Kinetics and Mechanism of Hexachloroiridate(IV) Oxidation of Arsenic(III) in Acidic Perchlorate Solutions
1992 ◽
Vol 57
(7)
◽
pp. 1451-1458
◽
Keyword(s):
The kinetics of oxidation of arsenic(III) by hexachloroiridate(IV) at lower acid concentrations and at constant ionic strength of 1.0 mol dm-3 have been investigated spectrophotometrically. A first-order reaction in [IrCl62-] and fractional order with respect to arsenic(III) have been observed. A kinetic evidence for the formation of an intermediate complex between the hydrolyzed arsenic(III) species and the oxidant was presented. The results showed that decreasing the [H+] is accompanied by an appreciable acceleration of the rate of oxidation. The activation parameters have been evaluated and a mechanism consistent with the kinetic results was suggested.