Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Linear Relationships between Thermodynamic Parameters (Part II) Applicabiliy of New Equations

熱力學函數間의 直線關係 (第2報) 適用性의 檢討

  • 이익춘 (原子力硏究所 化學硏究室) ;
  • 박용자 (原子力硏究所 化學硏究室)
  • Published : 19631200
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Abstract

Linear relationships between thermodynamic parameters, ,${\Delta}{\Delta}H^{\neq}=a{\sigma}+b{\Delta}{\Delta}S^{\neq}$, and $\Delta{\Delta}F^\neq=a\sigma+(b-T)\Delta{\Delta}S^\neq$, which were derived in the previous report have been tested with 57 reactions from literature. Linearities of plots $\Delta{\Delta}H^\neq-a\sigma$ vs. $\Delta{\Delta}S^\neq$ were generally good and the average correlation coefficient was 0.983 and the average of standard deviations from regression lines was 0.11. For 15 out of 57 reactions, Hammett plots were unsatisfactory and most of the reaction did not satisfy the Leffler equation. The general applicability of the new equations has been confirmed by the analysis of each reaction for which existing equations failed to correlate.

前報에서 誘導한 새로운 直線關係式,${\Delta}{\Delta}H^{\neq}=a{\sigma}+b{\Delta}{\Delta}S^\neq$ 및 ${\Delta}{\Delta}F^{\neq}=a{\sigma]+(b-T){\Delta}{\Delta}S^{\neq}$, 의 適用性을 57個反應으로 檢討하였다. 57個反應에 대한 ${\Delta}{\Delta}H^{\neq}-a{\sigma}$, 對 ${\Delta}{\Delta}S^{\neq}$의 直線關係 相關係數의 平均은 0.983이었고 直線으로부터의 標準備差의 平均値는 0.11이었다. 57個反應中 15個反應에 對해서는 Hammett方程式이 成立되지 않었고, 또 大部分의 反應에 對해서 Leffier의 式이 成立하지 않었다. 이와같이 從來의 關係式 이 成立하지 않는 反應도 새로운 關係式으로 設明되며, 그 理由를 檢討해 봄으로써 上記 2式이 더 一般的으로 適用되는 關係式임을 確認하였다.

Keywords

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