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3 Bulletin of the Polish Academy of Sciences. Chemistry

3 2003

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Mechanistic studies on the oxidation of acrylic acid by quinolinium chlorochromate (QCC)

Mishra K., Singh J. V., Pandey A.

Bulletin of the Polish Academy of Sciences. Chemistry

2003

Vol. 51, No. 1

15-23

The kinetics of oxidation of acrylic acid with a recently developed new mild Cr(VI) reagent quinolinium chlorochromate (QCC) has been investigated in acetic acid-water mixture (50% v/v). The order in [QCC], [acrylic acid] and [H+] is unity. The increase in the amount of acetic acid in its reaction mixture increases the rate. The effect of ionic strength is negligible. The reaction rates have been determined at different temperatures and the activation parameters have been computed. Stoichiometry indicates that one mole of acrylic acid reacts with one mole of QCC. The mechanism consistent with the observed results has been discussed.

Kinetics and mechanism of oxidation of some unsaturated organic substrates by quinolinium chlorochromate

Mishra K., Singh J. V., Pandey A.

Bulletin of the Polish Academy of Sciences. Chemistry

2003

Vol. 51, No. 1

25-33

The oxidation of unsaturated organic compounds, viz. crotyl alcohol, allyl alcohol, crotonaldehyde and maleic acid by quinolinium chlorochromate (QCC) in acetic acid-water medium (50% v/v) leads to the formation of corresponding epoxide. The reaction is of first order each in QCC and the reductant. The reaction is catalysed by hydrogen ions. The increase in dielectric constant of the medium decreases the rate, while variation I in ionic strength has no perceptible change in rate. The reaction rates have been determined at different temperatures and the activation parameters have been evaluated. The mechanism consistent with the observed results has been discussed.

Kinetics and mechanism of oxidation of D-galactose by quinolinium chlorochromate (QCC) in aqueous acetic acid medium

Singh J. V., Mishra K., Pandey A.

Bulletin of the Polish Academy of Sciences. Chemistry

2003

Vol. 51, No. 1

35-43

The oxidation kinetics of D-galactose with quinolinium chlorochromate, C(9)H(7)NHCrO(3)Cl, has been studied in aqueous acetic acid medium 50% (v/v) in the presence of perchloric acid at constant ionic strength. The reaction under pseudo-first order condition, is first order with respect to both the [oxidant] and the [substrate]. The reaction is markedly catalysed by [H+] and the effect of [NaClO(4)] is negligible. Increasing the dielectric constant of medium decreases the reaction rate. A 1 : 1 stoichiometry is observed and the reaction did not induce the polymerisation of acrylonitrile. The reaction has been carried out at different temperatures and the various activation parameters have been computed. A probable mechanism of the reaction is suggested.