Kinetics and Mechanism of Hexachloroiridate(IV) Oxidation of Arsenic(III) in Acidic Perchlorate Solutions
The kinetics of oxidation of arsenic(III) by hexachloroiridate(IV) at lower acid concentrations and at constant ionic strength of 1.0 mol dm<sup>-3</sup> have been investigated spectrophotometrically. A first-order reaction in [IrCl<sub>6</sub><sup>2-</sup>] 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<sup>+</sup>] 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.
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