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.

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