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1.
The kinetics of the reactions of C2H radical with ethane (k1), propane (k2), and n-butane (k3) are studied over the temperature range of T = 96-296 K with a pulsed Laval nozzle apparatus that utilizes a pulsed laser photolysis-chemiluminescence technique. The C2H decay profiles in the presence of both the alkane reactant and O2 are monitored by the CH(A2Δ) chemiluminescence tracer method. The results, together with available literature data, yield the following Arrhenius expressions: k1(T) = (0.51 ± 0.06) × 10−10 exp[(−76 ± 30)K/T] cm3 molecule−1 s−1 (T = 96-800 K), k2(T) = (0.98 ± 0.32) × 10−10exp[(−71 ± 60)K/T] cm3 molecule−1 s−1 (T = 96-361 K), and k3(T) = (1.23 ± 0.26) × 10−10 cm3 molecule−1 s−1 (T = 96-297 K). At T = 296 K, k1 is measured as a function of total pressure and has little or no pressure dependence. The results from this work support a direct hydrogen abstraction mechanism for the title reactions. Implications to the atmospheric chemistry of Titan are discussed. 相似文献
2.
The HCN emission features near 3 μm recently detected by Geballe et al. (2003, Astrophys. J. 583, L39) are analyzed with a model for fluorescence of sunlight in the ν3 band of HCN. The emission spectrum is consistent with current knowledge of the atmospheric temperature profile and the HCN distribution inferred from millimeter-wave observations. The spectrum is insensitive to the abundance of HCN in the thermosphere and the thousand-fold enhancement relative to photochemical models suggested by Geballe et al. (2003, Astrophys. J. 583, L39) is not required to explain the observations. We find that the spectrum can be matched with temperatures from 130 to 200 K, with slightly better fits at high temperature, contrary to the temperature determination of 130±10 K of Geballe et al. (2003, Astrophys. J. 583, L39). The HCN emission spectrum is sensitive to the collisional de-excitation probability, P10, for the ν3 state and we determine a value of 10−5 with an accuracy of about a factor of two. Analysis of absorption lines in the C2H2ν3 band near 3 μm, detected in the same spectrum, indicate a C2H2 mole fraction near 0.01 μbar of 10−5 for P10=10−4. The derived mole fraction, however, is dependent upon the value adopted for P10 and lower values are required if P10 at Titan temperatures is less than its room temperature value. 相似文献
3.
We investigate the role of seasonal variations of Titan’s stratospheric composition on the temperature. We use a general circulation model coupled with idealized chemical tracers that reproduce variations of ethane (C2H6), acetylene (C2H2), and hydrogen cyanide (HCN). Enhancement of the mole fractions of these compounds, at high latitudes in the winter hemisphere relative to their equatorial values, induces a relative decrease in temperature above approximately 0.2 mbar, with a peak amplitude around −20 K, and a relative increase in temperature below, around 1 mbar, with a peak amplitude around +7 K. These thermal effects are mainly due to the variations of the cooling to space induced by the varying distributions. The ethane, acetylene, and hydrogen cyanide variations affect the cooling rates in a similar way, with the dominant effect being due to ethane, though its latitudinal variations are small. 相似文献
4.
R.E. Hartle E.C. Sittler R.E. Johnson F. Crary D.T. Young D. Simpson D. Reisenfeld J.J. Berthelier J. Vilppola N. Andre 《Planetary and Space Science》2006,54(12):1211-1224
The Cassini plasma spectrometer (CAPS) instrument made measurements of Titan's plasma environment when the Cassini Orbiter flew through the moon's plasma wake October 26, 2004 (flyby TA). Initial CAPS ion and electron measurements from this encounter will be compared with measurements made by the Voyager 1 plasma science instrument (PLS). The comparisons will be used to evaluate previous interpretations and predictions of the Titan plasma environment that have been made using PLS measurements. The plasma wake trajectories of flyby TA and Voyager 1 are similar because they occurred when Titan was near Saturn's local noon. These similarities make possible direct, meaningful comparisons between the various plasma wake measurements. They lead to the following: (A) The light and heavy ions, H+and N+/O+, were observed by PLS in Saturn's magnetosphere in the vicinity of Titan while the higher mass resolution of CAPS yielded H+ and H2+as the light constituents and O+/CH4+ as the heavy ions. (B) Finite gyroradius effects were apparent in PLS and CAPS measurements of ambient O+ ions as a result of their absorption by Titan's extended atmosphere. (C) The principal pickup ions inferred from both PLS and CAPS measurements are H+, H2+, N+, CH4+ and N2+. (D) The inference that heavy pickup ions, observed by PLS, were in narrow beam distributions was empirically established by the CAPS measurements. (E) Slowing down of the ambient plasma due to pickup ion mass loading was observed by both instruments on the anti-Saturn side of Titan. (F) Strong mass loading just outside the ionotail by a heavy ion such as N2+ is apparent in PLS and CAPS measurements. (G) Except for the expected differences due to the differing trajectories, the magnitudes and structures of the electron densities and temperatures observed by both instruments are similar. The high-energy electron bite-out observed by PLS in the magnetotail is consistent with that observed by CAPS. 相似文献
5.
Titan has been observed with UVES, the UV-Visual Echelle Spectrograph at the Very Large Telescope, with the aim of characterizing the zonal wind flow. We use a retrieval scheme originally developed for absolute stellar accelerometry [Connes, P., 1985. Astrophys. Space Sci., 110, 211-255] to extract the velocity signal by simultaneously taking into account all the lines present in the spectrum. The method allows to measure the Doppler shift induced at a given point by the zonal wind flow, with high precision. The short-wavelength channel (4200-5200 Å) probes one scale height higher than the long-wavelength one (5200-6200 Å), and we observe statistically significant evidence for stronger winds at higher altitudes. The results show a high dispersion. Globally, we detect prograde zonal winds, with lower limits of 62 and 50 m s−1 at the regions centered at 200 and 170 km altitude, but approximately a quarter of the measurements indicates null or retrograde winds. 相似文献
6.
Robert E. Samuelson 《Planetary and Space Science》2003,51(2):127-145
Heating occurs in Titan's stratosphere from the absorption of incident solar radiation by methane and aerosols. About 10% of the incident sunlight reaches Titan's surface and causes heating there. Thermal radiation redistributes heat within the atmosphere and cools to space. The resulting vertical temperature profile is stable against convection and a state of radiative equilibrium is established. Equating theoretical and observed temperature profiles enables an empirical determination of the vertical distribution of thermal opacity. A uniformly mixed aerosol is responsible for most of the opacity in the stratosphere, whereas collision-induced absorption of gases is the main contributor in the troposphere. Occasional clouds are observed in the troposphere in spite of the large degrees of methane supersaturation found there. Photochemistry converts CH4 and N2 into more complex hydrocarbons and nitriles in the stratosphere and above. Thin ice clouds of trace organics are formed in the winter and early spring polar regions of the lower stratosphere. Precipitating ice particles serve as condensation sites for supersaturated methane vapor in the troposphere below, resulting in lowered methane degrees of supersaturation in the polar regions. Latitudinal variations of stratospheric temperature are seasonal, and lag instantaneous response to solar irradiation by about one season for two reasons: (1) an actual instantaneous thermal response to a latitudinal distribution of absorbing gases, themselves out of phase with the sun by about one season, and (2) a sluggish dynamical response of the stratosphere to the latitudinal transport of angular momentum, induced by radiative heating and cooling. Mean vertical abundances of stratospheric organics and aerosols are determined primarily by atmospheric chemistry and condensation, whereas latitudinal distributions are more influenced by meridional circulations. In addition to preferential scavenging by precipitating ice particles from above, the polar depletion of supersaturated methane results from periodic scavenging by short-lived tropospheric clouds, coupled with the steady poleward march of the continuously drying atmosphere due to meridional transport. 相似文献
7.
A time-dependent microphysical model is used to study the evolution of ethane ice clouds in Titan’s atmosphere. The model simulates nucleation, condensational growth, evaporation, coagulation, and transport of particles. For a critical saturation of 1.15 (a lower limit, determined by laboratory experiments), we find that ethane clouds can be sustained between altitudes of 8 and 50 km. Growth due to coalescence is inefficient, limiting the peak in the size distribution (by number) to 10 μm. These clouds vary with a period of about 20 days. This periodicity disappears for higher critical saturation values where clouds remain subvisible. Rainout of ethane due to methane cloud formation raises the altitude of the ethane cloud bottom to near the tropopause and may eliminate ethane clouds entirely if methane cloud formation occurs up to 30 km. However, clouds formed above the troposphere from other gases in Titan’s atmosphere could be sustained even with rainout up to 30 km. Although the optical depth of ethane clouds above 20 km is typically low, short-lived clouds with optical depths of order 0.1-1 can be created sporadically by dynamically driven atmospheric cooling. Ethane cloud particles larger than 25 μm can fall to the surface before total evaporation. However, ethane clouds remain only a small sink for tholin particles. At the peak of their cycle, the optical depth of ethane clouds could be comparable to that of tholin in the near-infrared, resulting in a 5% increase in Titan’s albedo for wavelengths between 1 and 2 μm. A number of factors limit our ablility to predict the ethane cloud properties. These factors include the mixing time in the troposphere, the critical saturation ratio for ethane ice, the existence of a surface reservoir of ethane, the magnitude and timing of dynamically driven temperature perturbations, and the abundance and life cycle of methane clouds. 相似文献
8.
We present a 2D general circulation model of Titan's atmosphere, coupling axisymmetric dynamics with haze microphysics, a simplified photochemistry and eddy mixing. We develop a parameterization of latitudinal eddy mixing by barotropic waves based on a shallow-water, longitude-latitude model. The parameterization acts locally and in real time both on passive tracers and momentum. The mixing coefficient varies exponentially with a measure of the barotropic instability of the mean zonal flow. The coupled GCM approximately reproduces the Voyager temperature measurements and the latitudinal contrasts in the distributions of HCN and C2H2, as well as the main features of the zonal wind retrieved from the 1989 stellar occultation. Wind velocities are consistent with the observed reversal time of the North-South albedo asymmetry of 5 terrestrial years. Model results support the hypothesis of a non-uniform distribution of infrared opacity as the cause of the Voyager temperature asymmetry. Transport by the mean meridional circulation, combined with polar vortex isolation may be at the origin of the latitudinal contrasts of trace species, with eddy mixing remaining restricted to low latitudes most of the Titan year. We interpret the contrasts as a signature of non-axisymmetric motions. 相似文献
9.
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
10.
We model the chemical evolution of Titan, wherein primordial NH3 reacts with sulfate-rich brines leached from the silicate core during its hydration. The resulting differentiated body consists of a serpentinite core overlain by a high-pressure ice VI mantle, a liquid layer of aqueous ammonium sulfate, and a heterogeneous shell of methane clathrate, low-pressure ice Ih and solid ammonium sulfate. Cooling of the subsurface ocean results in underplating of the outer shell with ice Ih; this gravitationally unstable system can produce compositional plumes as ice Ih ascends buoyantly. Ice plumes may aid in advection of melt pockets through the shell and, in combination with surface topography, provide the necessary hydraulic pressure gradients to drive such melts to the surface. Moreover, contact between the magma and wall rock (methane clathrate) will allow some methane to dissolve in the magma, as well as eroding fragments of wall rock that can be transported as xenoliths. Upon rising to the clathrate decomposition depth (∼2 MPa, or 1700 m), the entrained xenoliths will break down to ice + methane gas, powering highly explosive eruptions with lava fountains up to several kilometers high. Hence we predict that Titan is being resurfaced by cryoclastic ash consisting of ice and ammonium sulfate (or its tetrahydrate), providing an abundance of sedimentary grains, a potential source of bedload for fluvial transport and erosion, and of sand-sized material for aeolian transport and dune-building. The infrared reflectance spectrum of ammonium sulfate makes it a plausible candidate for the 5 μm-bright material on Titan's surface. 相似文献