Armstrong, E. orcid.org/0009-0002-0930-1857, Yeandel, S.R. orcid.org/0000-0002-6977-1677, Harding, J.H. orcid.org/0000-0001-8429-3151 et al. (1 more author) (2025) Surface free energies and entropy of aqueous CaCO₃ interfaces. Langmuir. ISSN 0743-7463
Abstract
This work uses a recently proposed methodology to calculate the free energies of calcite and aragonite interfaces with water. This method properly includes the entropic contributions, ignored or approximated in previous work. By including this entropic component, we show that the aqueous calcite {101̅4} surface has a lower free energy than any of the aragonite surfaces. This resolves the discrepancies in previous simulation work that suggested that an aragonite nucleus would be more stable than a calcite one. Our analysis of the water structure highlights the generally greater entropic contribution to the interfacial free energy at the aragonite/water interface than at the calcite one. These methods are applied to a range of temperatures to examine how the solution temperature alters the interfacial energies. Our results are then discussed in the context of calcium carbonate nucleation and polymorph-morphology selection under different environmental conditions.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2025 The Authors. For the purpose of open access, the author has applied a Creative Commons Attribution (CC BY - https://creativecommons.org/licenses/by/4.0/) license to any Author Accepted Manuscript version arising. |
Keywords: | Calcite; Enthalpy; Entropy; Free energy; Interfaces |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Engineering (Sheffield) > School of Chemical, Materials and Biological Engineering The University of Sheffield > Faculty of Social Sciences (Sheffield) > Information School (Sheffield) |
Funding Information: | Funder Grant number ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL EP/R018820/1 Engineering and Physical Sciences Research Council EP/X035859/1 |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 27 Mar 2025 09:10 |
Last Modified: | 27 Mar 2025 09:10 |
Status: | Published online |
Publisher: | American Chemical Society (ACS) |
Refereed: | Yes |
Identification Number: | 10.1021/acs.langmuir.4c04738 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:224904 |
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