Kinetics of the oxidation of isopropyl alcohol by bis(2,2′-bipyridine)silver(II) ions

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 [Ag^I] a back reaction is found and this is discussed in terms of the influence of Ag^I ions in the solvent wall of a cage before the Ag^I and radical formed in the oxidation can diffuse out. Values for ΔH* and ΔS* for the oxidation at low [Ag^I] are compared with ΔH* and ΔS* for the oxidation of PrⁱOH and aqua-cations.