Temperature Effect on Decay of Ions and Radicals in Supercooled Liquids as Studied by Pulse Radiolysis and γ-Radiolysis: 1-Propanol and Ethanol

Abstract

The decay-rate constants, k, of dipentyl disulfide anions or benzyl radicals in 1-propanol and ethanol were measured over a temperature range of 107–230 K by pulse- and γ-radiolysis method. The decay-rate constants were found to range over nine orders of magnitude. The decay kinetics is a composite first-order reaction. Since the decay rates of reaction intermediates observed are diffusion-controlled, the decay-rate constants represent directly the rates of molecular transport in the supercooled liquids. It was found that the temperature dependence of the decay-rate constants could be expressed by the following equation. log\frackT=−\fracAT–Tg+B, where T is the absolute temperature, A and B are constants. Tg is the glass transition temperature. The molecular diffusion of the ions or radicals in the supercooled liquids was completely suppressed at the glass transition temperature. The temperature dependence of the decay-rate constant was compared with that of the viscosity of the matrix. It was found that the temperature, at which the molecular diffusion is completely suppressed is much higher than the temperature at which the viscosity is infinite.