Kinetic-study of SO5•- and HO2• radicals reactivity in aqueous-phase bisulfite oxidationстатья
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Аннотация:A continuous radiolysis has been used for the kinetic study of the radical driven bisulfite oxidation in oxygenated and N2O-O-2 saturated solutions. The initiation rates and initial bisulfite concentrations were varied over the ranges (3 x 10(-10))-(3 x 10(-4)) M s(-1) and 10(-4)-(3 x 10(-3)) M, respectively. For oxygenated and N2O-O-2 saturated solutions the long chain length bisulfite oxidation with the rate determining propagation reaction SO5- + HSO3- (k(6)) was observed at low initiation rates. The measurement of the peroxydisulfate formation rates has shown that the main termination step in an N2O-O-2 saturated solution is the reaction SO5- + SO5- --> S2O82- + O-2 (k(7b)) and in oxygenated solution is the reaction SO5- + HO2 (k(10)). The rate constants k(6) = (3.6 +/- 0.5) x 10(3) and k(10) = (5 +/- 1) x 10(7) M(-1) s(-1) have been derived. The upper limit of the initiation reaction between of hydroperoxyl radical and bisulfite HO2 + HSO3- has been estimated as 20 M(-1) s(-1)