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焓-熵补偿(EEC)效应:再探讨

Enthalpy-Entropy Compensation (EEC) Effect: A Revisit.

作者信息

Pan Animesh, Biswas Tapas, Rakshit Animesh K, Moulik Satya P

机构信息

Centre for Surface Science, Department of Chemistry, Jadavpur University , Kolkata 700032, India.

Indian Society for Surface Science & Technology, Department of Chemistry, Jadavpur University , Kolkata 700032, India.

出版信息

J Phys Chem B. 2015 Dec 31;119(52):15876-84. doi: 10.1021/acs.jpcb.5b09925. Epub 2015 Dec 17.

Abstract

A short account of the developments and perspectives of IKR (iso-kinetic relation) and EEC (enthalpy (H) - entropy (S) compensation) has been presented. The IKR and EEC are known to be extra thermodynamic or empirical correlations though linear H-S correlation can be thermodynamically deduced. Attempt has also been made to explain the phenomena in terms of statistical thermodynamics. In this study, we have briefly revisited the fundamentals of both IKR and EEC from kinetic and thermodynamic grounds. A detailed revisit of the EEC phenomenon on varied kinetic and equilibrium processes has been also presented. Possible correlations among the free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes of different similar and nonsimilar chemical processes under varied conditions have been discussed with possible future projections.

摘要

本文简要介绍了等动力学关系(IKR)和焓(H)-熵(S)补偿(EEC)的发展历程与前景。虽然线性H-S相关性可从热力学推导得出,但IKR和EEC是已知的额外热力学或经验相关性。同时也尝试从统计热力学角度解释这些现象。在本研究中,我们从动力学和热力学基础简要回顾了IKR和EEC的基本原理。还详细回顾了EEC现象在不同动力学和平衡过程中的情况。讨论了不同相似和不相似化学过程在不同条件下自由能(ΔG)、焓(ΔH)和熵(ΔS)变化之间可能的相关性以及未来可能的预测。

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