Abstract
The oxidation of oxalic acid by tetrachloroaurate(III) ion in 0.005 ⩽ [HClO 4] ⩽ 0.5 mol dm −3 is first order in [ AuCl 4 - ] and a fractional order in [oxalic acid], the reactive entities being AuCl 3(OH) − and HC 2 O 4 - ions. The pseudo first-order rate, k obs, with respect to [Au(III)], is retarded by increasing [H +] and [Cl −]. The retardation by H + ion is caused by the dissociation equilibrium ( COOH ) 2 ⇌ HC 2 O 4 - + H + . A mechanism in which a substitution complex, AuCl 3 C 2 O 4 2 - is formed from AuCl 3(OH) − and HC 2 O 4 - ions prior to its rate limiting disproportionation into products is suggested. The rate limiting constant, k, has been evaluated and its activation parameters are reported. The equilibrium constant K 1 for the formation of the substitution complex AuCl 3 C 2 O 4 2 - and its thermodynamic parameters are also reported.
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