Kinetics and mechanism of the oxidation of hydrazine with the dichlorotriaquoruthenium(V)-oxo complex in aqueous solution

Taqui Khan, M. M. ; Prakash Rao, A. ; Chatterjee, Debabrata ; Sanal Kumar, S. (1992) Kinetics and mechanism of the oxidation of hydrazine with the dichlorotriaquoruthenium(V)-oxo complex in aqueous solution Journal of Molecular Catalysis, 73 (1). pp. 17-21. ISSN 0304-5102

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Official URL: http://www.sciencedirect.com/science/article/pii/0...

Related URL: http://dx.doi.org/10.1016/0304-5102(92)80058-O

Abstract

The kinetics and mechanism of the oxidation of hydrazine by dichlorotriaquomono-oxoruthenium(V) [O=RuV(H2O)3Cl2]+ (1) was studied spectrophotometrically as a function of complex and hydrazine concentrations at ionic strength (μ=0.1-0.3 M) of Na2SO4 at a constant pH of 1.85. The rate of the reaction was followed by monitoring the disappearance of the MLCT band of the oxo complex, 1, at 420 nm. The rate of oxidation of hydrazine by 1 is first order with respect to complex and hydrazine concentrations. The rate increases when the ionic strength of the medium is increased. The oxidation of hydrazine was studied at three different temperatures, and the activation parameters ΔH and ΔS were evaluated. A mechanism involving the formation of an active diazene (HN=NH) intermediate (in a rate-determining step) that rapidly undergoes two-electron oxidation to give N2 is proposed for an overall four-electron oxidation of hydrazine.

Item Type:Article
Source:Copyright of this article belongs to Elsevier Science.
ID Code:57796
Deposited On:30 Aug 2011 10:31
Last Modified:30 Aug 2011 10:31

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