Experimental and theoretical study of hydrocarbon photochemistry applied to Titan stratosphere     

V. Vuitton  J.-F. Doussin  F. Raulin 《Icarus》2006,185(1):287-300

None of the Titan photochemical models currently available have been able to reproduce the full set of stratospheric molecular mixing ratios inferred from observations. In order to assess how well reaction sets describe hydrocarbon chemistry, theoretical modeling predictions were compared to the results of a laboratory experiment. A CH₄-C₂H₂ mixture was irradiated at 185 nm in an atmospheric simulation chamber and the evolution of the gas mixture was followed in situ and in real time by infrared spectroscopy. In parallel, a 0D theoretical model of the laboratory experiment was developed. A new reaction set describing Titan's chemistry was built and incorporated in the model. Lebonnois et al. [Lebonnois, S., Toublanc, D., Hourdin, F., Rannou, P., 2001. Icarus 152, 384-406] reaction set was also used for comparison. The presence of small amounts of atmospheric O₂ in the experiment was properly accounted for and led us to suggest that oxygenated chemistry might be a source of C₂H₄ in Titan's atmosphere. With Lebonnois et al. [Lebonnois, S., Toublanc, D., Hourdin, F., Rannou, P., 2001. Icarus 152, 384-406] reaction set, the model could not fit at all the experimental evolution of the compounds. This is explained by some of the choices made for crucial kinetic parameters such as the quantum yield of photolysis of C₂H₂. Also, the absence of some reactions led to the enhancement of pathways that would otherwise be negligible. For example, the lack of reactions between C₄H₄ and radicals induced an erroneously high photolysis rate for this species. With the reaction set built in this study, the model much better fits the experiment, especially when the “soot,” which includes C₄H₄, is recycled into C₂H₂. This shows that photochemistry of the larger species has a role in determining the lighter species concentrations and that considering that they are simply lost from the system is not a valid assumption. Including even an abridged set of C₄ + hydrocarbon reactions will be required in future photochemical models. Especially, photolysis rates and yields for C₂H₂, C₄H₂, and C₄H₄, are important parameters in need of a better determination.  相似文献   

Meridional distribution of CH₃C₂H and C₄H₂ in Saturn’s stratosphere from CIRS/Cassini limb and nadir observations     

Sandrine Guerlet  Thierry Fouchet  Bruno Bézard  Leigh N. Fletcher  F. Michael Flasar 《Icarus》2010,209(2):682-7965

Limb and nadir spectra acquired by Cassini/CIRS (Composite InfraRed Spectrometer) are analyzed in order to derive, for the first time, the meridional variations of diacetylene (C₄H₂) and methylacetylene (CH₃C₂H) mixing ratios in Saturn’s stratosphere, from 5 hPa up to 0.05 hPa and 80°S to 45°N. We find that the C₄H₂ and CH₃C₂H meridional distributions mimic that of acetylene (C₂H₂), exhibiting small-scale variations that are not present in photochemical model predictions. The most striking feature of the meridional distribution of both molecules is an asymmetry between mid-southern and mid-northern latitudes. The mid-southern latitudes are found depleted in hydrocarbons relative to their northern counterparts. In contrast, photochemical models predict similar abundances at north and south mid-latitudes. We favor a dynamical explanation for this asymmetry, with upwelling in the south and downwelling in the north, the latter coinciding with the region undergoing ring shadowing. The depletion in hydrocarbons at mid-southern latitudes could also result from chemical reactions with oxygen-bearing molecules.Poleward of 60°S, at 0.1 and 0.05 hPa, we find that the CH₃C₂H and C₄H₂ abundances increase dramatically. This behavior is in sharp contradiction with photochemical model predictions, which exhibit a strong decrease towards the south pole. Several processes could explain our observations, such as subsidence, a large vertical eddy diffusion coefficient at high altitudes, auroral chemistry that enhances CH₃C₂H and C₄H₂ production, or shielding from photolysis by aerosols or molecules produced from auroral chemistry. However, problems remain with all these hypotheses, including the lack of similar behavior at lower altitudes.Our derived mean mixing ratios at 0.5 hPa of (2.4 ± 0.3) × 10⁻¹⁰ for C₄H₂ and of (1.1 ± 0.3) × 10⁻⁹ for CH₃C₂H are compatible with the analysis of global-average ISO observations performed by Moses et al. (Moses, J.I., Bézard, B., Lellouch, E., Gladstone, G.R., Feuchtgruber, H., Allen, M. [2000a]. Icarus 143, 244-298). Finally, we provide values for the ratios [CH₃C₂H]/[C₂H₂] and [C₄H₂]/[C₂H₂] that can constrain the coupled chemistry of these hydrocarbons.  相似文献   

Chemical reactions in the Titan’s troposphere during lightning     

Tamás Kovács  Tamás Turányi 《Icarus》2010,207(2):938-947

In the lower troposphere of the Titan the temperature is about 90 K, therefore the chemical production of compounds in the CH₄/N₂ atmosphere is extremely slow. However, atmospheric electricity could provide conditions at which chemical reactions are fast. This paper is based on the assumption that there are lightning discharges in the Titan’s lower atmosphere. The temporal temperature profile of a gas parcel after lightning was calculated at the conditions of 10 km above the Titan’s surface. Using this temperature profile, composition of the after-lightning atmosphere was simulated using a detailed chemical kinetic mechanism consisting of 1829 reactions of 185 species. The main reaction paths leading to the products were investigated. The main products of lighting discharges in the Titan’s atmosphere are H₂, HCN, C₂N₂, C₂H₂, C₂H₄, C₂H₆, NH₃ and H₂CN. The annual production of these compounds was estimated in the Titan’s atmosphere.  相似文献   

Detection of new hydrocarbons in Uranus' atmosphere by infrared spectroscopy     

Martin Burgdorf  Glenn Orton  Victoria Meadows 《Icarus》2006,184(2):634-637

Ethane (C₂H₆), methylacetylene (CH₃C₂H or C₃H₄) and diacetylene (C₄H₂) have been discovered in Spitzer 10-20 μm spectra of Uranus, with 0.1-mbar volume mixing ratios of (1.0±0.1)×¹⁰⁻⁸, (2.5±0.3)×¹⁰⁻¹⁰, and (1.6±0.2)×¹⁰⁻¹⁰, respectively. These hydrocarbons complement previously detected methane (CH₄) and acetylene (C₂H₂). Carbon dioxide (CO₂) was also detected at the 7-σ level with a 0.1-mbar volume mixing ratio of (4±0.5)×¹⁰⁻¹¹. Although the reactions producing hydrocarbons in the atmospheres of giant planets start from radicals, the methyl radical (CH₃) was not found in the spectra, implying much lower abundances than in the atmospheres of Saturn or Neptune where it has been detected. This finding underlines the fact that Uranus' atmosphere occupies a special position among the giant planets, and our results shed light on the chemical reactions happening in the absence of a substantial internal energy source.  相似文献   

Radial distribution of production rates, loss rates and densities corresponding to ion masses ?40 amu in the inner coma of Comet Halley: Composition and chemistry     

S.A. Haider 《Icarus》2005,177(1):196-216

In this paper we have studied the chemistry of C, H, N, O, and S compounds corresponding to ions of masses ?40 amu in the inner coma of the Comet 1P/Halley. The production rates, loss rates, and ion mass densities are calculated using the Analytical Yield Spectrum approach and solving coupled continuity equation controlled by the steady state photochemical equilibrium condition. The primary ionization sources in the model are solar EUV photons, photoelectrons, and auroral electrons of the solar wind origin. The chemical model couples ion-neutral, electron-neutral, photon-neutral and electron-ion reactions among ions, neutrals, electrons, and photons through over 600 chemical reactions. Of the 46 ions considered in the model the chemistry of 24 important ions (viz., CH₃OH⁺₂, H₃CO⁺, NH⁺₄, H₃S⁺, H₂CN⁺, H₂O⁺, NH⁺₃, CO⁺, C₃H⁺₃, OH⁺, H₃O⁺, CH₃OH⁺, C₃H⁺₄, C₂H⁺₂, C₂H⁺, HCO⁺, S⁺, CH⁺₃, H₂S⁺, O⁺, C⁺, CH⁺₄, C⁺₂, and O⁺₂) are discussed in this paper. At radial distances <1000 km, the electron density is mainly controlled by 6 ions, viz., NH⁺₄, H₃O⁺, CH₃OH⁺₂, H₃S⁺, H₂CN⁺, and H₂O⁺, in the decreasing order of their relative contribution. However, at distances >1000 km, the 6 major ions are H₃O⁺, CH₃OH⁺₂, H₂O⁺, H₃CO⁺, C₂H⁺₂, and NH⁺₄; along with ions CO⁺, OH⁺, and HCO⁺, whose importance increases with further increase in the radial distance. It is found that at radial distances greater than ∼1000 km (±500 km) the major chemical processes that govern the production and loss of several of the important ions in the inner coma are different from those that dominate at distances below this value. The importance of photoelectron impact ionization, and the relative contributions of solar EUV, and auroral and photoelectron ionization sources in the inner coma are clearly revealed by the present study. The calculated ion mass densities are compared with the Giotto Ion Mass Spectrometer (IMS) and Neutral Mass Spectrometer (NMS) data at radial distances 1500, 3500, and 6000 km. There is a reasonable agreement between the model calculation and the Giotto measurements. The nine major peaks in the IMS spectra between masses 10 and 40 amu are reproduced fairly well by the model within a factor of two inside the ionopause. We have presented simple formulae for calculating densities of the nine major ions, which contribute to the nine major peaks in the IMS spectra, throughout the inner coma that will be useful in estimating their densities without running the complex chemical models.  相似文献   

Epistemic bimodality and kinetic hypersensitivity in photochemical models of Titan's atmosphere     

M. Dobrijevic  N. Carrasco  E. Hébrard  P. Pernot 《Planetary and Space Science》2008,56(12):1630-1643

We show that photochemical models of Titan's atmosphere can give rise to bimodal distributions in the abundances of some major compounds, like C₂H₂ and C₂H₄. Sensitivity analysis enabled us to identify the causes and conditions of this bimodality. We propose several methods to control this behavior in photochemical models. In particular, we point out the importance of two key reactions and the needs for a critical evaluation of the kinetic data. We also show that the abundances of some compounds are hypersensitive to the ratio [CH₄]/[H], suggesting that a time-dependent variation of this ratio might lead to a real bistability in the high atmosphere of Titan.  相似文献   

An experimental study of the reaction kinetics of C₂(XΣ_g) with hydrocarbons (CH₄, C₂H₂, C₂H₄, C₂H₆ and C₃H₈) over the temperature range 24-300 K: Implications for the atmospheres of Titan and the Giant Planets     

André Canosa  Alejandra Páramo  Sébastien D. Le Picard 《Icarus》2007,187(2):558-568

The reactivity of C₂(X¹Σ⁺_g) with simple saturated (CH₄, C₂H₆ and C₃H₈) and unsaturated (C₂H₂ and C₂H₄) hydrocarbons has been studied in the gas phase over the temperature range 24-300 K using the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique. All reactions have been found to be very rapid in this temperature range and the rate coefficients are typically ?10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ with the exception of methane for which the rate coefficient is one order of magnitude lower: ∼10⁻¹¹ cm³ molecule⁻¹ s⁻¹. These results have been analyzed in terms of potential destruction sources of C₂(X¹Σ⁺_g) in the atmospheres of Titan and the Giant Planets. It appears that the rate coefficient of the reaction ¹C₂ + CH₄ should be updated with our new data and that reactions with C₂H₂, C₂H₄ and C₂H₆ should also be included in the existing photochemical models.  相似文献   

Reflectance and transmittance spectra (2.2-2.4 μm) of ion irradiated frozen methanol     

R. Brunetto  G.A. Baratta  G. Strazzulla 《Icarus》2005,175(1):226-232

We present near-IR (2.2-2.4 μm) reflectance and transmittance spectra of frozen (16 and 77 K) methanol (CH₃OH) and water-methanol (1:1) mixtures before and after irradiation with 30 keV He⁺ and 200 keV H⁺ ions. Spectra of other simple hydrocarbons (CH₄, C₂H₂, C₂H₄, C₂H₆) and CO have also been obtained both to help in the identification of the new molecules formed after ion irradiation of methanol-rich ices, and to get insight into the question of the presence of simple frozen hydrocarbons on the surface of some objects in the outer Solar System. The results confirm what obtained by studies performed in different spectral ranges, namely the ion-induced formation of CO and CH₄, and, for the first time, evidence a strong decrease of the intensity of the methanol band at about 2.34 μm in comparison with that at 2.27 μm. The results are discussed in view of their relevance for icy objects in the Solar System (namely comets, Centaurs, and Kuiper belt objects) where CH₃OH has been observed or suggested to be present.  相似文献   

Deuterium chemistry and airglow in the jovian thermosphere     

C.D. Parkinson  J.C. McConnell  A.Y.-T. Lee  E. Griffioen 《Icarus》2006,183(2):451-470

We present a detailed study of the distribution of key deuterated species (viz., atomic D and HD) and the associated deuterium Lyman-α airglow in the jovian thermosphere. The reactions that appear to govern the abundances of these deuterated species are used in conjunction with C₂-chemistry in a 1-D photochemical-diffusion model. While the D abundance is mainly sensitive to H densities and the vibrational temperature profile, the D vertical distribution also depends on other parameters such as eddy mixing and the uncertain values of some of the reaction rate constants. We consider different scenarios by varying several parameters controlling the D distribution in the thermosphere. A radiative transfer model with coupling of the H and D Lyman-α lines is employed to obtain line profiles and total intensities at disk center for these scenarios. This allows a comparison of the impact of various parameters on the jovian D Lyman-α emission. A consequence of these chemical processes in the jovian thermosphere is the formation of CH₂D, CH₃D, and C₂H₅D, and other deuterated species. We also discuss the source of these deuterated hydrocarbons and their abundance. We find that HD vibrational chemistry impacts D in the thermosphere, CH₃D and C₂H₅D are vibrationally enhanced in the thermosphere, and variations in abundance of CH₃D and C₂H₅D in the thermosphere may reflect dynamical activity (i.e., Kh) in the jovian upper atmosphere. An observing program dedicated to providing such measurements of these testable phenomena would provide further insight into the synergistic coupling between chemistry, energetics and airglow in the jovian upper atmosphere.  相似文献   

The photochemical formation of a titan haze analog. Structural analysis by x-ray photoelectron and infrared spectroscopy     

Buu N. Tran  John J. Chera 《Icarus》2003,162(1):114-124

The photochemical flow reactor (D.W. Clarke et al., 2000, Icarus 147, 282-291) has been modified to minimize the incorporation of oxygen and other impurities in the photoproducts. A mixture of gases that approximate their mixing ratios on Titan (N₂, CH₄, H₂, C₂H₂, C₂H₄, and HC₃N) (0.98, 0.018, 0.002, 3.5 × 10⁻⁴, 3 × 10⁻⁴, 1.7 × 10⁻⁵, respectively) was irradiated in the flow photochemical reactor using a 185-nm source to give a Titan haze analog as a solid product. X-ray photoelectron spectroscopy (XPS) gave a composition of 93.3% C, 5.3% N, and 1.4% O. Of the 93.3% carbon, high-resolution XPS revealed that 81.2% was present as CH, CC, and CC groups, 12.1% may be CO, CN, CN, CN, and/or CN groups, 5.3% as a CN group. The peak for N was symmetrical and was assigned to the CN while that for oxygen was assigned to the CO and/or the CO group. Some of these assignments were confirmed by FTIR spectroscopy. The polymeric product had a C:N ratio of 17.6, which is significantly greater than that for Titan haze analogs prepared in discharge reactions. When the polymer was exposed to air for seven days the oxygen content increased by 6% along with an increase in the infrared absorption at 1710 cm⁻¹ assigned to the CO group of a ketone. The oxidation is attributed to the reaction of oxygen with free radicals trapped in the polymer matrix. It is proposed that the photochemical initiation of Titan haze formation from compounds formed from starting materials formed high in Titan’s atmosphere is a more plausible model than haze formed in reactions initiated by solely by discharges. These data will be helpful in the interpretation of the data returned from the Huygens probe of the Cassini mission.  相似文献   

Experimental impact shock chemistry on planetary icy satellites     

Delphine Nna-Mvondo  Bishun Khare  Tomoko Ishihara  Christopher P. McKay 《Icarus》2008,194(2):822-835

We present new experimental results on impact shock chemistry into icy satellites of the outer planets. Icy mixtures of pure water ice with CO₂, Na₂CO₃, CH₃OH, and CH₃OH/(NH₄)₂SO₄ at 77 K were ablated with a powerful pulsed laser—a new technique used to simulate shock processes which can occur during impacts. New products were identified by GC-MS and FTIR analyses after laser ablation. Our results show that hydrogen peroxide is formed in irradiated H₂O/CO₂ ices with a final concentration of 0.23%. CO and CH₃OH were also detected as main products. The laser ablation of frozen H₂O/Na₂CO₃ generates only CO and CO₂ as destruction products from the salt. Pulsed irradiation of water ice containing methanol leads also to the formation of CO and CO₂, generates methane and more complex molecules containing carbonyl groups like acetaldehyde, acetone, methyl formate, and a diether, dimethyl formal. The last three compounds are also produced when adding ammonium sulfate to H₂O/CH₃OH ice, but acetone is more abundant. The formation of two hydrocarbons, CH₄ and C₂H₆ is observed as well as the production of three nitrogen compounds, nitrous oxide, hydrogen cyanide, and acetonitrile.  相似文献   

Studies of proton-irradiated cometary-type ice mixtures     

Marla H. Moore  Bertram Donn  Raj Khanna  Michael F. A&#x;Hearn 《Icarus》1983,54(3):388-405

Radiation synthesis has been proposed as a mechanism for changing the nature of the outer few meters of ice in a comet stored 4.6 billion years in the Oort cloud and may explain some of the differences observed between new and more evolved comets. Cometary-type ice mixtures were studied in a laboratory experiment designed to approximately simulate the expected temperature, pressure, and radiation environment of the interstellar Oort cloud region. The 2.5- to 15-μm infrared absorption features of thin ice films were analyzed near 20°K before and after 1 MeV proton irradiation. Various ice mixtures included the molecules H₂O, NH₃, CH₄, N₂, C₃H₈, CO, and CO₂. All experiments confirm the synthesis of new molecular species in solid phase mixtures at 20°K. The synthesized molecules, identified by their infrared signatures, are C₂H₆, CO₂, CO, N₂O, NO, and CH₄ (weak). Synthesized molecules, identified by gas chromatographic (GC) analysis of the volatile fraction of the warmed irradiated ice mixture, are C₂H₄ or C₂H₆, and C₃H₈. When CH₄ is present in the irradiated ice mixture, long-chained volatile hydrocarbons and CO₂ are synthesized along with high-molecular-weight carbon compounds present in the room temperature residue. Irradiated mixtures containing CO and H₂O synthesize CO₂ and those CO₂ and H₂O synthesize CO. Due to radiation synthesis, ～1% of the ice was converted into a nonvolatile residue containing complicated carbon compounds not present in blank samples. These results suggest that irrespective of the composition of newly accreted comets, initial molecular abundances can be altered and new species created as a result of radiation synthesis. Irradiated mixtures exhibited thermoluminescence and pressure enhancements during warming; these phenomena suggest irradiation synthesis of reactive species. Ourbursts in new comets resulting from similar radiation induced exothermic activity would be expected to occur beginning at distances of the order of 100 AU.  相似文献   

Infrared polar brightening on Jupiter: III. Spectrometry from the Voyager 1 IRIS experiment     

Sang J. Kim  John Caldwell  A.R. Rivolo  R. Wagener  Glenn S. Orton 《Icarus》1985,64(2):233-248

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 in discussed in terms of the literature on C₂H₂ polymerization. The relation of C₆H₆ to cuprene is also discussed.  相似文献   

Vertical abundance profiles of hydrocarbons in Titan's atmosphere at 15° S and 80° N retrieved from Cassini/CIRS spectra     

Sandrine Vinatier  Bruno Bézard  Nick A. Teanby  Patrick G.J. Irwin  Conor A. Nixon  F. Michael Flasar 《Icarus》2007,188(1):120-138

Limb spectra recorded by the Composite InfraRed Spectrometer (CIRS) on Cassini provide information on abundance vertical profiles of C₂H₂, C₂H₄, C₂H₆, CH₃C₂H, C₃H₈, C₄H₂, C₆H₆ and HCN, along with the temperature profiles in Titan's atmosphere. We analyzed two sets of spectra, one at 15° S (Tb flyby) and the other one at 80° N (T3 flyby). The spectral range 600-1400 cm⁻¹, recorded at a resolution of 0.5 cm⁻¹, was used to determine molecular abundances and temperatures in the stratosphere in the altitude range 100-460 km for Tb and 170-495 km for T3. Both temperature profiles show a well defined stratopause, at around 310 km (0.07 mbar) and 183 K at 13° S, and 380 km (0.01 mbar) with 207 K at 80° N. Near the north pole, stratospheric temperatures are colder and mesospheric temperatures are warmer than near the equator. C₂H₂, C₂H₆, C₃H₈ and HCN display vertical mixing ratio profiles that increase with height at 15° S and 80° N, consistent with their formation in the upper atmosphere, diffusion downwards and condensation in the lower stratosphere, as expected from photochemical models. The CH₃C₂H and C₄H₂ mixing ratios also increase with height at 15° S. But near the north pole, their profiles present an unexpected minimum around 300 km, observed for the first time thanks to the high vertical resolution of the CIRS limb data. C₂H₄ is the only molecule having a vertical abundance profile that decreases with height at 15° S. At 80° N, it also displays a minimum of its mixing ratio around the 0.1-mbar level. For C₆H₆, an upper limit of 1.1 ppb (in the 0.3-10 mbar range) is derived at 15° S, whereas a constant mixing ratio profile of is inferred near the north pole. At 15° S, the vertical profile of HCN exhibits a steeper gradient than other molecules, which suggests that a sink for this molecule exists in the stratosphere, possibly due to haze formation. All molecules display a more or less pronounced enrichment towards the north pole, probably due, in part, to subsidence of air at the north (winter) pole that brings air enriched in photochemical compounds from the upper atmosphere to lower levels.  相似文献   

Crossed molecular beam study of gas phase reactions relevant to the chemistry of planetary atmospheres: The case of C₂+C₂H₂     

Francesca Leonori  Enrico Segoloni  Sébastien D. Le Picard 《Planetary and Space Science》2008,56(12):1658-1673

The reaction between dicarbon (C₂) and acetylene was recently suggested as a possible competitive reaction in the atmospheres of Titan, Saturn and Uranus by rate constant measurements at very low temperatures [see Canosa, A., Páramo, A., Le Picard, S.D., Sims, I.R., 2007. An experimental study of the reaction kinetics of C₂(X¹Σ_g⁺) with hydrocarbons (CH₄, C₂H₂, C₂H₄, C₂H₆ and C₃H₈) over the temperature range 24-300 K: implications for the atmospheres of Titan and the Giant Planets. Icarus 187, 558-568]. We have investigated the reaction of the two low lying electron states of C₂ and acetylene by the crossed molecular beam (CMB) technique with mass spectrometric detection. C₄H, already identified as a primary product in previous CMB experiments, is confirmed as such, even though the mechanism of formation is inferred to be partly different with respect to the previous study. An experimental setup has been devised to characterize the internal population of C₂ and refine the interpretation of the scattering results. The implications for the modelling of the atmospheres of Giant Planets and Titan, as well as cometary comae and the interstellar medium, are discussed.  相似文献   

Measured ion-molecule reaction rates for modelling Titan's atmosphere     

Seksan Dheandhanoo  Rainer Johnsen  Manfred A. Biondi 《Planetary and Space Science》1984,32(10):1301-1305

Rate coefficients for several two- and three-body ion-molecule reactions involving hydrocarbons have been determined at thermal energies and above using drift tube-mass spectrometer techniques. The measured rates for clustering and breakup reactions involving CH₅⁺ and C₂H₅⁺ ions in methane are found to be strongly temperature dependent in the range from 80 to 240 K. The equilibrium constants determined for these reactions differ somewhat from those of Hiraoka and Kebarle. Rate coefficients for two-body reactions of CH₅⁺, C₂H₅⁺, N⁺, H⁺ and D⁺ ions with methane and/or ethane have been measured. The results indicate that the product yields of several of the fast ion-molecule reactions depend strongly on ion energy (temperature), and therefore previous room-temperature results may be of limited value for model calculations of Titan's atmosphere.  相似文献   

Identification of C4H5, C4H4, C3H3 and CH3 radicals produced from the reaction of atomic carbon with propene: Implications for the atmospheres of Titan and giant planets and for the interstellar medium     

Chih-Hao Chin  Wei-Kan Chen  Wen-Jian Huang  Yi-Cheng Lin  Shih-Huang Lee 《Icarus》2013,222(1):254-262

We observed the products C₄H₅, C₄H₄, C₃H₃ and CH₃ of the C(³P) + C₃H₆ reaction using product time-of-flight spectroscopy and selective photoionization. The identified species arise from the product channels C₄H₅ + H, C₄H₄ + 2H and C₃H₃ + CH₃. Product isomers were identified via measurements of photoionization spectra and calculations of adiabatic ionization energy. Product C₄H₅ probably involves three isomers HCCCHCH₃, H₂CCCCH₃ and H₂CCCHCH₂. In contrast, products C₄H₄ and C₃H₃ involve exclusively HCCCHCH₂ and H₂CCCH, respectively. Reaction mechanisms are unraveled with crossed-beam experiments and quantum-chemical calculations. The ³P carbon atom attacks the π orbital of propene (C₃H₆) to form a cyclic complex c-H₂C(C)CHCH₃ that rapidly opens the ring to form H₂CCCHCH₃ followed by decomposition to HCCCHCH₃/H₂CCCCH₃/H₂CCCHCH₂ + H and H₂CCCH + CH₃; the corresponding branching ratios are 7:5:10:78 predicted with RRKM calculations at collision energy 4 kcal mol^?1. Nascent C₄H₅ with enough internal energy further decomposes to HCCCHCH₂ + H. Ratios of products C₄H₅, C₄H₄ and C₃H₃ are experimentally evaluated to be 17:8:75. This work provides a comprehensive look at product channels of the title reaction and gives implications for the formation of hydrocarbons in extra-terrestrial environments such as Titan and carbon-rich interstellar media. We suggest that the title reaction, hitherto excluded in any chemical networks, needs to be taken into account at least in the atmosphere of Titan and carbon-rich molecular clouds where rapid neutral–neutral reactions are dominant and carbon atoms and propene are abundant.  相似文献   

Shock waves and the chemical structure of interstellar clouds     

M. Y. Amin  M. S. El-Nawawy  M. A. El-Shalaby 《Astrophysics and Space Science》1991,185(2):277-294

In this paper we study the effect of shock waves on the chemical structure of the interstellar clouds. A model of molecular cloud has been assumed. The chemistry is investigated in a time dependent model. Our chemical network contains 56 species in 251 reactions to including molecules of the elements H, O, C, N, S, and Si.The results indicate that the calculated fractional abundance of the molecules NS, H₂O, CN, NH, CO, and SO agrees well with the observations. The molecules OH, H₂S, CS, H₂CS, HS, NO, SiO, CH, CH₂, CH₃, HCO, C₂, and HCN reach high post-shock abundances.  相似文献   

The molecular composition of Comet C/2007 W1 (Boattini): Evidence of a peculiar outgassing and a rich chemistry     

G.L. Villanueva  M.J. Mumma  B.P. Bonev  E.L. Gibb  G.A. Blake 《Icarus》2011,216(1):227-240

We measured the chemical composition of Comet C/2007 W1 (Boattini) using the long-slit echelle grating spectrograph at Keck-2 (NIRSPEC) on 2008 July 9 and 10. We sampled 11 volatile species (H₂O, OH^∗, C₂H₆, CH₃OH, H₂CO, CH₄, HCN, C₂H₂, NH₃, NH₂, and CO), and retrieved three important cosmogonic indicators: the ortho-para ratios of H₂O and CH₄, and an upper-limit for the D/H ratio in water. The abundance ratios of almost all trace volatiles (relative to water) are among the highest ever observed in a comet. The comet also revealed a complex outgassing pattern, with some volatiles (the polar species H₂O and CH₃OH) presenting very asymmetric spatial profiles (extended in the anti-sunward hemisphere), while others (e.g., C₂H₆ and HCN) showed particularly symmetric profiles. We present emission profiles measured along the Sun-comet line for all observed volatiles, and discuss different production scenarios needed to explain them. We interpret the emission profiles in terms of release from two distinct moieties of ice, the first being clumps of mixed ice and dust released from the nucleus into the sunward hemisphere. The second moiety considered is very small grains of nearly pure polar ice (water and methanol, without dark material or apolar volatiles). Such grains would sublimate only very slowly, and could be swept into the anti-sunward hemisphere by radiation pressure and solar-actuated non-gravitational jet forces, thus providing an extended source in the anti-sunward hemisphere.  相似文献   

The organic composition of Comet C/2001 A2 (LINEAR): I. Evidence for an unusual organic chemistry     

Karen Magee-Sauer  Michael J. Mumma  Neil Dello Russo  Boncho P. Bonev  G.L. Villanueva 《Icarus》2008,194(1):347-356

We used the NIRSPEC instrument on the Keck-2 telescope atop Mauna Kea, HI to observe Comet C/2001 A2 (LINEAR) in a Target of Opportunity campaign on UT 2001 July 9.5, 10.5 August 4.4, 10.5. We measured seven organic parent volatiles (C₂H₆, C₂H₂, HCN, CH₄, CO, CH₃OH, H₂CO) simultaneously with H₂O. We obtained absolute production rates and relative abundances for parent volatiles, and also measured rotational temperatures for several of these species. The chemical composition of C/2001 A2 differs substantially from any comet we have observed to date. The abundances we measure (relative to H₂O) for C₂H₆, C₂H₂, HCN, and CH₃OH are enriched by a factor of ∼2 to 3 in C/2001 A2 compared with most comets in our database. Other molecular species were detected within the typical range of measured abundances. C/2001 A2 presented a unique opportunity to study the chemistry of a fragmenting comet where pristine areas are exposed to the Sun.  相似文献