Electron-transfer kinetics and mechanism of the reduction of octacyanometallates(IV) (M = Mo,W) by hydroxide ion in aqueous solution |
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Authors: | Michail Bogdanov Ryszard Gryboś Alina Samotus Konstantin Bogolitsyn |
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Institution: | (1) Faculty of Chemistry, Jagiellonian University, 3 Kraków, Ingardena, Poland;(2) Faculty of Chemistry, Forest Engineering Institute, 163007 Archangelsk, Russia |
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Abstract: | Summary The kinetics of the reduction of octacyanometallates(IV) in alkaline aqueous medium have been studied spectrophotometrically. The experimental results are in agreement with following rate law:-dM(CN)
inf8
sup3–
]/dt = k
obsM(CN)
inf8
sup3–
]2OH–]Na+] where k
obs = 4.1 × 10–2M–3s–1 (Mo) and 4.0 × 10–4 M–3 s–1 (W). The rate data were used to calculate the thermodynamic activation parameters H
and S
. A mechanism of the reaction is discussed.On leave from Faculty of Chemistry, Forest Engineering Institute, Archangelsk, Russia. |
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Keywords: | |
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