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1.
Measured rates are presented for the reaction of He+ ions with H2 (and D2) molecules to form H+, H2+, and HeH+ ions, as well as for the subsequent reactions of H+ and HeH+ ions with H2 to form H3+. The neutralization of H3+ (and H5+) ions by dissociative recombination with electrons is shown to be fast. The reaction He+ + H2 is slow (k = 1.1 × 10?13 cm3/sec at300°K) and produces principally H+ by the dissociative charge transfer branch. It is concluded that there may be a serious bottleneck in the conversion of two of the primary ions of the upper Jovian ionosphere, H+ and He+ (which recombine slowly), to the rapidly recombining H3+ ion (α[H3+]?3.4 × 10?7 cm3/sec at 150°K).  相似文献   

2.
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   

3.
Photoionization of the upper atmosphere of Titan by sunlight is expected to produce a substantial ionospheric layer. We have solved one-dimensional forms of the mass, momentum, and energy conservation equations for ions and electrons and have obtained electron number densities of about 103 cm?3, using various model atmospheres. The significant ions in a CH4H2 atmosphere are H+, H3+, CH5+, CH5+, CH3+, and C2H5+. Electron temperatures may be as high as 1000°K, depending on the abundance of hydrogen in the high atmosphere. Interaction of the solar wind with the ionosphere is also discussed.  相似文献   

4.
The problem of the ionospheric formation in the Jovian upper atmosphere is examined. By adopting two plausible atmospheric models, we solve coupled time-dependent continuity equations for ions H2+, H5+, H+, H3+ and HeH+ simultaneously. It is shown that both radiative and three body association of H+ to H2 are important for the determination of the structure of the Jovian ionosphere. The maximum electron density in the daytime is found to be about 105 cm?3. It is also shown that diurnal variation with large-amplitude can exist in the Jovian ionosphere.  相似文献   

5.
Laboratory measurements of reaction rate constants of magnesium ions and magnesium containing ions with O3, NO, HNO3, and H2O2 have been carried out in a flowing afterglow experiment. Mg+ ions react with O3 to produce MgO+ ions, which in turn react with O3 to produce Mg+ ions. Mg+ ions react with HNO3 and H2O2 to produce MgOH+ ions. MgOH+ ions react rapidly with HNO3 to produce NO+2 ions and Mg(HO)2. One can therefore conclude that Mg+, MgO+, or MgOH+ ions could not have significant concentrations in the stratosphere if gas phase magnesium compounds were present. The failure to observe these ions therefore cannot be used as evidence that the stratospheric magnesium, resulting from meteor ablation at higher altitudes, is in condensed phases. This is in contrast to the case for sodium where the ion chemistry is such that the failure to observe hydrated Na+ ions proves that gas phase sodium compounds are not present in the stratosphere.  相似文献   

6.
L.A. Capone  S.S. Prasad 《Icarus》1973,20(2):200-212
This paper reports results obtained on ionosphere formation in the Jovian upper atmosphere with special reference to some of the recently available reaction rates, and to recent models of the Jovian neutral atmosphere based on the possibility of a warmer mesopause. We find that the role of the hypothetical radiative association of H+ to H2 to form H3+, as brought to light in our earlier study, is still important, even with a reaction rate as low as 10?15 cm3sec?1. In the lower regions of the ionosphere three-body processes leading to the formation of H3+ and H5+ ions, which have very fast dissociative recombination rates, produce a dramatic reduction in the electron density. When no radiative association takes place, and the H+ ions are lost by radiative recombination alone, we confirm that the photochemical equilibrium profile is also the diffusive equilibrium profile. However, with collisional-radiative recombination, whose rate becomes altitude-dependent, diffusion tends to bring about some redistribution of the ionization. Inclusion of radiative association enhances the role of diffusion. In this case, diffusion brings about all the expected changes. In particular, the differences in the electron density profile, originated in the lower-middle ionosphere by radiative association, are propagated up to all higher altitudes by diffusion. The rate constant of radiative association is, however, unknown. It is hoped that the critical importance of this reaction for the Jovian ionosphere will be an incentive towards a careful laboratory determination of its rate coefficient. In the older models of the Jovian ionosphere the major ions were H+ which were lost only by pure radiative recombination. This led to high electron densities and practically no diurnal change. In contrast, our new models have relatively much smaller electron densities, especially in lower regions, and may be susceptible to significant diurnal variation.  相似文献   

7.
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   

8.
The evolution of the charged particles are followed during contraction of a model of an interstellar cloud, with initial density number of n = 10 cm–3. The contraction is followed up to density increase by five orders of magnitude. Special care is given to the details of the negative ions. In addition, we have tested the ambipolar diffusion according to the results of the ion density.The results predict the importance of atomic ions in the diffuse regions. H+ and C+ are distinctly enhanced in the beginning of contraction but decrease as contraction proceeds. Molecular ions enhance as contraction proceeds and becomes important in dense regions. The most enhanced molecular ions are HCO+, O2 +, C2H3 +, H3O+ and SO+, H3 + is less abundant. The atomic ions (except metalic ions) decrease noticeably as density increases. In general the negative ions are of negligible fractional abundances. It has also been found that the time of ambipolar diffusion is shorter than the dynamical time, hence the magnetic field should be weakened in the central core as the central density increases to n = 104 cm–3.  相似文献   

9.
The production rate of H2O molecules at a heliocentric distance of 1 AU for comet Halley and the abundance ratio with respect to water (H2O) of parent molecules at the cometary nucleus from the paper of Yamamoto (1987) have been used to compute the number densities of positive ions viz. H3O+, H3S+, H2CN+, H3CO+, CH3OH 2 + and NH 4 + at various cometocentric distances within 600 kms from the nucleus.The role of proton transfer reactions in producing major ionic species is discussed. A major finding of the present investigation is that NH 4 + ion which may be produced through proton transfer reactions is the most abundant ion near the nucleus of a comet unless the abundance of NH3 as a parent is abnormally low. Using the quoted value of Q(NH3)/Q(H2O) for comet Halley and the life times of NH3 and H2O molecules, the abundance ratio N(NH3)/N(H2O) is found to be one-third of that used in the present paper. The consequent proportionate decrease in the NH 4 + ions does not, however, affect its superiority in number density over other ions near the nucleus.The number density of the next most abundant ion viz. H3O+ is found to be 4 × 104 cm-3 at the nucleus of comet Halley and decreases by a factor of two only upto a distance of 600 K ms from the nucleus. The ionic mass peak recorded by VEGA and GIOTTO spacecrafts atm/q = 18 is most probably composite of the minor ionic species H2O+, as its number density = 102 cm-3 remains virtually constant in the inner coma and of NH 4 + , the number density of which at large cometocentric distances may add to the recorded peak atmlq = 18. The number densities of other major ions produced through proton transfer from H3O+ are also discussed in the region within 600 K ms from the nucleus of comet Halley.  相似文献   

10.
On 14 December 1971, during the maximum of the Geminid Meteor Shower, the positive ion composition was measured in the D- and E-regions above Sardinia. The payload was launched at 12:11 UT, and measurements were made between 68.5 and 152 km altitude. A magnetic sector type mass spectrometer with dual collector and a liquid helium cryopump was used. The instrument covered the mass range from 11 to 73 AMU and had a resolution at the 1 % level of MM = 60.In the E-region two distinct metal ion layers were observed, centred at 95 and 119 km, respectively. In the lower layer Fe+ and Mg+ were the most abundant metal ions, and in the upper layer Si+ was dominant. Si+ ions were conspicuously absent in the lower layer (Si+/Mg+ < 2 × 10−3). This particular behaviour of Si could be due to the inability of atomic oxygen to reduce SiO, whereas in the upper layer Si+ions might be formed directly by the charge rearrangement reaction SiO + O+ → Si++ O2. In addition, Na+, Al+, K+, Ca+, Ti+, Cr+, Ni+ and Co+ were also identified. The metal oxide ions AlO+ and SiO+ were detected, and probably also MgO+ and SiOH+. The concentrations of NO+ and O2+ show a deep minimum at the maximum of the lower metal ion layer. A very high neutral metal density of 6 × 107 cm−3 would be required to explain this feature as resulting from charge transfer reactions between the molecular and metal ions Such a high metal density is in contradiction to direct measurements and to cosmic dust influx rates. The isotopic ratios of Mg+, Si+, and of the major isotopes of Fe+ and Ni+ were measured, some of them with an accuracy of a few per cent (25Mg+/24Mg+ = 0.124 ± 0.006; 26Mg+/24Mg+ = 0.139 ± 0.008; 29Si+/28Si+ = 0.050 ± 0.004; 54Fe+/56Fe+ = 0.069 ± 0.005; 57Fe+/56Fe+ = 0.029 ± 0.004; 60Ni+/58Ni+ = 0.31 ± 0.12). The isotopic ratios agree within the experimental errors with the corresponding terrestrial ratios, thus giving evidence that these elements have the same isotopic composition in the Geminid meteors as in the Earth's crust, in chrondrites, and in lunar material.In the D-region the ions Na+H2O, Na+(H2O)2, NaO+ and NaOH+ were tentatively identified. Below 95 km altitude the relative abundances of the ions 32+, 33+ and 34+ deviate from the values expected for molecular oxygen isotopes. Their abundances can not be explained by the presence of S-ions only, and we conclude that HO2+ and H2O2+ are present.The ion density profiles of the major D-region constituents show some remarkable deviations from typical D-region conditions. These deviations are related to the winter anomaly in ionospheric absorption observed over Spain during the launch day, and our data represent the first ion composition measurements during such conditions. In particular, H+(H2O)2 is the major ion only up to 77 km, and at 80 km altitude the NO+ concentration exceeds the total water cluster ion density by almost two orders of magnitude. An increase of the mesospheric NO, O3 and O concentrations as well as of the O/H2O ratio could explain the observed ion profiles. The low NO+/O2+ ratios of approximately unity measured in the E-region are in agreement with a strong downward transport of NO and/or O into the mesosphere during the launch day. A simple four-ion model was used to interpret our D-region data. The calculated neutral NO concentration increases from about 2 × 107 cm−3 at 85 km to 5 × 107 cm−3 at 80 km. In addition, evidence for an increased O2+ production rate above 83 km was found, probably due to an enhanced O3 concentration. We conclude that our data strongly support vertical transport of minor neutral consituents as cause of the winter anomaly.  相似文献   

11.
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   

12.
The quadrupole mass spectrometer flown by the Air Force Geophysics Laboratory on STS-4 in 1982 detected large intensities of several ions, primarily O+, H2O+ and H3O+, with energies less than 1.5 e V with respect to the Shuttle Orbiter. Ion-molecule reactions and non-reactive scattering between the outgassing neutral flux from the Orbiter surfaces and the ambient ionic species are identified as the primary source of these low energy ions.  相似文献   

13.
Ionization of the atmosphere of Titan by galactic cosmic rays is a very significant process throughout the altitude range of 100 to 400 km. An approximate form of the Boltzmann equation for cosmic ray transport has been used to obtain local ionization rates. Models of both ion and neutral chemistry have been employed to compute electron and ion density profiles for three different values of the H2/CH4 abundance ratio. The peak electron density is of the order 103 cm?3. The most abundant positive ions are C2H9+ and C3H9+, while the predicted densities of the negative ions H? and CH3? are very small (<10?4 that of the positive ions). It is suggested that inclusion of the ion chemistry is important in the computation of the H and CH3 density profiles in the lower ionosphere.  相似文献   

14.
Loss processes which remove Si+ ions selectively relative to other meteor-derived atomic ions in the E- and D-regions of the ionosphere have been identified and measured in the laboratory. The major Si+ loss in the E-region is the reaction Si+ + H2O → HSiO+ + H (1) with a rate constant 2.3 ± 0.9 × 10?10 cm3s?1 at 300 K. The corresponding reactions with Fe+, Mg+ and other metallic meteor ions are endothermic. Presumably (1) is followed by a fast dissociative-recombination with electrons to produce neutral SiO or Si. At lower altitudes Si+ ions associate in a three-body reaction with O2 with a much larger rate constant than the corresponding associations of Fe+ and Mg+ with O2.  相似文献   

15.
Following the recent mass spectrometric observations of the ambient stratospheric positive and negative ions we have carried out co-ordinated laboratory experiments using a selected ion flow tube apparatus and a flowing afterglow apparatus for the following purposes: (i) to consider whether CH3CN is a viable candidate molecule for the species X in the observed stratospheric ion series H+ (H2On (X)m and (ii) to determine the binary mutual neutralization rate coefficients αi for the reactions ofH+ (H2O4 and H+(H2O)(CH3CN)3 with several of the negative ion species observed in the stratosphere. We conclude from (i) that CH3CN is indeed a viable candidate for X and from (ii) that the αi for stratospheric ions are within the limited range (5–6) × 10?8 cm3 s?1.  相似文献   

16.
We have constructed a chemical reaction model in a contracting interstellar cloud including 104 species which are involved in a network of 557 reactions. The chemical kinetic equations were integrated as a function of time by using gear package. The evolution of the system was followed in the density range 10–107 particles cm-3.The calculated fractional abundances of the charged species are in good agreement with those given by other investigators. The charge density has been followed in diffuse, intermediate and dense regions. The most dominant ionic species are metallic ions, HCO+ and H 3 + in the shielded regions and atomic ions H+, C+, Si+, He+, S+ and metal ions in the diffuse and intermediate regions. The abundances of negatively charged ions were found to be negligible. The results of the calculations on the different metallic ions are interpreted.  相似文献   

17.
We have investigated the role of several ion-molecule reactions in the conversion of N2O5 to HNO3. In the proposed conversion, an N2O5 molecule would react with an H2O molecule clustered to an inert ion to produce two HNO3 molecules. Subsequent clustering of an H2O molecule to the inert ion would make the reaction catalytic. If such an ion-catalysed conversion of N2O5 to HNO3 occurs, it would probably play a role in the stratospheric chemistry at high latitudes in winter. In this paper we present reaction rate constant measurements made in a flowing afterglow apparatus for hydrated H3O+, H+(CH3CN)m (m = 1, 2, 3), and several negative ions reacting with N2O5. Slow rate constants were found for these ions for hydration levels that are predominant in the stratosphere. With the known stratospheric ion density, these slow rate constants preclude significant N2O5 conversion by ion-molecule reactions.  相似文献   

18.
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   

19.
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   

20.
We present infrared absorption studies on the effects of 50-100 keV Ar+ and 100 keV H+ ion irradiation of water ice films at 20-120 K. The results support the view that energetic ions can produce hydrogen peroxide on the surface of icy satellites and rings in the outer Solar System, and on ice mantles on interstellar grains. The ion energies are characteristic of magnetospheric ions at Jupiter, and therefore the results support the idea that radiolysis by ion impact is the source of the H2O2 detected on Europa by the Galileo infrared spectrometer. We found that Ar+ ions, used to mimic S+ impacts, are roughly as efficient as H+ ions in producing H2O2, and that 100 keV H+ ions can produce hydrogen peroxide at 120 K. The synthesized hydrogen peroxide remained stable while warming the ice film after irradiation; the column density of the formed H2O2 is constant until the ice film begins to desorb, but the concentration of H2O2 increases with time during desorption because the water sublimes at a faster rate. Comparing the shape of the 3.5-μm absorption feature of H2O2 to the one measured on Europa shows excellent agreement in both shape and position, further indicating that the H2O2 detected on Europa is likely caused by radiolysis of water ice.  相似文献   

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