Studies of reactions of importance in the stratosphere. III. Rate constant and products of the reaction between ClO and HO2 radicals at 298 K

Article abstract of DOI:10.1063/1.439484

The rate constant for the radical-radical reaction ClO+HO2<*>HOCl+O2 was measured at 298 K by the discharge flow technique using mass spectrometry for detection of the HOCl product m/e=52.The ClO radical was generated by reacting ozone with chlorine atoms produced in a microwave discharge, and the concentration of ClO determined by measuring the decrease in ion current due to Cl2⁺ at m/e=70 upon activation of the discharge.This method was found to be in agreement with a nitric oxide titration of ClO and with the stochiometric conversion of ClO to NO2 by reactionwith a large excess of NO followed by absolute calibration for NO2 at m/e=46.Two reactions were used to generate the hydroperoxyl radical: (1) H+O2+M->HO2+M, and (2) Cl+H2O2->HCl+HO2.The rate constant k₁ was found to be independent of pressure over the range 2-6 Torr, the result being k₁=(4.5+/-0.9)*10^-12 cm³molecule^-1s^-1, where the error includes our estimate of the maximum possible systematic error.An upper limit of 2percent for the branching ratio to the alternative products of this reaction, HCl+O3, was established by attempting to detect ozone as a reaction product.For these measurements the reactions Cl+ClOCl->Cl2+ClO and Cl+OClO->2ClO were used to generate the ClO radical in the absence of ozone.No other reaction products could be identified in the mass spectrum.

Full text of DOI:10.1063/1.439484

Studies of reactions of importance in the stratosphere. III. Rate constant and products
of the reaction between ClO and HO2 radicals at 298 K
Thomas J. Leck, JacE L. Cook, and John W. Birks
Citation: The Journal of Chemical Physics 72, 2364 (1980); doi: 10.1063/1.439484
View online: http://dx.doi.org/10.1063/1.439484
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/72/4?ver=pdfcov
Published by the AIP Publishing
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