A pulse radiolysis study of solvated electrons in tert-butanol/water solutions

Abstract

Many solutes, added to water in amounts of a few mol%, cause an increase in the yield of solvated electrons (e s − ) measured by pulse radiolysis. A pulse radiolysis study of tert-butanol (tBuOH) in D 2 O has been carried out to investigate this phenomenon. Detailed measurements of the yield, measured as Gε max (e s − ), and the deeay of solvated electrons were made at 6, 25, and 46 °C over the range 0–5mol% tBuOH. The maximum Gε max (e s − ) occurs at about 1 mol% tBuOH, but the exact concentration depends on the temperature of the sample and the time after the pulse at which the measurement is made. Three factors are examined as contributing to the increased Gε max (e s − ) in the presence of tBuOH and certain other solutes. They are (i) the change in viscosity produced by the added solute, (ii) the scavenging of OH radicals by the solute, thereby reducing the reaction of OH with e s − and (iii) the possibility that the addition of the solute leads to an increase in the thermalization distance of the secondary electrons. It is concluded that effects (i) and (ii) are sufficient to explain the existing experimental data.

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