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Recent ground-based infrared solar spectra at 0.02 per cm resolution in the 3000 per cm region have been analyzed for the atmospheric content of HCl. Nonlinear spectral least-squares fitting applied to spectra obtained at several zenith angles shows little sensitivity of the results to tropospheric HCl but provides an accurate measurement of the total column amount.
In a study concerning Antarctic ozone depletion, reactions of dinitrogen pentoxide with water and hydrochloric acid were studied on ice surfaces in a Knudsen cell flow reactor. The N2O5 reacted on ice at 185 K to form condensed-phase nitric acid (HNO3). This reaction may provide a sink for odd nitrogen, NO(x), during the polar winter, a requirement in nearly all models of Antarctic ozone depletion. The reaction of N2O5 on HCl-ice surfaces at 185 K produced gaseous nitryl chloride (ClNO2) and condensed-phase HNO3 and proceeded until all of the HCl within the ice was depleted. The ClNO2 which did not react or condense on ice at 185 K, can be readily photolyzed in the Antarctic spring to form atomic chlorine for catalytic ozone destruction cycles. The other photolysis product, gaseous nitrogen dioxide may be important in the partitioning of NO(x) between gaseous and condensed phases in the Antarctic winter.
In situ stratospheric measurements of the concentrations of the reservoir species HNO3 and HCl made during two flights of the high-resolution (0.0005/cm) balloon-borne laser in situ sensor instrument from Palestine, Texas, are reported. A measured HNO3 volume mixing ratio of 4.3 parts per billion by volume (ppbv) at 31 km altitude is about 1 ppbv larger than previously reported measurements at 32 deg N. An HCl mixing ratio of 1.6 ppbv at 29 km is in agreement with values obtained from earlier remote sensing techniques within the experimental uncertainties. Upper limits at 31 km of 0.4 ppbv for H2O2 and 0.2 ppbv for HOCl are also derived from analyses of spectra recorded near 1252/cm.
The balloon-borne instruments used in the two Balloon Intercomparison Campaigns in 1982 and 1983 to measure stratospheric HCl included five different IR spectrometers, three of which operated in the solar absorption mode and two in emission mode (at distinctly different wavelengths). This paper describes the instruments and the data reduction and analysis procedures used in each case, together with the sources and estimated magnitudes of associated errors. Comparisons are made between different techniques (absorption vs emission) used on the same gondola, as well as between the same technique used on different gondolas. The final results yield a mean profile of HCl concentration between 18 and 40 km altitude. The absolute accuracy of the final profile is estimated to be no worse than 10 percent.
Results are presented on a reanalysis and reinterpretation of solar IR absorption spectra obtained during April-May 1985 observations by the Atmospheric Trace Molecule Spectroscopy instrument aboard Spacelab 3. Results yield updated volume mixing ratio profiles of ClONO2, HCl, and HF. It is shown that the updated HCl and HF results reflect changes below 30 km due to the use of smaller pressure-broadened half-widths, and that the changes in updated ClONO2 profiles are a consequence of adopting improved sets of line parameters. The new ClONO2 have an accuracy of + or - 20 percent.
The vertical profiles of ClO, HCl, HO2, and O3 were determined from thermal emission measurements by a balloon-borne spectrometer operating near 640 GHz. Results are in broad agreement with previous measurements and models, but differ significantly with model photochemistry for the ratio of ClO to HCl.
The relationship between the chemical composition and the interlayer spacing (d002) of organic materials (OM's) is known for various terrestrial OM's. We improved this general trend by correlation with corresponding trend of natural solid bitumens (asphaltite-kerite-anthraxolite) up to graphite. Using the improved trend we identified bitumen analogs of carbonaceous chondrite OM's residued after HF-HCl treatment. Our laboratory experiment revealed that these analogs and, hence, structure and chemical composition of carbonaceous chondrite OM's are very sensitive to the HF-HCl treatment. So, usual extraction of OM from carbonaceous chondrites may change significantly structural and chemical composition of extracted OM.
The solubility of HCl in sulfuric acid was measured using a Knudsen cell technique. Effective Henry's law constants are reported for sulfuric acid concentrations between 50 and 60 weight percent and for temperatures between 220 and 230 K. The measured values indicate that very little HCl will be dissolved in the stratospheric sulfate aerosol particles.
The reaction of HOCl + HCl -> Cl2 + H20 in the presence of Cl has been studied using ab initio methods. This reaction has been shown to have a high activation barrier of 46.5 kcal/mol. The chlorine anion, Cl- is found to catalyze the reaction, viz. two mechanisms. The first involves Cl- interacting through the concerted four-center transition state of the neutral reaction. The other mechanism involves the formation of a HCl-HOCl-Cl- intermediate which dissociates into Cl2 + Cl- + H20. The steps are found to have no barriers. The overall exothermicity is 15.5 kcal/mol.
The heterogeneous reactions of HNO3(g) + NaCl(s) Yields HCL(g) + NaNO3(s) and N2O5(g) + NaCl(s) Yields ClNo2(g) + NaNO3(s)were investigated over a temperature range of 223-296 K in a flow-tube reactor coupled to a quadrupole mass spectrometer. The implications for volcanic enhancement of the HCl and HNO3 column density in the lower stratosphere are discussed.
Concentration dependent Q and D type transitions of HCl in Ar, Kr and Xe solids, noting sites of dimers
Venus atmosphere HCl and HF abundances from Venera 4 data, discussing sources and atmospheric models
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