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 k_9a=(8.5 ± 0.4)× 10⁹ dm³ mol^–1 s^–1 and k_9b=(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.