Kinetics and mechanism of oxidation of some nickel(II)–imine–oxime complexes by peroxodisulfate in aqueous acidic solutions
Tóm tắt
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, k
obs, 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 k
obs, 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.
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