ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The rate constant k1 for the reaction of OH radicals with CIO2 molecules was measured in a discharge flow system over the temperature range 293 ≤ T ≤ 473 K and at low pressures, 0.5 ≤ P ≤ 1.4 torr, using electron paramagnetic resonance or laser-induced fluorescence to monitor the pseudo first-order decay of OH concentrations. At 293 K, the value obtained for k1 was (7.2 ± 0.5) × 10-12 cm3 molecule-1 s-1. Within the temperature range of this study, a negative temperature dependence was observed: k1 = (4.50 ± 0.75) × 10-13 exp[(804 ± 114)/T] cm3 molecule-1 s-1. HOCl was detected by mass spectrometry as a product of the reaction and was titrated using OH + Cl2 as a source in the calibration experiments. A simulation of the mechanism of the OH + ClO2 reaction indicated that HOCl was mainly produced in the first reaction step. Both this result and the observed T dependence of k1 suggest that this reaction proceeds via an intermediate adduct with a cyclic geometry.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550180805
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