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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 9, Number 1
February 20, 1965 

Linear Relationships between Thermodynamic Parameters (Part Ⅴ) Critical Evaluation and Mechanistic Significances of the Relationship

열역학함수간의 직선관계 (제5보) 관계식의 평가와 반응기구상의 의의
Ikchoon Lee

일반식중의 potential energy 변수로서 σ와 Y를 사용할 수 있음을 밝혔고 또 관계식의 반응기구상의 의미를 논하였다. Benzyl chlorides의 solvolysis반응 data를 적용함으서 물질상수 a'는 2개의 뚜렷한 게열을 형성하며 치환기상수 σ와는 각계열마다 별도로 직선관계를 가지면 이로서 SN1으로부터 SN2로의 반응구조의 변화를 알 수가 있었다.

Justifications for the use of σ and Y as independent potential energy variables in the general equation have been reviewed and some mechanistic significances of the relationship discussed. Analysis of the activation parameters for the solvolysis of benzyl chlorides in ethanol-water mixture showed that there are two distinct series of substrate constants a', which can be correlated linearly within a series with the substituent constants σ conforming to the generally accepted concept of change in mechanism from SN1 to SN2.

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