Oxidation of Bis(1,4,7-Triazacyclononane)nickel(ii) ...

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Title Oxidation of Bis(1,4,7-Triazacyclononane)nickel(ii) by the peroxodisulfate anion in aqueous and binary aqueous-media
Author(s) Robert I. Haines, L. Butt, M. K. Park, D. Wheeler
Journal Canadian Journal of Chemistry-Revue Canadienne De Chimie
Date 1993
Volume 71
Issue 7
Start page 976
End page 982
Abstract The kinetics of oxidation of bis(1,4,7-triazacyclononane)nickel(II), [Ni(tacn)2]2+, by the peroxodisulphate anion has been studied in water as a function of S2O82- concentration and temperature. The reaction is first order in both the nickel(II) complex and S2O82-, with a second-order rate constant of 1.13 mol dm-3 s-1 at 298 K. The activation energy for the reaction is 38.3 +/- 1.8 kJ mol-1. The reaction was also studied at 298 K in a series of mixed aqueous solvents. Rate retardation relative to water was observed in all solvent mixtures studied. Correlation of the solvent effects on the kinetics of reaction has been made with the free energy of transfer of the initial state and the transition state.

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