Issue 21, 2022

Understanding specific ion effects and the Hofmeister series

Abstract

Specific ion effects (SIE), encompassing the Hofmeister Series, have been known for more than 130 years since Hofmeister and Lewith's foundational work. SIEs are ubiquitous and are observed across the medical, biological, chemical and industrial sciences. Nevertheless, no general predictive theory has yet been able to explain ion specificity across these fields; it remains impossible to predict when, how, and to what magnitude, a SIE will be observed. In part, this is due to the complexity of real systems in which ions, counterions, solvents and cosolutes all play varying roles, which give rise to anomalies and reversals in anticipated SIEs. Herein we review the historical explanations for SIE in water and the key ion properties that have been attributed to them. Systems where the Hofmeister series is perturbed or reversed are explored, as is the behaviour of ions at the liquid–vapour interface. We discuss SIEs in mixed electrolytes, nonaqueous solvents, and in highly concentrated electrolyte solutions – exciting frontiers in this field with particular relevance to biological and electrochemical applications. We conclude the perspective by summarising the challenges and opportunities facing this SIE research that highlight potential pathways towards a general predictive theory of SIE.

Graphical abstract: Understanding specific ion effects and the Hofmeister series

Supplementary files

Article information

Article type
Perspective
Submitted
20 Febr. 2022
Accepted
13 Apr. 2022
First published
09 Maijs 2022
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2022,24, 12682-12718

Understanding specific ion effects and the Hofmeister series

K. P. Gregory, G. R. Elliott, H. Robertson, A. Kumar, E. J. Wanless, G. B. Webber, V. S. J. Craig, G. G. Andersson and A. J. Page, Phys. Chem. Chem. Phys., 2022, 24, 12682 DOI: 10.1039/D2CP00847E

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