Kinetics and Mechanism of Silver Ion Catalysed Oxidation of Diols with Terminal Hydroxyl Groups by Peroxydisulphate Ion(l)

  • S. P. Srivastava
  • Anil Kumar

Abstract

Kinetic study of Ag+ catalysed oxidation of diols having term¬inal hydroxyl groups viz. propane-1, 3-diol, butane-1, 4-diol, pen- tane-1, 5-diol, and hexane-1, 6-diol by peroxydisulphate ion reveals that these reactions, unlike other diols studied so far, do not fol¬low simple first order kinetics. Each reaction follows first order behaviour in the initial stages, followed by half order inhibition. However, first order specific rate for the initial stage has been found to vary with initial concentration of the reactants. The negative salt effect is of primary exponential type in each case. Various thermodynamic parameters have been evaluated. On the basis of a detailed kinetic study of the initial stage of the reaction (before the onset of inhibition) and product identification, a gen¬eral mechanism for these reactions has been proposed and the rate law derived therefrom. Incidentally, this study has provided a simpler method for the synthesis of corresponding hydroxyaldehydes.

Keywords

Entropy Aldehyde Recrystallization Diethyl Isopropyl Alcohol 

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Copyright information

© Plenum Press, New York 1979

Authors and Affiliations

  • S. P. Srivastava
    • 1
  • Anil Kumar
    • 1
  1. 1.Department of ChemistryUniversity of RoorkeeRoorkeeIndia

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