Issue 12, 2010
From the journal:

Soft Matter

Ion association in low-polarity solvents: comparisons between theory, simulation, and experiment

Chantal Valeriani,ab   Philip J. Camp,*c   Jos W. Zwanikken,de   René van Roijd  and  Marjolein Dijkstrab  

* Corresponding authors

a SUPA, School of Physics and Astronomy, The University of Edinburgh, Mayfield Road, Edinburgh, UK

b Soft Condensed Matter, Debye Institute for NanoMaterials Science, Utrecht University, Princetonplein 5, Utrecht, The Netherlands

c School of Chemistry, The University of Edinburgh, West Mains Road, Edinburgh, UK
E-mail: philip.camp@ed.ac.uk

d Institute for Theoretical Physics, Utrecht University, Leuvenlaan 4, Utrecht, The Netherlands

e Department of Material Science and Engineering, Northwestern University, 2220 Campus Drive, Evanston, Illinois, USA

Abstract

The association of ions in electrolyte solutions at very low concentration and low temperature is studied using computer simulations and quasi-chemical ion-pairing theory. The specific case of the restricted primitive model (charged hard spheres) is considered. Specialised simulation techniques are employed that lead to efficient sampling of the arrangements and distributions of clusters and free ions, even at conditions corresponding to nanomolar solutions of simple salts in solvents with dielectric constants in the range 5–10, as used in recent experimental work on charged-colloid suspensions. A direct comparison is effected between theory and simulation using a variety of clustering criteria and theoretical approximations. It is shown that conventional distance-based cluster criteria can give erroneous results. A reliable set of theoretical and simulation estimators for the degree of association is proposed. The ion-pairing theory is then compared to experimental results for salt solutions in low-polarity solvents. The agreement is excellent, and on this basis some calculations are made for the screening lengths which will figure in the treatment of colloid-colloid interactions in such solutions. The accord with available experimental results is complete.

Graphical abstract: Ion association in low-polarity solvents: comparisons between theory, simulation, and experiment

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Article information

DOI
https://doi.org/10.1039/C001577F
Article type
Paper
Submitted
25 Jan 2010
Accepted
22 Mar 2010
First published
13 May 2010

Soft Matter, 2010,6, 2793-2800

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Ion association in low-polarity solvents: comparisons between theory, simulation, and experiment

C. Valeriani, P. J. Camp, J. W. Zwanikken, R. van Roij and M. Dijkstra, Soft Matter, 2010, 6, 2793 DOI: 10.1039/C001577F

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