Pulse radiolysis and product analysis of 1,1-diphenyl-ethylene and related compounds in methanol
- 1 January 1983
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
- Vol. 79 (10) , 2389-2404
- https://doi.org/10.1039/f19837902389
Abstract
Pulse radiolysis of 1,1-diphenylethylene (DPE) in methanol in the presence of oxygen, as well as of 1,1-diphenyl-2-chloroethylene (DPE-2-Cl), 1,1-diphenyl-1-chloroethane (DP-1-Cl-Et) and 1,1-diphenyl-2-chloroethane (DP-2-Cl-Et) in methanol saturated with argon, was performed. The products formed under pulse-radiolysis conditions were also analysed. Spectroscopic and kinetic data of the corresponding transients are presented. The reaction rate constants determined in methanol are k(e– s+ O2)=(2.0 ± 0.1)× 1010 dm3 mol–1 s–1, k(e– s+ DPE-2-Cl)=(1.1 ± 0.1)× 1010 dm3 mol–1 s–1, k(e– s+ DP-1-Cl-Et)⩽ 1.5 × 1010 dm3 mol–1 s–1, k(e– s+ DP-2-Cl-Et)=(1.3 ± 0.2)× 1010 dm3 mol–1 s–1, k(H + DPE-2-Cl)=(2.0 ± 0.6)× 1010 dm3 mol–1 s–1, k(H + DP-1-Cl-Et)⩽ 8 × 109 dm3 mol–1 s–1, k(H + DP-2-Cl-Et)⩽1 × 108 dm3 mol–1 s–1. It has been established that the solutes are primarily attacked by e– s and H, whereas the CH2OH species (or O2) react with the intermediates thus produced. Reaction mechanisms consistent with the spectroscopic and kinetic data are presented.Keywords
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