Pulse radiolysis of methanolic solutions of tetranitromethane

Abstract

The rate constant for the reaction of solvated electrons with tetranitromethane (TNM) was measured to be k6=(2.89 ± 0.20)× 1010 dm3 mol–1 s–1 at room temperature. Measurements on nitrous oxide saturated solutions containing TNM indicate that ·CH2OH radicals react rapidly with TNM forming an unstable intermediate C(NO2)4+˙CH2OH [graphic omitted] [X] [graphic omitted] C(NO2)–3+ H++ HCHO + NO2(9), for which k9a=(8.5 ± 0.4)× 109 dm3 mol–1 s–1 and k9b=(2.9 ± 0.1)× 106 s–1. The yields of nitroform anion (NF–) in argon and nitrous oxide saturated solutions of G(NF–)= 5.63 ± 0.05 and 6.45 ± 0.05 are equated to the scavengeable radical yields in these solutions. The difference is ascribed to reactions in spurs between e–s and CH3O˙ radical. The yields obtained are compared with those measured in γ-irradiated systems.