Understanding specific ion effects and the Hofmeister series
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 the...
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| Published in | Physical chemistry chemical physics : PCCP Vol. 24; no. 21; pp. 12682 - 12718 |
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| Main Authors | , , , , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
Royal Society of Chemistry
01.06.2022
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| Subjects | |
| Online Access | Get full text |
| ISSN | 1463-9076 1463-9084 1463-9084 |
| DOI | 10.1039/d2cp00847e |
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| Summary: | 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.
This perspective reviews the historical explanations for specific ion effects, and explores the frontiers of the field before summarising its challenges and opportunities. |
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| Bibliography: | In 1998 Gunther Andersson completed his PhD applying ion scattering spectroscopy on liquid surfaces at the University of Witten/Herdecke (Germany) under the supervision of Prof Harald Morgner. The following two years he was at the Technical University Eindhoven on a project on polymer based light emitting diodes. In 2000 Gunther moved to Leipzig University (Germany) were he developed the method neutral impact collision ion scattering spectroscopy (NICISS) for investigation of soft matter surfaces to its current stage. He completed his Habilitation in 2006. In 2007 he was appointed at Flinders University (Australia). He is now leading as a full Professor a research group with activities in photocatalysis based on metal clusters on surfaces, and liquid and polymer surfaces and interfaces. His laboratories are equipped with instruments for electron spectroscopy (MIES, XPS, UPS, IPES), ion scattering spectroscopy (NICISS) and infrared spectroscopy (FTIR). Anand is a PhD student studying at Flinders University (Australia) under the supervision of Prof. Gunther Andersson and Prof. Vince Craig. He received a Bachelor in Physics/Nanotechnology with First class with distinction from SRM University (India) in 2018. For his Bachelor's final year research thesis, he worked at Flinders University and SRM research institute under supervision of Prof. Andersson where he achieved a high distinction grade. His PhD research work involves investigation of Specific ion effects at liquid surfaces employing NICISS. Alister Page received his PhD from the University of Newcastle in 2008. In 2009 he was awarded a Fukui postdoctoral fellowship in the group of Prof. Keiji Morokuma at the Fukui Institute for Fundamental Chemistry, Kyoto University, and in 2012 he was appointed as a Research Fellow at the University of Newcastle. He took up a faculty position in Newcastle in 2013, where he is now Professor in the Discipline of Chemistry and leads the University of Newcastle Computational Chemistry Group. His research focuses on developing and applying quantum chemical methods to topics including self-assembly, carbon & inorganic nanomaterials, ionic liquids, deep eutectic solvents, heterogeneous & photocatalysis, and specific ion effects. Erica Wanless is Professor and Head of Chemistry at the University of Newcastle (Australia). She graduated with a PhD in Surface Science from the Australian National University in 1995. She then completed a postdoctoral fellowship at the University of Otago, New Zealand. She joined the University of Newcastle Chemistry Department in 1996. Erica is a colloid and interface scientist who has built an international research profile for her investigations of surfactant, polymer or colloidal materials at interfaces. In recent years her research has been focussed on stimulus responsive polymer brush coatings which are tuned by changes in pH, temperature, ionic strength and/or ion identity. Erica is the current president of the Australasian Colloid and Interface Society. Hayden Robertson is a PhD student at the University of Newcastle under the supervision of Prof. Erica Wanless and Prof. Grant Webber. Hayden graduated from a combined degree of Bachelor of Mathematics (Pure) and Bachelor of Science (Hons)(Chemistry) from the University of Newcastle in 2019. His research includes investigating specific ion effects in complex environments using surface techniques such as neutron reflectometry and ellipsometry. Vince Craig leads the Colloids group in the Department of Materials Physics at the Australian National University. He completed both his BSc (Honours in Chemistry in 1992) and PhD degrees (jointly in the Departments of Applied Maths and Chemistry in 1997) at the ANU before postdoctoral positions at UC Davis, California and the University of Newcastle, NSW, Australia. His research interests include the measurement of surface forces in particular the long range hydrophobic interaction, adsorption of surfactants and polymers, specific ion effects, wetting and bubbles, including nanobubbles. He was awarded an ARC Postdoctoral fellowship in 1998, an ARC Research Fellowship in 2001 and an ARC Future Fellowship in 2009. He has worked with numerous industry partners as a consultant, advisor and in the provision of research. Vince was a Director and Treasurer of the Australasian Colloid and Interface Society (ACIS) from 2013 to 2018 and is currently Treasurer on the LOC for IACIS2022, to be held in Brisbane (26-29th June). Kasimir obtained a Bachelor of Mathematics/Bachelor of Science (Hons - Chemistry) from the University of Newcastle in 2018 and is a PhD candidate there under the supervision of Prof. Alister Page, Prof. Erica Wanless and Prof. Grant Webber. In 2022 he started apostdoctoral appointment position at the Australian National University under the guidance of Prof. Vince Craig. He is investigating specific ion effects via computational and quantum chemistry, as well as surface force measurements. Electronic supplementary information (ESI) available. See DOI Gareth is a PhD student studying at the University of Newcastle (Australia) under the supervision of Prof. Alister Page, Prof. Erica Wanless and Prof. Grant Webber. He received a Bachelor of Mathematics/Bachelor of Science (Hons) with first class honours from UoN. He is currently investigating specific ion effects in various solvents at high concentrations using molecular dynamics. https://doi.org/10.1039/d2cp00847e Grant Webber is a research chemical engineer, working across discipline boundaries to uncover the links between nanoscale behaviours and macroscale properties. His research combines cutting-edge experiments and precision modelling and simulation methods to study colloidal and interfacial phenomena with relevance to personal care products, pharmaceuticals, the minerals industry, water treatment, micro- and nanomechanical devices, food production and biomedical device manufacture. Grant has deployed neutron reflection and scattering, ellipsometry, atomic force microscopy and quartz crystal microbalance measurements to resolve specific ion effects in polymer brush systems with high spatial and temporal resolution. 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| ISSN: | 1463-9076 1463-9084 1463-9084 |
| DOI: | 10.1039/d2cp00847e |