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Kinetics studies of reactions of OH radicals with four haloethanes part I. Experiment and BEBO calculation
Author(s) -
Xing ShiBen,
Shi SuHao,
Qiu LianXiong
Publication year - 1992
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.550240102
Subject(s) - chemistry , arrhenius equation , radical , reaction rate constant , kinetics , atmospheric temperature range , analytical chemistry (journal) , transition state theory , activation energy , thermodynamics , organic chemistry , physics , quantum mechanics
The rate constants for reactions of OH with ClCH 2 CH 2 Cl, Cl 2 CHCHCl 2 , BrCH 2 CH 2 Br, CH 3 CH 2 Br have been measured by using a discharge flow‐resonance fluorescence (DF‐RF) technique over the temperature range 293–418 K. The rate constants as a function of temperature were fitted to the Arrhenius expression as follows: ( k 's units are 10 −12 cm 3 molecule −1 s −1 , and E a 's units are cal/mol)\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm OH} + {\rm ClCH}_2 {\rm CH}_2 {\rm Cl}:} & {k_1 = (8.91 \pm 1.63)^ \ast {\rm EXP}((-2164.5 \pm 119.9)/RT)}\\[10pt] {{\rm OH} + {\rm BrCH}_2 {\rm CH}_2 {\rm Br}:} & {k_2 = (14.36 \pm 2.70)^ \ast {\rm EXP}((- 2521.4 \pm 123.5)/RT)}\\[10pt] {{\rm OH} + {\rm Cl}_2 {\rm CHCHCl}_2:} & {k_3 = (5.01 \pm 0.89)^ \ast {\rm EXP}((- 1825.8 \pm 116.7)/RT)} \\[10pt] {{\rm OH} + {\rm CH}_3 {\rm CH}_2 {\rm Br}:} & {k_4 = (23.45 \pm 4.62)^ \ast {\rm EXP}((- 2558.2 \pm 124.1)/RT)}\end{array} $$\end{document} The experimental data have been compared with theoretical calculations of the semi‐empirical BEBO‐transition state method. Life‐times of the four haloethanes in the troposphere have been estimated.