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1.
We propose a new interpretation of the D/H ratio in CH4 observed in the atmosphere of Titan. Using a turbulent evolutionary model of the subnebula of Saturn (O. Mousis et al. 2002, Icarus156, 162-175), we show that in contrast to the current scenario, the deuterium enrichment with respect to the solar value observed in Titan cannot have occurred in the subnebula. Instead, we argue that values of the D/H ratio measured in Titan were obtained in the cooling solar nebula by isotopic thermal exchange of hydrogen with CH3D originating from interstellar methane D-enriched ices that vaporized in the nebula. The rate of the isotopic exchange decreased with temperature and became fully inhibited around 200 K. Methane was subsequently trapped in crystalline ices around 10 AU in the form of clathrate hydrates formed at 60 K, and incorporated into planetesimals that formed the core of Titan. The nitrogen-methane atmosphere was subsequently outgassed from the decomposition of the hydrates (Mousis et al. 2002). By use of a turbulent evolutionary model of the solar nebula (O. Mousis et al. 2000, Icarus148, 513-525), we have reconstructed the entire story of D/H in CH4, from its high value in the early solar nebula (acquired in the presolar cloud) down to the value measured in Titan's atmosphere today. Considering the two last determinations of the D/H ratio in Titan—D/H=(7.75±2.25)×10−5 obtained from ground-based observations (Orton 1992, In: Symposium on Titan, ESA SP-338, pp. 81-85), and D/H=(8.75+3.25−2.25)×10−5, obtained from ISO observations (Coustenis et al. 2002, submitted for publication)—we inferred an upper limit of the D/H ratio in methane in the early outer solar nebula of about 3×10−4. Our approach is consistent with the scenario advocated by several authors in which the atmospheric methane of Titan is continuously replenished from a reservoir of clathrate hydrates of CH4 at high pressures, located in the interior of Titan. If this scenario is correct, observations of the satellite to be performed by the radar, the imaging system, and other remote sensing instruments aboard the spacecraft of the Cassini-Huygens mission from 2004 to 2008 should reveal local disruptions of the surface and other signatures of the predicted outgassing.  相似文献   

2.
In Titan's atmosphere consisting of N2 and CH4, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N2 and CH4 gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×10−3×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.  相似文献   

3.
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   

4.
To explain the observed abundances of CO2 in Titan's atmosphere, a relatively high water deposition into the atmosphere needs to be invoked due to the importance of H2O photolysis in CO2 production. A likely source of H2O is icy dust particles from space. This paper considers the direct dust input to Titan's atmosphere from the interplanetary environment, and also ejecta particles from micrometeoroid impacts with the icy satellites Hyperion, Iapetus and Phoebe. It is found that the likely mass influx to Titan is 10–16 to 10–15 kg m–2 s–1. This mass influx is an order of magnitude too low to explain the observed levels of CO2 in Titan's atmosphere in the context of a recent photochemical model. This leads one to speculate as to the likelihood of one large impact to Titan in the recent past;i.e., that the atmosphere is not in equilibrium but is cnrrently losing CO2.  相似文献   

5.
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   

6.
For several years now, an experimental simulation of Titan's atmosphere has been on going at LISA. A cold plasma is established in a gas mixture representative of the atmosphere of the satellite. In these experiments, more than 70 organic compounds have been identified, including the first identification in this type of experimental simulation of C4N2 already detected in its solid form on Titan, which suggests that the setup correctly mimics the chemistry of Titan's atmosphere.We have carried out the first experimental simulation including O-containing compounds in order to study the influence of the presence of CO on the chemical behavior of Titan's atmosphere. With the help of gas chromatography–mass spectrometry (GC–MS) and infrared spectroscopy (IRS) we can thus determine which minor species still undetected in Titan's atmosphere are likely to be present and understand the complex chemistry of the atmosphere of this satellite. Surprisingly we have identified unpredicted O-containing gaseous compounds, mainly ethylene oxide (also named oxirane, C2H4O). This molecule has been observed in the interstellar medium by observation in the millimeter region (Astrophys. J. 489 (1997) 553; Astron. Astrophys. 337 (1998) 275). On the contrary, the predicted O-compounds (formaldehyde and methanol) have not been identified in this experiment. Furthermore, we have identified NH3 in the gaseous products with an initial mixture of N2 (98%) and CH4 (2%).The paper describes the experimental device used in this work, in particular the IRS and GC–MS techniques. We also comment the results related to the detection of the O-containing compounds and NH3 and their implications on our knowledge of the chemistry of Titan's atmosphere and on the retrieval of the future Titan data expected from Cassini-Huygens.  相似文献   

7.
Discovery by Cassini's plasma instrument of heavy positive and negative ions within Titan's upper atmosphere and ionosphere has advanced our understanding of ion neutral chemistry within Titan's upper atmosphere, primarily composed of molecular nitrogen, with ~2.5% methane. The external energy flux transforms Titan's upper atmosphere and ionosphere into a medium rich in complex hydrocarbons, nitriles and haze particles extending from the surface to 1200 km altitudes. The energy sources are solar UV, solar X-rays, Saturn's magnetospheric ions and electrons, solar wind and shocked magnetosheath ions and electrons, galactic cosmic rays (GCR) and the ablation of incident meteoritic dust from Enceladus’ E-ring and interplanetary medium. Here it is proposed that the heavy atmospheric ions detected in situ by Cassini for heights >950 km, are the likely seed particles for aerosols detected by the Huygens probe for altitudes <100 km. These seed particles may be in the form of polycyclic aromatic hydrocarbons (PAH) containing both carbon and hydrogen atoms CnHx. There could also be hollow shells of carbon atoms, such as C60, called fullerenes which contain no hydrogen. The fullerenes may compose a significant fraction of the seed particles with PAHs contributing the rest. As shown by Cassini, the upper atmosphere is bombarded by magnetospheric plasma composed of protons, H2+ and water group ions. The latter provide keV oxygen, hydroxyl and water ions to Titan's upper atmosphere and can become trapped within the fullerene molecules and ions. Pickup keV N2+, N+ and CH4+ can also be implanted inside of fullerenes. Attachment of oxygen ions to PAH molecules is uncertain, but following thermalization O+ can interact with abundant CH4 contributing to the CO and CO2 observed in Titan's atmosphere. If an exogenic keV O+ ion is implanted into the haze particles, it could become free oxygen within those aerosols that eventually fall onto Titan's surface. The process of freeing oxygen within aerosols could be driven by cosmic ray interactions with aerosols at all heights. This process could drive pre-biotic chemistry within the descending aerosols. Cosmic ray interactions with grains at the surface, including water frost depositing on grains from cryovolcanism, would further add to abundance of trapped free oxygen. Pre-biotic chemistry could arise within surface microcosms of the composite organic-ice grains, in part driven by free oxygen in the presence of organics and any heat sources, thereby raising the astrobiological potential for microscopic equivalents of Darwin's “warm ponds” on Titan.  相似文献   

8.
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: CH4, C2H2 and C2H6. This is the first measurement of 12C/13C in any C2 molecule on Titan, and the first measurement of 12CH4/13CH4 (non-deuterated) on Titan by remote sensing. Our spectra cover five widely-spaced latitudes, 65° S to 71° 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 CH4 alone, we find (1-σ), essentially in agreement with the 12CH4/13CH4 measured by the Huygens Gas Chromatograph/Mass Spectrometer instrument (GCMS) [Niemann, H.B., and 17 colleagues, 2005. Nature 438, 779-784]: 82.3±1.0, and also with measured values in H13CN and 13CH3D by CIRS at lower precision [Bézard, B., Nixon, C., Kleiner, I., Jennings, D., 2007. Icarus 191, 397-400; Vinatier, S., Bézard, B., Nixon, C., 2007. Icarus 191, 712-721]. For the C2 species, we find in C2H2 and 89.8±7.3 in C2H6, 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 , 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 (88±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.  相似文献   

9.
One of the key components controlling the chemical composition and climatology of Titan's atmosphere is the removal of reactive atomic hydrogen from the atmosphere. A proposed process of the removal of atomic hydrogen is the heterogeneous reaction with organic aerosol. In this study, we investigate the effect of heterogeneous reactions in Titan's atmospheric chemistry using new measurements of the heterogeneous reaction rate [Sekine, Y., Imanaka, H., Matsui, T., Khare, B.N., Bakes, E.L.O., McKay, C.P., Sugita, S., 2008. Icarus 194, 186-200] in a one-dimensional photochemical model. Our results indicate that 60-75% of the atomic hydrogen in the stratosphere and mesosphere are consumed by the heterogeneous reactions. This result implies that the heterogeneous reactions on the aerosol surface may predominantly remove atomic hydrogen in Titan's stratosphere and mesosphere. The results of our calculation also indicate that a low concentration of atomic hydrogen enhances the concentrations of unsaturated complex organics, such as C4H2 and phenyl radical, by more than two orders in magnitude around 400 km in altitude. Such an increase in unsaturated species may induce efficient haze production in Titan's mesosphere and upper stratosphere. These results imply a positive feedback mechanism in haze production in Titan's atmosphere. The increase in haze production would affect the chemical composition of the atmosphere, which might induce further haze production. Such a positive feedback could tend to dampen the loss and supply cycles of CH4 due to an episodic CH4 release into Titan's atmosphere.  相似文献   

10.
The existence of methane in the martian atmosphere may be an indicator of subsurface life. Biological processes are known to fractionate the common isotopologues of methane, and hence measuring these isotopic ratios may yield constraints on the nature of the methane source. Any measurement of the isotopic ratios of atmospheric methane must consider the additional fractionation due to photochemistry in order to quantify the isotopic ratios of the source. Using a one-dimensional photochemical model, we find that photochemistry has a small (4.5‰) contribution to δ13C(CH4) but has a large (114‰) contribution to δD(CH4). Confirmation of these fractionation values will require additional laboratory data on key model inputs, particularly the ultraviolet absorption cross sections of 13CH4 and kinetic rate coefficients for the reactions of 13CH4 and CH3D with OH and O(1D) at pressures and temperatures relevant to the martian atmosphere.  相似文献   

11.
A global-mean model of coupled neutral and ion chemistry on Titan has been developed. Unlike the previous coupled models, the model involves ambipolar diffusion and escape of ions, hydrodynamic escape of light species, and calculates the H2 and CO densities near the surface that were assigned in some previous models. We tried to reduce the numbers of species and reactions in the model and remove all species and reactions that weakly affect the observed species. Hydrocarbon chemistry is extended to C12H10 for neutrals and C10H+11 for ions but does not include PAHs. The model involves 415 reactions of 83 neutrals and 33 ions, effects of magnetospheric electrons, protons, and cosmic rays. UV absorption by Titan's haze was calculated using the Huygens observations and a code for the aggregate particles. Hydrocarbon, nitrile, and ion chemistries are strongly coupled on Titan, and attempt to calculate them separately (e.g., in models of ionospheric composition) may result in significant error. The model densities of various species are typically in good agreement with the observations except vertical profiles in the stratosphere that are steeper than the CIRS limb data. (A model with eddy diffusion that facilitates fitting to the CIRS limb data is considered as well.) The CO densities are supported by the O+ flux from Saturn's magnetosphere. The ionosphere includes a peak at 80 km formed by the cosmic rays, steplike layers at 500-700 and 700-900 km and a peak at 1060 km (SZA = 60°). Nighttime densities of major ions agree with the INMS data. Ion chemistry dominates in the production of bicyclic aromatic hydrocarbons above 600 km. The model estimates of heavy positive and negative ions are in reasonable agreement with the Cassini results. The major haze production is in the reactions C6H + C4H2, C3N + C4H2, and condensation of hydrocarbons below 100 km. Overall, precipitation rate of the photochemical products is equal to 4-7 kg cm−2 Byr−1 (50-90 m Byr−1 while the global-mean depth of the organic sediments is ∼3 m). Escape rates of methane and hydrogen are 2.9 and 1.4 kg cm−2 Byr−1, respectively. The model does not support the low C/N ratio observed by the Huygens ACP in Titan's haze.  相似文献   

12.
In this paper we present an in-depth study of the distributions of various neutral species in Titan's upper atmosphere, between 950 and 1500 km for abundant species (N2, CH4, H2) and between 950 and 1200 km for other minor species. Our 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. To untangle the overlapping cracking patterns, we adopt Singular Value Decomposition (SVD) to determine simultaneously the densities of different species. Except for N2, CH4, H2 and 40Ar (as well as their isotopes), all species present density enhancements measured during the outbound legs. This can be interpreted as a result of wall effects, which could be either adsorption/desorption of these molecules or heterogeneous surface chemistry of the associated radicals on the chamber walls. In this paper, we provide both direct inbound measurements assuming ram pressure enhancement only and abundances corrected for wall adsorption/desorption based on a simple model to reproduce the observed time behavior. Among all minor species of photochemical interest, we have firm detections of C2H2, C2H4, C2H6, CH3C2H, C4H2, C6H6, CH3CN, HC3N, C2N2 and NH3 in Titan's upper atmosphere. Upper limits are given for other minor species.The globally averaged distributions of N2, CH4 and H2 are each modeled with the diffusion approximation. The N2 profile suggests an average thermospheric temperature of 151 K. The CH4 and H2 profiles constrain their fluxes to be and , referred to Titan's surface. Both fluxes are significantly higher than the Jeans escape values. The INMS data also suggest horizontal/diurnal variations of temperature and neutral gas distribution in Titan's thermosphere. The equatorial region, the ramside, as well as the nightside hemisphere of Titan appear to be warmer and present some evidence for the depletion of light species such as CH4. Meridional variations of some heavy species are also observed, with a trend of depletion toward the north pole. Though some of the above variations might be interpreted by either the solar-driven models or auroral-driven models, a physical scenario that reconciles all the observed horizontal/diurnal variations in a consistent way is still missing. With a careful evaluation of the effect of restricted sampling, some of the features shown in the INMS data are more likely to be observational biases.  相似文献   

13.
Cyanoacetylene (HC3N) and diacetylene (C4H2) play an important role in the photochemistry of Titan's atmosphere, in part because of their strong absorption between 110 and 180 nm. Accurate photoabsorption cross-sections at temperatures representative of Titan's atmosphere are required to interprete Cassini observations and to calculate photolysis rates used in photochemical models. Using synchrotron radiation as a tunable vacuum ultraviolet (VUV) light source, we have measured absolute photoabsorption cross-sections of C4H2 and HC3N with a spectral resolution of 0.05 nm in the region between 80 and 225 nm and at different temperatures between 173 and 295 K. The measured cross-sections are used to model transmission spectra of Titan atmosphere in the VUV.  相似文献   

14.
Solar and X-ray radiation and energetic plasma from Saturn's magnetosphere interact with the upper atmosphere producing an ionosphere at Titan. The highly coupled ionosphere and upper atmosphere system mediates the interaction between Titan and the external environment. A model of Titan's nightside ionosphere will be described and the results compared with data from the Ion and Neutral Mass Spectrometer (INMS) and the Langmuir probe (LP) part of the Radio and Plasma Wave (RPWS) experiment for the T5 and T21 nightside encounters of the Cassini Orbiter with Titan. Electron impact ionization associated with the precipitation of magnetospheric electrons into the upper atmosphere is assumed to be the source of the nightside ionosphere, at least for altitudes above 1000 km. Magnetospheric electron fluxes measured by the Cassini electron spectrometer (CAPS ELS) are used as an input for the model. The model is used to interpret the observed composition and structure of the T5 and T21 ionospheres. The densities of many ion species (e.g., CH+5 and C2H+5) measured during T5 exhibit temporal and/or spatial variations apparently associated with variations in the fluxes of energetic electrons that precipitate into the atmosphere from Saturn's magnetosphere.  相似文献   

15.
Methane is key to sustaining Titan's thick nitrogen atmosphere. However, methane is destroyed and converted to heavier hydrocarbons irreversibly on a relatively short timescale of approximately 10-100 million years. Without the warming provided by CH4-generated hydrocarbon hazes in the stratosphere and the pressure induced opacity in the infrared, particularly by CH4-N2 and H2-N2 collisions in the troposphere, the atmosphere could be gradually reduced to as low as tens of millibar pressure. An understanding of the source-sink cycle of methane is thus crucial to the evolutionary history of Titan and its atmosphere. In this paper we propose that a complex photochemical-meteorological-hydrogeochemical cycle of methane operates on Titan. We further suggest that although photochemistry leads to the loss of methane from the atmosphere, conversion to a global ocean of ethane is unlikely. The behavior of methane in the troposphere and the surface, as measured by the Cassini-Huygens gas chromatograph mass spectrometer, together with evidence of cryovolcanism reported by the Cassini visual and infrared mapping spectrometer, represents a “methalogical” cycle on Titan, somewhat akin to the hydrological cycle on Earth. In the absence of net loss to the interior, it would represent a closed cycle. However, a source is still needed to replenish the methane lost to photolysis. A hydrogeochemical source deep in the interior of Titan holds promise. It is well known that in serpentinization, hydration of ultramafic silicates in terrestrial oceans produces H2(aq), whose reaction with carbon grains or carbon dioxide in the crustal pores produces methane gas. Appropriate geological, thermal, and pressure conditions could have existed in and below Titan's purported water-ammonia ocean for “low-temperature” serpentinization to occur in Titan's accretionary heating phase. On the other hand, impacts could trigger the process at high temperatures. In either instance, storage of methane as a stable clathrate-hydrate in Titan's interior for later release to the atmosphere is quite plausible. There is also some likelihood that the production of methane on Titan by serpentinization is a gradual and continuous on-going process.  相似文献   

16.
We investigate the chemical transition of simple molecules like C2H2 and HCN into aerosol particles in the context of Titan's atmosphere. Experiments that synthesize analogs (tholins) for these aerosols can help illuminate and constrain these polymerization mechanisms. Using information available from these experiments, we suggest chemical pathways that can link simple molecules to macromolecules, which will be the precursors to aerosol particles: polymers of acetylene and cyanoacetylene, polycyclic aromatics, polymers of HCN and other nitriles, and polyynes. Although our goal here is not to build a detailed kinetic model for this transition, we propose parameterizations to estimate the production rates of these macromolecules, their C/N and C/H ratios, and the loss of parent molecules (C2H2, HCN, HC3N and other nitriles, and C6H6) from the gas phase to the haze. We use a one-dimensional photochemical model of Titan's atmosphere to estimate the formation rate of precursor macromolecules. We find a production zone slightly lower than 200 km altitude with a total production rate of 4×10−14 g cm−2 s−1 and a C/N?4. These results are compared with experimental data, and to microphysical model requirements. The Cassini/Huygens mission will bring a detailed picture of the haze distribution and properties, which will be a great challenge for our understanding of these chemical processes.  相似文献   

17.
The Electron Spectrometer (ELS), one of the sensors making up the Cassini Plasma Spectrometer (CAPS) revealed the existence of numerous negative ions in Titan's upper atmosphere. The observations at closest approach (∼1000 km) show evidence for negatively charged ions up to ∼10,000 amu/q, as well as two distinct peaks at 22±4 and 44±8 amu/q, and maybe a third one at 82±14 amu/q. We present the first ionospheric model of Titan including negative ion chemistry. We find that dissociative electron attachment to neutral molecules (mostly HCN) initiates the formation of negative ions. The negative charge is then transferred to more acidic molecules such as HC3N, HC5N or C4H2. Loss occurs through associative detachment with radicals (H and CH3). We attribute the three low mass peaks observed by ELS to CN−, C3N−/C4H− and C5N−. These species are the first intermediates in the formation of the even larger negative ions observed by ELS, which are most likely the precursors to the aerosols observed at lower altitudes.  相似文献   

18.
Photochemical reaction pathways in Titan's atmosphere were investigated by irradiation of the individual components and the mixture containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene. The quantum yields for the loss of the reactants and the formation of products were determined. Photolysis of ethylene yields mainly saturated compounds (ethane, propane, and butane) while photolysis of acetylene yields the same saturated compounds as well as ethylene and diacetylene. Irradiation of cyanoacetylene yields mainly hydrogen cyanide and small amounts of acetonitrile. When an amount of methane corresponding to its mixing ratio on Titan was added to these mixtures the quantum yields for the loss of reactants decreased and the quantum yields for hydrocarbon formation increased indicative of a hydrogen atom abstraction from methane by the photochemically generated radicals. GC/MS analysis of the products formed by irradiation of mixtures of all these gases generated over 120 compounds which were mainly aliphatic hydrocarbons containing double and triple bonds along with much smaller amounts of aromatic compounds like benzene, toluene and phenylacetylene. The reaction pathways were investigated by the use of 13C acetylene in these gas mixtures. No polycyclic aromatic compounds were detected. Vapor pressures of these compounds under conditions present in Titan's atmosphere were calculated. The low molecular weight compounds likely to be present in the atmosphere and aerosols of Titan as a result of photochemical processes are proposed.  相似文献   

19.
Far-IR (25-50 μm, 200-400 cm−1) nadir and limb spectra measured during Cassini's four year prime mission by the Composite InfraRed Spectrometer (CIRS) instrument have been used to determine the abundances of cyanogen (C2N2), methylacetylene (C3H4), and diacetylene (C4H2) in Titan's stratosphere as a function of latitude. All three gases are enriched at northern latitudes, consistent with north polar subsidence. C4H2 abundances agree with those derived previously from mid-IR data, but C3H4 abundances are about 2 times lower, suggesting a vertical gradient or incorrect band intensities in the C3H4 spectroscopic data. For the first time C2N2 was detected at southern and equatorial latitudes with an average volume mixing ratio of 5.5±1.4×10−11 derived from limb data (>3-σ significance). This limb result is also corroborated by nadir data, which give a C2N2 volume mixing ratio of 6±3×10−11 (2-σ significance) or alternatively a 3-σ upper limit of 17×10−11. Comparing these figures with photochemical models suggests that galactic cosmic rays may be an important source of N2 dissociation in Titan's stratosphere. Like other nitriles (HCN, HC3N), C2N2 displays greater north polar relative enrichment than hydrocarbons with similar photochemical lifetimes, suggesting an additional loss mechanism for all three of Titan's main nitrile species. Previous studies have suggested that HCN requires an additional sink process such as incorporation into hazes. This study suggests that such a sink may also be required for Titan's other nitrile species.  相似文献   

20.
R.L. Hudson  M.H. Moore 《Icarus》2004,172(2):466-478
Motivated by detections of nitriles in Titan's atmosphere, cometary comae, and the interstellar medium, we report laboratory investigations of the low-temperature chemistry of acetonitrile, propionitrile, acrylonitrile, cyanoacetylene, and cyanogen (CH3CN, CH3CH2CN, CH2CHCN, HCCCN, and NCCN, respectively). A few experiments were also done on isobutyronitrile and trimethylacetonitrile ((CH3)2CHCN and (CH3)3CCN, respectively). Trends were sought, and found, in the photo- and radiation chemical products of these molecules at 12-25 K. In the absence of water, all of these molecules isomerized to isonitriles, and CH3CN, CH3CH2CN, and (CH3)2CHCN also formed ketenimines. In the presence of H2O, no isonitriles were detected but rather the cyanate ion (OCN−) was seen in all cases. Although isonitriles, ketenimines, and OCN− were the main focus of our work, we also describe cases of hydrogen loss, to make smaller nitriles, and hydrogen addition (reduction), to make larger nitriles. HCN formation also was seen in most experiments. The results are presented in terms of nitrile ice chemistry on Titan, in cometary ice, and in the interstellar medium. Possible connections to prebiotic chemistry are briefly discussed.  相似文献   

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