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

  • S. P. Srivastava
  • Anil Kumar


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.


Bond Cleavage Oxide Structure Homogeneous Catalysis Free Aldehyde Detailed Kinetic Study 
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  1. 1.
    Accepted for poster presentation in the 1st International Symposium on Homogeneous Catalysis, 34th Southwest Regional Meeting, American Chemical Society, Texas.Google Scholar
  2. 2.
    M. M. Khan and S. P. Srivastava, J. Indian Chem. Soc., 46, 574 (1969).Google Scholar
  3. 3.
    G. D. Menghani and G. V. Bakore, Curr. Sci., 37, 641 (1968).Google Scholar
  4. 4.
    Z. G. Szabo, L. Csanyi, and H. Galiba, Z. Anal. Chem., 135, 269 (1952).CrossRefGoogle Scholar
  5. 5.
    K. C. Khulbe and S. P. Srivastava, Agra Univ. J. Res. (Sci.), 9, 177 (1960).Google Scholar
  6. 5a.
    K. C. Khulbe and S. P. Srivastava, Agra Univ. J. Res. (Sci.), 14, 85 (1965).Google Scholar
  7. 6.
    J. E. Mclsaac, Jr. and J. O. Edwards, J. Org. Chem., 34, 2565 (1969).CrossRefGoogle Scholar
  8. 7.
    A. R. Gallopo and J. O. Edwards, J. Org. Chem., 36, 4089 (1971).CrossRefGoogle Scholar
  9. 8.
    K. J. Laidler; ‘Chemical Kinetics’, McGraw-Hill Book Co., Inc., New York, July 1950; Chapter 1, 18.Google Scholar
  10. 9.
    L. S. Levitt, Canad. J. Res., 31, 915 (1953).Google Scholar
  11. 10.
    E. Howard, Jr. and L. S. Levitt, J. Am. Chem. Soc., 75, 6170 (1953).CrossRefGoogle Scholar
  12. 11.
    L. S. Levitt and E. Howard, Jr., Abst. of Papers, Dallas Meeting, A.C.S., 1956, 51 - N.Google Scholar
  13. 12.
    E. R. Malinowski and L. S. Levitt, J. Am. Chem. Soc., 80, 5334 (1958).CrossRefGoogle Scholar
  14. 13.
    K. C. Khulbe and S. P. Srivastava, Agra Univ. J. Res. (Sci.), XIV, Part III, 125 (1965).Google Scholar
  15. 14.
    C. D. Hurd and W. H. Saunders, Jr., J. Am. Chem. Soc., 74, 5324 (1952).CrossRefGoogle Scholar
  16. 15.
    L. F. Fieser and M. Fieser, Organic Chemistry, Reinhold Pub¬lishing Corporation, New York, 3rd Ed., 1960, Ch. 14, 361.Google Scholar
  17. 16.
    B. Tollens; 1841-1918, b. Hamburg; Ph.D. Göttingen, Göttingen.Google Scholar
  18. 17.
    H. C. Brown, R. S. Fletcher, and R. B. Johannensen, J. Am. Chem. Soc., 73, 212 (1951).CrossRefGoogle Scholar
  19. 18.
    S. P. Srivastava, S. K. Singhal, and R. G. Sharma, Indian J. Chem., 12, 684 (1974).Google Scholar
  20. 19.
    E. Bekier and W. Kijowski, Roez. Chem., 14, 1004 (1934).Google Scholar
  21. 19a.
    E. Bekier and W. Kijowski, Roez. Chem., 15, 136 (1935).Google Scholar
  22. 20.
    N. M. Beilerian and O. R. Chaltykyan, Dokt. Akad. Nauk. Arm. S.S.R., 31, 147 (1960).Google Scholar
  23. 21.
    J. A. McMillan and B. Smaller, J. Chem. Phys., 35, 1698 (1961).CrossRefGoogle Scholar
  24. 22.
    A. Ledwith, P. J. Russell, and L. H. Sutcliffe, J. Chem. Soc. Perkin II, 630 (1973).Google Scholar
  25. 23.
    O. P. Chawla and R. W. Fessenden, J. Phys. Chem., 79, 2693 (1975).CrossRefGoogle Scholar
  26. 24.
    M. Anbar and P. Neta, Ind. J. Appl. Radiat. Isotop., 18, 493 (1967).CrossRefGoogle Scholar
  27. 25.
    E. Hayon and M. Simic, J. Am. Chem. Soc., 94, 42 (1972).CrossRefGoogle Scholar
  28. 26.
    R. O. C. Norman, P. M. Storey, and P. R. West, J. Chem. Soc., B, 1087 (1970).Google Scholar
  29. 27.
    B. C. Gilbert, J. P. Larkin, and R. 0. C. Norman, J. Chem. Soc., Perkin II, 1272 (1972).Google Scholar
  30. 28.
    S. Steenken, P. O’Neill, and D. Schulte-Frohlinde, J. Phys. Chem., 81 26 (1977).CrossRefGoogle Scholar
  31. 29.
    L. R. Subbaraman and M. Santappa, Zeit. Physik. Chemie., Neue Folge, I and II, 48, 3 /4 (1966).Google Scholar
  32. 30.
    W. C. E. Higginson and J. W. Marshall, J. Chem. Soc., 447 (1957).Google Scholar
  33. 31.
    F. S. Dainton, ‘Chain Reaction’, Metheuen, London (1956).Google Scholar
  34. 32.
    W. C. Vasudeva, M. I. Taha, and S. Wasif, J. Inorg. Nucl. Chem., 34, 3159 (1972).CrossRefGoogle Scholar
  35. 33.
    H. Eibenberger, S. Steenken, S. Neill and P. O. Schulte-Frohlinde, J. Phys. Chem., 82, 750 (1978).CrossRefGoogle Scholar

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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