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Crystallized HS2O7NO was obtained by reacting excess NO2 gas with liquid HSO3Cl. Stable to a melting point of approximately 105 deg, this reacted with nitrates from about 25 deg and formed M2S2O7, with an acid disulphate intermediary. Excess NO2, whether liquid or gas, reacted with HS2O7NO to five (NO)2S2O7.
Ozone formation in a reaction chamber at room temperature and atmospheric pressure were studied for the photolysis of mixtures of NO with either Cl2 or CFCl3 in air. Both Cl2 + NO and CFCl3 + NO in air strongly inhibited O3 formation during the entire 3 to 4 hour reaction. A chemical mechanism that explains the results was presented. An important part of this mechanism was the formation and destruction of chlorine nitrate. Computations were performed with this same mechanism for CFCl3-NO-air mixtures at stratospheric temperatures, pressures, and concentrations. Results showed large reductions in steady-state O3 concentrations in these mixtures as compared with pure air.
Processing treatments were applied to as-nitrided reaction sintered silicon nitride (RSSN) with the purposes of improving strength after processing to above 350 MN/m2 and improving strength after oxidation exposure. The experimental approaches are divided into three broad classifications: sintering of surface-applied powders; impregnation of solution followed by further thermal processing; and infiltration of molten silicon and subsequent carburization or nitridation of the silicon. The impregnation of RSSN with solutions of aluminum nitrate and zirconyl chloride, followed by heating at 1400-1500 C in a nitrogen atmosphere containing silicon monoxide, improved RSSN strength and oxidation resistance. The room temperature bend strength of RSSN was increased nearly fifty percent above the untreated strength with mean absolute strengths up to 420 MN/m2. Strengths of treated samples that were measured after a 12 hour oxidation exposure in air were up to 90 percent of the original as-nitrided strength, as compared to retained strengths in the range of 35 to 60 percent for untreated RSSN after the same oxidation exposure.
Combinations of chemical compounds that reportedly reduce the corrosion of aluminum in fresh water were evaluated. These included combinations of borates, nitrates, nitrites, phosphates, silicates, and mercaptobenzothiazole. Eight of fifty inhibitor combinations evaluated gave excellent corrosion protection and compared favorably with sodium chromate, which has generally been considered standard for many years.
A large volume of atmospheric constituent data is being collected in the global airlanes by specially equipped B-747 aircraft. This NASA program also obtains data from the similarly equipped NASA CV-990 aircraft during dedicated flights such as a recent near pole-to-pole latitude survey mission. Aerosol composition data are also collected with a NASA F-106 aircraft. Present measurements include ozone, carbon monoxide, water vapor, aerosol and condensation nuclei number densities, sulphates, nitrates, and the chlorofluoromethanes. Meteorological and flight parameters are also recorded for use in data analysis. The present aircraft operations obtain data between 6 and 13.5 km from 65 deg N between Europe and the North Pacific, and from 23 deg S over South America and 42 deg S over New Zealand. Typical constituent data from the aircraft operations during the first one and a half years are presented. Instrumentation is discussed.
Candidate propellant systems for the shuttle booster solid rocket motor (SRM), which would eliminate, or greatly reduce, the amount of HCl produced in the exhaust of the shuttle SRM were investigated. Ammonium nitrate was selected for consideration as the main oxidizer, with ammonium perchlorate and the nitramine, cyclo-tetramethylene-tetranitramine as secondary oxidizers. The amount of ammonium perchlorate used was limited to an amount which would produce an exhaust containing no more than 3% HCl.
The Global Atmospheric Sampling Program (GASP) is collecting and analyzing data on gaseous and aerosol trace contaminants in the upper troposphere and lower stratosphere. Measurements are obtained from automated systems installed on four 747 airliners flying global air routes. Improved instruments and analysis techniques are providing an expanding data base for trace species including ozone, carbon monoxide, water vapor, condensation nuclei, and mass concentration of sulfates and nitrates. Simultaneous measurements of several trace species obtained frequently can be used to identify the source of the air mass as being typically tropospheric or stratospheric.
An analytical and experimental program is being conducted on a one-tenth scale model of a high-temperature (584 K) phase-change thermal energy storage system for installation in a solar total energy test facility at Albuquerque, New Mexico, U.S.A. The thermal storage medium is anhydrous sodium hydroxide with 8% sodium nitrate. The program will produce data on the dynamic response of the system to repeated cycles of charging and discharging simulating those of the test facility. Data will be correlated with a mathematical model which will then be used in the design of the full-scale system.
The partitioning of trace elements between ionic crystals and the melt has been correlated with lattice energy of the host. The solid-liquid partition coefficient has been expressed in terms of the difference in relative ionic radius of the trace element and the homogeneous and heterogeneous strain of the host lattice. Predictions based on this model appear to be in general agreement with data for alkali nitrates and for rare-earth elements in natural garnet phenocrysts.
A realistic assessment of the potential depletion of stratospheric ozone due to manmade emissions requires a knowledge of the sources and sinks of the potential threat. The reactions ClO + NO2 + M yield products and Cl + NO2 + M yield products are of interest because they represent possible sink mechanism for both odd chlorine and odd nitrogen species. In this paper, the Troe method (1977) is used to calculate the low-pressure limit rate constants of the above three-body reactions. The result for the Cl + NO2 + M reaction is found to be in excellent agreement with the experimental finding of Niki et al. (1978), where both nitryl chloride and chlorine nitrate are products of the cited reaction. An explanation is proposed to account for apparent discrepancy between the measured rate constants for ClO + NO2 + M in the forward and reverse directions. Stratospheric implications are also discussed.
The atmospheric sampling system developed for use on board commercial airliners as part of the Global Atmospheric Sampling Program (GASP) is described. The automated air-constituent measuring system is installed in a Boeing 747 airliner below the passenger cabin floor near the nose wheel well. It consists of an air sample flow system, composed of air inlet and pressurization systems, computerized data acquisition and system control units which direct system operation in 15 modes, and commercial instruments significantly modified to measure low levels of atmospheric constituents (ozone, water vapor, nitrogen oxides, carbon monoxide, chlorofluoromethanes, particulates, condensation nuclei, sulfates and nitrates). Flight and meteorological data, including air temperature and altitude, are also recorded. The system is designed for servicing at 14-day intervals, and to require a minimum of aircrew involvement.
Combinations of borates, nitrates, phosphates, silicates, and sodium MBT protect aluminum from corrosion in fresh water. Most effective combinations contained sodium phosphate and were alkaline. These inhibitors replace toxic chromates which are subject to governmental restrictions, but must be used in larger quantities. Experimental exposure times varied from 1 to 14 months depending upon nature of submersion solution.
The development of thermal energy storage subsystems for solar thermal large power applications is described. The emphasis is on characterizing the behavior of molten nitrate salts with regard to thermal decomposition, environmental interactions, and corrosion. Electrochemical techniques to determine the ionic species in the melt and for use in real time studies of corrosion are also briefly discussed.
Five tasks to select, design, fabricate, test and evaluate candidate active heat exchanger modules for future applications to solar and conventional utility power plants were discussed. Alternative mechanizations of active heat exchange concepts were analyzed for use with heat of fusion phase change materials (PCMs) in the temperature range of 250 to 350 C. Twenty-six heat exchange concepts were reviewed, and eight were selected for detailed assessment. Two candidates were selected for small-scale experimentation: a coated tube and shell heat exchanger and a direct contact reflux boiler. A dilute eutectic mixture of sodium nitrate and sodium hydroxide was selected as the PCM from over 50 candidate inorganic salt mixtures. Based on a salt screening process, eight major component salts were selected initially for further evaluation. The most attractive major components in the temperature range of 250 to 350 C appeared to be NaNO3, NaNO2, and NaOH. Sketches of the two active heat exchange concepts selected for test are given.
An inventory of released volatiles on Mars has been derived based upon Viking measurements of atmospheric and surface chemical composition, and upon the inferred mineralogy of a ubiquitous regolith, assumed to average 200m in depth. This model is consistent with the relative abundances of volatiles (except for S) on the earth's surface, but implies one-fifteenth of the volatile release of earth if starting materials were comparable. All constituents are accommodated as chemical components of, or absorbed phases on, regolith materials - without the necessity of invoking unobservable deposits of carbonates, nitrates, or permafrost ice.
Thermodynamic quantities for the gas-phase clustering equilibria of NO2(-) and NO3(-) were determined with high-pressure mass spectrometry. A comparison of values of the free energy of hydration derived from the data shows good agreement with formerly reported values at 296 K. New data for larger NO2(-) and NO3(-) hydrates as well as NO2(-)(HNO2)n were obtained in this study. To aid in understanding the bonding and stability of the hydrates of nitrite and nitrate ions, CNDO/2 calculations were performed, and the results are discussed. A correlation between the aqueous-phase total hydration enthalpy of a single ion and its gas-phase hydration enthalpy was obtained. Atmospheric implications of the data are also briefly discussed.
The reflectance spectrum of Io is presented from 2.8 to 5.2 microns demonstrating the full extent of the broad and deep spectral absorption between 3.5 and 4.8 microns. Laboratory spectra of nitrates and carbonates diluted with sulfur do not satisfactorily reproduce the Io spectrum, but new information based on recently discovered volcanic activity on the satellite lead to consideration of other classes of compounds reported by Fanale et al. (1979). It is concluded that the variability of the supply of condensible SO2 gas to the surface of Io, its removal by sublimination, and the temporal variations in the strength of the SO2 band may provide an index of volcanic activity on Io that can be monitored from the earth.
A two-dimensional model is used to predict the 1990 reduction in ozone due to the chlorine compounds formed by chlorofluoromethane (CFM) photolysis when the CFM release rate is held constant at the 1975 value. The predicted globally averaged ozone reduction of 3.5% is similar to that predicted by one-dimensional models that did not include chlorine nitrate chemistry, and used lower values for the reactions rates of NO + HO2 yielding NO2 + OH and O3 + HO2 yielding OH + 2O2. When the 5.7 ppbv increase in chlorine compounds predicted by one-dimensional models to occur under steady-state conditions is simulated by the two-dimensional model, a 26% decrease in atmospheric ozone is predicted. The latitude dependence of the ozone reduction is discussed in terms of the relevant photochemical reaction and transport. The chemical reactions that most strongly influence the meridional dependence of the ozone depletion are identified as those associated with the reactions of chlorine monoxide and atomic oxygen, the recombination of ozone and atomic oxygen, and the photodissociation of molecular oxygen.