| Abstrakt: |
1.The method of coupled oxidation with selective inhibitors has been used to measure relative rate constant for the reactions of n-hexadecane and diethyleneglycol dicaprylate peroxide radicals with monatomic (1-decanol, 1-nonanol, and 2-octanol) and polyatomic (ethanediol, 1,4-butanediol,1,3-butanediol,2,3-butanediol,1,2-dihydroxypyropyl ether,1,1,1-trimethylolpropane, 2-methylol-3,4-dihydroxytetrahydrofuran, and 2,2-dimethyl-1,3-propanediol) alcohols.2.The rule of additivity of partial rate constants does not apply to the reactions of peroxide radicals with polyatomic alcohols. Breakdown of the rule is explained in terms of multidipole interactions in the original polyfunctional molecule and in the transition state for the reaction. |
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