Abstract

Abstract— ESR studies have been made of the kinetics of semiquinone radical formation and disappearance resulting from the reversible photosensitization by chlorophyll of hydroquinone oxidation in a pyridine‐water solvent. The rate of radical decay was found to be second order with respect to the radical concentration, with a rate constant of 6.7 × 105 l./mole sec at ‐30°C and an activation energy of 6900 cal/mole. The rate of radical formation was recombination‐limited and, through the use of β‐carotene as a quencher, the rate constant was determined to be 8.81 × 105 l./mole sec at ‐30°C. The effect of light intensity and hydroquinone concentration on the rate of semiquinone radical formation and on the steady state radical concentration was also investigated and possible mechanisms to explain the results are discussed.

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