Journal of Solution Chemistry p. 187 - 199 (2012)
Update date:2022-08-24
Topics:
Sharanabasamma
Angadi, Mahantesh A.
Salunke, Manjalee S.
Tuwar, Suresh M.
The kinetics of oxidation of L-valine by a copper(III) periodate complex was studied spectrophotometrically. The inverse second-order dependency on [OH-] was due to the formation of the protonated diperiodatocuprate(III) complex ([Cu(H3IO6) 2]-) from [Cu(H2IO6) 2]3-. The retarding effect of initially added periodate suggests that the dissociation of copper(III) periodate complex occurs in a pre-equilibrium step in which it loses one periodate ligand. Among the various forms of copper(III) periodate complex occurring in alkaline solutions, the monoperiodatocuprate(III) appears to be the active form of copper(III) periodate complex. The observed second-order dependency of [L-valine] on the rate of reaction appears to result from formation of a complex with monoperiodatocuprate(III) followed by oxidation in a slow step. A suitable mechanism consistent with experimental results was proposed. The rate law was derived as: (Equation presented) The temperature effect on the rate of reaction was also studied. The activation parameters of the reaction Ea, ΔH#, ΔS#, ΔG#, and log 10 A are 49 ± 2 kJ·mol-1, 47.5 ± 2 kJ·mol-1, -49 ± 2 J·K -1·mol-1, 62 ± 3 kJ·mol-1 and 6.0 ± 0.1, respectively. Springer Science+Business Media, LLC 2012.
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