Radiolysis of aqueous solutions containing nitric oxide and aliphatic alcohols

Abstract

Aliphatic alcohols increase the yields of N₂O observed in the radiolysis of NO solutions and are oxidized to the corresponding aldehyde in the process. The following reactions occur in addition to those previously suggested ¹ for the NO radiolysis: OH+ROH → H₂O+˙ROH ˙ROH+3NO → N₂O+HNO₂+R˙= 0(aldehyde) where R = Me, Et, i-Pr.

Values of the rate constant ratio k_(OH+NO)/k_(OH+ROH) have been obtained (a) from studies of G(N₂O) and (b), for methanol only, from the formaldehyde yields. Measurements of the decrease of G(CH₂O) caused by the addition of a third solute to solutions of NO and methanol are also reported. From these the ratio k_(OH+solute)/k_(OH+MeOH) has been determined for the two solutes bromide ion and nitrite ion. Rate constants for reactions of OH are found to be in the ratio: 0.35 for MeOH, 1.0 for EtOH, 1.0 for i-PrOH, 1.5 for Br^–, 2.2 for NO^–₂, and 4.3 for NO.