Linear Relationships between Thermodynamic Parameters (Part I) Theoretical

熱力學 函數間의 直線關係 (第1報) 理論

  • Ikchoon Lee (Atomic Energy Research Institute, Korea)
  • 이익춘 (原子力硏究所 化學硏究室)
  • Published : 19630900

Abstract

Inter-relationship between the Hammett equation and the linear enthalpy-entropy effect has been discussed by deriving a new set of equations; ${\Delta}{\Delata}H^{\neq}=a{\sigma}+b{\Delta}{\Delta}S^{\neq}$ and ${\Delta}{\Delta}F^{\neq}=a{sigma}+(b-T){\Delta}{\Delta}S^{\neq}$ where a = -1.36p. Theoretical analysis show that the Hammett, Leffler and Brown equations are special limited forms of these general equations. A necessary and sufficient test of substituent effect can thus be provided by the plot of $({\Delta}{\Delta}H^{\neq}-a{\sigma)$ versus ${\Delta}{\Delta}S^{\neq}$.

Keywords

References

  1. Physical Organic Chemistry L.P. Hammett
  2. Steric Effects in Organic Chemistry R.W. Taft, Jr.;M.S. Newman(ed.)
  3. The Kinetics of Chemical Change C.N. Hinshelwood
  4. J.Org. Chem. v.20 J.E. Leffler
  5. J. Org. Chem. v.27 R.F. Brown
  6. J. Am. Chem. Soc. v.59 K.S. Pitzer
  7. J. Phys. Chem. v.65 L.G. Helper;W.F. O'Hara
  8. Z. physik. Chem. v.14 P. Ruetschi
  9. The Theory of Rate Processes S. Glasstone;K.J. Laidler;H. Eyring
  10. Investigation of Rates and Mechanisms of Reactions J.F. Bunnett;A. Weissberger(ed.)
  11. The Foundations of Chemical Kinetics S.W. Benson
  12. J. Chem. Phys. v.19 R. Powell;W. Latimer
  13. J. Am. Chem. Soc. v.79 H.C. Brown;Y. Okamoto
  14. J. Org. Chem. v.22 Y Okamoto;H.C. Brown