Pulse radiolysis studies of the reactions of e(aq)(-) and (OH)-O-center dot with ClO3- ions in aqueous solution

The rate constants of the reactions of e(aq)(-) and (OH)-O-. with ClO3- in aqueous solutions are determined by pulse radiolysis studies. The hydrated electron reacts with ClO3- with a rate constant of 1.6 x 10(5) M-1 s(-1) to yield the ClO32- radical anion. Its optical absorption exhibits two bands at 245 nm (epsilon = 900 M-1 cm(-1)) and at 500 nm (epsilon = 500 M-1 cm(-1 )). The reaction of the (OH)-O-. radical with ClO3- is too slow to measure a rate constant; an upper limit is estimated to be < 1 x 10(5) M-1 s(-1). T he rate constants for the reactions of the ClO32- radical anion with the (O H)-O-. radical and the O-.(-) radical ion are determined to be 1 x 10(10) a nd 1.2 x 10(9) M-1 s(-1). respectively. (C) 2000 Elsevier Science Ltd. All rights reserved.