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The kinetics of the reactions of methyl radicals with Br 2 , Cl 2 , and BrCl
Author(s) -
Evans Brian S.,
Whittle Eric
Publication year - 1978
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.550100708
Subject(s) - chemistry , radical , kinetics , halogen , enthalpy , polar , atmospheric temperature range , gas phase , standard enthalpy change of formation , chemical kinetics , photochemistry , computational chemistry , standard enthalpy of formation , thermodynamics , organic chemistry , alkyl , physics , quantum mechanics , astronomy
A general competitive method is described for the study of the kinetics of the reactions of radicals with halogens and interhalogen compounds in the gas phase. The method is applied to the reactionsover the temperature range of 48°–199°C. It is found that\documentclass{article}\pagestyle{empty}\begin{document}$$ \log (k_6 /k_5) = \log (k_\varepsilon /k_7) = (- 0.042 \pm 0.060) - (8700 \pm 1300)/\theta $$\end{document}where Θ=2.303RT J/mol. Also\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} A_7 = 1/2A_{5,} \,\,\,\,\,\,\,\,\,\,\,\,E_7 = E_5 \\ A_8 = 1/2A_{6,} \,\,\,\,\,\,\,\,\,\,\,\,E_8 = E_6 \\ \end{array} $$\end{document}There is no correlation between differences in activation energies and differences in enthalpy changes for these reactions, but polar effects may be important in reactions (7) and (8).