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Relative rate constants of the gas‐phase decomposition reactions of the s ‐butoxy radical
Author(s) -
Drew Roger M.,
Alistair Kerr J.,
Olive Jonathan
Publication year - 1985
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.550170205
Subject(s) - chemistry , thermochemistry , arrhenius equation , propionaldehyde , reaction rate constant , radical , decomposition , acetaldehyde , arrhenius plot , atmospheric temperature range , yield (engineering) , torr , thermal decomposition , thermodynamics , organic chemistry , activation energy , kinetics , ethanol , physics , quantum mechanics
Abstract s ‐Butoxy radicals have been generated by reacting fluorine with s ‐butanol:\documentclass{article}\pagestyle{empty}\begin{document}$$ \mathop {\rm F}\limits^{\rm .} + {\rm CH}_3 {\rm CH}_2 {\rm CH}({\rm OH}){\rm CH}_3 \to {\rm HF} + {\rm CH}_3 {\rm CH}_2 {\rm CH}(\mathop {\rm O}\limits^{\rm .}){\rm CH}_3 $$\end{document}Over the temperature range 398.6 to 493.3 K the s ‐butoxy radical decomposes by two different pathways to yield acetaldehyde and propionaldehyde, acetaldehyde being the major product:The ratio k 1 / k 2 was found to be temperature dependent. An Arrhenius plot of the data (398.6 to 493.3 K) yields the relative Arrhenius parameters, E 1 ‐ E 2 = −11.2 ± 0.8 kJ mol −1 and ( A 1 / A 2 ) = 0.59 ± 0.14. The ratio of rate constants k 1 / k 2 was shown to be independent of total pressure (80–600 torr) and of the pressure of s ‐butanol (2–13 torr). The kinetic results for these s ‐butoxy decomposition reactions are discussed in relation to the literature data and in terms of the thermochemistry of the reactions.