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At least 361 records · Page 20

Upper bound and probable value of the rate constant of the reaction OH + HO2 yields H2O + O2

Discharge-flow experiments at 295 K of the OH + HO2 reaction are described in which excess O3 is added to OH through a movable injector; OH concentration is measured downstream by resonance fluorescence with and without addition of excess NO just upstream of the detector so that both OH concentration and OH concentration + HO2 concentration are determined independently. The data are compared with a computer model involving 12 reaction steps. A simple sensitivity analysis is carried out to establish how errors in the other 'known' rate constants affect the data fit. Best agreement is obtained between computer calculations and experiments when k1 for the OH + HO2 reaction is in the range 2-3 x 10 to the -11th cu cm/s. Values above about 5 x 10 to the -11th are very unlikely whereas those below about 1 x 10 to the -11th are less strongly excluded.

Chang, J. S.↗

H2O masers near OB associations

Four new water masers have been found in the vicinity of three OB associations. One of these, in Cep OB3, is among the most intense sources yet discovered and may be related to the most recent epoch of star formation in the OB association. Two others, one in CMa OB1, the other in M16, have large radial velocities relative to their associated molecular clouds. These results are discussed in the context of star formation and CO line self-reversal within the individual sources.

Blitz, L.↗

Intensities and N2 collision-broadening coefficients measured for selected H2O absorption lines between 715 and 732 nm

Intensities and N2 collision-broadening coefficients are measured for 62 water vapor absorption lines between 715 and 732 nm potentially applicable to laser remote sensing of atmospheric water vapor. Absolute line strengths and widths were determined from spectra corrected for instrument resolution, air-path absorption and Lorentz and Doppler broadening for pure water vapor and water vapor-nitrogen mixtures in a multipass absorption cell with a base path length of 25 m (White cell). Line strengths are observed to range from 4 x 10 to the -25th to 4 x 10 to the -23rd kayser/molecule per sq cm, and collision broadening coefficients are found to be approximately equal to 0.1 kayser/atm.

Wilkerson, T. D.↗

Hydrogen production by photoelectrolytic decomposition of H2O using solar energy

Photoelectrochemical systems for the efficient decomposition of water are discussed. Semiconducting d band oxides which would yield the combination of stability, low electron affinity, and moderate band gap essential for an efficient photoanode are sought. The materials PdO and Fe-xRhxO3 appear most likely. Oxygen evolution yields may also be improved by mediation of high energy oxidizing agents, such as CO3(-). Examination of several p type semiconductors as photocathodes revealed remarkable stability for p-GaAs, and also indicated p-CdTe as a stable H2 photoelectrode. Several potentially economical schemes for photoelectrochemical decomposition of water were examined, including photoelectrochemical diodes and two stage, four photon processes.

Rauh, R. D.↗

The properties of clusters in the gas phase. IV - Complexes of H2O and HNOx clustering on NOx/-/

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.

Lee, N.↗

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.↗

Kinetics of the reaction OH + H2O2 yields HO2 + H2O

The paper describes an experimental study of the title reaction that uses the discharge-flow technique, laser-induced-fluorescence detection of OH and simultaneous monitoring of O and H atoms in the 250-459 K range. The reaction is normal and free from surface effect interference in Teflon or halocarbon wax-coated tube, but not in clean Pyrex. OH radicals are generated in three ways and at low concentrations to eliminate side reactions. The rate constants were determined at 298 K and over the 250-459 K range, with a factor of two higher at 298 K and factors of 3 to 5 higher at 10 to 30 km altitude in the terrestrial atmosphere than previous studies have indicated. The effect of the higher rate constant on atmospheric processes and on recent laboratory measurements of other reactions is also discussed.

Sridharan, U. C.↗

Fractional capacity electrolyzer development for CO2 and H2O electrolysis

The electrolyzer module was designed to produce 0.24 kg/d (0.53 lb/d) of breathable oxygen from the electrolysis of metabolic carbon dioxide and water vapor. The fractional capacity electrolyzer module is constructed from three electrochemical tube cells and contains only three critical seals. The module design illustrated an 84 percent reduction in the total number of seals for a one person capacity oxygen generating system based on the solid electrolyte carbon dioxide and water vapor electrolysis concept. The electrolyzer module was successfully endurance tested for 71 days.

Wynveen, R. A.↗

H2O frost point detection on Mars

The Viking Mars landers contain meteorological instrumentation to measure wind, temperature, and pressure but not atmospheric water content. The landings occurred during local summer, and it was observed that the nocturnal temperature decrease at sensor height (1.6 m) did not exhibit a uniform behavior at either site. It was expected that the rate of decrease would gradually slow, leveling off near sunrise. Instead, a leveling occurred several hours earlier. Temperature subsequently began a more rapid decrease which slowed by sunrise. This suggested that the temperature sensors may be detecting the frost point of water vapor. Analysis of alternative hypotheses demonstrates that none of these are viable candidates. The frost point interpretation is consistent with other lander and orbiter observations, with terrestrial experience, and with modeling of Mars' atmospheric behavior. It thus appears that the meteorology experiment can help provide a basis toward understanding the distribution and dynamics of Martian water vapor.

Ryan, J. A.↗

Surface temperatures and retention of H2O frost on Ganymede and Callisto

Surface temperatures and ice evaporation rates are calculated for Ganymede and Callisto as functions of latitude, time of day, and albedo, according to a model that uses surface thermal properties determined by eclipse radiometry and albedos determined from photometrically decalibrated Voyager images. The difference in temperature between Ganymede and Callisto is not great enough to account for the lack of bright polar caps on Callisto, which seems instead to reflect a real deficiency in the amount of available water frost relative to Ganymede. The temperature difference between Ganymede's grooved and cratered terrains also cannot account for the high concentration of bright ray craters in the former, suggesting that an internal geologic process has enriched the grooved terrain in ice content relative to the cratered terrain.

Squyres, S. W.↗

A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

Wine, P. H.↗

Kinetics of the reaction OH + HO2 yields H2O + O2 at 296 K

The rate constant of the title reaction was measured in a discharge-flow reactor by addition of excess HO2 from a movable double injector to a gas stream containing small concentrations of OH. The concentration of OH was measured by laser-induced fluorescence, HO2 by conversion to OH, and H and O by vacuum-UV resonance fluorescence. Five sets of experiments, each with different excess concentration of HO2, gave an average rate constant of (7.5 + or - 1.2) x 10 to the -11th cu cm/s where the error limits (single sigma) include uncertainties of all experimental parameters. This result is compared with other findings and is discussed in terms of its importance in stratospheric chemistry and in rate theory.

Sridharan, U. C.↗