The kinetics of the oxidation of [Ni(II)(H2L1)](ClO4)2, (H2L1 = 3,8-dimethyl-4,7-diaza-3,7-decadiene-2,9-dione dioxime) and [Ni(II)(HL2)]ClO4, (H2L2 = 3,9-dimethyl-4,8-diaza-3,8-undecadiene-2,10-dione dioxime) by peroxodisulfate anion (PDS) in aqueous media at 298.0 K have been studied. The kinetics of oxidation of both Ni(II) complexes was found to be first order in the complex concentration. The dependence of the pseudo-first-order rate constant, kobs, for both complexes showed first-order dependence on PDS concentration. The kinetics of oxidation of [Ni(II)(H2L1)]2+ complex showed a complex dependence on [H+] over the pH range of 4.98–7.50, whereas that of [Ni(II)(HL2)]+ is independent of pH over the pH range of 5.02–7.76. The value of kobs, for both complexes, decreased with increasing ionic strength consistent with the involvement of oppositely charged ions in the rate-determining step. The effect of ionic strength is more pronounced for [Ni(II)(H2L1)]2+–PDS reaction than for [Ni(II)(HL2)]+–PDS reaction, confirming the higher charges of the latter.
Oxime Peroxodisulfate Diacetyl Monoxime Diprotonated Form Oxime Ligand
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S. F. A. F. acknowledges the award of a Sandwich program by the Universiti Sains Malaysia, Penang, Malaysia, and for providing her the facilities that enabled her to carry out most of this work. She also wishes to thank Prof. R. A. of USM for allowing her to conduct the work in her research laboratory. The authors also wish to acknowledge the University of Khartoum for financial support.