Engineering topics
Publications and source records attributed to Kurylo, M. J..
Evaluated sets of rate constants and photochemical cross sections are presented. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.
The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.
The paper presents photolysis absorption spectroscopy experimental results which show rapid vibrational quenching of O2(1 Delta, v not less than 1) molecular oxygen fragments in an atmospheric environment. The reactions of this species were determined by flash photolysis of ozone in the Hartley band combined with absorption spectroscopic detection of O2(1 Delta v equals 0) fragments and resonance fluorescence detection of O(3P). It was shown that rapid vibrational deactivation occurs under atmospheric conditions; in addition, an upper limit was determined for the photolytic channel of the O(1D) + O3 yields O2(1 Sigma) reaction.
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The absolute rate constant for the reaction OH + CH3CCl3 yields H2O + CH2CCl3 was determined by the flash photolysis resonance fluorescence method from 253 to 363K. The use of the Arrhenius equation with atmospheric observational data on methyl chloroform nearly doubles the predicted tropospheric OH reaction sink strength for the removal of atmospheric gases whose lifetimes are controlled by OH. The increased use of methyl chloroform instead of the restricted trichloroethylene focused attention to its role in stratospheric ozone depletion, producing modeling analyses to determine the amount of released methyl chloroform which reaches the stratosphere. Since the primary atmospheric loss of CH3CCl3 is considered by reaction with OH radicals, these data are used to compute an average tropospheric OH concentration and the strength of the 'global tropospheric OH reaction sink'.
The flash photolysis resonance fluorescence technique was employed to investigate the rate constant for the reaction Cl + CH2O yields HCl + CHO from 223 to 323 K. An Arrhenius fit of the data gives a rate constant equal to (1.09 + or - 0.40) x 10 to the -10th exp/-(131 + or - 98)/T/ in units of cu cm/molecule per sec. The results are compared to two very recent kinetic studies and are assessed in view of the reaction's role in disrupting the Cl-ClO stratospheric ozone depletion chain.
An evaluated set of rate constants and photochemical cross sections were compiled for use in modelling stratospheric processes. The data are primarily relevant to the ozone layer, and its possible perturbation by anthropogenic activities. The evaluation is current to, approximately, January, 1979.
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The rate constant for the reaction of O (P-3) atoms with ClONO2 at 10 torr total pressure is assessed over the temperature range 225-273 K by the flash photolysis resonance fluorescence technique. The data, taken together with results given by Molina et al. (1977), have been used to formulate an Arrhenius expression suitable for stratospheric modeling applications. Comparison of the rate of ClONO2 destruction via the oxygen atom reaction with the solar photolysis rate shows that chemical reaction accounts for less than 15% of the CLONO2 removal at altitudes between 20 and 30 km.
Rate constants for the removal of Cl(2P) atoms by homogeneous gas phase reaction with ClONO2 were measured using the flash photolysis resonance fluorescence technique at 224, 250, and 273 K. The values obtained have been used to derive the above Arrhenius equation. The uncertainties expressed are 95% confidence limits obtained using the statistical standard deviation of the individual rate constants plus a 15% additional estimated uncertainty attributed to difficulties in chlorine nitrate concentration measurements. The results indicate that destruction of chlorine nitrate by reaction with chlorine atoms is perhaps the least important of the atmospheric reactive channels, and is at least three orders of magnitude slower than calculated photodissociation rates at all stratospheric altitudes.
Compositions of gas samples are frequently studied by laser absorption spectroscopy. Sensitivity is improved by two orders of magnitude when absorption cell is placed inside an organic-dye laser cavity.
Absorption spectra enhancement by organic dye laser quenching, considering applications for absorbing species spectroscopic detection