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Ionisation Constants of .OH and HO2. in Aqueous Solution up to 200 deg C. A Pulse Radiolysis Study

DOI: 10.1039/f19888401113

Source and publish data:

Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 1113 - 1122 (1988)

Update date:2022-08-30

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Authors:

Buxton, George V.Buxton, George V.

Wood, Nicholas D.Wood, Nicholas D.

Dyster, SallyDyster, Sally

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Article abstract of DOI:10.1039/f19888401113

The ionisation constant of .OH has been determined up to 200 deg C from measurements of its rate of reaction with CO32- in alkaline solution, where O.- is unreactive.The Van't Hoff plot shows the same curvature as that for Kw, so that .OH and H2O have the same heats of ionisation. ΔH for the equilibrum is independent of temperature and equal to -15.4 +/- 0.5 kJ mol-1. ΔH for the ionisation of HO2. has been measured as zero within experimental error up to 175 deg C by determining the concentrations of HO2. and O2.- at equilibrum from optical absorbance measurements.The activation energies for the reaction of .OH with CO32- and HCO3- are idependent of temperature and equal to 23.6 +/- 0.4 and 21.2 +/- 0.2 kJ mol-1, respectively, although k(.OH + CO32-) ca. 50 k(.OH + HCO3-).The G values for eaq- and .OH increase by 27percent between 20 and 200 deg C in the pH range 4.4-9.2, but appear to be independent of temperature at pH 2.

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