From alcohols to sugars-how does the reactivity of alpha-hydroxyalkyl radicals change with structure? A quantitative examination by pulse radiolysis.
Rate constants are reported for the 1-electron reduction of the azo dye Orange II in water (pH 7.0) by 10 different alpha-hydroxy radicals. The radicals were created by pulse radiolysis of aqueous solutions of the corresponding alcohol/sugar. The rate constants varied from 1 x 10(8) to 2.7 x 10(9) mol(-1) dm(3) s(-1) and radicals with beta-hydroxy groups had the lowest rate constant. The reaction was found to be controlled by the reduction potentials of the radicals, with steric influences having little effects. Good fits of the data were obtained using the Marcus equation with lambda =140 kJ/mol.
Yadav
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P
Madhava Rao
B S
BS
Batchelor
S N
SN
O'Neill
P
P