Molecular interpretation of the linear relationship between the entropy and the enthalpy of activation of charge transfer reactions in polar liquids

  • A Chandra
  • B Bagchi
Physical and Theoretical

Abstract

The well-known linear relationship (TΔS# =αΔH# +β, where 1 >α > 0,β > 0) between the entropy (ΔS#) and the enthalpy (ΔH#) of activation for reactions in polar liquids is investigated by using a molecular theory. An explicit derivation of this linear relation from first principles is presented for an outersphere charge transfer reaction. The derivation offers microscopic interpretation for the quantitiesα andβ. It has also been possible to make connection with and justify the arguments of Bell put forward many years ago

Keywords

Molecular interpretation linear relationship entropy enthalpy of activation polar liquids charge transfer reactions 

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References

  1. Amis E S 1966Solvent effects on reaction rates and mechanisms (New York: McMillan)Google Scholar
  2. Bagchi B 1989Annu. Rev. Phys. Chem. 40 115CrossRefGoogle Scholar
  3. Bagchi B and Chandra A 1989aJ. Chem. Phys. 90 7338CrossRefGoogle Scholar
  4. Bagchi B and Chandra A 1989bChem. Phys. Lett. 155 533CrossRefGoogle Scholar
  5. Bagchi B and Chandra A 1991Adv. Chem. Phys. 80 1CrossRefGoogle Scholar
  6. Barbara P F and Jarzeba W 1988Acc. Chem. Res. 21 195CrossRefGoogle Scholar
  7. Barbara P F and Jarzeba W 1990Adv. Photochem. 15 1CrossRefGoogle Scholar
  8. Bell R P 1937Trans. Faraday Soc. 33 496CrossRefGoogle Scholar
  9. Chandra A and Bagchi B 1989aJ. Chem. Phys. 90 1832CrossRefGoogle Scholar
  10. Chandra A and Bagchi B 1989bJ. Chem. Phys. 91 2954Google Scholar
  11. Chandra A and Bagchi B 1989cJ. Chem. Phys. 91 3056CrossRefGoogle Scholar
  12. Chandra A and Bagchi B 1989dJ. Chem. Phys. 91 7181CrossRefGoogle Scholar
  13. Chandra A and Bagchi B 1989eJ. Phys. Chem. 93 6996CrossRefGoogle Scholar
  14. Chandra A and Bagchi B 1990J. Phys. Chem. 94 3152CrossRefGoogle Scholar
  15. Chandra A and Bagchi B 1991.J. Chem. Phys. 94 2258CrossRefGoogle Scholar
  16. Entelis S G and Tiger R P 1976Reaction kinetics in the liquid phase (New York: Wiley)Google Scholar
  17. Evans Polanyi M 1936Trans. Faraday Soc. 32 1333CrossRefGoogle Scholar
  18. Fleming G R and Wolynes P G 1990Physics Today 43 36CrossRefGoogle Scholar
  19. Frohlich H 1958Theory of dielectrics (Oxford: University Press)Google Scholar
  20. Glasstone S, Laidler K J and Eyring H 1941The theory of rate processes (New York: McGraw Hill)Google Scholar
  21. Grey C G and Gubbins K E 1984Theory of molecular fluids (Oxford: Clarendon) vol. IGoogle Scholar
  22. Hansen J P and McDonald I R 1986Theory of simple liquids (London: Academic Press)Google Scholar
  23. Hynes J T 1985Annu. Rev. Phys. Chem. 36 573CrossRefGoogle Scholar
  24. Kosower E M and Huppert D 1986Annu. Rev. Phys. Chem. 37 127CrossRefGoogle Scholar
  25. Marcus R 1956J. Chem. Phys. 966 979CrossRefGoogle Scholar
  26. Marcus R 1964Annu. Rev. Phys. Chem. 15 155CrossRefGoogle Scholar
  27. Marroncelli M, McInnis J and Fleming G R 1989Science 243 1674CrossRefGoogle Scholar
  28. McMannis G E and Weaver M J 1989J. Chem. Phys. 90 912, 1720CrossRefGoogle Scholar
  29. Neuman M 1986Mol. Phys. 57 97CrossRefGoogle Scholar
  30. Onsager L 1953J. Am. Chem. Soc. 58 1485Google Scholar
  31. Raineri F O, Zhou Y, Friedman H L and Stell G 1991Chem. Phys. (in press)Google Scholar
  32. Reichardt C 1979Solvent effects in organic chemistry (New York: Verlag Chemie)Google Scholar
  33. Simon J D 1988Acc. Chem. Res. 21 128CrossRefGoogle Scholar
  34. Wei D and Patey G N 1990J. Chem. Phys. 93 1399CrossRefGoogle Scholar
  35. Wertheim M S 1971J. Chem. Phys. 55 4291CrossRefGoogle Scholar
  36. Wynne-Jones W F K and Eyring H 1935J. Chem. Phys. 3 492CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 1992

Authors and Affiliations

  • A Chandra
    • 1
  • B Bagchi
    • 1
  1. 1.Solid State and Structural Chemistry UnitIndian Institute of ScienceBangaloreIndia
  2. 2.Department of ChemistryUniversity of British ColumbiaVancouverCanada

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