Kinetics and mechanism of the oxidation of hydrazine with [RuIII(pic)3] in aqueous solution

Abstract

The kinetics and mechanism of the oxidation of hydrazine by [RuIII(pic)3] (pic- = picolinate anion) were studied spectrophotometrically as a function of hydrazine concentrations at a constant pH of 5.5. The rate of the reaction was followed by monitoring the appearance of the MLCT band of [RuII(pic)3]- at 466 nm. The reaction rate was found to be first-order for Ru(III)-complex concentration. The observed rate constant (k obs) values increased linearly with increase in the hydrazine concentration. The oxidation reaction was studied at varied temperature (20–40 °C). The ΔH≠ (73 ± 3 kJ mol−1 kJ·mol−1) and the negative ΔS≠ (34 ± 7 J·deg−1mol−1) values are consistent with the proposed outer-sphere electron transfer process operative in the oxidation of hydrazine with [RuIII(pic)3]. A working mechanism involving the formation of an active diazene (HN = NH) intermediate followed by its rapid two-electron oxidation by [RuIII(pic)3] in a kinetically inconsequential step producing N2 as sole product is proposed for an overall four-electron oxidation of hydrazine to dinitrogen.