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Nucleation of NaCl from aqueous solution : critical sizes, ion-attachment kinetics, and rates
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Zimmermann, Nils E. R., Vorselaars, Bart, Quigley, David and Peters, Baron (2015) Nucleation of NaCl from aqueous solution : critical sizes, ion-attachment kinetics, and rates. Journal of the American Chemical Society, 137 (41). pp. 13352-13361. doi:10.1021/jacs.5b08098 ISSN 0002-7863.
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Official URL: http://dx.doi.org/10.1021/jacs.5b08098
Abstract
Nucleation and crystal growth are important in material synthesis, climate modeling, biomineralization, and pharmaceutical formulation. Despite tremendous efforts, the mechanisms and kinetics of nucleation remain elusive to both theory and experiment. Here we investigate sodium chloride (NaCl) nucleation from supersaturated brines using seeded atomistic simulations, polymorph-specific order parameters, and elements of classical nucleation theory. We find that NaCl nucleates via the common rock salt structure. Ion desolvation—not diffusion—is identified as the limiting resistance to attachment. Two different analyses give approximately consistent attachment kinetics: diffusion along the nucleus size coordinate and reaction-diffusion analysis of approach-to-coexistence simulation data from Aragones et al. (J. Chem. Phys. 2012, 136, 244508). Our simulations were performed at realistic supersaturations to enable the first direct comparison to experimental nucleation rates for this system. The computed and measured rates converge to a common upper limit at extremely high supersaturation. However, our rate predictions are between 15 and 30 orders of magnitude too fast. We comment on possible origins of the large discrepancy.
Item Type: | Journal Article | ||||||
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Subjects: | Q Science > QD Chemistry Q Science > QH Natural history |
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Divisions: | Faculty of Science, Engineering and Medicine > Research Centres > Centre for Complexity Science Faculty of Science, Engineering and Medicine > Science > Physics |
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Library of Congress Subject Headings (LCSH): | Biomineralization, Nucleation, Crystal growth | ||||||
Journal or Publication Title: | Journal of the American Chemical Society | ||||||
Publisher: | American Chemical Society | ||||||
ISSN: | 0002-7863 | ||||||
Official Date: | 15 September 2015 | ||||||
Dates: |
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Volume: | 137 | ||||||
Number: | 41 | ||||||
Page Range: | pp. 13352-13361 | ||||||
DOI: | 10.1021/jacs.5b08098 | ||||||
Status: | Peer Reviewed | ||||||
Publication Status: | Published | ||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||
Date of first compliant deposit: | 2 September 2016 | ||||||
Date of first compliant Open Access: | 2 September 2016 | ||||||
Funder: | National Science Foundation (U.S.) (NSF), Engineering and Physical Sciences Research Council (EPSRC) | ||||||
Grant number: | 095502 (NSF), EP/H00341X/1 (EPSR) | ||||||
Open Access Version: |
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