Kinetics and mechanism of electron transfer reactions. Osmium(VIII) catalyzed oxidation of mannitol by hexacyanoferrate(III) in aqueous alkaline medium期刊界 All Journals 搜尽天下杂志传播学术成果专业期刊搜索期刊信息化学术搜索

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Kinetics and mechanism of electron transfer reactions. Osmium(VIII) catalyzed oxidation of mannitol by hexacyanoferrate(III) in aqueous alkaline medium

Authors:

Mridula?Sharma Gayatri?Sharma Beena?Agrawal C?L?Khandelwal Email author" target="_blank">P?D?Sharma Email author

Institution:

(1) Department of Chemistry, University of Rajasthan, Jaipur, 302004, India

Abstract:

The kinetics of electron transfer from mannitol to hexacyanoferrate(III), catalyzed by osmium(VIII), has been studied in alkaline medium. The substrate order is complex, whereas it is one with respect to the catalyst. The rate is independent of the concentration of oxidant. Also, the rate increases with increasing concentration of hydroxide ion in a complex manner. A kinetic rate law corresponding to the proposed mechanism has been suggested as follows:

$- { 1 \over 2} {\hbox{d}\hbox{Fe}(\hbox{CN})_{6}^{3-}] \over \hbox{d}t}={( k_1 K_2 + k_2 K_1 K_3 \hbox{OH}^{-}] \hbox{Os}^{\rm VIII}] \hbox{Mtol}]) \over 1 + K_1 \hbox{OH}^{-}] + K_2\hbox{Mtol}]+K_1 K_3\hbox{Mtol}]\hbox{OH}^{-}]}$

where Mtol] is for mannitol. The kinetic parameters have been evaluated and the value of K₁ is in agreement with the value determined spectrophotometrically.

Keywords:

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