Gas phase kinetic study of the thermal reactions of t‐butoxy radicals with germane, phosphine, and trimethylsilane

Abstract

The hydrogen abstraction reactions of tert-butoxyl radicals 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 (t-BuO decompose+ CH3COCH3 + CH,) and hydrogen abstraction reaction. (t-BuO RH -+ t-BuOH + R, where RH = GeH,, PH,, and HSiMe,)The Arrhenius parameters are found to be as follows:E,(kcal mol-') Log A t-BuO + SiHMe, 2.1 t-BuO + GeH, 1.9t-BuO + PH3

Gas‐Phase Chemistry and Mass Spectrometry ofGe‐,Sn‐ andPb‐Containing Compounds

“…This is the case for the reaction of the t-BuO • radical with germane 229 for which E a was determined to be 7.9 kJ mol −1 . A somewhat higher activation energy has been measured for the hydrogen abstraction by O ( 3 P) from methyl groups attached to germanium 230 .…”

Peculiar Features in Lean Butane Flames

“…[F(c,HIOJlo (6) From the literature data for the rate coefficients of acetone reaction with O-atoms (Ambidge et al, 1976;Mix and Wagner, 1983;Lee and Choo, 1986;Roscoe, 1986;Herron, 1988), with H-atoms (Azatyan et al, 1972;Ambidge et al, 1976) and with OH radicals (Wallington and Kurylo, 1987;Bott and Cohen, 1991) the following coefficients have been used:…”