Manganese(II) catalysed oxidation of glycerol by cerium(IV) in aqueous sulphuric acid medium: a kinetic and mechanistic study |
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Authors: | Anita P Savanur Sharanappa T Nandibewoor Shivamurti A Chimatadar |
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Institution: | (1) Department of Studies in Chemistry, Karnatak University, Pavate Nagar, Dharwad, 580003, India; |
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Abstract: | The manganese(II) catalysed oxidation of glycerol by cerium(IV) in aqueous sulphuric acid has been studied spectrophotometrically
at 25 °C and I = 1.60 mol dm−3. Stoichiometry analysis shows that one mole of glycerol reacts with two moles of cerium(IV) to give cerium(III) and glycolic
aldehyde. The reaction is first order in both cerium(IV) and manganese(II), and the order with respect to glycerol concentration
varies from first to zero order as the glycerol concentration increases. Increase in sulphuric acid concentration, added sulphate
and bisulphate all decrease the rate. Added cerium(III) retards the rate of reaction, whereas glycolic aldehyde had no effect.
The active species of oxidant and catalyst are Ce(SO4)2 and Mn(H2O)4]2+. A mechanism is proposed, and the reaction constants and activation parameters have been determined. |
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