Browsing by Author "Rasburn, Eric J."

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    Conductimetric Study of the Kinetics of Electrons in Pulse Irradiated n-Hexane and Cyclohexane at Room Temperature
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1974, 70 (1-6), 1974) Baxendale, John H.; Keene, John P.; Rasburn, Eric J.
    Measurements of the ion current following an electron pulse have given values of kr/µ(where kr is the ion recombination rate constant and µ the electron mobility) and Gµ(extrapolated to zero field) of 1.00(± 0.08)× 10–6 V cm and 1.13(± 0.05)× 10–2 cm2 V–1 respectively for n-hexane, and 0.91(± 0.07)× 10–6 V cm and 5.0(± 0.3)× 10–2 cm2 V–1 for cyclohexane. For n-hexane these and results obtained optically are consistent with kr= 6(± 1)× 1013 dm3 mol–1 s–1, G= 0.13 and µ= 0.09 cm2 V–1 s–1. Using µ= 0.35 cm2 V–1 for cyclohexane, kr= 1.93(± 0.14)× 1014 dm3 mol–1 s–1. Rate constants for reaction of solutes with electrons in n-hexane have been measured which confirm those obtained optically. For electron reactions in cyclohexane k(e–+ S)× 10–11 dm3 mol–1 s–1 are 1.70, 43, 43, 33, 66, 90 and 3.5 when S is O2, CO2, CCl4, Ph2, diphenylanthracene, galvinoxyl and perfluoromethylcyclohexane respectively. The mobility of the electron in n-hexane + alcohol mixtures is found to be unaffected until the alcohol concentration approaches 30 mmol dm–3 and at these low concentrations the electron reacts with the alcohol.
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    Pulse Radiolysis Study of the Kinetics of Electron Reactions in Liquid n-Hexane at Room Temperature
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1974, 70 (1-6), 1974) Baxendale, John H.; Rasburn, Eric J.
    The behaviour of solvated electrons, e–s, produced by the pulse radiolysis of n-hexane at 20°C has been followed using optical absorption techniques. Rate constants for the reaction of e–s with naphthalene, biphenyl, galvinoxyl, chloroform, carbon tetrachloride, perfluoromethylcyclohexane, carbon dioxide, nitrous oxide and oxygen have been determined and are in the range 0.1–1.8 × 1012 dm3 mol–1 s–1. The rate constant, kr, for the recombination of e–s with solvent cations has been redetermined. If G(e–s)= 0.13 then kr= 7.1(± 0.8)× 1013 dm3 mol–1 s–1. The changes in the absorption spectrum of e–s which occur on the addition of alcohols and water have been investigated and the variation in mobility of e–s which accompanies these changes have been measured by observing e– reaction rates in the mixtures. The mechanism of solvation by alcohol is discussed and it is concluded that it occurs by electron diffusion to already formed clusters of alcohol rather than by aggregation of alcohol around the electron.