Sources of HCl and HF in the atmosphere of Venus.
Correlations between physical conditions and chemistry of Venus atmosphere - sources of HCl and HF in atmosphere
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Correlations between physical conditions and chemistry of Venus atmosphere - sources of HCl and HF in atmosphere
UV absorption cross sections of CO, HCl and ICN, analyzing reactions causing various spectral features
IR absorption properties of CO, HCl and sulfur dioxide measured for role in Venus greenhouse effect
Fugacities of hCl and HF compared with abundance in volcanic fumarolic emanations, indicating magma undersaturation
CW chemical lasers operation from partially inverted transitions of HCl, HF and DF molecules in subsonic flow
Aqueous HCl solutions refractive index calculation from concentration dependence for Venus clouds composition
The exhaust products of a solid rocket motor using as propellant 14% binder, 16% aluminum, and 70% (wt) ammonium perchlorate consist of hydrogen chloride, water, alumina, and other compounds. The equilibrium and some frozen compositions of the chemical species upon interaction with the atmosphere were computed. The conditions under which hydrogen chloride interacts with the water vapor in humid air to form an aerosol containing hydrochloric acid were computed for various weight ratios of air/exhaust products. These computations were also performed for the case of a combined SRM and hydrogen-oxygen rocket engine. Regimes of temperature and relative humidity where this aerosol is expected were identified. Within these regimes, the concentration of HCL in the aerosol and weight fraction of aerosol to gas phase were plotted. Hydrochloric acid aerosol formation was found to be particularly likely in cool humid weather.
To test the accuracy of the Gordon-Kim theory of intermolecular forces, predicted and experimental values are compared for Ar-HCl. The method appears to accurately predict the short-range repulsive forces and also the position (but possibly not the depth) of the potential well.
Measurements results are presented for the rate constant of the reaction OH + HCl yields H2O + Cl determined in a flow tube over the temperature range of 224 to 460 K using resonance fluorescence detection of OH. Stratospheric and reaction kinetic implications are briefly discussed.
Steady stream of air is drawn into system and passes between light source and photocell. Incoming gases are sprayed with ammonia forming white cloud of NH4Cl if any HCl is present.
Accurate close coupling scattering calculations are presented for thermal energy HCl-He collisions. The interaction potential is obtained from the Gordon-Kim electron gas model, adjusted to have the correct long-range multipole form. A variety of phenomenological cross sections are computed from the close coupling S matrix, and these are compared with results from several commonly employed approximate methods. In particular, it is found that the total integral, total differential, and gas kinetic cross sections are accurately predicted by the central field approximation which retains just the spherical average of the interaction. Integral inelastic cross sections are represented quite accurately by the coupled states approximation of McGuire and Kouri, but only qualitatively by the effective potential method of Rabitz.
A laser fluorescence technique is used for the direct observation of the vibrational relaxation of H2 in the presence of D2 and HCl. The technique used is much simpler than the Raman absorption laser-schlieren method and has the advantage that the direct observation of changes in the vibrational energy of H2 permits the study of V-V relaxation processes in mixtures of H2 with other gases. The rapid V-V transfer between HF and H2 is used to permit the selective vibrational excitation of H2 by trace amounts of HF excited by laser absorption. The subsequent relaxation of vibrational energy from the coupled HF and H2 molecules is monitored by the laser induced fluorescence of HF.
In order to compute relaxation 'cross sections' for molecule-molecule collisions, it is convenient to employ a coupled angular-momentum representation which differs from that generally used. An explicit expression for collision-induced spectral pressure broadening in this representation is given, and this is used to examine the difference between para- and ortho-H2 for broadening of HCl.
The flash photolysis resonance fluorescence technique was employed to investigate the rate constant for the reaction Cl + CH2O yields HCl + CHO from 223 to 323 K. An Arrhenius fit of the data gives a rate constant equal to (1.09 + or - 0.40) x 10 to the -10th exp/-(131 + or - 98)/T/ in units of cu cm/molecule per sec. The results are compared to two very recent kinetic studies and are assessed in view of the reaction's role in disrupting the Cl-ClO stratospheric ozone depletion chain.
The technique of laser flash photolysis-resonance fluorescence is employed to study the kinetics of the reaction Cl(2P) + CH4 yields CH3 + HCl over the temperature range 221-375 K. At temperatures less than or equal to 241 K the apparent bimolecular rate constant is found to be dependent upon the identity of the chemically inert gases in the reaction mixture. For Cl2/CH4/He reaction mixtures (total pressure = 50 torr) different bimolecular rate constants are measured at low and high methane concentrations. For Cl2/CH4/CCl/He and Cl2/CH4/Ar reaction mixtures, the bimolecular rate constant is independent of methane concentration, being approximately equal to the rate constant measured at low methane concentrations for Cl2/CH4/He mixtures. These rate constants are in good agreement with previous results obtained using the discharge flow-resonance fluorescence and competitive chlorination techniques. At 298 K the measured bimolecular rate constant is independent of the identity of the chemically inert gases in the reaction mixture and in good agreement with all previous investigations. The low-temperature results obtained in this investigation and all previous investigations can be rationalized in terms of a model which assumes that the Cl(2P 1/2) state reacts with CH4 much faster than the Cl(2P 3/2) state. Extrapolation of this model to higher temperatures, however, is not straightforward.
Balloon measurements of the stratospheric HF/HCl ratio are reported. Seven far-infrared rotational lines of HF and HCl were observed at elevation angles of 25, 18 and 8 deg by a far-infrared Fourier-transform spectrometer on board a balloon platform at 28.5 km. Analysis of line intensities yields an average HF/HCl ratio of 0.18 + or - 0.02 at an effective altitude of 33 km, with a water vapor mixing ratio of about 4 ppmv. Results are noted to be in reasonable agreement with the calculated profile of Sze and Ko (1981) with 4.5 ppmv H2O.
A physical-chemical model is developed and used to investigate gaseous absorption by water droplets from trace gas mixtures. The model is an extension of that of Carmichael and Peters (1979) and includes the simultaneous absorption of SO2, NH3, HNO3, CO2, and HCl. Gas phase depletion is also considered. Presented results demonstrate that the absorption behavior of raindrops is strongly dependent on drop size, fall distance, trace gas concentrations, and the chemical and physical properties of the constituents of the mixture. In addition, when gas phase depletion is considered, the absorption rates and equilibrium values are also dependent on the precipitation rate itself. Also, the trace constituents liquid phase concentrations may be a factor of six or more lower when gas depletion is considered then when the depletion is ignored. However, the hydrogen ion concentration may be insensitive to the gas phase depletion.
Soil samples were fractionated and analyzed in order to assess the physical and chemical interactions of entrained soil with solid-rocket exhaust clouds. The sandy soil consisted primarily of quartz (silica) particles, 30 to 500 microns in diameter, and also contained seashell fragments. Differential and cumulative soil-mass size distributions are presented along with mineralogy, elemental compositions, and solution pH histories. About 90 percent of the soil mass consisted of particles 165 microns in diameter. Characteristic reaction times in aqueous HC1 slurries varied from a few minutes to several days, and capacities for reaction under acidic conditions varied from 10 to 40 g HCl/kg soil, depending on particle size. Airborne lifetimes of particles 165 microns are conservatively 30 min, and this major grouping is predicted to represent a small short-term chemical sink for up to 5% of the total HC1. The smaller and more minor fractions, below a 165 micron diameter, may act as giant cloud condensation nuclei over much longer airborne lifetimes. Finally, the demonstrated time dependency of neutralization is a complicating factor; it can influence the ability to deduce in-cloud HCl scavenging with reaction and can affect the accuracy of measured chemical compositions of near-field wet deposition.