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1.
Thermochemical data for several ion-molecule clustering of hydrocarbon ions with N2 or CH4 were obtained from clustering equilibria studies in gas mixtures irradiated by alpha-particles. High-pressure mass spectrometry was used to determine the enthalpy and entropy changes of clustering (delta H0 and delta S0, respectively) for the reactions X+(N2)n-1 + 2N2 <==> X(+)(N2)n + N2 with X = CH5, n = 1-2; X = C2H5, n = 1-4; and X = C3H7, n = 1. For X = CH5, the values (delta H0; delta S0) are found to be (-6.8 kcal mol-1; -19.7 cal mol-1 K-1) for n = 1, and (-5.3 kcal mol-1; -15.9 cal mol-1 K-1) for n = 2. For X = C2H5, (delta H0; delta S0) = (-6.9 kcal mol-1; -18.2 cal mol-1 K-1), for n = 1, and (-4.6 kcal mol-1; -20.8 cal mol-1 K-1) for n = 2. From the equilibrium measurements at 129 K, estimates of the thermochemical values could be obtained for n = 3-4. The results obtained for the free energy, delta G0, were -1.4 kcal mol-1 for n = 3, and -1.1 kcal mol-1 for n = 4. For X = C3H7 we found delta G0 = -0.7 kcal mol-1 at 213 K. The association reactions X+ + 2CH4 <==> X+(CH4) + CH4 with X = CH5, C2H5, C2H7, and C3H7 were also studied, resulting in free energy values at 206 K of -3.1, -1.9, -0.5 and -1.3 kcal mol-1, respectively. The results for CH5, C2H5 and C3H7 are compared with previously reported measurements.  相似文献   

2.
Nair H  Allen M  Anbar AD  Yung YL  Clancy RT 《Icarus》1994,111(1):124-150
The factors governing the amounts of CO, O2, and O3 in the martian atmosphere are investigated using a minimally constrained, one-dimensional photochemical model. We find that the incorporation of temperature-dependent CO2 absorption cross sections leads to an enhancement in the water photolysis rate, increasing the abundance of OH radicals to the point where the model CO abundance is smaller than observed. Good agreement between models and observations of CO, O2, O3, and the escape flux of atomic hydrogen can be achieved, using only gas-phase chemistry, by varying the recommended rate constants for the reactions CO + OH and OH + HO2 within their specified uncertainties. Similar revisions have been suggested to resolve discrepancies between models and observations of the terrestrial mesosphere. The oxygen escape flux plays a key role in the oxygen budget on Mars; as inferred from the observed atomic hydrogen escape, it is much larger than recent calculations of the exospheric escape rate for oxygen. Weathering of the surface may account for the imbalance. Quantification of the escape rates of oxygen and hydrogen from Mars is a worthwhile objective for an upcoming martian upper atmospheric mission. We also consider the possibility that HOx radicals may be catalytically destroyed on dust grains suspended in the atmosphere. Good agreement with the observed CO mixing ratio can be achieved via this mechanism, but the resulting ozone column is much higher than the observed quantity. We feel that there is no need at this time to invoke heterogeneous processes to reconcile models and observations.  相似文献   

3.
The evaluation of OH radical reactions as a global sink for many trace gases in the troposphere requires a detailed knowledge of the OH production rate as a function of latitude and altitude. The OH production rate may be expressed as a product of the primary rate P1 from the reaction of O(1D) with water vapor and an amplification factor ? due to a re-cycling mechanism. The primary rate and its diurnal and seasonal averages have been computed as a function of latitude and altitude for the northern hemisphere, using only observational data for the involved parameters. For the southern hemisphere this procedure is not possible at present, because sufficiently detailed ozone measurements are not available. The calculation of the amplification factor requires in addition to the latitudinal distributions of atmospheric mixing ratios of CH4 and CO, those of nitrogen dioxide for which observational data are almost entirely lacking. Accordingly the distribution of NO2 mixing ratios was estimated to obtain values for the amplification factor ?. Effective OH production rates are given assuming that primary OH production rates obtained for the northern hemisphere are applicable also in the southern hemisphere. Due to the many uncertainties entering specifically into the values for the amplification factor the derived OH production rates must be considered a first approximation.  相似文献   

4.
Sandford SA  Allamandola LJ 《Icarus》1993,106(2):478-488
In an extension of previously reported work on ices containing CO, CO2, H2O, CH3OH, NH3, and H2, measurements of the physical and infrared spectral properties of ices containing molecules relevant to Jupiter's moon Io are presented. These include studies on ice systems containing SO2, H2S, and CO2. The condensation and sublimation behaviors of each ice system and surface binding energies of their components are discussed. The surface binding energies can be used to calculate the residence times of the molecules on a surface as a function of temperature and thus represent important parameters for any calculation that attempts to model the transport of these molecules on Io's surface. The derived values indicate that SO2 frosts on Io are likely to anneal rapidly, resulting in less fluffy, "glassy" ices and that H2S can be trapped in the SO2 ices of Io during night-time hours provided that SO2 deposition rates are on the order of 5 micrometers/hr or larger.  相似文献   

5.
We have searched for millimetre-wave line emission from ethylene oxide (c-C2H4O) and its structural isomer acetaldehyde (CH3CHO) in 11 molecular clouds using SEST. Ethylene oxide and acetaldehyde were detected through multiple lines in the hot cores NGC 6334F, G327.3-0.6, G31.41+0.31, and G34.3+0.2. Acetaldehyde was also detected towards G10.47+0.03, G322.2+0.6, and Orion 3'N, and one ethylene oxide line was tentatively detected in G10.47+0.03. Column densities and rotational excitation temperatures were derived using a procedure which fits the observed line intensifies by finding the minimum chi 2-value. The resulting rotational excitation temperatures of ethylene oxide and acetaldehyde are in the range 16-38 K, indicating that these species are excited in the outer, cooler parts of the hot cores or that the excitation is significantly subthermal. For an assumed source size of 20", the deduced column densities are (0.6-1)x10(14) cm-2 for ethylene oxide and (2-5)x10(14) cm-2 for acetaldehyde. The fractional abundances with respect to H2 are X[c-C2H4O]=(2-6)xl0(-10), and X[CH3CHO]=(0.8-3)x10(-9). The ratio X[CH3CHO]/X[c-C2H4O] varies between 2.6 (NGC 6334F) and 8.5 (G327.3-0.6). We also detected and analysed multiple transitions of CH3OH, CH3OCH3, C2H5OH, and HCOOH. The chemical, and possibly evolutionary, states of NGC 6334F, G327.3-0.6, G31.41+0.31, and G34.3+0.2 seem to be very similar.  相似文献   

6.
A new interstellar molecular ion, H2COH+ (protonated formaldehyde), has been detected toward Sgr B2, Orion KL, W51, and possibly in NGC 7538 and DR21(OH). Six transitions were detected in Sgr B2(M). The 1(1,0)-1(0,1) transition was detected in all sources listed above. Searches were also made toward the cold, dark clouds TMC-1 and L134N, Orion (3N, 1E), and a red giant, IRC + 10216, without success. The excitation temperatures of H2COH+ are calculated to be 60-110 K, and the column densities are on the order of 10(12)-10(14) cm-2 in Sgr B2, Orion KL, and W51. The fractional abundance of H2COH+ is on the order of 10(-11) to 10-(9), and the ratio of H2COH+ to H2CO is in the range 0.001-0.5 in these objects. The values in Orion KL seem to be consistent with the "early time" values of recent model calculations by Lee, Bettens, & Herbst, but they appear to be higher than the model values in Sgr B2 and W51 even if we take the large uncertainties of column densities of H2CO into account. We suggest production routes starting from CH3OH may play an important role in the formation of H2COH+.  相似文献   

7.
The University of Wisconsin–Madison and NASA–Goddard conducted acomprehensive multi-wavelength observing campaign of coma emissionsfrom comet Hale–Bopp, including OH 3080 Å, [O I] 6300 Å H2O+ 6158 Å, H Balmer-α 6563 Å, NH2 6330 Å, [C I] 9850 ÅCN 3879 Å, C2 5141 Å, C3 4062 Å,C I 1657 Å, and the UV and optical continua. In thiswork, we concentrate on the results of the H2O daughter studies.Our wide-field OH 3080 Å measured flux agrees with other, similarobservations and the expected value calculated from published waterproduction rates using standard H2O and OH photochemistry.However, the total [O I] 6300 Å flux determined spectroscopically overa similar field-of-view was a factor of 3-4 higher than expected.Narrow-band [O I] images show this excess came from beyond theH2O scale length, suggesting either a previously unknown source of[O I] or an error in the standard OH + ν→ O(1 D) + H branching ratio. The Hale–Bopp OH and[O I] distributions, both of which were imaged tocometocentric distances >1 × 106 km, were more spatiallyextended than those of comet Halley (after correcting for brightnessdifferences), suggesting a higher bulk outflow velocity. Evidence ofthe driving mechanism for this outflow is found in the Hα lineprofile, which was narrower than in comet Halley (though likelybecause of opacity effects, not as narrow as predicted by Monte-Carlomodels). This is consistent with greater collisional coupling betweenthe suprathermal H photodissociation products and Hale–Bopp's densecoma. Presumably because of mass loading of the solar wind by ionsand ions by the neutrals, the measured acceleration of H2O+ downthe ion tail was much smaller than in comet Halley. Tailwardextensions in the azimuthal distributions of OH 3080 Å,[O I], and [C I] , as well as a Doppler asymmetry in the[O I] line profile, suggest ion-neutral coupling. While thetailward extension in the OH can be explained by increased neutralacceleration, the [O I] 6300 Å and [C I] 9850 Å emissions show 13%and >200% excesses in this direction (respectively), suggesting anon-negligible contribution from dissociative recombination of CO+and/or electron collisional excitation. Thus, models including theeffects of photo- and collisional chemistry are necessary for the fullinterpretation of these data.  相似文献   

8.
Models are developed to describe the photochemistry of ozone on Mars. Catalytic reactions involving H, OH and HO2 play a major role at low latitudes where they ensure a vertical column density for O3 of less than 2 × 10?4 cm atm. The source for odd hydrogen (H + OH + HO2) is relatively smaller at high latitudes in winter due to the small concentrations of H2O present there at that time. Odd hydrogen is also efficiently removed from the high-latitude winter atmosphere by condensation of H2O2. The role of catalytic chemistry is reduced accordingly and the vertical column density of O3 may be as large as 5.7 × 10?3 cm atm in accord with earlier observations carried out by Barth and co-workers with instruments on Mariner 9.  相似文献   

9.
The attempt to understand the temperature dependence of the HNC/HCN abundance ratio in interstellar clouds has been long standing and indecisive. In this paper we report quantum chemical and dynamical studies of two neutral–neutral reactions thought to be important in the formation of HNC and HCN, respectively – C+NH2→HNC+H, and N+CH2→HCN+H. We find that although these reactions do lead initially to the products suggested by astronomers, there is so much excess energy available in both reactions that the HCN and HNC products are able to undergo efficient isomerization reactions after production. The isomerization leads to near equal production rates of the two isomers, with HNC slightly favoured if there is sufficient rotational excitation. This result has been incorporated into our latest chemical model network of dense interstellar clouds.  相似文献   

10.
It is argued that ozone measurements made by Weeks et al. (1972) can be interpreted in terms of the enhanced ionization present. The conversion of O2+ ions to oxonium, H3O+ · (H2O)n, ions plus the dissociative recombination of these ions provides for an increased OH and/or H formation rate. The resulting enhanced OH and HO2 concentrations reduce the ambient atomic oxygen and hence ozone populations. The net excess H + OH formation rate is found to lie between one and two times the ionization production rate at altitudes where oxonium ions are the dominant positive ion species.  相似文献   

11.
A coupled problem of diffusion and condensation is solved for the H2SO4-H2O system in Venus' cloud layer. The position of the lower cloud boundary and profiles of the H2O and H2SO4 vapor mixing ratios and of the H2O/H2SO4 ratio of sulfuric acid aerosol and its flux are calculated as functions of the column photochemical production rate of sulfuric acid, phi H2SO4. Variations of the lower cloud boundary are considered. Our basic model, which is constrained to yield fH2O (30 km) = 30 ppm (Pollack et al. 1993), predicts the position of the lower cloud boundary at 48.4 km coinciding with the mean Pioneer Venus value, the peak H2SO4 mixing ratio of 5.4 ppm, and the H2SO4 production rate phi H2SO4 = 2.2 x 10(12) cm-2 sec-1. The sulfur to sulfuric acid mass flux ratio in the clouds is 1 : 27 in this model, and the mass loading ratio may be larger than this value if sulfur particles are smaller than those of sulfuric acid. The model suggests that the extinction coefficient of sulfuric acid particles with radius 3.7 micrometers (mode 3) is equal to 0.3 km-1 in the middle cloud layer. The downward flux of CO is equal to 1.7 x 10(12) cm-2 sec-1 in this model. Our second model, which is constrained to yield fH2SO4 = 10 ppm at the lower cloud boundary, close to the value measured by the Magellan radiooccultations, predicts the position of this boundary to be at 46.5 km, which agrees with the Magellan data; fH2O(30 km) = 90 ppm, close to the data of Moroz et al. (1983) at this altitude; phi H2SO4 = 6.4 x 10(12) cm-2 sec-1; and phi co = 4.2 x 10(12) cm-2 sec-1. The S/H2SO4 flux mass ratio is 1 : 18, and the extinction coefficient of the mode 3 sulfuric acid particles is equal to 0.9 km-1 in the middle cloud layer. A strong gradient of the H2SO4 vapor mixing ratio near the bottom of the cloud layer drives a large upward flux of H2SO4, which condenses and forms the excessive downward flux of liquid sulfuric acid, which is larger by a factor of 4-7 than the flux in the middle cloud layer. This is the mechanism of formation of the lower cloud layer. Variations of the lower cloud layer are discussed. Our modeling of the OCS and CO profiles in the lower atmosphere measured by Pollack et al. (1993) provides a reasonable explanation of these data and shows that the rate coefficient of the reaction SO3 + CO --> CO2 + SO2 is equal to 10(-11) exp(-(13,100 +/- 1000)/T) cm3/s. The main channel of the reaction between SO3 and OCS is CO2 + (SO)2, and its rate coefficient is equal to 10(-11) exp(-(8900 +/- 500)T)cm3/s. In the conditions of Venus' lower atmosphere, (SO)2 is removed by the reaction (SO)2 + OCS --> CO + S2 + SO2. The model predicts an OCS mixing ratio of 28 ppm near the surface.  相似文献   

12.
McDonald GD  Thompson WR  Sagan C 《Icarus》1992,99(1):131-142
Low-pressure continuous-flow laboratory simulations of plasma induced chemistry in H2/He/CH4/NH3 atmospheres show radiation yields of hydrocarbons and nitrogen-containing organic compounds that increase with decreasing pressure in the range 2-200 mbar. Major products of these experiments that have been observed in the Jovian atmosphere are acetylene (C2H2), ethylene (C2H4), ethane (C2H6), hydrogen cyanide (HCN), propane (C3H8), and propyne (C3H4). Major products that have not yet been observed on Jupiter include acetonitrile (CH3CN), methylamine (CH3NH2), propene (C3H6), butane (C4H10), and butene (C4H8). Various other saturated and unsaturated hydrocarbons, as well as other amines and nitriles, are present in these experiments as minor products. We place upper limits of 10(6)-10(9) molecules cm-2 sec-1 on production rates of the major species from auroral chemistry in the Jovian stratosphere, and calculate stratospheric mole fraction contributions. This work shows that auroral processes may account for 10-100% of the total abundances of most observed organic species in the polar regions. Our experiments are consistent with models of Jovian polar stratospheric aerosol haze formation from polymerization of acetylene by secondary ultraviolet processing.  相似文献   

13.
Hydroxyl nightglow is intensively studied in the Earth atmosphere, due to its coupling to the ozone cycle. Recently, it was detected for the first time also in the Venus atmosphere, thanks to the VIRTIS-Venus Express observations. The main Δν=1, 2 emissions in the infrared spectral range, centred, respectively, at 2.81 and 1.46 μm (which correspond to the (1-0) and (2-0) transitions, respectively), were observed in limb geometry (Piccioni et al., 2008) with a mean emission rate of 880±90 and 100±40 kR (1R=106 photon cm−2 s−1 (4πster)−1), respectively, integrated along the line of sight. In this investigation, the Bates-Nicolet chemical reaction is reported to be the most probable mechanism for OH production on Venus, as in the case of Earth, but HO2 and O may still be not negligible as mechanism of production for OH, differently than Earth. The nightglow emission from OH provides a method to quantify O3, HO2, H and O, and to infer the mechanism of transport of the key species involved in the production. Very recently, an ozone layer was detected in the upper atmosphere of Venus by the SPICAV (Spectroscopy for Investigation of Characteristics of the Atmosphere of Venus) instrument onboard Venus Express (Montmessin et al., 2009); this discovery enhances the importance of ozone to the OH production in the upper atmosphere of Venus through the Bates-Nicolet mechanism. On Venus, OH airglow is observed only in the night side and no evidence has been found whether a similar emission exists also in the day side. On Mars it is expected to exist both on the day and night sides of the planet, because of the presence of ozone, though OH airglow has not yet been detected.In this paper, we review and compare the OH nightglow on Venus and Earth. The case of Mars is also briefly discussed for the sake of completeness. Similarities from a chemical and a dynamical point of view are listed, though visible OH emissions on Earth and IR OH emissions on Venus are compared.  相似文献   

14.
Post-perihelion observed emission fluxes at 388 nm (CN) and 516 nm (C2) of the coma of comets Austin (1982g) and Bradfield (1980t) are analysed in the framework of the Haser model. Ratios of Haser model CN and C2 parent production rates with expansion velocity show that each comet behaves normally. For comet Austin (1982g), the Q CN/v and Q c2/v values decrease with increase of heliocentric distance of comet. For an assumed %; activity of the total spherical surface area of the nucleus, the water vaporization theory coupled with derived water production rates from the International Ultraviolet Explorer H and OH flux data yields a nuclear diameter of about 6 km for comet Austin (1982g). For comet Bradfield (1980t), the derived nuclear diameter is expected to be of about 1 km. In each comet, the dust mass production rates as well as ratio of dust-to-gas mass production rates decrease with increase of heliocentric distance of comet.  相似文献   

15.
The rotational temperature of the airglow hydroxyl emissions arising from various schemes of vibrational transitions was obtained by using spectroscopic data from six observational sources. The rotational temperature was found to depend systematically on the quantum number (ν') of the upper vibrational level from which the relevant band originates. It has a doubly degrading characteristic with respect to ν' taking maximal values at ν' = 6 and 9, which exceed considerably the atmospheric temperature. It drops off quickly as ν' decreases from 9 to 7, and then from 6 to 3 after making an abrupt rise at ν' = 6. This ν'-dependence of the rotational temperature is in favor of the hypothesis that there are two routes of excitation of the hydroxyl airglow: O3 + H = OH(ν ? 9) + O2, and HO2 + O = OH(ν ? 6) + O2. The present result implies also that the relaxation time of rotation of OH in the upper mesosphere is as long as 0.1 sec; a value an order of magnitude larger than that inferred in earlier laboratory experiments.  相似文献   

16.
Methane and ammonia abundances in the coma of Halley are derived from Giotto IMS data using an Eulerian model of chemical and physical processes inside the contact surface to simulate Giotto HIS ion mass spectral data for mass-to-charge ratios (m/q) from 15 to 19. The ratio m/q = 19/18 as a function of distance from the nucleus is not reproduced by a model for a pure water coma. It is necessary to include the presence of NH3, and uniquely NH3, in coma gases in order to explain the data. A ratio of production rates Q(NH3)/Q(H2O) = 0.01-0.02 results in model values approximating the Giotto data. Methane is identified as the most probable source of the distinct peak at m/q = 15. The observations are fit best with Q(CH4)/Q(H2O) = 0.02. The chemical composition of the comet nucleus implied by these production rate ratios is unlike that of the outer planets. On the other hand, there are also significant differences from observations of gas phase interstellar material.  相似文献   

17.
T.Y. Kong  M.B. McElroy 《Icarus》1977,32(2):168-189
A variety of models are explored to study the photochemistry of CO2 in the Martian atmosphere with emphasis on reactions involving compounds of carbon, hydrogen, and oxygen. Acceptable models are constrained to account for measured concentrations of CO and O above 90 km, with an additional requirement that they should be in accord with observations of CO, O2, and O3 in the lower atmosphere. Dynamical mixing must be exceedingly rapid at altitudes above 90 km, with effective eddy diffusion coefficients in excess of 107 cm2 sec?1. If recombination of CO2 is to occur mainly by gas phase chemistry, catalyzed by trace quantities of H, OH, and HO2, mixing must be rapid over the altitude interval 30 to 40 km. The value implied for the diffusion coefficient in this region is a function of assumptions made regarding the rates for reaction of OH with HO2 to form H2O and of the rate for reaction of HO2 with itself to form H2O2. If rates for these reactions are taken to have values similar to rates used in current models for the Earth's stratosphere, the eddy diffusion coefficient at 40 km on Mars should be about 5 × 107 cm2 sec?1, consistent with Zurek's (1976) estimate for this parameter inferred from tidal theory. Surface chemistry could have an influence on the abundances of atmospheric CO and O2, but a major effect would imply sluggish mixing at all altitudes below 50 km and in addition would carry implications for the magnitude of the rates for reaction of OH with HO2 and HO2 with itself.  相似文献   

18.
We have studied the escape of neutral helium from the terrestrial atmosphere through exothermic charge exchange reactions between He+ ions and the major atmospheric constituents N2, O2, and O. Elastic collisions with the neutral background particles were treated quantitatively using a recently developed kinetic theory approach. An interhemispheric plasma transport model was employed to provide a global distribution of He+ ions as a function of altitude, latitude and local solar time and for different levels of solar ionization. Combining these ion densities with neutral densities from an MSIS model and best estimates for the reaction rate coefficients of the charge exchange reactions, we computed the global distribution of the neutral He escape flux. The escape rates show large diurnal and latitudinal variations, while the global average does not vary by more than a factor of three over a solar cycle. We find that this escape mechanism is potentially important for the overall balance of helium in the Earth's atmosphere. However, more accurate values for the reaction rate coefficients of the charge exchange reactions are required to make a definitive assessment of its importance.  相似文献   

19.
A model for the hydrogen coma of a comet on the basis of the Monte Carlo method is presented. In this model isotropic ejections of H atoms produced by photodissociation of H2O and OH, thermalization of the H atoms due to collisions with ambient H2O molecules, and the solar radiation pressure have been taken into account. A production spectrum of H atoms from OH is evaluated by using the predissociation rates and the level populations of OH, confirming that the spectrum has a sharp peak around 8.0 km sec?1 with the standard deviation of 0.1 km sec?1. Including the above effects, velocity distribution functions of the H atoms at various positions in the coma for the first time, as well as their density and outflow velocity profiles, have been calculated. It is pointed out that the collisional thermalization process in the inner coma is an important factor at small heliocentric distances in determining the density profiles and the velocity distributions. It is shown that thermalization leads to an increase in the H density in the inner coma larger than those expected from other models such as the vectorial model, in which collision is not taken into account. Lyman α isophotes and its line profiles in the optically thin region are computed by using the velocity distribution function.  相似文献   

20.
Observations of comet Hale-Bopp (C/1995 O1) have been carried out near perihelion (1997 March) at millimeter wavelengths using the NRAO 12 m telescope. The J=1-->0, 2-->1, and 3-->2 lines of HCN at 88, 177, and 265 GHz were measured in the comet as well as the J=3-->2 lines of H13CN, HC15N, and HNC. The N=2-->1 transition of CN near 226 GHz was also detected, and an upper limit was obtained for the J=2-->1 line of HCNH+. From the measurements, column densities and production rates have been estimated. A column density ratio of [HCN]/[HNC] = 7+/-1 was observed near perihelion, while it was found that [HCN]/[HCNH+] greater, similar 1. The production rates at perihelion for HCN and CN were estimated to be Q(HCN) approximately 1x1028 s-1 and Q(CN) approximately 2.6x1027 s-1, respectively, resulting in a ratio of [HCN]/[CN] approximately 3. Consequently, HCN is sufficiently abundant to be the parent molecule of CN in Hale-Bopp, and HCNH+ could be a source of HNC. Finally, carbon and nitrogen isotope ratios of 12C/13C = 109+/-22 and 14N/15N = 330+/-98 were obtained from HCN measurements, in agreement with previous values obtained from J=4-->3 data. Such ratios suggest that comet Hale-Bopp formed coevally with the solar system.  相似文献   

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