Calculations on ionic solvation. Part 1.—Free energies of solvation of gaseous univalent ions using a one-layer continuum model
Calculations on ionic solvation. Part 1.—Free energies of solvation of gaseous univalent ions using a one-layer continuum model
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第 1 部分：使用单层连续介质模型计算气态单价离子的溶剂化自由能。
DOI：
10.1039/f19787401604
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发表时间：
1978
期刊：
影响因子：
--
通讯作者：
J. Liszi
中科院分区：
文献类型：
--
作者：
M. Abraham;J. Liszi
离子溶剂化的静电自由能可以用一个模型来计算，在这个模型中，半径为a、介电常数为Iµi= 1的离子被厚度为（b-a）、介电常数为Iµ1的溶剂层所包围，并浸入介电常数为Iµ0的本体溶剂中。静电能与非静电的溶剂化自由能相结合，从实验数据获得的气体非极性溶质的溶液的自由能，以产生在溶剂中的气体离子的溶剂化的总自由能。发现当a为离子晶体半径，（b-a）为溶剂半径，Iμ1= 2时，一价阳离子和阴离子在1，1-二氯乙烷、1，2-二氯乙烷、四氢呋喃、1，2-二甲氧基乙烷、氨、丙酮、乙腈、硝基甲烷、正丙醇、乙醇、甲醇和水等溶剂中的溶剂化反应与实验符合得很好.有限的数据表明，该方法也可以应用于苯，溴苯，氯苯，苯甲酸乙酯，乙酸乙酯和硝基苯中的离子的溶液。
The electrostatic free energy of solvation of an ion has been calculated using a model in which an ion of radius a and dielectric constant Iµi= 1 is surrounded by a solvent layer of thickness (b–a) and dielectric constant Iµ1, immersed in the bulk solvent of dielectric constant Iµ0. The electrostatic energy is combined with the nonelectrostatic free energy of solvation, obtained from experimental data on the free energy of solution of gaseous non-polar solutes, to yield the total free energy of solvation of a gaseous ion in a solvent. It is found that when a is taken as the ionic crystal radius, (b–a) as the solvent radius and Iµ1= 2 there is excellent agreement with experiment for the solvation of gaseous univalent cations and anions in the solvents, 1,1-dichloroethane, 1,2-dichloroethane, tetrahydrofuran, 1,2-dimethoxyethane, ammonia, acetone, acetonitrile, nitromethane, 1-propanol, ethanol, methanol and water. Limited data suggest that the method can also be applied to solution of ions in benzene, bromobenzene, chlorobenzene, ethyl benzoate, ethyl acetate and nitrobenzene.