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Kinetics of Oxidation of Hydrazine and of t-Butylhydrazine using Tris(dimethylglyoximato)nickelate(IV) in the Presence of Added Cu(2+) (aq)

DOI: 10.1039/DT9840001477

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1477 - 1484 (1984)

Update date:2022-08-11

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Authors:

Acharya, SridharaAcharya, Sridhara

Neogi, GautamNeogi, Gautam

Panda, Rama KrushnaPanda, Rama Krushna

Ramaswamy, DoraiRamaswamy, Dorai

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Article abstract of DOI:10.1039/DT9840001477

The kinetics of the oxidation of hydrazine and t-butylhydrazine using tris(dimethylglyoximato)nickelate(IV), (2-), in the presence of added Cu(2+)(aq), and in the pH range 5.0 - 7.0 at 35 deg C and I = 0.25 mol dm-3 in aqueous medium, follow pseudo-first-order and pseudo-zero-order disappearance of the NiIV complex, respectively.Results of the Cu(2+) (aq)-promoted oxidation of hydrazine by (2-) are consistent with a probable scheme involving pH-dependent equilibrium formation of intermediate adducts between the NiIV and CuII-hydrazine complex species present in the solution and subsequent rate-determining electron transfer(s) to the adduct(s) from the hydrazine species in the presence of H(1+).Results of the Cu(2+) (aq)-catalyzed oxidation of t-butylhydrazine are interpreted in terms of a probable mechanism involving a rate-determining decomposition of the 1:1 intermediate complex between the CuII and t-butylhydrazine species in the solution, with a concomitant electron transfer.While the oxidation of hydrazine leads to nitrogen, the main products of the t-butylhydrazine oxidation are nitrogen and t-butyl alcohol.

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