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Relative rate measurements of some reactions of hydroxyl radicals with alkanes studied under atmospheric conditions
Author(s) -
Harris Stephen J.,
Kerr J. Alistair
Publication year - 1988
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550201203
Subject(s) - chemistry , radical , arrhenius equation , pentane , butane , atmospheric temperature range , alkane , thermodynamics , analytical chemistry (journal) , photochemistry , organic chemistry , hydrocarbon , activation energy , catalysis , physics
A flow system has been developed to study relative rate coefficients of hydroxyl radicals reacting with alkanes under conditions relating to tropospheric chemistry. Relative Arrhenius parameters have been measured over the temperature range 243–328 K for pairs of alkanes from a list consisting of n ‐butane, 2‐methylpropane, n ‐pentane, n ‐hexane, 2,2‐ and 2,3‐dimethylbutane, 2,3,3‐trimethylbutane, and 2,3,4‐trimethylpentane. The results have been incorporated into a Structure‐Activity Relation for hydroxylalkane reactions which leads to the following group rate coefficients for a temperature range of 240–500 K.\documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{rcl} k_{{\rm prime}}^0 &=& 3.13 \times 10^{ - 12}\, {\rm exp(} - 904/T)\,{\rm cm}^{\rm 3}\, {\rm molecule}^{ - 1}\, {\rm s}^{ - 1} \\ k_{{\rm sec}}^0 &=& 2.45 \times 10^{ - 12} \,{\rm exp(} - 320/T)\,{\rm cm}^{\rm 3}\, {\rm molecule}^{ - 1}\, {\rm s}^{ - 1} \\ k_{{\rm tert}}^0 &=& 1.88 \times 10^{ - 12} \,{\rm cm}^{\rm 3}\, {\rm molecule}^{ - 1}\, {\rm s}^{ - 1} \end{array}$$\end{document}