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At least 37 records · Page 2

Stratospheric limb radiance simulations for the HCl channel of CLAES

The earthlimb radiance of the HCl detector array of the CLAES instrument is simulated in order to specify and optimize the free spectral range for the etalon used in this spectral region and to select sampling positions which facilitate the recovery of HCl profiles. Considerations entering into the limb radiance computation of each contributing species are discussed. Simulations are then presented for tangent heights of 15 to 5 km for daytime and nighttime conditions, and their significance for HCl retrievals is addressed. The simulation results indicate that the HCl (P2) feature should be observable in the earth limb emission spectrum, and that an etalon with an FSR of 12.6/cm optimally avoids interference from OH emission lines blended with the HCl feature by adjacent transmission peaks.

Mergenthaler, J. L.↗

More rapid polar ozone depletion through the reaction of HOCl with HCl on polar stratospheric clouds

The direct reaction of HOCl with HCl is shown here to play a critical part in polar ozone loss. Observations of high levels of OClO and ClO in the springtime Antarctic stratosphere confirm that most of the available chlorine is in the form of ClO(x). But current photochemical models have difficulty converting HCl to ClO(x) rapidly enough in early spring to account fully for the observations. Here, a chemical model is used to show that the direct reaction of HOCl with HCl provides the missing mechanism. As alternative sources of nitrogen-containing oxidants have been converted in the late autumn to inactive HNO3 by known reactions on the sulfate layer aerosols, the reaction of HOCl with HCl on polar stratospheric clouds becomes the most important pathway for releasing that stratospheric chlorine which goes into polar night as HCl.

Prather, Michael J.↗

Measurements and model calculations of HCl column amounts and related parameters over McMurdo during the austral spring in 1989

Solar spectra obtained from a ground-based Fourier transform infrared instrument at McMurdo (Antarctica) in the spring of 1989 have been analyzed to determine total HCl column amounts. A one-dimensional photochemical model was used to simulate the rate of recovery of HCl in the springtime. Low column amounts (about 1 x 10 exp 15 molecules/sq cm) were observed in early September and may be attributed to the heterogeneous conversion of HCl to active chlorine species during the polar night. The rate of recovery of HCl is consistent with its production by chlorine atoms reacting with methane and is dependent on concentrations of active chlorine species and NO molecules in the altitude region from 12 to 22 km. High HCl column amounts (about 7 x 10 exp 15 molecules/sq cm) were observed following recovery in late October, suggesting that the lower stratosphere in the polar region had descended relative to mid-latitudes and that the degree of dechlorination of the transported air was very small.

Liu, X.↗

Measurement of HCl absorption coefficients with a DF laser

Absorption coefficients in the fundamental P-branch of HCl at several DF laser transitions from 2439.02/cm to 2862.87/cm have been measured experimentally. The 2-1 P(3) DF laser transition has been shown to overlap the P(6) HCl-37 absorption line within the halfwidth of an atmospherically broadened line. The absorption coefficient k was measured to be 5.64 plus or minus 0.28/(atm-cm) for a 0.27% mixture of HCl in N2 at a total pressure of 760 torr. A theoretical and experimental comparison of the pressure dependence of k showed that the 2-1 P(3) DF transition lies 1.32 plus or minus 0.15 GHz from the center of the P(6) HCl absorption line. Applications of these results to differential absorption lidar and to heterodyne detection are discussed.

Bair, C. H.↗

Radiometric measurement of stratospheric HCl

On March 17, 1976, the atmospheric absorption of solar infrared radiation at sunset was measured by a balloon-borne pressure modulator, whose major feature was a cell containing gaseous HCl, through which the incoming radiation passed. The side-band:wide-band ratio which is related to the amount of atmospheric HCl in the path between the instrument and the sun, was also measured. The vertical mixing ratio profile for gaseous HCl for the altitude range 16-39 km, was derived from the data by using a computer model. The shape of the profile implies that the major source of HCl in the stratosphere is around 32 km. The importance of this profile in determining the effects of man-made chlorine compounds on atmospheric ozone is stressed.

Eyre, J. R.↗

Spectroscopic requirements for HALOE: An analysis of the HCl and HF channels

Spectral line parameters that have absorption features within the HCl and HF channels of the Halogen Occultation Experiment (HALOE) were evaluated. Line positions and identification of stratospheric and solar absorption features in both channels are presented based on an analysis of high-resolution, balloon-borne solar occultation spectra. For the relevant HCl and HF lines and for transitions of the interfering species, the accuracy of the following spectral parameters was assessed: line positions, line strengths, lower state energies, air-broadened collisional half-widths, and temperature dependence of the air-broadened half-widths. In addition, since the HALOE instrument and calibration cells are filled with mixtures of HCl in N2 and HF in N2, the self-broadened and N2-broadened HF and HCl half-widths were also considered.

Rinsland, C. P.↗

Reactions of chlorine nitrate with HCl and H2O

The kinetics of the reactions of chlorine nitrate with HCl and H2O are characterized using a static photolysis/Fourier transform infrared spectrophotometer apparatus. For the homogeneous gas-phase reaction with HCl, an upper limit for the rate constant of less than 8.4 x 10 to the -21st, and for the reaction with H2O, a limit of less than 3.4 x 10 to the -21st cu cm/molecule per s, were obtained at 296 + or - 2 K. The yield of HNO3 is almost unity in both cases, and no synergistic effect is noted between HCl and H2O. The kinetic behavior of the reaction with H2O is well described by simple first-order kinetics, while the behavior of the reaction with HCl is described in terms of the Langmuir adsorption isotherm.

Hatakeyama, Shiro↗

Stratospheric Chlorine partitioning: Constraints from Shuttle-borne Measurements of [HCl], [ClNO3] and [ClO]

Measured stratospheric mixing ratios of HCl, ClNO3, and ClO from ATMOS and MAS are poorly reproduced by models using recommended kinetic parameters. This discrepancy is not resolved by new rates for the reactions Cl+CH4 and OH+HCl derived from weighted fits to laboratory measurements. A deficit in modeled [HCl] and corresponding overprediction of [ClNO3] and [ClO], which increases with altitude, suggests that production of HCl between 20 and 50 km is much faster than predicted from recommended rates.

Michelsen, H. A.↗

Using Satellite Measurements of N2O to Remove Dynamical Variability from HCl Measurements

Column HCl measurements show deviations from the expected slow decline following the regulation of chlorine-containing compounds by the Montreal Protocol. We use the simultaneous measurements of N2O and HCl by the Microwave Limb Sounder (MLS) instrument on the Aura satellite to examine this problem. We find that the use of N2O measurements at a specific altitude to represent the impact of dynamical variability on HCl results in a derived linear trend in HCl that is negative (ranging from -2.5 to 5.3%decade-1) at all altitudes between 68 and 10 hPa. These trends are at or near 2 sigma statistical significance at all pressure levels between 68 and 10 hPa. This shows that analysis of simultaneous measurements of several constituents is a useful approach to identify small trends from data records that are strongly influenced by dynamical interannual variability.

Stolarski, Richard↗

Interaction of NaCl(g) and HCl(g) with condensed NA2SO4

The interaction of Na2SO4(l) with NaCl(g), HCl(g) and H2O(g) was studied in atmospheric pressure flowing air and oxygen at Na2SO4(l) temperatures of 900 and 1000 C. Thermomicrogravimetric and high pressure mass spectrometric sampling techniques were used. Experimental results establish that previously reported enhanced rates of weight loss of Na2SO4(l) in the presence of NaCl(g) are due to the reaction: Na2SO4(c) + 2HCl(g) = 2NaCl(g) + SO2(g) + H2O(g) + 1/2O2(g) being driven to the right in flowing gas systems. The HCl(g) is the product of hydrolysis of NaCl caused by small but significant amounts of H2O(g) present in the system. Thermochemical calculations are used to show that even with sub-ppm levels of H2O(g) present, significant quantities of HCl(g) are produced.

Stearns, C. A.↗

Far infrared measurement of stratospheric HCl

Thermal emission from three rotational lines of H(Cl-35) and H(Cl-37) was observed with a Fourier transform spectrometer from a balloon platform at 28.9 km. The measured HCl line-of-sight density at 1.9 deg elevation above 28.9 km is 4.7 + or - 1.3 x 10 to the 15th/sq cm, implying an average volume mixing ratio of 0.8 + or - 0.2 x 10 to the -9th at the mean sampling altitude of 32.5 km. For a uniform mixing ratio model, this corresponds to a vertical column density of 2.4 + or - 0.6 x 10 to the 14th/sq cm. This result is in reasonable agreement with near infrared spectroscopic determinations and an abundance from a chemical sampling technique of HCl at this altitude; a pressure modulator radiometer measurement yields a significantly higher amount of HCl.

Chance, K. V.↗

Recent observations of HF and HCl in the upper stratosphere

Concentrations of gas phase hydrofluoric acid and hydrochloric acid have been determined in the upper stratosphere from near-infrared solar spectra recorded in the course of balloon flights from Palestine, Texas, in October 1978 and in September 1979. The average mixing ratios for HF deduced respectively from these flights are (4.8 plus or minus .3) x 10 to the -10th ppv above 30.3km and (6.2 plus or minus .5) x 10 to the -10th ppv above 36.8km. This observed difference is ascribed to an increase in the HF concentration out to at least 37km. The HCl mixing ratios deduced from the 1978 flight yield (4.5 plus or minus .6) x 10 to the -10th ppv at 21.7km, (7.5 plus or minus .7) x 10 to the -10th ppv at 27.5 km and (2.1 plus or minus .4) x 10 to the -9th ppv above 30.5km. Observations in 1979 imply an average HCl mixing ratio above 36.8km of (2.4 plus or minus .4) x 10 to the -9th ppv. Our data do not indicate a measurable temporal trend of the HCl concentration above 30km.

Zander, R.↗

HCl in rocket exhaust clouds - Atmospheric dispersion, acid aerosol characteristics, and acid rain deposition

Both measurements and model calculations of the temporal dispersion of peak HCl (g + aq) concentration in Titan III exhaust clouds are found to be well characterized by one-term power-law decay expressions. The respective coefficients and decay exponents, however, are found to vary widely with meteorology. The HCl (g), HCl (g + aq), dewpoint, and temperature-pressure-altitude data for Titan III exhaust clouds are consistent with accurately calculated HCl/H2O vapor-liquid compositions for a model quasi-equilibrated flat surface aqueous aerosol. Some cloud evolution characteristics are also defined. Rapid and extensive condensation of aqueous acid clearly occurs during the first three min of cloud rise. Condensation is found to be intensified by the initial entrainment of relatively moist ambient air from lower levels, that is, from levels below eventual cloud stabilization. It is pointed out that if subsequent dilution air at stabilization altitude is significantly drier, a state of maximum condensation soon occurs, followed by an aerosol evaporation phase.

Pellett, G. L.↗

Chlorine in dense interstellar clouds - The abundance of HCl in OMC-1

The first detection of a chlorine-bearing molecular species in the interstellar medium via emission from the J = 1-0 transition of HCl at 625.9 GHz toward OMC-1 is reported. The relative strengths, widths, and velocities of the resolved hyperfine components are consistent with moderate optical depth emission originating from dense, quiescent molecular cloud material. The overall emission strength implies a fractional abundance of f(HCl/H2) of about (0.5-5.0) x 10 to the -8th, depending on the density of the emitting region. This is approximately an order of magnitude below previous theoretical estimates and a factor of 3-30 below the cosmic abundance of Cl. Recent laboratory work suggests that the lowered fractional abundance of HCl is caused by a combination of depletion onto grains with gas-phase loss processes such as the reaction of HCl with C(+).

Blake, G. A.↗

Heterogeneous reactions of N2O5 with H2O and HCl on ice surfaces - Implications for Antarctic ozone depletion

This paper reports on the measurements of reaction probabilities for heterogeneous reaction of N2O5 with H2O and HCl on ice surfaces at 195 K, using a fast-flow reactor coupled with a quadrupole mass spectrometer. The reaction probability for N2O5 on pure-water ice was found to be 0.028 + or - 0.011, with nitric acid in the solid phase as the sole product. In the presence of HCl in ice, the probability of N2O5 reaction was enhanced (to 0.037); the reaction produced, besides solid-phase nitric acid, ClNO2 and ClONO which were released into the gas phase within a few milliseconds. The latter two compounds can be readily photolyzed in the austral spring to form active chlorine which would remove stratospheric ozone. It is suggested that, since the polar stratospheric clouds are believed to contain HCl-ice mixture on the surface, the reactions of N2O5 on H2O/HCl particles is a major factor in the Antarctic springtime ozone depletion.

Leu, Ming-Taun↗

Airborne observations of SO2, HCl, and O3 in the stratospheric plume of the Pinatubo volcano in July 1991

A high-resolution IR spectrometer aboard the NASA Electra aircraft to measure the total column amount of SO2, O3, and HCl above the aircraft while flying over the Caribbean three weeks after the June 15 eruption of Mt. Pinatubo in the Philippines. South of 20 deg N latitude columns of SO2 were observed ranging from 2.0-3.7 x 10 exp 16 molecules/sq cm. In addition, the column amount of HCl averaged 1.5 x 10 exp 15 molecules/sq cm in the region of the plume. This represents a small increase in HCl above the amount, estimated from the previous measurements, that would have been presented had there been no volcanic eruption, but the increase is substantially less than that seen following the 1982 eruptions of El Chichon.

Mankin, William G.↗

Stratospheric chlorine injection by volcanic eruptions - HCl scavenging and implications for ozone

Because the output of volatile chlorine during a major volcanic event can greatly exceed the annual anthropogenic emissions of chlorine to the atmosphere, the fate of volcanic chlorine must be known. Although numerous observations have shown that volcanoes do not significantly contribute to the stratospheric chlorine burden, no quantitative explanation has been published. Hydrogen chloride (HCl) scavenging processes during the early phases of a volcanic eruption are discussed. A plume dynamics and thermodynamics model is used to show that HCl removal in condensed supercooled water can reduce HCl vapor concentrations by up to four orders of magnitude, preventing substantial stratospheric chlorine injection.

Tabazadeh, A.↗

Balloon measurements of stratospheric HCl and HF by far infrared emission spectroscopy

We have analyzed atmospheric thermal emission spectra obtained with the balloon-borne FIRS-2 far infrared Fourier transform spectrometer during balloon flights from Palestine, Texas on May 12-13, 1988 and from Fort Sumner, New Mexico on September 26-27, 1989 and on July 4-5, 1990. Seven and two pure rotational transition lines in 100-205 cm(exp -1) range are analyzed for deriving vertical profiles of stratospheric HCl and HF, respectively. We obtain both the daytime and nighttime average vertical profiles from 15 to 50 km. We compare these profiles with the ones obtained in June, 1983 with the first version of FIRS spectrometer during the Balloon Intercomparison Campaign (BIC-2). BIC-2 results were revised to be consistent with the present analysis which uses the latest spectral parameters. According to our comparison results no increase is recognized for HCl but about 3 percent per year increase for HF from 1983 to 1990, assuming a linear trend. These annual increase rates are smaller than those reported by other groups. Recently Rinsland et al. (1991) and Wallace and Livingston (1991) reported long term behavior of total HCl and HF observed on Kit Peak between 1977 and 1990. As Kit Peak is located near both balloon launching sites, Palestine and Fort Sumner, we think our results are favorably comparable with theirs. Comparison results with ours and ground-based measurements will be presented and discussed.

Shibasaki, Kazuo↗