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


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 ${\Delta}{\Delta}S^{\neq}$.



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