高温及超临界条件下MgCl2与CaCl2水溶液中离子水化与缔合的量子化学计算

化学学报 ›› 2004, Vol. 62 ›› Issue (14): 1287-1292. 上一篇下一篇

高温及超临界条件下MgCl₂与CaCl₂水溶液中离子水化与缔合的量子化学计算

丁皓¹, 朱宇¹, 王俊¹, 陆小华¹, 马晶²

1. 南京工业大学化工学院, 南京, 210009;
2. 南京大学化学系, 理论与计算化学研究所, 南京, 210093

投稿日期:2003-10-10 修回日期:2004-03-20 发布日期:2014-02-17
通讯作者: 陆小华,E-mail:xhlu@njuct.edu.cn E-mail:xhlu@njuct.edu.cn
基金资助:
国家自然科学基金(No.20376032)、国家杰出青年科学基金(No.29925616)、国家自然科学重点基金(No.20236010)、江苏省自然科学基金(No.BK97124)资助项目.

Quantum Chemical Calculations on the Hydration and Association of MgCl₂ and CaCl₂ Solutions at High and Supercritical Temperatures

DING Hao¹, ZHU Yu¹, WANG Jun¹, LU Xiao-Hua¹, MA Jing²

1. College of Chemical Engineering, Nanjing University of Technology, Nanjing 210009;
2. Institute of Theoretical and Computational Chemistry, Department of Chemistry, Nanjing University, Nanjing 210093

Received:2003-10-10 Revised:2004-03-20 Published:2014-02-17

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摘要/Abstract

对NaCl等碱金属水溶液的研究表明,室温条件下,离子在溶液中以水合形式存在,而在高温及超临界时,阴阳离子将结合成为离子对.采用量子化学计算,研究了MgCl₂与CaCl₂水溶液中水化与缔合的情况.通过Gaussian 98软件包计算了阳离子的水化自由能以及离子对的生成能,从而获得水合离子与离子对的热力学稳定性及其随温度、压力的变化情况.通过比较热力学稳定性,考察了两种溶液中水化与缔合的变化情况.研究结果表明,MgCl₂与CaCl₂水溶液中离子水化与缔合的变化趋势与碱金属溶液基本一致,但是存在一个过渡区域,该区域内离子对与水合离子共存,因此需要采用不同于碱金属溶液的方法处理MgCl₂与CaCl₂水溶液.

关键词: 水化, 缔合, 超临界, 量子化学, MgCl₂与CaCl₂水溶液

Studies on aqueous alkali metal solutions, especially NaCl solution, have shown that most ions exist in a hydrated form at ambient temperatures and ion pairs dominate at elevated temperatures.The quantum chemical calculations have been performed to investigate the hydration and association in aqueous MgCl₂ and CaCl₂ solutions.The hydration free energies of cations and formation energies of ion pairs were calculated by software package Gaussian 98 under different conditions.These calculations give the thermodynamic stabilities of hydrated cations and ion pairs and the variation depending on temperature and pressure.By comparing the stabilities of hydrated cation and ion pair, the variation for hydration and association can be determined.The results indicate that the tendencies for hydration and association in MgCl₂ and CaCl₂ solutions agree with those in alkali metal ion solutions, but there is a different area where ion pairs and hydrated ions coexist and both hydration and association have important influences on the solution.In this area, thermodynamic models for NaCl solution are not applicable and new models must be established for MgCl₂ and CaCl₂ solutions.

Key words: hydration, association, supercritical, quantum chemistry, aqueous MgCl₂ and CaCl₂ solutions

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丁皓, 朱宇, 王俊, 陆小华, 马晶. 高温及超临界条件下MgCl₂与CaCl₂水溶液中离子水化与缔合的量子化学计算[J]. 化学学报, 2004, 62(14): 1287-1292.

DING Hao, ZHU Yu, WANG Jun, LU Xiao-Hua, MA Jing. Quantum Chemical Calculations on the Hydration and Association of MgCl₂ and CaCl₂ Solutions at High and Supercritical Temperatures[J]. Acta Chimica Sinica, 2004, 62(14): 1287-1292.

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高温及超临界条件下MgCl₂与CaCl₂水溶液中离子水化与缔合的量子化学计算

Quantum Chemical Calculations on the Hydration and Association of MgCl₂ and CaCl₂ Solutions at High and Supercritical Temperatures

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