Browsing by Author "Salmon, G. Arthur"

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    In Situ Radiolysis Electron Spin Resonance Study of the Radical-anions of Substituted Nitroimidazoles and Nitroaromatic Compounds
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (3), 1978) Ayscough, Peter B.; Elliot, A. John; Salmon, G. Arthur
    Reaction of e–aq, (CH3)2ĊOH, (CH3)2CO[graphic omitted] or CO[graphic omitted]2 with a number of substituted nitroimidazoles and nitrobenzenes results in the formation of their radical-anions and in no case were radical-adducts detected. Changes in the e.s.r. spectra of the product species with pH are interpreted in terms of either the protonation of the radical-anion (metronidazole) or the loss of a proton from the radical anion (2-methyl-5-nitroimidazole, 4-nitroimidazole and nitrophenols) and pK values of some of these processes are evaluated. In several cases the dynamics of these acid–base reactions influence the linewidths of the e.s.r. spectra.
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    Pulse Radiolysis of Methanolic Solutions of Tetranitromethane
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1977, 73 (2), 1977) Johnson, David W.; Salmon, G. Arthur
    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.
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    Pulse Radiolysis Study of the Reaction of Solvated Electrons with Sulphur Hexafluoride in Methanolic Solution
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1977, 73 (12), 1977) Johnson, David W; Salmon, G. Arthur
    The rate constant for the reaction of e–s with SF6 in deaerated methanolic solution has been determined to be k3=(1.88 ± 0.06)× 1010 dm3 mol–1 s–1. The product of this reaction, ·SF5, has an absorption spectrum with a maximum at 300 nm with ε= 1300 dm3 mol–1 cm–1 and decays by mixed first- and second-order kinetics.