Abstract
The oxidation of isopropyl alcohol by [Ag(bipy)2]2+ is first order in [Ag(bipy)2]2+ and the order in PriOH is between zero and unity. The kinetics show that intermediate complexes are involved and from the variation of rate with acidity one formed between [Ag(bipy)]2+ and PriOH can be specified as the only one involved. At high added [AgI] a back reaction is found and this is discussed in terms of the influence of AgI ions in the solvent wall of a cage before the AgI and radical formed in the oxidation can diffuse out. Values for ΔH* and ΔS* for the oxidation at low [AgI] are compared with ΔH* and ΔS* for the oxidation of PriOH and aqua-cations.
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