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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.
HNO3 crystallizes in the monoclinic P2_1 space group. The structure is zero-dimensional and consists of sixteen nitric acid molecules. N5+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of N–O bond distances ranging from 1.22–1.38 Å. H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.01 Å. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a water-like geometry to one N5+ and one H1+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to one N5+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one N5+ atom.
High resolution spectra in the region of the 2-nu9 band of nitric acid have been obtained for selected portions of the HNO3 spectrum using tunable diode laser techniques. Continuous spectra are presented from 891.25/cm to 898.77/cm, with a spectral resolution less than or equal to 0.001/cm (30 MHz). Absolute line intensities and line positions are presented. Absolute wavelength calibration was obtained by frequency mixing the diode laser with a C(13)O2(16) isotope laser. Self and foreign gas (N2) broadening coefficients were iteratively calculated from the experimental data and were determined.
An inversion algorithm has been developed to simultaneously infer the concentrations of two gases with overlapping spectral signatures using limb emission measurements. The algorithm provides a solution in two or three iterations and has been tested in a simulation study for the inference of stratospheric NO2-H2O and HNO3-CF2Cl2. Existing satellite instrumentation was the basis for errors used in the calculations. These included noise, scale and bias errors, angular registration errors, spacecraft motion effects, and effects due to a finite instrument field of view. It is estimated that concentrations of all four gases can be measured globally from a satellite with errors of less than 20%.
High resolution spectra in the region of the v(2) band of nitric acid have been obtained for selected portions of the HNO3 spectrum using tunable diode laser techniques. Continuous spectra are presented from 1718.97/cm to 1729.57/cm, with a spectral resolution not greater than 0.001/cm (30 MHz). Absolute line intensities and line positions are presented. Self- and foreign-gas (N2) broadening coefficients were iteratively calculated from the experimental data and were determined to be alpha(a) = 0.74/cm atm and alpha (f) = 0.13/cm atm, respectively.
Laboratory spectra have been obtained for HNO3 with a Michelson-type Fourier transform interferometer using absorption cells with path lengths of 10.3, 25.5, and 49.8 cm at temperatures of 240, 248, 283, and 294 K. The measurements lead to a total band intensity value of 642 plus or minus 5% per sq cm amagat, which is a temperature independent value after the gas density correction has been made. However, the temperature dependence of the spectral absorption coefficients is apparent in the 885 kayser region.
The Limb Infrared Monitor of the Stratosphere (LIMS) experiment, launched on-board the Nimbus satellite, was designed to measure both day and night limb radiance which is used to infer upper atmosphere temperature profiles and chemical compound concentrations important in the study of ozone chemistry. The LIMS instrument is a six channel, limb scanning, thermal radiometer which uses HgCdTe detectors, cooled to approximately 64 K. Measurements include ozone, water vapor, nitrogen dioxide, and nitric acid. The ozone and nitric acid channels are centered at approximately 9.6 microns and 11.3 microns, respectively. Results from the channels are described with an emphasis on data validation. The O3 and HNO3 channels have demonstrated high measurement precision.
A program for the measurement of latitudinal, seasonal, and diurnal variations in stratospheric N2O, NO, NO2 and HNO3 is described, which uses airborne Fourier transform absorption spectroscopy to simultaneously determine columns, above 12 km, of the four molecules. The data may prove useful for comparison with two-dimensional models of stratospheric chemistry, since simultaneous measurement of several species with the same technique provides an inherently more reliable set for model comparisons, by eliminating uncorrelated atmospheric variability and reducing differences in instrumental biases.
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.
The technique of Stark modulation spectroscopy for unraveling and assigning rotationally resolved dense molecular spectra has been employed using a tunable diode laser (TDL) source. Doppler-limited absorption and Stark modulation spectra of the HNO3 7.5-micron band near the 1326/cm band origin are presented with preliminary values of the excited-state rovibrational constants derived from both TDL and Bomem Fourier transform IR spectra.
Absolute line strengths of selected lines in the nu 2 band of HNO3 have been measured using a tunable diode laser spectrometer operating in a sweep integration mode. The direct measurement technique has been employed to obtain line intensities at 296 K for 22 isolated lines in the 1720-1725/cm region. The reported line strengths have estimated uncertainties of 4 percent, a significant portion of this uncertainty arising from spectral interference from hot band transitions. From these line-strength measurements, an integrated band intensity of 1375/sq cm per atm at 296 K is inferred.
Preliminary results are reported of the direct measurement of accommodation coefficients for HNO3, N2O5 and HCl on water drops, aqueous sulfuric acid drops and ice particles. The heterogeneous chemistry of these species together with ClONO2 has been implicated in the ozone depletion observed in the Antarctic stratosphere during the spring in the last eight years. The most plausible chemical mechanism involves the removal of nitrogen oxide species via condensation on ice particles in polar stratospheric clouds resulting in a increase in the active chlorine species responsible for the ozone depletion. The observation of low NO2 and high ClO densities in the Antarctic stratosphere last summer appear to be consistent with such a mechanism.
A liquid-nitrogen cooled Fourier transform spectrometer (SIRIS) measures thermal limb-emission of the stratosphere from a balloon platform at a nominal altitude of 40 km, under night and day conditions, with a 3 km vertical resolution. N2O5 and HNO3 mixing ratios inferred from emission spectra are compared with previous measurements and with the predictions from a one-dimensional photochemical model.
Infrared solar spectra were obtained from the ground at McMurdo, Antarctica, during September and October 1987. Absorption features due to HNO3 and HCl have been analyzed to determine the vertical column content of these compounds for the days when observations were made. The variation of these column amounts with time is presented and discussed.
Ice particles created in polar stratospheric cooling events are predicted to descend into Type I PSCs and accrete a coating of nitric acid trihydrate (NAT) that inhibits evaporation. Coated particles efficiently strip HNO3 from the atmosphere, providing a mechanism for denitrification without significant dehydration. Coatings that disintegrate may release large particles of NAT that influence subsequent particle growth.
Measurements were performed for both O2 and N2 broadening in the 100-380 K temperature range by using a heated equilibrium cell for elevated temperatures and the utilization of a collisionally cooled cell at the lower temperatures where HNO3 has a small vapor pressure. Observed pressure-broadening data can be fit to the normal empirical law, giving n values between 0.62 and 0.84.
The effects of heterogeneous processing by a parameterized lower stratospheric sulfate aerosol layer on model calculations were examined using a 2D photochemical model. Model results were compared with zonally averaged LIMS data on HNO3 and NO2 and in situ measurements of NO, NO(y), and ClO, taken by the ER-2 aircraft. The results obtained are contradictory: some comparisons favor heterogeneous chemistry, and some do not. It is suggested that the assumptions made to parameterize the sulfate aerosol chemistry result in a rate of heterogeneous processing that is too vigorous.
In May of 1991 a tunable diode laser heterodyne spectrometer built by the National Physical Laboratory was operated at the International Scientific Station of the Jungfraujoch (46.5 deg N, 8.0 deg E, altitude 3.56 km). Nitric acid spectra in the region of 868 wavenumbers were recorded at sunset and sunrise on two separate days at a resolution of 0.0013 wavenumbers with a signal-to-noise ratio of approximately 130:1. A vertical column amount of HNO3 of 1.61 x 10(exp 16) molecules/sq cm was determined using an atmospheric transmission model developed at the University of Denver. The mean of a number of mid-latitude, northern hemisphere profiles was used as the initial profile for the inversion. A comparison of different initial profiles provides information on the sensitivity of the retrieved column amount of 1.61 x 10(exp 16) molecules/sq cm lies within the range of values published in the World Meteorological Organization Report no. 16 (1986), but is considerably larger than the value of (0.99 - 1.29) x 10(exp 16) reported by Rinsland et al. (1991) for June during the period 1986 to 1990.