Abstract
The kinetics of reduction of tris(acetylacetonato)cobalt(III) by hydrazine in aqueous perchloric acid medium have been studied under different conditions. The complex Co(acac)3 and its protonated form Co(acac)2(acacH+) are both reduced by N2H4 with specific rate constants kR and kH,R respectively. These reactions occur concurrently with the self reduction of the complex in acid media having a specific rate constant kH. From detailed analysis of the effects of acid and hydrazine concentration on the rate, values of kH, kR and kH,R have been determined at 30°, 40° and 50°C at an ionic strength of 2 and from these the corresponding activation parameters ΔH≠ and ΔS≠ have been evaluated. The mechanism appears to involve the formation of intermediates in which N2H62+ is hydrogen bonded to Co(acac)3 and Co(acac)2(acacH+) respectively each of which possibly decomposes (rate determining) by H atom transfer from N2H62+ to the bound acetylacetonate ligand, leading to an electron transfer to cobalt(III) forming cobalt(II). Kinetik und Mechanismus der Reduktion von Kobalt(III)-Trisacetylacetonat durch Hydrazin in saurem Medium Die Kinetik der Reduktion von Kobalt(III)-Trisacetylacetonat durch Hydrazin in wasrig-perchlorsaurer Losung wurde unter unterschiedlichen Bedingungen untersucht.
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