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Understanding the role of ions and water molecules in the NaCl dissolution process

Klimeš, J; Bowler, DR; Michaelides, A; (2013) Understanding the role of ions and water molecules in the NaCl dissolution process. J Chem Phys , 139 (23) 234702 - ?. 10.1063/1.4840675. Green open access

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Abstract

The dissolution of NaCl in water is one of the most common everyday processes, yet it remains poorly understood at the molecular level. Here we report the results of an extensive density functional theory study in which the initial stages of NaCl dissolution have been examined at low water coverages. Our specific approach is to study how the energetic cost of moving an ion or a pair of ions to a less coordinated site at the surface of various NaCl crystals varies with the number of water molecules adsorbed on the surface. This "microsolvation" approach allows us to study the dependence of the defect energies on the number of water molecules in the cluster and thus to establish when and where dissolution becomes favorable. Moreover, this approach allows us to understand the roles of the individual ions and water molecules in the dissolution process. Consistent with previous work we identify a clear preference for dissolution of Cl ions over Na ions. However, the detailed information obtained here leads to the conclusion that the process is governed by the higher affinity of the water molecules to Na ions than to Cl ions. The Cl ions are released first as this exposes more Na ions at the surface creating favorable adsorption sites for water. We discuss how this mechanism is likely to be effective for other alkali halides.

Type: Article
Title: Understanding the role of ions and water molecules in the NaCl dissolution process
Location: United States
Open access status: An open access version is available from UCL Discovery
DOI: 10.1063/1.4840675
Publisher version: http://dx.doi.org/10.1063/1.4840675
Language: English
Additional information: © 2013 Author(s). Published through AIP's Author Select initiative under the terms of the Creative Commons 3.0 Unported License.
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy
URI: https://discovery.ucl.ac.uk/id/eprint/1423475
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