Reaction rates of hydroxyl radical with nitric acid and with hydrogen peroxide

Article abstract of DOI:10.1063/1.443998

The rates of the reactions HO + HNO3 <*> H20 + NO3, (1), HO + H2O2 <*> H2O + HOO (2) have been studied by laser flash photolysis of reactants and resonance fluoroscence of hydroxyl radicals.The recently reported high rate constants at room temperature for both reactions and the negative activation energy for Reaction (1) at low temperature have been confirmed.Results obtained here are: k₁ = 1.52*10^-14 exp(644/T) cm³ molecule^-1 s^-1 from 218-363 K and k₂ = 1.81*10^-12 cm³ molecule^-1 s^-1 at 298 K.These two reactions have been examined by transition-state theory; (1) is assigned a cyclic and (2) a chainlike transition state.Even with no potential energy barrier, the reaction coordinate of (1) involves a quantum-mechanical, temperature independent frequency; and with this model the low pre-exponential factor and negative activation energy of Reaction (1) can be explained.

Full text of DOI:10.1063/1.443998

Reaction rates of hydroxyl radical with nitric acid and with hydrogen peroxide
William J. Marinelli and Harold S. Johnston
Citation: The Journal of Chemical Physics 77, 1225 (1982); doi: 10.1063/1.443998
View online: http://dx.doi.org/10.1063/1.443998
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/77/3?ver=pdfcov
Published by the AIP Publishing
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