Probing the Hofmeister series beyond water: Specific-ion effects in non-aqueous solvents

被引:51
作者
Mazzini, Virginia [1 ]
Liu, Guangming [2 ]
Craig, Vincent S. J. [1 ]
机构
[1] Australian Natl Univ, Res Sch Phys & Engn, Dept Appl Math, Canberra, ACT 2601, Australia
[2] Univ Sci & Technol China, Hefei Natl Lab Phys Sci Microscale, Dept Chem Phys, Hefei 230026, Anhui, Peoples R China
基金
澳大利亚研究理事会; 中国国家自然科学基金;
关键词
SIZE-EXCLUSION CHROMATOGRAPHY; PARTIAL MOLAR VOLUMES; BUBBLE COALESCENCE; POLYELECTROLYTE BRUSHES; PREFERENTIAL SOLVATION; ELECTROLYTE-SOLUTIONS; BIOLOGICAL STRUCTURE; PROPYLENE CARBONATE; STABILITY; MIXTURES;
D O I
10.1063/1.5017278
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We present an experimental investigation of specific-ion effects in non-aqueous solvents, with the aim of elucidating the role of the solvent in perturbing the fundamental ion-specific trend. The focus is on the anions: CH3COO- > F- > Cl- > Br- > I- > ClO4- > SCN- in the solvents water, methanol, formamide, dimethyl sulfoxide (DMSO), and propylene carbonate (PC). Two types of experiments are presented. The first experiment employs the technique of size exclusion chromatography to evaluate the elution times of electrolytes in the different solvents. We observe that the fundamental (Hofmeister) series is observed in water and methanol, whilst the series is reversed in DMSO and PC. No clear series is observed for formamide. The second experiment uses the quartz crystal microbalance technique to follow the ion-induced swelling and collapse of a polyelectrolyte brush. Here the fundamental series is observed in the protic solvents water, methanol, and formamide, and the series is once again reversed in DMSO and PC. These behaviours are not attributed to the protic/aprotic nature of the solvents, but rather to the polarisability of the solvents and are due to the competition between the interaction of ions with the solvent and the surface. A rule of thumb is proposed for ion specificity in non-aqueous solvents. In weakly polarisable solvents, the trends in specific-ion effects will follow those in water, whereas in strongly polarisable solvents the reverse trend will be observed. Solvents of intermediate polarisability will give weak specific-ion effects. Published by AIP Publishing.
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页数:12
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