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Gas phase kinetic study of the thermal reactions of t ‐butoxy radicals with germane, phosphine, and trimethylsilane
Author(s) -
Lee YongEun,
Choo Kwang Yul
Publication year - 1986
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.550180211
Subject(s) - trimethylsilane , chemistry , germane , arrhenius equation , phosphine , reaction rate constant , hydrogen atom abstraction , radical , decomposition , thermal decomposition , atmospheric temperature range , hydrogen , halogen , photochemistry , medicinal chemistry , kinetics , activation energy , organic chemistry , alkyl , thermodynamics , germanium , physics , quantum mechanics , silicon , catalysis
Abstract The hydrogen abstraction reactions of tert ‐butoxyl with germane, phosphine, and trimethylsilane were studied by pyrolyzing di‐ t ‐butyl peroxide in the temperature range of 403 to 458 K. From the reported rate constant for the tert ‐butoxy radical decomposition in the literature, the absolute rate constants were determined from the study of competitive reaction between t ‐butoxy radical decomposition\documentclass{article}\pagestyle{empty}\begin{document}$$ (t - {\rm BuO }\;{\hbox to 45pt{\rightarrowfill}} {\hskip-42pt ^{{\rm decompose}}}{\hskip1em} {\rm CH}_{\rm 3} {\rm COCH}_{\rm 3} + {\rm CH}_{\rm 3}) $$\end{document}and hydrogen abstraction reaction. ( t ‐BuO + RH → t ‐BuOH + R, where RH = GeH 4 , PH 3 , and HSiMe 3 ) The Arrhenius parameters are found to be as follows: TextE a (kcal mol −1 ) Log A (1.mol −1 s −1 )t ‐BuO + SiHMe 3 2.1 8.5t ‐BuO + GeH 4 1.9 9.1t ‐BuO + PH 3 1.4 9.0