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

• Published in: Canadian journal of chemistry Vol. 64; no. 8; pp. 1548 - 1552
• Main Authors: Cygler, Joanna, Klassen, Norman V, Ross, Carl K
• Format: Journal Article
• Language: English
• Published: Ottawa, Canada NRC Research Press 01.08.1986; National Research Council of Canada
• Subjects: Chemistry; Exact sciences and technology; General and physical chemistry; Physical chemistry of induced reactions (with radiations, particles and ultrasonics); Radiation chemistry; Viscosity; Aliphatic compound; Tertiary alcohol; Saturated compound; Kinetics; Aqueous solution; Deuterium Oxides; Quantum yield; Pulse radiolysis; Labelled compound; Solvated electron
• ISSN: 0008-4042; 1480-3291
• DOI: 10.1139/v86-255

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 G 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 G 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 G 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.