Pulse radiolysis study of some radical protonation reactions

Abstract

The rates of establishment of the acid-base equilibria for the radical anions of benzaldehyde, benzamide, benzonitrile, benzophenone, p-cyanoacetophenone and fluorenone have been studied by pulse radiolysis. In each case a first order rate of reaction was observed with k_obs=k′+k″[H⁺], the constants having values of k′=(0.3–7.8)× 10⁴ s^–1 and k″=(0.7–2.5)× 10¹⁰ dm³ mol^–1 s^–1. These rate constants are associated with the reaction of the radical anion with water (k′) and H⁺(k″). The nature of the radical ions involved is discussed.