非水介质中的贺夫迈斯特现象：碳酸亚乙酯中电解质的溶解度。

Hofmeister phenomena in nonaqueous media: the solubility of electrolytes in ethylene carbonate.

机构信息

Department of Chemistry and CSGI, University of Florence, 50019 Sesto Fiorentino (Firenze), Italy.

出版信息

J Phys Chem B. 2012 Dec 13;116(49):14398-405. doi: 10.1021/jp309157x. Epub 2012 Nov 30.

Abstract

The solubility of some potassium salts (KF, KCl, KBr, KI, KNO(3), KClO(4), KSCN, and KSeCN) in ethylene carbonate (EC) was determined at different temperatures with an inductively coupled plasma atomic emission spectrometer. From the solubility measurements, the thermodynamic parameters ΔG, ΔH, and ΔS, of solution and of solvation, were calculated. Measurements were carried out via XRD, ATR, and FTIR to determine the effect of each salt on the properties of the solvent. The open question of whether specific ion (Hofmeister) effects are restricted to hydration peculiar to water is resolved. As for water, the effects are due to solute (ion, dipolar) induced solvent structure not accounted for by electrostatic forces. Cooperative quantum mechanical forces are necessary to understand the phenomena.

摘要

采用感应耦合等离子体原子发射光谱法在不同温度下测定了一些钾盐（KF、KCl、KBr、KI、KNO3、KClO4、KSCN 和 KSeCN）在碳酸亚乙酯（EC）中的溶解度。根据溶解度测量结果，计算了溶液和溶剂化的热力学参数 ΔG、ΔH 和 ΔS。通过 XRD、ATR 和 FTIR 进行了测量，以确定每种盐对溶剂性质的影响。解决了特定离子（Hofmeister）效应是否仅限于水的特殊水合作用的问题。对于水，这些效应是由于溶质（离子、偶极子）引起的溶剂结构，而不是由静电力引起的。需要协同量子力学力来理解这些现象。