Standard Glbbs Energy of Formation of the Hydroxyl Radical in Aqueous Solution. Rate Constants for the Reaction C102- -t O3 S 03- -t CIO,

The rate constants of the following reactions were determined by pulse radiolysis and stopped-flow experiments: C102- + O3 + C102 + 03-(k f= (4 f 1) X lo6 dm3 mol-' s-', k, = (1.8 f 0.2) X lo5 dm3 mol-' s-]); C102 + OH - C103- + H+ (k = (4.0 * 0.4) X lo9 dm3 mol-' s-l); C102 + 0- - C103- (k = (2.7 * 0.4) X lo9 dm3 mol-' s-l); and O3 + C102 - C103 + O2 (k = (1.05 f 0.10) X lo3 dm3 mol-l s-'), where kf is the forward rate of reaction and k, is the reverse rate of reaction. The standard Gibbs energy of formation of OH in aqueous solution A&O,,(OH) and the corresponding standard oxidation potential Eoa,(OH/OH-) were determined by means of kf and k,, the equilibrium constant of 03- + O2 + 0-, the pK of the hydroxyl radical, A&Oa, of 030, 2a,n d OH-i n aqueous solution, and E0,,(C1O2/C1O2-) = 0.934 V determined in the present work. Apoa,(OH) = 26.8 * 1 kJ mol-' and Eoao(OH/OH-) = 1.91 * 0.01 V are obtained.