KINETICS OF OXIDATION OF METHANOL AND MONO-DEUTERO-METHANOL BY CHROMIUM(VI) IN PERCHLORIC ACID MEDIUM

Article abstract of DOI:10.1016/S0040-4020(01)83487-6

Kinetics of the oxidation of methanol and mono-deutero-methanol by Cr(VI) over a wide range of temperature (25-40 deg C) have been studied in perchloric acid medium at constant ionic strength (μ=1.0 M) adjusted with sodium perchlorate.Each reaction is first order with respect to the substrate and dichromate concentrations but the order with respect to +> is nearly 3 in each case.Both these reactions take place at almost the same rate under identical experimental conditions.The activation parameters of the reactions are not widely different and the values of ΔH(excit) and ΔS(excit) for the oxidation of methanol are 79.5 kJ mole^-1 and -38.1 J deg^-1 respectively, whereas the corresponding values for the deuterated compound are 83.8 kJ mole^-1 and -23.9 J deg^-1 mole^-1.The probable mechanism of the reactions is discussed.