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  • Chem Sci Trans., 2015, 4(2),  pp 498-502  

    DOI:10.7598/cst2015.1035

    Research Article

    Oxidative Decarboxylation of Dicarboxylic Acid by Pyridiniumdichromate- Kinetic and Mechanistic Study

  • RAKESH KUMAR SHARMA1, DASHRATH SINGH RATHORE1 and B. K. DANGARH2
  • 1 Department of Chemistry, Pacific University, Udaipur, India
    2Department of Chemistry, Govt. P. G. College, Neemuch, India
  • Abstract

    Oxidation of dicarboxylic acid viz-oxalic acid by pyridiniumdichromate (PDC) in perchloric acid medium has been studied. Active oxidizing species involved is protonated PDC. First order plot is observed for log(a-x) versus time. Effect of concentration of PDC, HClO4, Mn(II), Ce(III) and ionic strength has been investigated. Thermodynamic parameters have been evaluated. Energy of activation is 51.22 kJ mol-1. Entropy of activation is low and negative. The activation energy does not correspond to C-C bond breaking, but the reaction products indicate C-C bond breaking. A cyclic complex formation, which undergoes C-C fission, has been suggested.

    Keywords

    Oxalic acid, Pyridiniumdichromate, Oxidation, Kinetics

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