatile hydrocarbons with higher C/H ratios. These species diffuse from their production regions into colder levels where the ices of C2H2, C2H6, and C4H2 condense. Some studies have also considered condensation of C3H8, C4H10, C6H6, and C6H2. Gunk: The hydrocarbon ices are thought to become polymerized due to irradiation from solar UV. The exact composition of the resulting gunk is not known. Solid-state photochemical processing may produce the traces of reddish (blue-absorbing) haze material, present in the troposphere at temperatures warm enough to sublimate the simple hydrocarbon ices. Tropospheric ices: In the region accessible to probes under study (P

The 12C/13C Isotopic Ratio In Titan's HydrocarbonsNASA Astrophysics Data System (ADS) Nixon, Conor A.; Achterberg, R. K.; Vinatier, S.; Bezard, B.; Coustenis, A.; Teanby, N. A.; Irwin, P. G.; Cassini CIRS Team updating Isotopic ratios in planetary atmospheres are of considerable interest, yielding insights both about currently occurring processes, and also the formation and early evolution of the body. Before Cassini, ground-based measurements of Titan's 12C/13C in HCN showed no firm evidence of deviation from the terrestrial inorganic standard (88.9) - albeit with large error bars of 20% - contrasting the enrichment in nitrogen (15N/14Nâ4.5 terrestrial). Since 2004, the Composite Infrared Spectrometer (CIRS) instrument on Cassini has recorded spectra of Titan's stratosphere globally, including the emissions of multiple isotopologues for certain hydrocarbons. We selected spectra for analysis from four flybys (T4, T12, T19, T22), covering five latitudes from 65Â°S to 71Â°N. By means of a radiative transfer code and inversion scheme, we have first modeled the Î½4 band of 12CH4 at 1304 cm-1 to retrieve stratospheric temperatures, and subsequently the emissions of 13CH4, 12C2H2, 13C12CH2, 12C2H6 and 13C12CH6. Our results indicate 12C/13C = 81.2Â±2.0 for all three species combined over all five latitudes, in excellent agreement with the Huygens GCMS value of 12CH4/13CH4 = 82.3Â±1.0 (Niemann et al. 2005), some 9% lower than terrestrial inorganic, and lower than in ethane on Saturn (updating)) and Jupiter (updating)) (Sada et al. 1996). No latitude variation was detected, however the 12C/13C in the C2 species (83.9Â±3.1 in acetylene, 89.9Â±7.2 in ethane) were consistently higher than in methane (78.0Â±2.7) after considering random errors. Although it is possible that this is a real chemical or physical (condensation) effect, it is more likely due to systematic errors in our temperature profile, as our spectra do not yield independent temperature information at 10 mbar where the emissions of 13C12CH2 and 13C12CH6 originate, and we default to the Huygens probe temperatures. In future, this problem may be resolved by modeling CIRS limb spectra.
Titan's methane clockNASA Astrophysics Data System (ADS) Nixon, C. A.; Jennings, D. E.; Romani, P. N.; Teanby, N. A.; Irwin, P. G. J.; Flasar, F. M. updating Measurements of the 12C/13C and D/H isotopic ratios in Titan's methane show intriguing differences from the values recorded in the giant planets. This implies that either (1) the atmosphere was differently endowed with material at the time of formation, or (2) evolutionary processes are at work in the moon's atmosphere - or some combination of the two. The Huygens Gas Chromatograph Mass Spectrometer Instrument (GCMS) found 12CH4/13CH4 = 82 +/- 1 (Niemann et al. 2005), some 7% lower than the giant planets' value of 88 +/- 7 (Sada et al. 1996), which closely matches the terrestrial inorganic standard of 89. The Cassini Composite Infrared Spectrometer (CIRS) has previously reported 12CH4/13CH4 of 77 +/-3 based on nadir sounding, which we now revise upwards to 80 +/- 4 based on more accurate limb sounding. The CIRS and GCMS results are therefore in agreement about an overall enrichment in 13CH4 of ~10%. The value of D/H in Titan's CH4 has long been controversial: historical measurements have ranged from about 8-15 x 10-5 (e.g. Coustenis et al. 1989, Coustenis et al. 2003). A recent measurement based on CIRS limb data by Bezard et al. (2007) puts the D/H in CH4 at (13 +/- 1) x 10-5, very much greater than in Jupiter and Saturn, ~2 x 10-5 (Mahaffy et al. 1998, Fletcher et al. 2009). To add complexity, the 12C/13C and D/H vary among molecules in Titan atmosphere, typically showing enhancement in D but depletion in 13C in the daughter species (H2, C2H2, C2H6), relative to the photochemical progenitor, methane. Jennings et al. (2009) have sought to interpret the variance in carbon isotopes as a Kinetic Isotope Effect (KIE), whilst an explanation for the D/H in all molecules remains elusive (Cordier et al. 2008). In this presentation we argue that evolution of isotopic ratios in Titan's methane over time forms a ticking 'clock', somewhat analogous to isotopic ratios in geochronology. Under plausible assumptions about the initial values and subsequent replenishment, various
Spectroscopic study of low pressure, low temperature H2-CH4-CO2 microwave plasmas used for large area deposition of nanocrystalline diamond films. Part II: on plasma chemical processesNASA Astrophysics Data System (ADS) Nave, A. S. C.; Baudrillart, B.; Hamann, S.; BÃ©nÃ©dic, F.; Lombardi, G.; Gicquel, A.; van Helden, J. H.; RÃ¶pcke, J. updating In a distributed antenna array (DAA) reactor, microwave H2 plasmas with admixtures of 2.5% CH4 and 1% CO2 used for the deposition of nanocrystalline diamond films have been studied by infrared laser absorption and optical emission spectroscopy (OES) techniques. The experiments were carried out in order to analyze the dependence of plasma chemical phenomena on power and pressure at relatively low pressures, up to 0.55âmbar, and power values, up to 3 kW. The evolution of the concentration of the methyl radical, CH3, of five stable molecules, CH4, CO2, CO, C2H2 and C2H6, and of vibrationally excited CO in the first and second hot band was monitored in the plasma processes by in situ infrared laser absorption spectroscopy using tunable lead salt diode lasers (TDL) and an external-cavity quantum cascade laser (EC-QCL) as radiation sources. OES was applied simultaneously to obtain complementary information about the degree of dissociation of the H2 precursor and of its gas temperature. The experimental results are presented in two separate parts. In Part I, the first paper in a two-part series, the measurement of the gas (T gas), rotational (T rot) and vibrational (T vib) temperatures of the various species in the complex plasma was the main focus of interest. Depending on the different plasma zones the gas temperature was found to range between about 360 and 1000âK inside the DAA reactor (Nave et al 2016 Plasma Sources Sci. Technol. updating). In Part II, the present paper, taking into account the temperatures determined in the first paper, the concentrations of the various species, which were found to be in a range between 1011 and 1015 cm-3, are the focus of interest. The influence of the discharge parameters power and pressure on the molecular concentrations has been studied. To achieve further insight into general plasma chemical aspects the dissociation of the carbon precursor gases including their fragmentation and conversion to the reaction products has been
Models for Temperature and Composition in Uranus from Spitzer, Herschel and Ground-Based Infrared through Millimeter ObservationsNASA Astrophysics Data System (ADS) Orton, Glenn S.; Fletcher, Leigh N.; Feuchtgruber, Helmut; Lellouch, Emmanuel; Moreno, Raphel; Encrenaz, Therese; Hartogh, Paul; Jarchow, Christopher; Swinyard, Bruce; Cavalie, Thibault; Moses, Julianne; Burgdorf, Martin; Hammel, Heidi; Line, Michael; Mainzer, Amy K.; Hofstadter, Mark; Sandell, Goran H.; Dowell, C. Darren; Pantin, Eric; Fujiyoshi, Takuya updating Photometric and spectroscopic observations of Uranus in the thermal infrared were combined to create self-consistent models of its global-mean temperature profile and vertical distribution of gases. These were derived from a suite of observations from Spitzer and Herschel, together with ground-based observations from UKIRT, CSO, Gemini, VLT and Subaru. Observations of the collision-induced absorption and quadrupoles of H2 have constrained the temperature structure for pressures of nearly 2 bars down to 0.1 millibars. We coupled the vertical distribution of CH4 in the stratosphere of Uranus with models for the vertical mixing in such a way to be consistent with the mixing ratios of hydrocarbons. Spitzer and Herschel data constrain the abundances of CH3, CH4, C2H2, C2H6, C3H4, C4H2, H2O and CO2. The Spitzer IRS data, in concert with photochemical models, show that the homopause is at much higher atmospheric pressures than for the other outer planets, with the predominant trace constituents for pressures lower than 30 Âµbar being H2O and CO2. The ratio of the oxygen-bearing molecules is consistent with exogenic origins in KBOs or comets. At millimeter wavelengths, there is evidence that an additional opacity source is required besides the H2 collision-induced absorption and the NH3 absorption needed to match the microwave spectrum; this can reasonably (but not uniquely) be attributed to H2S. This model is of âprogrammaticâ interest because it serves as a standard calibration source; the cross-comparison of its spectrum with model spectra for Mars and Neptune shows consistency to within 3%. Near equinox, the IRS spectra at different longitudes showed rotationally variable stratospheric emission that is consistent with a temperature anomaly â¤10 K near ~0.1-0.2 mbar. Spatial variability of tropospheric temperatures observed in ground-based observations from 2006 to 2011 is generally consistent with Voyager infrared (IRIS) results.
A Contextual Comparison of Native Ice Abundances in Comet C/2013 US10 (Catalina) based on Infrared SpectroscopyNASA Astrophysics Data System (ADS) DiSanti, Michael A.; Gibb, Erika L.; Roth, Nathanial; Bonev, Boncho P.; Keane, Jacqueline; Meech, Karen Jean; Villanueva, Geronimo Luis; Paganini, Lucas; Mumma, Michael J. updating The primitive nature of comets makes them the best available carriers of information pertaining to conditions in the early solar system. High-resolution spectrometers operating at IR wavelengths (~ 1 - 5 Âµm) permit quantifying molecular species (aka "parent volatiles") released into the coma upon sublimation of ices contained in the cometary nucleus (i.e., native ices). Over the past 20 years we used first CSHELL at the IRTF, then NIRSPEC at Keck and CRIRES at the VLT, amassing production rates and abundance ratios in 30-plus comets.We present a summary of molecular abundances in long period Comet C/2013 US10 (Catalina), which passed perihelion on UT 2015 November 15.7 at heliocentric distance Rh = 0.822 AU. We used CSHELL on UT 2015 November 23 (Rh = 0.84 AU), December 15 - 17 (Rh = 1.0 AU) and 2016 February 28 (Rh = 1.95 AU), and NIRSPEC on 2016 January 24 (Rh = 1.49 AU). We targeted H2O, CO, H2CO, CH3OH, OCS, HCN, NH3, CH4, C2H2, and C2H6, and obtained production rates or stringent upper limits for all of these. This allowed testing for potential changes in relative abundances as a function of Rh. Such IR measurements spanning a range in Rh are still rare, but are very important for testing possible heterogeneous nucleus composition and/or heliocentric dependence of abundances, for example through release from grains heated in the coma. Our measurements will be inter-compared, and also placed in the context of our current (and continually evolving) compositional taxonomy of comets.We gratefully acknowledge support from the NASA Solar System Observations/Planetary Astronomy Program (SSO15-0028 to MAD, PAST11-0045 to MJM), Planetary Atmospheres Program (NNX12AG60G to BPB), NASA Astrobiology Institute (13-13NAI7-0032 to MJM, NN09DA77A to KJM), and NSF Astronomy and Astrophysics Research Grants (AST-1211362 to BPB and ELG, and AST-1413736 to KJM). The IRTF is operated by the University of Hawaii under contract NNH14CK55B with the National Aeronautics and Space
Photochemical Modeling of CH3 Abundances in the Outer Solar SystemNASA Technical Reports Server (NTRS) Lee, Anthony Y. T.; Yung, Yuk L.; Moses, Julianne updating Recent measurements of methyl radicals (CH3) in the upper atmospheres of Saturn and Neptune by the Infrared Space Observatory (ISO) provide new constraints to photochemical models of hydrocarbon chemistry in the outer solar system. The derived column abundances of CH3 on Saturn above 10 mbar and Neptune above the 0.2 mbar pressure level are (updating) x 10(exp 13) / sq cm and (updating) x 10(exp 13) / sq cm, respectively. We use the updated Caltech/Jet Propulsion Laboratory photochemical model, which incorporates hydrocarbon photochemistry, vertical molecular and bulk atmospheric eddy diffusion, and realistic radiative transfer modeling, to study the CH3 abundances in the upper atmosphere of the giant planets and Titan. We identify the key reactions that control the concentrations of CH3 in the model, such as the three-body recombination reaction, CH3 + CH3 + M yields C2H6 + M. We evaluate and extrapolate the three-body rate constant of this reaction to the low-temperature limit (1.8 x 10(exp -16) T(sup -3.75) e(sup -300/T), T C2H2 + H2, (sup 1)CH2 + H2 yields CH3 + H, and H + C2H5 yields 2CH3, the branching ratios of CH4 photolysis, vertical mixing in the five atmospheres, and Lyman alpha photon enhancement at the orbit of Neptune have all been tested. The results of our model CH3 abundances for both Saturn (5.1 x 10(exp 13) / sq cm) and Neptune (2.2 x 10(exp 13) / sq cm) show good agreement with ISO Short Wavelength Spectrometer measurements. Using the same chemical reaction set, our calculations also successfully generate vertical profiles of stable hydrocarbons consistent with Voyager and ground-based measurements in these outer solar system atmospheres. Predictions of CH3 column concentrations (for p
Seasonal variations of temperature, acetylene and ethane in Saturn's atmosphere from 2005 to 2010, as observed by Cassini-CIRSNASA Astrophysics Data System (ADS) Sinclair, J. A.; Irwin, P. G. J.; Fletcher, L. N.; Moses, J. I.; Greathouse, T. K.; Friedson, A. J.; Hesman, B.; Hurley, J.; Merlet, C. updating Acetylene (C2H2) and ethane (C2H6) are by-products of complex photochemistry in the stratosphere of Saturn. Both hydrocarbons are important to the thermal balance of Saturn's stratosphere and serve as tracers of vertical motion in the lower stratosphere. Earlier studies of Saturn's hydrocarbons using Cassini-CIRS observations have provided only a snapshot of their behaviour. Following the vernal equinox in August 2009, Saturn's northern and southern hemispheres have entered spring and autumn, respectively, however the response of Saturn's hydrocarbons to this seasonal shift remains to be determined. In this paper, we investigate how the thermal structure and concentrations of acetylene and ethane have evolved with the changing season on Saturn. We retrieve the vertical temperature profiles and acetylene and ethane volume mixing ratios from ÎÎ½Ë=15.5cm-1 Cassini-CIRS observations. In comparing 2005 (solar longitude, Ls Ë 308Â°), 2009 (Ls Ë 3Â°) and 2010 (Ls Ë 15Â°) results, we observe the disappearance of Saturn's warm southern polar hood with cooling of up to 17.1 K Â± 0.8 K at 1.1 mbar at high-southern latitudes. Comparison of the derived temperature trend in this region with a radiative climate model (Section 4 of Fletcher et al., 2010 and Greathouse et al. (2013, in preparation)) indicates that this cooling is radiative although dynamical changes in this region cannot be ruled out. We observe a 21 Â± 12% enrichment of acetylene and a 29 Â± 11% enrichment of ethane at 25Â°N from 2005 to 2009, suggesting downwelling at this latitude. At 15Â°S, both acetylene and ethane exhibit a decrease in concentration of 6 Â± 11% and 17 Â± 9% from 2005 to 2010, respectively, which suggests upwelling at this latitude (though a statistically significant change is only exhibited by ethane). These implied vertical motions at 15Â°S and 25Â°N are consistent with a recently-developed global circulation model of Saturn's tropopause and stratosphere(Friedson and Moses, 2012), which
Titan's Aerosol and Condensation Cloud Properties in the Far-IR Between 2005 and 2010NASA Technical Reports Server (NTRS) Anderson, Carrie; Samuelson, Robert updating ) (125 micron), possibly due to C2H6 ice or dominated by an ethane-acetylene composite ice, given that CzH6 then C2H2 are the two most abundant hydrocarbons next to methane in Titan's atmosphere.
A Tale of âTwoâ Comets: The Primary Volatile Composition of Comet 2P/Encke Across ApparitionsNASA Astrophysics Data System (ADS) Roth, Nathan X.; Gibb, Erika L.; Bonev, Boncho P.; DiSanti, Michael A.; Dello Russo, Neil; Vervack, Ronald J.; McKay, Adam J.; Kawakita, Hideyo updating 2P/Encke is one of the most frequently observed comets in history, yet its highly favorable 2017 apparition allowed the first comprehensive comparison of primary volatile abundances in the same comet across multiple apparitions. It offered an opportunity to address pressing questions in cometary science, including investigating evolutionary and/or heliocentric distance effects on volatile production, sampling the hypervolatiles CO and CH4 in an ecliptic comet, and probing volatile release at small Rh (0.4 AU). The faint nature of ecliptic comets and low geocentric velocity during most apparitions make these observations in the near-infrared rare (in particular at small Rh) and of high scientific impact. On March 21, 22, and 25 we characterized the volatile composition of 2P post-perihelion using the high-resolution near-infrared iSHELL spectrograph at the 3 m NASA-IRTF on Maunakea, HI. We detected fluorescent emission from eight primary volatiles (H2O, CO, C2H6, CH3OH, CH4, H2CO, NH3, and HCN) and three secondary volatiles (OH*, NH2, and CN). Upper limits were derived for OCS and C2H2. We report rotational temperatures, production rates, and mixing ratios (with respect to H2O). Compared to median relative abundances in comets observed in the near-infrared to date, mixing ratios of trace gases in 2P/Encke are depleted for all detected species except HCN and NH3, which are consistent with the median. The detection of the hypervolatiles CO and CH4 is particularly notable given the paucity of measurements of these species in ecliptic comets. We observed significant differences in primary volatile composition compared to published pre-perihelion results from the 2003 apparition at larger Rh (~1.2 AU) (Radeva et al. 2013). We will discuss possible mechanisms for these effects, including asymmetry about perihelion in 2P (Sekanina 1988a, b), and discuss the results in the context of findings from the Rosetta mission and ground-based studies of comets. This work was
Assessing the long-term variability of acetylene and ethane in the stratosphere of JupiterNASA Astrophysics Data System (ADS) Melin, Henrik; Fletcher, L. N.; Donnelly, P. T.; Greathouse, T. K.; Lacy, J. H.; Orton, G. S.; Giles, R. S.; Sinclair, J. A.; Irwin, P. G. J. updating Acetylene (C2H2) and ethane (C2H6) are both produced in the stratosphere of Jupiter via photolysis of methane (CH4). Despite this common source, the latitudinal distribution of the two species is radically different, with acetylene decreasing in abundance towards the pole, and ethane increasing towards the pole. We present six years of NASA IRTF TEXES mid-infrared observations of the zonally-averaged emission of methane, acetylene and ethane. We confirm that the latitudinal distributions of ethane and acetylene are decoupled, and that this is a persistent feature over multiple years. The acetylene distribution falls off towards the pole, peaking at â¼ 30Â°N with a volume mixing ratio (VMR) of â¼ 0.8 parts per million (ppm) at 1 mbar and still falling off at Â± 70Â° with a VMR of â¼ 0.3 ppm. The acetylene distributions are asymmetric on average, but as we move from 2013 to 2017, the zonally-averaged abundance becomes more symmetric about the equator. We suggest that both the short term changes in acetylene and its latitudinal asymmetry is driven by changes to the vertical stratospheric mixing, potentially related to propagating wave phenomena. Unlike acetylene, ethane has a symmetric distribution about the equator that increases toward the pole, with a peak mole fraction of â¼ 18 ppm at about Â± 50Â° latitude, with a minimum at the equator of â¼ 10 ppm at 1 mbar. The ethane distribution does not appear to respond to mid-latitude stratospheric mixing in the same way as acetylene, potentially as a result of the vertical gradient of ethane being much shallower than that of acetylene. The equator-to-pole distributions of acetylene and ethane are consistent with acetylene having a shorter lifetime than ethane that is not sensitive to longer advective timescales, but is augmented by short-term dynamics, such as vertical mixing. Conversely, the long lifetime of ethane allows it to be transported to higher latitudes faster than it can be chemically depleted.
Chemistry in TitanNASA Astrophysics Data System (ADS) Plessis, S.; Carrasco, N.; Pernot, P. updating Modelling the chemical composition of Titan's ionosphere is a very challenging issue. Latest works perform either inversion of CASSINI's INMS mass spectra (neutral[1] or ion[2]), or design coupled ion-neutral chemistry models[3]. Coupling ionic and neutral chemistry has been reported to be an essential feature of accurate modelling[3]. Electron Dissociative Recombination (EDR), where free electrons recombine with positive ions to produce neutral species, is a key component of ion-neutral coupling. There is a major difficulty in EDR modelling: for heavy ions, the distribution of neutral products is incompletely characterized by experiments. For instance, for some hydrocarbon ions only the carbon repartition is measured, leaving the hydrogen repartition and thus the exact neutral species identity unknown[4]. This precludes reliable deterministic modelling of this process and of ion-neutral coupling. We propose a novel stochastic description of the EDR chemical reactions which enables efficient representation and simulation of the partial experimental knowledge. The description of products distribution in multi-pathways reactions is based on branching ratios, which should sum to unity. The keystone of our approach is the design of a probability density function accounting for all available informations and physical constrains. This is done by Dirichlet modelling which enables one to sample random variables whose sum is constant[5]. The specifics of EDR partial uncertainty call for a hierarchiral Dirichlet representation, which generalizes our previous work[5]. We present results on the importance of ion-neutral coupling based on our stochastic model. C repartition H repartition (measured) (unknown ) Ã¢ÂÂ C4H2 + 3H2 + H .. -Ã¢ÂÂ C4 . Ã¢ÂÂ C4H2 + 7H Ã¢ÂÂ C3H8. + CH C4H+9 + e- -Ã¢ÂÂ C3 + C .. Ã¢ÂÂ C3H3 + CH2 + 2H2 Ã¢ÂÂ C2H6 + C2H2 + H .. -Ã¢ÂÂ C2 + C2 . Ã¢ÂÂ 2C2H2 + 2H2 + H (1) References [1] J. Cui, R.V. Yelle, V. Vuitton, J.H. Waite Jr., W.T. Kasprzak
Ethylene Removal by a Biofilter with Immobilized BacteriaPubMed Central Elsgaard, Lars updating A biofilter which eliminated ethylene (C2H4) from the high parts-per-million range to levels near the limit for plant hormonal activity (0.01 to 0.1 ppm) was developed. Isolated ethylene-oxidizing bacteria were immobilized on peat-soil in a biofilter (687 cm3) and subjected to an atmospheric gas flow (73.3 ml minâ1) with 2 or 117 ppm of C2H4. Ethylene was eliminated to a minimum level of 0.017 ppm after operation with 2.05 ppm of C2H4 for 16 days. Also, the inlet C2H4 concentration of 117 ppm was reduced to C2H4, an increase in the C2H4 removal rate was observed, which was attributed to proliferation of the immobilized bacteria, notably in the first 0- to 5-cm segment of the biofilter. The maximal C2H4 elimination capacity of the biofilter was 21 g of C2H4 mâ3 dayâ1 during operation with 117 ppm of C2H4 in the inlet gas. However, for the first 0- to 5-cm segment of the biofilter, an elimination capacity of 146 g of C2H4 mâ3 dayâ1 was calculated. Transition of the biofilter temperature from 21 to 10Â°C caused a 1.6-fold reduction in the C2H4 removal rate, which was reversed during operation for 18 days. Batch experiments with inoculated peat-soil demonstrated that C2H4 removal still occurred after storage at 2, 8, and 20Â°C for 2, 3, and 4 weeks. However, the C2H4 removal rate decreased with increasing storage time and was reduced by ca. 50% after storage for 2 weeks at all three temperatures. The biofilter could be a suitable tool for C2H4 removal in, e.g., horticultural storage facilities, since it (i) removed C2H4 to 0.017 ppm, (ii) had a good operational stability, and (iii) operated efficiently at 10Â°C. PMID:9797261
Ethylene Removal at Low Temperatures under Biofilter and Batch ConditionsPubMed Central Elsgaard, Lars updating Removal of the plant hormone ethylene (C2H4) is often required by horticultural storage facilities, which are operated at temperatures below 10Â°C. The aim of this study was to demonstrate an efficient, biological C2H4 removal under such low-temperature conditions. Peat-soil, acclimated to degradation of C2H4, was packed in a biofilter (687 cm3) and subjected to an airflow (â¼73 ml minâ1) with 2 ppm (Î¼l literâ1) C2H4. The C2H4 removal efficiencies achieved at 20, 10, and 5Â°C, respectively, were 99.0, 98.8, and 98.4%. This corresponded to C2H4 levels of 0.022 to 0.032 ppm in the biofilter outlet air. At 2Â°C, the average C2H4 removal efficiency dropped to 83%. The detailed temperature response of C2H4 removal was tested under batch conditions by incubation of 1-g soil samples in a temperature gradient ranging from 0 to 29Â°C with increments of 1Â°C. The C2H4 removal rate was highest at 26Â°C (0.85 Î¼g of C2H4 g [dry weight]â1 hâ1), but remained at levels of 0.14 to 0.28 Î¼g of C2H4 g (dry weight)â1 hâ1 at 0 to 10Â°C. At 35 to 40Â°C, the C2H4 removal rate was negligible (0.02 to 0.06 Î¼g of C2H4 g [dry weight]â1 hâ1). The Q10 (i.e., the ratio of rates 10Â°C apart) for C2H4 removal was 1.9 for the interval 0 to 10Â°C. In conclusion, the present results demonstrated microbial C2H4 removal, which proceeded at 0 to 2Â°C and produced a moderately psychrophilic temperature response. PMID:updating
Synthesis, molecular structure, and C-C coupling reactions of carbeneruthenium(II) complexes with C5H5Ru(=CRR') and C5Me5Ru(=CRR') as molecular units.PubMed Braun, Thomas; MÃ¼nch, Gerhard; WindmÃ¼ller, Bettina; Gevert, Olaf; Laubender, Matthias; Werner, Helmut updating The ethene derivatives [(eta(5)-C(5)R(5))RuX(C(2)H(4))(PPh(3))] with R=H and Me, which have been prepared from the eta(3)-allylic compounds [(eta(5)-C(5)R(5))Ru(eta(3)-2-MeC(3)H(4))(PPh(3))] (1, 2) and acids HX under an ethene atmosphere, are excellent starting materials for the synthesis of a series of new halfsandwich-type ruthenium(II) complexes. The olefinic ligand is replaced not only by CO and pyridine, but also by internal and terminal alkynes to give (for X=Cl) alkyne, vinylidene, and allene compounds of the general composition [(eta(5)-C(5)R(5))RuCl(L)(PPh(3))] with L=C(2)(CO(2)Me)(2), Me(3)SiC(2)CO(2)Et, C=CHCO(2)R, and C(3)H(4). The allenylidene complex [(eta(5)-C(5)H(5))RuCl(=C=C=CPh(2))(PPh(3))] is directly accessible from 1 (R=H) in two steps with the propargylic alcohol HC triple bond CC(OH)Ph(2) as the precursor. The reactions of the ethene derivatives [(eta(5)-C(5)H(5))RuX(C(2)H(4))(PPh(3))] (X=Cl, CF(3)CO(2)) with diazo compounds RR'CN(2) yield the corresponding carbene complexes [(eta(5)-C(5)R(5))RuX(=CRR')(PPh(3))], while with ethyl diazoacetate (for X=Cl) the diethyl maleate compound [(eta(5)-C(5)H(5))RuCl[eta(2)-Z-C(2)H(2)(CO(2)Et)(2)](PPh(3))] is obtained. Halfsandwich-type ruthenium(II) complexes [(eta(5)-C(5)R(5))RuCl(=CHR')(PPh(3))] with secondary carbenes as ligands, as well as cationic species [(eta(5)-C(5)H(5))Ru(=CPh(2))(L)(PPh(3))]X with L=CO and CNtBu and X=AlCl(4) and PF(6), have also been prepared. The neutral compounds [(eta(5)-C(5)H(5))RuCl(=CRR')(PPh(3))] react with phenyllithium, methyllithium, and the vinyl Grignard reagent CH(2)=CHMgBr by displacement of the chloride and subsequent C-C coupling to generate halfsandwich-type ruthenium(II) complexes with eta(3)-benzyl, eta(3)-allyl, and substituted olefins as ligands. Protolytic cleavage of the metal-allylic bond in [(eta(5)-C(5)H(5))Ru(eta(3)-CH(2)CHCR(2))(PPh(3))] with acetic acid affords the corresponding olefins R(2)C=CHCH(3). The by-product of this process is the acetato
Computational and Experimental Study of Energetic Materials in a Counterflow Microgravity EnvironmentNASA Technical Reports Server (NTRS) Takahashi, Fumiaki (Technical Monitor); Urban, David (Technical Monitor); Smooke, M. D.; Parr, T. P.; Hanson-Parr, D. M.; Yetter, R. A.; Risha, G. updating Counterflow diffusion flames are studied for various fuels flowing against decomposition products from solid ammonium perchlorate (AP) pellets in order to obtain fundamental understanding of composite propellant flame structure and chemistry. We illustrate this approach through a combined experimental and numerical study of a fuel mixture consisting of C2H4 CO + H2, and C2H2 + C2H4 flowing against solid AP. For these particular AP-fuel systems, the resulting flame zone simulates the various flame structures that are ex+ to exist between reaction products from Ap crystals and a hydrocarbon binder. As in all our experimental studies, quantitative species and temperature profiles have been measured between the fuel exit and AP surface. Species measured included CN, NH, NO, OH, N2, CO2, CO, H2, CO, HCl, and H2O. Temperature was measured using a thermocouple at the exit, spontaneous Raman scattering measurements throughout the flame, OH rotational population distributions, and NO vibrational population distributions. The burning rate of AP was also measured as a function of strain rate, given by the separation distance between the AP surface and the gaseous hydrocarbon fuel tube exit plane. This distance was nominally set at 5 mm, although studies have been performed for variations in separation distance. The measured 12 scalars are compared with predictions from a detailed gas-phase kinetics model consisting of 86 species and 531 reactions. Model predictions are found to be in good agreement with experiment and illustrate the type of kinetic features that may be expected to occur in propellants when AP particle size distributions are varied. Furthermore, the results constitute the continued development of a necessary database and validation of a comprehensive model for studying more complex AP-solid fuel systems in microgravity. Exploratory studies have also been performed with liquid and solid fuels at normal gravity. Because of melting (and hence dripping) and deep
H 2Oî¸CH 4î¸NaClî¸CO 2 inclusions from the footwall contact of the Tanco granitic pegmatite: Estimates of internal pressure and composition from microthermometry, laser Raman spectroscopy, and gas chromatographyNASA Astrophysics Data System (ADS) Thomas, A. V.; Pasteris, J. D.; Bray, C. J.; Spooner, E. T. C. updating Fluid inclusions in tourmaline and quartz from the footwall contact of the Tanco granitic pegmatite, S.E. Manitoba were studied using microthermometry (MT), laser Raman spectroscopy (LRS) and gas chromatography (GC). CH 4-bearing, aqueous inclusions occur in metasomatic tourmaline of the footwall amphibolite contact. The internal pressures estimated from MT are lower than those obtained from LRS (mean difference = 54 Â± 19 bars). The difference is probably due to errors in the measurement of Th CH 4 (V) and to the presence of clathrate at Th CH 4 (V) into which CO 2 had been preferentially partitioned. LRS estimates of pressure (125-184 bars) are believed to be more accurate. Aqueous phase salinities based on LRS estimates of pressure are higher than those derived using the data from MT: 10-20 eq. wt% NaCl. The composition of the inclusions determined by GC bulk analysis is 97.3 mol% H 2O, 2.2 mol% CH 4, 0.4 mol% CO 2, 250 ppm C 2H 6, 130 ppm N 2, 33 ppm C 3H 8, 11 ppm C 2H 4, and 3 ppm C 3H 6, plus trace amounts of C 4 hydrocarbons. The composition is broadly similar to that calculated from MT (92% H 2O and 8% CH 4, with 7 eq. wt% NaCl dissolved in the aqueous phase and 2 mol% CO 2 dissolved in the CH 4 phase), as expected due to the dominance of a single generation of inclusions in the tourmaline. However, two important differences in composition are: (i) the CH 4 to CO 2 ratio of this fluid determined by GC is 5.33, which is significantly lower than that indicated by MT (49.0); and (ii) the H 2O content estimated from MT is 92 mol% compared to 98 mol% from GC. GC analyses may have been contaminated by the presence of secondary inclusions in the tourmaline. However, the rarity of the latter suggests that they cannot be completely responsible for the discrepancy. The differences may be accounted for by the presence of clathrate during measurement of Th CH 4 (critical), which would reduce CO 2 relative to CH 4 in the residual fluid, and by errors in visually
Electronic energy density in chemical reaction systemsNASA Astrophysics Data System (ADS) Tachibana, Akitomo updating The energy of chemical reaction is visualized in real space using the electronic energy density nE(râ) associated with the electron density n(râ). The electronic energy density nE(râ) is decomposed into the kinetic energy density nT(râ), the external potential energy density nV(râ), and the interelectron potential energy density nW(râ). Using the electronic energy density nE(râ) we can pick up any point in a chemical reaction system and find how the electronic energy E is assigned to the selected point. We can then integrate the electronic energy density nE(râ) in any region R surrounding the point and find out the regional electronic energy ER to the global E. The kinetic energy density nT(râ) is used to identify the intrinsic shape of the reactants, the electronic transition state, and the reaction products along the course of the chemical reaction coordinate. The intrinsic shape is identified with the electronic interface S that discriminates the region RD of the electronic drop from the region RA of the electronic atmosphere in the density distribution of the electron gas. If the R spans the whole space, then the integral gives the total E. The regional electronic energy ER in thermodynamic ensemble is realized in electrochemistry as the intrinsic Volta electric potential ÏR and the intrinsic Herring-Nichols work function Î¦R. We have picked up first a hydrogen-like atom for which we have analytical exact expressions of the relativistic kinetic energy density nTM(râ) and its nonrelativistic version nT(râ). These expressions are valid for any excited bound states as well as the ground state. Second, we have selected the following five reaction systems and show the figures of the nT(râ) as well as the other energy densities along the intrinsic reaction coordinates: a protonation reaction to He, addition reactions of HF to C2H4 and C2H2, hydrogen abstraction reactions of NH3+ from HF and NH3. Valence electrons possess their unique
Titan's Gas Behavior During the South Pole FallNASA Astrophysics Data System (ADS) Cottini, Valeria; Nixon, Conor A.; Achterberg, Richard K.; Jennings, Donald E.; Gorius, Nicolas; Irwin, Patrick G. J. updating Titanâs southern middle atmosphere has been showing several changes since the start of fall season in 2009. In 2012 a large cloud appeared [1], [2], [3], temperatures became very low and condensation and gas concentration at the South Pole increased [3], [4].In this work we will show the results of gas abundances retrievals in the South Pole and their latitudinal variation changes as the cold season evolved with time.We analyzed several Cassini Composite InfraRed Spectrometer (CIRS [5]) mid-infrared observations of the South Pole acquired during updating. The data coordinates were converted in order to be centered on the atmospheric pole and refer to the 1 mbar level and not to the surface. We first determine stratospheric temperatures from the same data and latitudes from the n4 band of methane centered around 1300 cm-1. We retrieve the temperature profiles applying a radiative transfer forward model combined with a non-linear optimal estimation inversion method [6]. We then retrieve the main gases abundances and track their variation with latitude using the same method.Latitudinal changes of the main Titanâs gases - HC3N, C4H2, C6H6, C2H2, C2H4, C3H8 and HCN - show different trends in the Southern polar regions over 2014, when winter was getting closer. We observe a ring-shape in some of the gas abundance distributions, with a local maximum peak around -75 deg of latitude. We also observe an increase of abundance of most of the gases toward the south pole, as seen previously in the North during the winter. The observed increase of benzene over the South Pole is definitely evident and strong. References: [1] West, R. A. et al. (2013) BAAS, 45, 305.03. [2] Jennings, D. E. et al. (2012) ApJ, 754, L3. [3] de Kok, R. et al. (2014), Nature, 514, 7520, 65-67. [4] Vinatier S. et al. (2015) Icarus, Volume 250, p. 95-115. [5] Flasar et al. (2004) Space Sci. Rev., 115, 169-297. [6] Irwin, P.G.J. et al. (2008) J. Quant. Spectrosc. Radiat. Trans., 109, updating.
Rate Constant and RRKM Product Study for the Reaction Between CH3 and C2H3 at T = 298KNASA Technical Reports Server (NTRS) Thorn, R. Peyton, Jr.; Payne, Walter A., Jr.; Chillier, Xavier D. F.; Stief, Louis J.; Nesbitt, Fred L.; Tardy, D. C. updating The total rate constant k1 has been determined at P = 1 Torr nominal pressure (He) and at T = 298 K for the vinyl-methyl cross-radical reaction CH3 + C2H3 yields products. The measurements were performed in a discharge flow system coupled with collision-free sampling to a mass spectrometer operated at low electron energies. Vinyl and methyl radicals were generated by the reactions of F with C2H4 and CH4, respectively. The kinetic studies were performed by monitoring the decay of C2H3 with methyl in excess, 6 C2H2, and C2H5 as products of the combination-stabilization, disproportionation, and combination-decomposition channels, respectively, of the CH3 + C2H3 reaction. We also observed the secondary C4H8 product of the subsequent reaction of C3H5 with excess CH3; this observation provides convincing evidence for the combination-decomposition channel yielding C3H5 + H. RRKM calculations with helium as the deactivator support the present and very recent experimental observations that allylic C-H bond rupture is an important path in the combination reaction. The pressure and temperature dependencies of the branching fractions are also predicted.
Computational Screening of MOFs for Acetylene SeparationNASA Astrophysics Data System (ADS) Nemati Vesali Azar, Ayda; Keskin, Seda updating Efficient separation of acetylene (C2H2) from CO2 and CH4 is important to meet the requirement of high-purity acetylene in various industrial applications. Metal organic frameworks (MOFs) are great candidates for adsorption-based C2H2/CO2 and C2H2/CH4 separations due to their unique properties such as wide range of pore sizes and tunable chemistries. Experimental studies on the limited number of MOFs revealed that MOFs offer remarkable C2H2/CO2 and C2H2/CH4 selectivities based on single-component adsorption data. We performed the first large-scale molecular simulation study to investigate separation performances of 174 different MOF structures for C2H2/CO2 and C2H2/CH4 mixtures. Using the results of molecular simulations, several adsorbent performance evaluation metrics, such as selectivity, working capacity, adsorbent performance score, sorbent selection parameter and regenerability were computed for each MOF. Based on these metrics, the best adsorbent candidates were identified for both separations. Results showed that the top three most promising MOF adsorbents exhibit C2H2/CO2 selectivities of 49, 47, 24 and C2H2/CH4 selectivities of 824, 684, 638 at 1 bar, 298 K and these are the highest C2H2 selectivities reported to date in the literature. Structure-performance analysis revealed that the best MOF adsorbents have pore sizes between 4-11 Ã, surface areas in the range of 600-1,200 m2/g and porosities between 0.4-0.6 for selective separation of C2H2 from CO2 and CH4. These results will guide the future studies for the design of new MOFs with high C2H2 separation potentials.

Computational Screening of MOFs for Acetylene SeparationPubMed Central Nemati Vesali Azar, Ayda; Keskin, Seda updating Efficient separation of acetylene (C2H2) from CO2 and CH4 is important to meet the requirement of high-purity acetylene in various industrial applications. Metal organic frameworks (MOFs) are great candidates for adsorption-based C2H2/CO2 and C2H2/CH4 separations due to their unique properties such as wide range of pore sizes and tunable chemistries. Experimental studies on the limited number of MOFs revealed that MOFs offer remarkable C2H2/CO2 and C2H2/CH4 selectivities based on single-component adsorption data. We performed the first large-scale molecular simulation study to investigate separation performances of 174 different MOF structures for C2H2/CO2 and C2H2/CH4 mixtures. Using the results of molecular simulations, several adsorbent performance evaluation metrics, such as selectivity, working capacity, adsorbent performance score, sorbent selection parameter, and regenerability were computed for each MOF. Based on these metrics, the best adsorbent candidates were identified for both separations. Results showed that the top three most promising MOF adsorbents exhibit C2H2/CO2 selectivities of 49, 47, 24 and C2H2/CH4 selectivities of 824, 684, 638 at 1 bar, 298 K and these are the highest C2H2 selectivities reported to date in the literature. Structure-performance analysis revealed that the best MOF adsorbents have pore sizes between 4 and 11 Ã, surface areas in the range of 600â1,200 m2/g and porosities between 0.4 and 0.6 for selective separation of C2H2 from CO2 and CH4. These results will guide the future studies for the design of new MOFs with high C2H2 separation potentials. PMID:updating
Sensitivity of wheat and rice to low levels of atmospheric ethyleneNASA Technical Reports Server (NTRS) Klassen, Stephen P.; Bugbee, Bruce updating Ethylene (C2H4) gas is produced throughout the life cycle of plants and can accumulate in closed growth chambers to levels 100 times higher than in outside environments. Elevated atmospheric C2H4 can cause a variety of abnormal responses, but the sensitivity to elevated C2H4 is not well characterized. We evaluated the C2H4 sensitivity of wheat (Triticum aestivum L.) and rice (Oryza sativa L.) in five studies. The first three studies compared the effects of continuous C2H4 levels ranging from 0 to 1000 nmol mol-1 (ppb) in a growth chamber throughout the life cycle of the plants. A short-term 1000 nmol mol-1 treatment was included in which exposure was stopped at anthesis. Yield was reduced by 36% in wheat and 63% in rice at 50 nmol mol-1 and both species were virtually sterile when continuously exposed to 1000 nmol mol-1. However, the yield reductions were much less with exposure that stopped at anthesis, suggesting the detrimental effect of C2H4 on yield was greatest around the time of seed set. Two additional studies evaluated the differential sensitivity of two wheat cultivars (Super Dwarf and USU-Apogee) to 50 nmol mol-1 C2H4 at three CO2 levels [350, 1200, 5000 micromoles mol-1 (ppm)] in a greenhouse. Yield of USU-Apogee was not significantly reduced by C2H4 but the yield of Super Dwarf was reduced by 60%. Elevated CO2 did not influence the sensitivity to C2H4. A difference in the C2H4 sensitivity of USU-Apogee between greenhouse and growth chamber trials suggests that C2H4 sensitivity is dependent on the environment. Collectively, the data suggest that relatively low levels of C2H4 could induce anomalous plant responses by accumulation in greenhouses and growth chambers with inadequate ventilation. The data also suggest that C2H4 sensitivity can be reduced by both genetic and environmental manipulations. 2002 Crop Science Society of America.
Efficient light hydrocarbon separation and CO2 capture and conversion in a stable MOF with oxalamide-decorated polar tubes.PubMed Li, Xiu-Yuan; Li, Yong-Zhi; Yang, Yun; Hou, Lei; Wang, Yao-Yu; Zhu, Zhonghua updating The first strontium-based MOF possessing polar tubular channels embedded with a high density of open Lewis acidic metal sites and basic oxalamide groups was constructed, which shows not only a high CO 2 and C 2 H 6 adsorption capability and significant selectivity for CO 2 over both CH 4 and CO, and for C 2 H 6 over CH 4 , but also size-selective chemical conversion of CO 2 with epoxides producing cyclic carbonates under ambient conditions.
Evaluating ethane and methane emissions associated with the development of oil and natural gas extraction in North AmericaNASA Astrophysics Data System (ADS) Franco, B.; Mahieu, E.; Emmons, L. K.; Tzompa-Sosa, Z. A.; Fischer, E. V.; Sudo, K.; Bovy, B.; Conway, S.; Griffin, D.; Hannigan, J. W.; Strong, K.; Walker, K. A. updating Sharp rises in the atmospheric abundance of ethane (C2H6) have been detected from 2009 onwards in the Northern Hemisphere as a result of the unprecedented growth in the exploitation of shale gas and tight oil reservoirs in North America. Using time series of C2H6 total columns derived from ground-based Fourier transform infrared (FTIR) observations made at five selected Network for the Detection of Atmospheric Composition Change sites, we characterize the recent C2H6 evolution and determine growth rates of Ë5% yr-1 at mid-latitudes and of Ë3% yr-1 at remote sites. Results from CAM-chem simulations with the Hemispheric Transport of Air Pollutants, Phase II bottom-up inventory for anthropogenic emissions are found to greatly underestimate the current C2H6 abundances. Doubling global emissions is required to reconcile the simulations and the observations prior to 2009. We further estimate that North American anthropogenic C2H6 emissions have increased from 1.6 Tg yr-1 in 2008 to 2.8 Tg yr-1 in 2014, i.e. by 75% over these six years. We also completed a second simulation with new top-down emissions of C2H6 from North American oil and gas activities, biofuel consumption and biomass burning, inferred from space-borne observations of methane (CH4) from Greenhouse Gases Observing SATellite. In this simulation, GEOS-Chem is able to reproduce FTIR measurements at the mid-latitudinal sites, underscoring the impact of the North American oil and gas development on the current C2H6 abundance. Finally we estimate that the North American oil and gas emissions of CH4, a major greenhouse gas, grew from 20 to 35 Tg yr-1 over the period updating, in association with the recent C2H6 rise.
Adsorptive separation studies of ethane-methane and methane-nitrogen systems using mesoporous carbon.PubMed Yuan, Bin; Wu, Xiaofei; Chen, Yingxi; Huang, Jianhan; Luo, Hongmei; Deng, Shuguang updating Adsorptive separations of C(2)H(6)/CH(4) and CH(4)/N(2) binary mixtures are of paramount importance from the energy and environmental points of view. A mesoporous carbon adsorbent was synthesized using a soft template method and characterized with TEM, TGA, and nitrogen adsorption/desorption. Adsorption equilibrium and kinetics of C(2)H(6), CH(4), and N(2) on the mesoporous carbon adsorbent were determined at 278, 298, and 318 K and pressures up to 100 kPa. The adsorption capacities of C(2)H(6) and CH(4) on the mesoporous carbon adsorbent at 298 K and 100 kPa are 2.20 mmol/g and 1.05 mmol/g, respectively. Both are significantly higher than those of many adsorbents including pillared clays and ETS-10 at a similar condition. The equilibrium selectivities of C(2)H(6)/CH(4) and CH(4)/N(2) at 298 K are 19.6 and 5.8, respectively. It was observed that the adsorption of C(2)H(6), CH(4), and N(2) gases on the carbon adsorbent was reversible with modest isosteric heats of adsorption, which implies that this carbon adsorbent can be easily regenerated in a cyclic adsorption process. These results suggest that the mesoporous carbon studied in this work is a promising alternative adsorbent for the separations of C(2)H(6)/CH(4) and CH(4)/N(2) gas mixtures. Copyright Â© 2012 Elsevier Inc. All rights reserved.
Detection of abundant ethane and methane, along with carbon monoxide and water, in comet C/1996 B2 Hyakutake: evidence for interstellar originNASA Technical Reports Server (NTRS) Mumma, M. J.; DiSanti, M. A.; Dello Russo, N.; Fomenkova, M.; Magee-Sauer, K.; Kaminski, C. D.; Xie, D. X. updating The saturated hydrocarbons ethane (C2H6) and methane (CH4) along with carbon monoxide (CO) and water (H2O) were detected in comet C/1996 B2 Hyakutake with the use of high-resolution infrared spectroscopy at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. The inferred production rates of molecular gases from the icy, cometary nucleus (in molecules per second) are 6.4 X 10(26) for C2H6, 1.2 X 10(27) for CH4, 9.8 X 10(27) for CO, and 1.7 X 10(29) for H2O. An abundance of C2H6 comparable to that of CH4 implies that ices in C/1996 B2 Hyakutake did not originate in a thermochemically equilibrated region of the solar nebula. The abundances are consistent with a kinetically controlled production process, but production of C2H6 by gas-phase ion molecule reactions in the natal cloud core is energetically forbidden. The high C2H6/CH4 ratio is consistent with production of C2H6 in icy grain mantles in the natal cloud, either by photolysis of CH4-rich ice or by hydrogen-addition reactions to acetylene condensed from the gas phase.
Investigating model deficiencies in the global budget of ethaneNASA Astrophysics Data System (ADS) Tzompa Sosa, Z. A.; Keller, C. A.; Turner, A. J.; Mahieu, E.; Franco, B.; Fischer, E. V. updating Many locations in the Northern Hemisphere show a statistically-significant sharp increase in measurements of ethane (C2H6) since 2009. It is hypothesized that the recent massive growth of shale gas exploitation in North America could be the source of this change. However, state-of-the-science chemical transport models are currently unable to reproduce the hemispheric burden of C2H6 or the recent sharp increase, pointing to a potential problem with current emission inventories. To resolve this, we used space-borne CH4 observations from the Greenhouse Gases Observing SATellite (GOSAT) to derive C2H6 emissions. By using known emission ratios to CH4, we estimated emissions of C2H6 from oil and gas activities, biofuels, and biomass burning over North America. The GEOS-Chem global chemical transport model was used to simulate atmospheric abundances of C2H6 with the new emissions estimates. The model is able to reproduce Northern Hemisphere surface concentrations. However, the model significantly under-predicts the amount of C2H6 throughout the column and the observed Northern Hemispheric gradient as diagnosed by comparisons to aircraft observations from the Hiaper Pole-to-Pole (HIPPO) Campaign.
Dubinin-Astakhov model for acetylene adsorption on metal-organic frameworksNASA Astrophysics Data System (ADS) Cheng, Peifu; Hu, Yun Hang updating Acetylene (C2H2) is explosive at a pressure above 29 psi, causing a safety issue for its storage and applications. C2H2 adsorption on metal-organic frameworks (MOFs) has been explored to solve the issue. However, a suitable isotherm equation for C2H2 adsorption on various MOFs has not been found. In this paper, it was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model to depict C2H2 adsorption on MOF-5, ZIF-8, HKUST-1, and MIL-53. In contrast, commonly used Langmuir and BET models exhibited their inapplicability for C2H2 adsorption on those MOFs.
Ethane C-C clumping in natural gas : a proxy for cracking processes ?NASA Astrophysics Data System (ADS) Clog, M. D.; Ferreira, A. A.; Santos Neto, E. V.; Eiler, J. M. updating Ethane (C2H6) is the second-most abundant alkane in most natural gas reservoirs, and is used to produce ethylene for petrochemical industries. It is arguably the simplest molecule that can manifest multiple 13C substitutions. There are several plausible controls on Î13C2H6in natural gas: thermodynamically controlled homogeneous isotope exchange reactions analogous to those behind carbonate clumped isotope thermometry; inheritance from larger biomolecules that undergo thermal degradation to produce natural gas; mixing of natural gases that differ markedly in bulk isotopic composition; diffusive fractionation; or combinations of these and/or other, less expected fractionations. There is little basis for predicting which of these will control isotopic variations among natural ethanes, but we think it likely that addition of this new isotopic proxy will reveal new insights into the natural chemistry of ethane. We have developed a method to measure the abundance of 13C2H6 in natural samples, using high-resolution mass spectrometry. We define Î13C2H6 as updatingC2H6/12C2H6)measured/(13C2H6/12C2H6)stochastic -1). We studied several suites of natural gas samples and experimentally produced or modified ethane. Natural ethanes, including closely related samples from a single natural gas field, exhibit surprisingly large ranges in Î13C2H6 (4 â° overall; up to 3 â° in one gas field). Such ranges cannot be explained by thermodynamic equilibrium at a range of different temperatures, or by diffusive fractionation. Kinetic isotope effects associated with 'cracking' reactions, and/or inheritance of non-equilibrium carbon isotope structures from source organics are more likely causes. We observe a correlation between Î13C2H6 and the concentration of alkanes other than methane in several suites of natural gases, suggesting the causes of clumped isotope variations are tied to the controls on gas wetness. An experiment examining ethane residual to high-temperature pyrolysis
The effect of nitrate on ethylene biofiltration.PubMed Lee, Sang-Hun; Li, Congna; Heber, Albert J updating This study investigated the effects of filter media types and nitrate (NO(3)(-)) concentrations in nutrient solutions on C(2)H(4) biofiltration. A new nutrient solution with zero NO(3)(-) concentration was supplied to two perlite-bed biotrickling filters, two perlite-bed biofilters, and two GAC (Granular Activated Carbon)-bed biofilters, while the other with 2 g L(-1) of NO(3)(-) was used for the other two GAC biofilters. All reactors underwent a total test duration of over 175 days with an EBRT (Empty Bed Residence Time) of 30 s, inlet gas flow rate of 7 L min(-1), and inlet C(2)H(4) concentrations of 20-30 mg m(-3). NO(3)(-) concentration and media type significantly affected the C(2)H(4) removal efficiencies in all types of biofiltration. The perlite media with no NO(3)(-) achieved C(2)H(4) removal efficiencies 10-50% higher than the others. A NO(3)(-) concentration as high as 2 g L(-1) in the original nutrient solution may act as an inhibitor that suppresses the growth or activity of C(2)H(4) degraders. In addition, the perlite media resulted in higher C(2)H(4) removal efficiencies than GAC media, because the hydrophilic surface of the perlite leads to a higher moisture content and thus to favorable microbial growth. Copyright Â© 2012 Elsevier B.V. All rights reserved.
Effect of Gamma Radiation on the Ripening of Bartlett Pears 1PubMed Central Maxie, E. C.; Sommer, N. F.; Muller, Carlos J.; Rae, Henry L. updating Gamma radiation at doses of 300 Krad or more inhibits the ripening of Bartlett pears (Pyrus communis L.). Immediately after irradiation there is a transitory burst of C2H4, which subsequently declines in fruits subjected to inhibitory doses. Ethylene production associated with ripening begins at the same time in unirradiated fruits and those subjected to noninhibitory doses, but the latter produces much more C2H4 at the climacteric peak. Fruits subjected to inhibitory doses produce low levels of C2H4 unless subjected to exogenously applied C2H4, whereupon they produce enough of the gas to induce ripening in unirradiated fruits. Pears subjected to 300 and 400 Krad of gamma rays did not ripen even when held in a flowing atmosphere containing 1000 ppm of C2H4 for 8 days at 20Â°. It is concluded that the action of gamma rays on Bartlett pears involves both an inhibition of C2H4 production and a decreased sensitivity of the fruit to the ripening action of the gas. Ripening of Bartlett pears is inhibited by gamma radiation only when applied to preclimacteric fruit. PMID:updating
The evolution of volatile production in C/2009 P1 (Garradd) during its updating apparitionNASA Astrophysics Data System (ADS) Gicquel, A.; Milam, S.; Cordiner, M.; Villanueva, G.; Charnley, S.; Coulson, I.; Remijan, A.; DiSanti, M.; Mumma, M.; Szutowicz, S. updating Comets are likely to be the most pristine objects in our Solar System. They provide a record of the physical and chemical conditions in the protosolar nebula between about 5 and 40 au during the epoch when the distinct cometary populations were being assembled (Festou et al. 2004; Jewitt 2004; Mumma & Charnley 2011). Cometary nuclei today reside in (at least) two distinct reservoirs, the Oort Cloud (OC) and the Kuiper Belt (KB). Past observations have shown that comets appear to contain a mixture of products from both interstellar and nebular chemistries and could also have been important for initiating prebiotic chemistry on the early Earth (Ehrenfreund & Charnley 2000). Although there are some differences, the volatile composition of cometary ices is generally similar to the inventory of molecules detected in the ices and gas of dense molecular clouds. Given the gradient in physical conditions expected across the proto-Solar nebula, chemical diversity in the comet population is to be expected. Here we report an analysis of long-term ground-based radio observations towards comet C/2009 P1 (Garradd). Comet C/2009 P1 Garradd is an OC comet that reached perihelion (at heliocentric distance R_h = 1.55 au) in late December 2011 and had its closest approach to the Earth on 5 March 2012. Like C/1995 O1 (Hale-Bopp) at 7.2 au, Garradd exhibited unusual activity at large R_h (8.68 au), displaying a 15'' diameter circular coma (IAUC 9062). It is well known that some comets exhibit volatile activity at large heliocentric distances, where water ice cannot sublime efficiently. Infrared (IRTF/CSHELL, Keck 2/NIRSPEC, and VLT/CRIRES) spectroscopy of Garradd showed clear CO (R1 & R2) emission near Î» = 4.7 Î¼ m (2150 cm^{-1}), as well as a suite of molecules (e.g., C_2H_6, CH_4, CH_3OH, H_2CO, HCN, C_2H_2, NH_3) that were also detected near or beyond R_h = 2 au (Villanueva et al. 2012; Paganini et al. 2012; DiSanti et al. 2014). We monitored the abundance of parent volatiles in
Comet C/2012 S1 (ISON)'s carbon-rich and micron-size-dominated coma dustNASA Astrophysics Data System (ADS) Wooden, D.; De Buizer, J.; Kelley, M.; Sitko, M.; Woodward, C.; Harker, D.; Reach, W.; Russell, R.; Kim, D.; Yanamadra-Fisher, P.; Lisse, C.; de Pater, I.; Gehrz, R.; Kolokolova, L. updating (NEAT)[11] had smaller and highly porous grains, whereas C/2007 N4 (Lulin)[12] and C/2006 P1 (McNaught)[13] had larger and compact porous grains. Radial transport to comet-forming disk distances (â¥ 20 au) is easier for smaller grains than for larger grains (â¤ 1 Î¼ m vs.Ë20 Î¼ m-like Stardust terminal particles) [14]. Perhaps Comet ISON formed either earlier in disk evolution whereby larger grains did not have the time to be transported to distances beyond Neptune, or the comet formed so far out in the disk that larger grains did not traverse such large radial distances. The high carbon-content of ISON's refractory dust appears to be complimented by the presence of limited-lifetime organic (CHON-like) grain materials: preliminary analyses of near-IR and high-resolution optical spectra indicate that gas-phase daughter molecules C_2, CN, and CH were more abundant than their parent molecules (HCN, C_2H_2, C_2H_6, measured in the near-IR) [15]. Dust composition as well as grain size distribution parameters (slope, peak grain size, and porosity) give clues to comet origins [16,17].
Comet C2012 S1 (ISON)s Carbon-rich and Micron-size-dominated Coma DustNASA Technical Reports Server (NTRS) Wooden, D.; De Buizer, J.; Kelley, M.; Sitko, M.; Woodward, C.; Harker, D.; Reach, W.; Russell, R.; Kim, D.; Yanamadra-Fisher, P.; updating (= 20 AU) is easier for smaller grains (=1 micron) than for larger grains (approx. 20 microns like Stardust terminal particles). The presence of predominantly micron-sized and smaller grains suggests comet ISON may have formed either earlier in disk evolution whereby larger grains did not have the time to be transported to distances beyond Neptune, or the comet formed so far out in the disk that larger grains did not traverse such large radial distances. The high carbon-content of ISON's refractory dust appears to be complimented by the presence of limitedlifetime organic (CHON-like) grain materials: preliminary analyses of near-IR and high-resolution optical spectra indicate that gas-phase daughter molecules C2, CN, and CH were more abundant than their parent molecules (C2H2, C2H6, measured in the near- IR). Dust composition as well as grain size distribution parameters (slope, peak grain size, and porosity) give clues to comet origins.
[Raman Characterization of Hydrate Crystal Structure Influenced by Mine Gas Concentration].PubMed Zhang, Bao-yong; Zhou, Hong-ji; Wu, Qiang; Gao, Xia updating CH4 /C2H6/N2 mixed hydrate formation experiments were performed at 2 degrees C and 5 MPa for three different mine gas concentrations (CH4/C2H6/N2, G1 = 54 : 36 : 10, G2 = 67.5 : 22.5 : 10, G3 = 81 : 9 : 10). Raman spectra for hydration products were obtained by using Microscopic Raman Spectrometer. Hydrate structure is determined by the Raman shift of symmetric C-C stretching vibration mode of C2H6 in the hydrate phase. This work is focused on the cage occupancies and hydration numbers, calculated by the fitting methods of Raman peaks. The results show that structure I (s I) hydrate forms in the G1 and G2 gas systems, while structure II (s II) hydrate forms in the G3 gas system, concentration variation of C2H6 in the gas samples leads to a change in hydrate structure from s I to s II; the percentages of CH4 and C2H6 in s I hydrate phase are less affected by the concentration of gas samples, the percentages of CH4 are respectively 34.4% and 35.7%, C2H6 are respectively 64.6% and 63.9% for gas systems of G1 and G2, the percentages of CH4 and 2 H6 are respectively 73.5% and 22.8% for gas systems of G3, the proportions of object molecules largely depend on the hydrate structure; CH4 and C2H6 molecules occupy 98%, 98% and 92% of the large cages and CH4 molecules occupy 80%, 60% and 84% of the small cages for gas systems of G1, G2 and G3, respectively; additionally, N2 molecules occupy less than 5% of the small cages is due to its weak adsorption ability and the lower partial pressure.
Synthesis and characterization of CrCN-DLC composite coatings by cathodic arc ion-platingNASA Astrophysics Data System (ADS) Wang, R. Y.; Wang, L. L.; Liu, H. D.; Yan, S. J.; Chen, Y. M.; Fu, D. J.; Yang, B. updating CrCN-DLC composite coatings were deposited onto silicon (1 0 0) and cemented carbides substrates using pure Cr targets under C2H2 ambient by cathodic arc ion plating system. The influence of C2H2 flow rate on the structure and mechanical properties of the coatings was investigated systemically. The coatings structure and bonding state were characterized by XRD, Raman and X-ray photoelectron spectroscopy. The chemical composition was measured by EDS. The mechanical performance and tribological behaviour of the coatings were studied by a hardness tester and ball-on-disc wear tester. The results showed that with increasing C2H2 flow rate from 50 to 100 sccm, the corresponding hardness of coatings increased firstly and then decreased with further addition of C2H2 flow rate. The coatings deposited at lower C2H2 flow rate (less than 200 sccm) exhibited a relatively higher hardness value (more than HVupdating) and then the hardness decrease with increasing C2H2 flow rate. The friction coefficient also exhibited similar variation trend, when the C2H2 flow rate was higher than 100 sccm, the friction coefficient decreased and then maintained in a relatively lower value from 0.18 to 0.24, which may be attribute to the increasing carbon content and the coating exhibited more diamond-like structure.
Gas-Phase Ion Chemistry in Interstellar, Circumstellar, and Planetary EnvironmentsNASA Astrophysics Data System (ADS) Demarais, Nicholas J. In the last century, astronomers, physicists, and chemists have shown that the environments of space are complex. Although we have learned a great amount about the interstellar medium, circumstellar medium, and atmospheres of other planets and moons, many mysteries still remain unsolved. The cooperation of astronomers, modelers, and chemists has lead to the detection of over 180 molecules in the interstellar and circumstellar medium, and the evolution of the new scientific field of astrochemistry. Gas-phase ion chemistry can determine the stability of ions in these complex environments, provide chemical networks, and guide searches for new interstellar molecules. Using the flowing afterglow-selected ion flow tube (FA-SIFT), we have characterized the reactions of positive and negative ions that are important in a variety of astrochemical environments. The detection of CF+ in photodissociation regions highlights the importance of fluorinated species in the interstellar medium. The viability of CF+ as a possible diffuse interstellar band (DIB) carrier is discussed as related to reactions with neutral molecules in various interstellar conditions; the reactions of CF+ with twenty-two molecules of interstellar relevance were investigated. The chemical reactions of HCNH+ with H2, CH 4, C2H2, and C2H4 were reexamined to provide insight into the overprediction of HCNH+ in Titan's ionosphere by current astrochemical models. In addition, this work suggests other chemical reactions that should be included in the current models to fully describe the destruction rates of HCNH+ in Titan's ionosphere. The reactions of polycyclic aromatic hydrocarbon (PAH) ions with H atoms and other small molecules were carried out to determine the stability of these species. In diffuse regions, where the photon flux is high, PAH cations are the dominant ionization state. This work continues our previous research to include PAHs of differing geometries as well as nitrogen-containing PAHs
Anaerobic oxidation of acetylene by estuarine sediments and enrichment culturesUSGS Publications Warehouse Culbertson, Charles W.; Zehnder, Alexander J. B.; Oremland, Ronald S. updating Acetylene disappeared from the gas phase of anaerobically incubated estuarine sediment slurries, and loss was accompanied by increased levels of carbon dioxide. Acetylene loss was inhibited by chloramphenicol, air, and autoclaving. Addition ofÂ 14C2H2Â to slurries resulted in the formation ofÂ 14CO2Â and the transient appearance ofÂ 14C-soluble intermediates, of which acetate was a major component. Acetylene oxidation stimulated sulfate reduction; however, sulfate reduction was not required for the loss of C2H2Â to occur. Enrichment cultures were obtained which grew anaerobically at the expense of C2H2.
Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and BrNASA Technical Reports Server (NTRS) Payne, W. A.; Nava, D. F.; Brunning, J.; Stief, L. J. updating The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.
Global atmospheric concentrations and source strength of ethaneNASA Technical Reports Server (NTRS) Blake, D. R.; Rowland, F. S. updating A study of the variation in ethane (C2H6) concentration between northern and southern latitudes over three years is presented together with a new estimate of its source strength. Ethane concentrations vary from 0.07 to 2 p.p.b.v. (parts per billion by volume) in air samples collected in remote surface locations in the Pacific (latitude 71 N-47 S) in all four seasons between September 1984 and June 1985. The variations are consistent with southerly transport from sources located chiefly in the Northern Hemisphere, further modified by seasonal variations in the strength of the reaction of C2H6 with OH radicals. These global data can be combined with concurrent data for CH4 and the laboratory reaction rates of each with OH to provide an estimate of three months as the average atmospheric lifetime for C2H6 and 13 + or - 3 Mtons for its annual atmospheric release.

[external_footer] Một số từ khóa tìm kiếm liên quan:

nhận biết c2h6, c2h4, c2h2, co2
Tách C2H2, C2H4 C2H6
Hỗn hợp X gồm 3 khí C2H4 C2H6, C2H2
CH4 C2H2 C2H4 C2H6 co2

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Sample records for c2h6 c2h4 c2h2

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