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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 7, Number 4
August 20, 1963 

Linear Relationships between Thermodynamic Parameters (Part Ⅲ) Application to Solvolysis Reaction

열역학함수간의 직선관계 (제3보) Solvolysis 반응에의 응용
Ikchoon Lee

전보에서 유도한 치환기효과 일반관계식은 용매조성에 따르는 상수, Y를 potential energy 항에 대치함으로서 solvolysis 반응에 응용할 수가 있다. 신방정식, △△H≠=a'Y+b△△S≠, 의 적용성은 문헌에 보고된 35개반응에 대한 직선관계를 조사해 봄으써 검사하였다. 결과로 평균 상관계수 0.977을 얻었고, 따라서 이 방정식이 solvolysis반응에 일반적으로 적용됨을 밝혔고, 또 Grunwald-Winstein의 식을 지니는 몇몇 난점을 해결할 수가 있음을 알 수 있었다. enthalypy-entopy 직선효과는 외부 enthalpy와 외부 entropy에 관한 것이며, 엄격히 말해서 외부 enthalpy entropy 직선효과임을 강조하였다.

The general equation for the substituent effect test, which was derived in the previous paper, has been extended to correlate thermodynamic parameters of solvolysis reaction by modifying the potential energy term to represent the effect of changes in solvent composition. The linear fits of the new equation, ΔΔH≠ = a'Y + bΔΔS≠, were tested with 35 examples from literature and average correlation coefficient of 0.977 was obtained. Examination of results showed that the equation is generally applicable to solvolysis reaction and helps elucidate some the difficulties experienced with the Grunwald-Winsteln equation. It has been stressed that the linear enthalpy-entropy effect exists only between the external enthalpy and entropy of activation, and therefore strictly it is the linear external enthalpy-entropy effect.

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