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At least 91 records · Page 5

A kinetics study of the homogeneous and heterogeneous components of the HCl + ClONO2 reaction

The kinetics of the reaction HCl + ClONO2 to Cl2 + HNO3 were investigated at 298 K using a flow reactor with FTIR analysis to assess the importance of this reaction for stratospheric chemistry. The observed reaction was characteristic of a heterogeneous process; an upper limit of 5 x 10 to the -18th cu cm/molecule per s was obtained for the homogeneous gas phase rate constant. From calculations of the first order wall rate constant, estimates were made of the reaction rate on stratospheric aerosols. Because both HCl and ClONO2 need to be adsorbed on the particle surface, the reaction will be of negligible importance under most stratospheric conditions.

Friedl, Randall R.↗

Quantification of HCl from high-resolution, ground-based, infrared solar spectra in the 3000 per cm region

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.

Goldman, A.↗

Antarctic ozone depletion chemistry - Reactions of N2O5 with H2O and HCl on ice surfaces

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.

Tolbert, Margaret A.↗

In situ stratospheric measurements of HNO3 and HCl near 30 km using the balloon-borne laser in situ sensor tunable diode laser spectrometer

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.

May, R. D.↗

Balloon Intercomparison Campaigns - Results of remote sensing measurements of HCl

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.

Farmer, C. B.↗

Stratospheric ClONO2, HCl, and HF concentration profiles derived from Atmospheric Trace Molecule Spectroscopy experiment Spacelab 3 observations - An update

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.

Zander, R.↗

Terrestrial bitumen analogue of orgueil organic material demonstrates high sensitivity to usual HF-HCl treatment

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.

Korochantsev, A. V.↗

Solubility of HCL in sulfuric acid at stratospheric temperatures

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.

Williams, Leah R.↗

Can Chlorine Anion Catalyze the Reaction fo HOCl with HCl?

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.

Richardson, S. L.↗

Heterogeneous Reactions of HNO3(g) + NaCl(s) Yields HCL(g) + NaNO3(s) and N2O5(g) + NaCl(s) Yields ClNo2(g) + NaNO3(s)

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.

heterogeneous↗

Materials Data on HCl by Materials Project

HCl is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is zero-dimensional and consists of four hydrochloric acid molecules and four hydrogen molecules.

36 MATERIALS SCIENCE↗

Materials Data on HCl by Materials Project

HCl is alpha carbon monoxide-like structured and crystallizes in the orthorhombic Cmc2_1 space group. The structure is zero-dimensional and consists of four hydrochloric acid molecules. H1+ is bonded in a single-bond geometry to one Cl1- atom. The H–Cl bond length is 1.30 Å. Cl1- is bonded in a single-bond geometry to one H1+ atom.

36 MATERIALS SCIENCE↗

Materials Data on HCl by Materials Project

HCl is Zincblende, Sphalerite structured and crystallizes in the orthorhombic Imm2 space group. The structure is zero-dimensional and consists of two hydrochloric acid molecules. H1+ is bonded in a single-bond geometry to one Cl1- atom. The H–Cl bond length is 1.28 Å. Cl1- is bonded in a single-bond geometry to one H1+ atom.

36 MATERIALS SCIENCE↗

Extraction of americium, curium, and californium with LN resin from HCl and HNO 3

The uptake of 241 Am, 244 Cm and 249 Cf with LN resin was studied in HCl and HNO3 solutions with concentrations ranging from 0.02 to 2.5 M. There is high uptake at concentrations < 0.1 M in both acids for all three isotopes with decreasing uptake at higher concentrations and negligible extraction at ≥ 0.6 M. Californium has a higher extraction than americium and curium, which are extremely similar. Kinetics studies showed rapid uptake of all three isotopes. Here, column studies were performed to demonstrate the separation of 241 Am and 249 Cf, and a bulk separation including nine stable lanthanides along with 241 Am, 249 Cf, and 88 Y.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

An Experimental Study of the Solubility of Rare Earth Chloride Salts (La, Nd, Er) in HCl Bearing Water Vapor from 350 – 425 °C

In this work, the solubilities of the rare earth chlorides REECl 3 , where REE = (La, Nd, Er), were measured in HCl bearing water vapor from 350 – 425°C with water partial pressures ranging from 8 – 170 bar. Solubility data were fit to the Pitzer-Pabalan quasi-chemical model in order to extract thermodynamic parameters for the formation of the gaseous REE-chloride-water clusters REECl 3 (H 2 O) n . The data show that the solubility of the REE chlorides are orders of magnitude higher than salts such as NaCl or CuCl at low water fugacities, despite their sublimation energies being substantially higher. This enhanced solubility is likely due to the high enthalpy associated with binding a single water molecule to form the species REECl 3 (H 2 O), with derived enthalpies ranging from –378 to –465 kJ/mol. Addition of further water molecules to form higher order clusters (n > 1) involves enthalpy changes of ~ -20 kJ/mol, and are in effect thermodynamically suppressed over the temperature range 350 – 425°C. Despite the enhanced solubility of small REECl 3 water clusters, simulations of boiling processes demonstrate that the REE show highly conservative behavior, partitioning strongly into the dense aqueous phase. Not surprisingly, the presence of phosphates in the system makes this effect even more pronounced, completely immobilizing the REE. This would reduce transport in both the vapor and aqueous phase to negligible levels. However, we suggest that vapor phase transport of the REE may play a significant role in systems having a relatively low partial pressure of water (below the saturation point), where the relatively high stability of the first hydrated REE chloride clusters (REECl 3 (H 2 O) and REECl 3 (H 2 O) 2 ) will give a preference for gas transport of the REE relative to other elements. This can likely happen in systems involving a gas/melt exchange in fumarolic exhalations, where water vapor discharges at relatively low (close to atmospheric) pressures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗