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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7

Characterization of hot hydrogen-atom reactions by kinetic spectrography.

The flash photolysis of hydrogen iodide in the presence of nitrous oxide, carbon dioxide, and water has been investigated by kinetic spectroscopy. Although the fraction of hydrogen iodide dissociated was very large, the only observable intermediate was imidogen. It was demonstrated that the rapid removal of imidogen and the apparent absence of hydroxyl radicals in each case is a result of the following two reactions, respectively: (1) NH + HI yields NH2 + I; and (2) OH + HI yields H2O + I.

Tomalesky, R. E.↗

Shock tube study of the reaction H plus O2 plus Ar yields HO2 plus Ar

Rate coefficient data for the recombination reaction H + 02 + Ar yields H02 + Ar have been determined from studies of lean hydrogen-oxygen mixtures behind incident shock waves over the temperature range of 948 to 1125 K. Hydroxyl radical concentration profiles were measured by ultraviolet absorption spectroscopy, and rate data were obtained through analysis of induction time and exponential growth parameter data. Analysis of the data yielded a rate coefficient which was generally lower than most of the more recent values obtained from shock tube studies. The effect of boundary layer formation on the conditions behind the shock was also examined and found to be negligible.

Jachimowski, C. J.↗

Diffusive ignition and combustion in a wall jet

Hydrogen is injected from a downstream facing step in a wall into a high-temperature stream. Temperature and hydroxyl radical concentration are measured downstream of the injection plane by means of ultraviolet absorption spectroscopy. The experimental results are compared with theory which is based on a finite-difference solution of boundary-layer equations. Finite-rate kinetics equations are included in the analysis. The analytic predictions are also compared with previously obtained experimental results which are based on probe measurements. Comparison is made between calculated and observed ignition distances.

Kurkov, A. P.↗

The molecular dynamics of atmospheric reaction

Detailed information about the chemistry of the upper atmosphere took the form of quantitative data concerning the rate of reaction into specified states of product vibration, rotation and translation for exothermic reaction, as well as concerning the rate of reaction from specified states of reagent vibration, rotation and translation for endothermic reaction. The techniques used were variants on the infrared chemiluminescence method. Emphasis was placed on reactions that formed, and that removed, vibrationally-excited hydroxyl radicals. Fundamental studies were also performed on exothermic reactions involving hydrogen halides.

Polanyi, J. C.↗

Diffusive ignition and combustion in a wall jet

Hydrogen is injected from a downstream facing step in a wall into a high-temperature stream. Temperature and hydroxyl radical concentration are measured downstream of the injection plane by means of ultraviolet absorption spectroscopy. The experimental results are compared with theory which is based on a finite-difference solution of boundary-layer equations. Finite-rate kinetics equations are included in the analysis. The analytic predictions are also compared with previously obtained experimental results which are based on probe measurements. Comparison is made between calculated and observed ignition distances.

Kurkov, A. P.↗

Some observations on the oscillatory behavior of carbon monoxide oxidation

The oscillatory behavior of the oxidation of carbon monoxide was experimentally studied in an attempt to further elucidate the reaction at low pressure. The phenomenon is observed as multiple explosions and involves successive flashes of light accompanying the slow reaction in a static system, including over 450 flashes in one case. Electronically excited hydroxyl radicals (water impurity) and carbon dioxide have been identified as components of the emission. The phase difference between the two was seen to be negligible. The nature of the temperature and pressure changes during a cycle indicates that the oscillation is purely kinetic rather than thermokinetic. A procedure is presented whereby sustained oscillations can be obtained for particular regions in the pressure-temperature plane, vessel surface pretreatments, and H2O-containing reactants.

Mccaffrey, B. J.↗

Balloon stratospheric research flights, April 1976 to December 1976

These flights were designed to measure the vertical concentration profile of trace stratospheric species which form major links in the chlorine photochemical system of the upper atmosphere, to measure the vertical concentration profiles of atomic oxygen, the hydroxyl radical and ozone in the stratosphere. An overview of the scientific goals of the program, a statement of program management and support functions, a brief description of the instrumentation flown, pertinent engineering and payload operations data, and a summary of the scientific data obtained for four flights are presented.

Allen, N. C.↗

Nightglow emissions of OH/X 2 pi/ - Comparison of theory and measurements in the /9-3/ band

The visible airglow experiments on the Atmosphere Explorer C and E satellites have viewed the (9-3) band nightglow emission of the excited hydroxyl radical in the lower thermosphere at tropical latitudes. The surface brightnesses observed at similar local times vary by approximately a factor of 2. Comparison of the measurements with time-dependent photochemical calculations shows reasonable agreement and indicates that temporal changes in atmospheric transport processes are the most likely explanation of the nightglow variations.

Frederick, J. E.↗

Three methods for in situ cross-linking of polyvinyl alcohol films for application as ion-conducting membranes in potassium hydroxide electrolyte

Three methods of in situ cross-linking polyvinyl alcohol films are presented. They are: (1) acetalization with a dialdehyde such as glutaraldehyde, (2) acetalization with aldehyde groups formed by selective oxidative cleaving of the few percent of 1,2 diol units present in polyvinyl alcohol, and (3) cross-linking by hydrogen abstraction by reaction with hydrogen atoms and hydroxyl radicals from irradiated water. For the third method, improvement in film conductivity in KOH solution at the expense of mechanical strength is obtained by the presence of polyacrylic acid in the polyvinyl alcohol films. Resistivities in 45 percent KOH are given for in situ cross-linked films prepared by each of the three methods.

Philipp, W. H.↗

The impact of chlorofluoromethane and NO/x/ injections on stratospheric ozone

The chlorofluoromethane problem and the SST problem have been subject to continuing evaluation by the use of one-dimensional stratospheric photochemistry models. The problems to some extent appear to be inversely related to one another through hydroxyl radical reactions; in other words, processes which tend to increase the amount of OH in a model tend to increase the sensitivity of the ozone column to ClX perturbations, while at the same time decreasing the sensitivity to NO(x) perturbations. Evaluations of sensitivity to ClX and NO(x) have varied as new input information has become available and modeling techniques have improved. It is clear that either NO(x) or ClX, or both, will affect the distribution of ozone with altitude.

Stolarski, R. S.↗

Sensitivity of the predicted CO-OH-CH4 perturbation to tropospheric NOx concentrations

Measurements indicate that ambient NOx(NO + NO2) concentrations vary over at least an order of magnitude in the troposphere. Thus it is of interest to study atmospheric chemistry with NOx concentrations covering this range. In this paper we present steady state calculations which show that as NOx concentrations are increased from very low values, the hydroxyl radical concentration increases at first and then decreases. This change of behavior occurs at a concentration of NO2 of about 0.23 ppb in the model. Also, the response of the atmosphere to increased CO fluxes undergoes a qualitative change as a function of the concentration of NOx. At low levels of NOx concentration, an increase in CO fluxes into the atmosphere depletes the OH concentration and increases the concentrations of CH4 and H2, as reported in the literature. However, at high values of NOx concentration, increased CO fluxes give rise to an increase in the OH concentration and, consequently, a decrease in the concentrations of CH4 and H2.

Hameed, S.↗

Oxidation of CS2 and COS - sources for atmospheric SO2

The oxidation of COS and CS2 by reaction with hydroxyl radicals is investigated as a possible source of atmospheric SO2 in remote marine regions. Calculations of the vertical profiles of SO2 were performed based on a one-dimensional photochemical model of the formation and destruction of SO2 by various processes for observed O3, CO, CH4 and H2O profiles at 15 deg S. Variations in the rate of SO2 destruction, the chosen deposition velocity and the loss due to aerosols are shown to lead to similar SO2 profiles, which indicate higher mixing ratios at high altitude, while the oxidation of dimethyl sulfide or hydrogen sulfide can not account for the profiles observed. Possible diffuse sources of CS2 and COS are indicated, and it is concluded that the oxidation of COS and possibly CS2 may provide an explanation for the existence of a uniform background level of SO2.

Logan, J. A.↗

Influence of gravity wave activity on lower thermospheric photochemistry and composition

The wind and temperature oscillations of internal gravity waves can cause horizontal variations of a factor of two in minor gas number densities in the lower thermosphere over length scales of several hundred kilometers. The variations are due both to vertical transport of constituents whose lifetimes are long compared to the wave period and to chemical activity driven by temperature dependent reaction rate coefficients. The nightglow emission of the hydroxyl radical provides a remote sensor of wave activity between 80 and 90 km. Theoretical calculations show that the horizontal variations in the atomic hydrogen distribution are the largest single contributor to wave structure in the nightglow followed by the effects of temperature fluctuations on the rate coefficient of the reaction H + O3 yields O2 + OH (nu prime is greater than 0).

Frederick, J. E.↗

Absolute rate constant of the reaction OH + H2O2 yields HO2 + H2O from 245 to 423 K

The absolute rate constant of the reaction between the hydroxyl radical and hydrogen peroxide was measured by using the discharge-flow resonance fluorescence technique at total pressure between 1 and 4 torr. At 298 K the result is (1.64 + or - 0.32) x 10 to the -12th cu cm/molecule s. The observed rate constant is independent of pressure, surface-to-volume ratio, the addition of vibrational quenchers, and the source of OH. The temperature dependence has also been determined between 245 and 423 K; the resulting Arrhenius expression is k cu cm/molecule s is equal to (2.51 + or - 0.6) x 10 to the -12th exp(-126 + or - 76/T).

Keyser, L. F.↗

A model of CO-CH4 global transport/chemistry. I - Chemistry model

A simplified chemistry model was developed to incorporate the CO-CH4 chemistry into the global transport model of these compounds. CO is important because of its effects on atmospheric chemistry and is partly responsible for controlling the hydroxyl radical (OH) concentration in the troposphere. The model includes the photodissociation rate coefficients expressed as functions of solar zenith angle and altitude, and it was applied to determine the sensitivity of the OH concentration to trace gaseous species, such as NOx, O3, and H2O. Also, the concentrations and diurnal variations of OH and HO2, and the contribution of individual reactions to OH generation and consumption were calculated.

Peters, L. K.↗