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Multiple insights call for revision of modern thermodynamic models to account for structural fluctuations in water |
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| Authors: | Evangelos Tsochantaris Aswin V Muthachikavil Baoliang Peng Xiaodong Liang Georgios M Kontogeorgis |
| Affiliation: | 1. Department of Chemical and Biochemical Engineering, Center for Energy Resources Engineering, Technical University of Denmark, Lyngby, Denmark
Contribution: Conceptualization (equal), Data curation (lead), Formal analysis (lead), Methodology (equal), Software (lead), Validation (lead), Visualization (lead), Writing - original draft (lead), Writing - review & editing (equal);2. Research Institute of Petroleum Exploration & Development (RIPED), PetroChina, Beijing, China Contribution: Conceptualization (equal), Funding acquisition (lead), Project administration (equal), Resources (equal), Supervision (equal), Writing - review & editing (equal);3. Department of Chemical and Biochemical Engineering, Center for Energy Resources Engineering, Technical University of Denmark, Lyngby, Denmark |
| Abstract: | Modern thermodynamic models incorporate the concept of association (hydrogen bonding) and they can describe very satisfactorily many properties of water containing mixtures. They have not been successful in representing water's anomalous properties and this work provides a possible explanation. We have analyzed and interpreted recent experimental data, molecular simulation results, and two-state theory approaches and compared against the predictions from thermodynamic models. We show that the dominance of the tetrahedral structure implemented in modern thermodynamic models may be the reason for their failure for describing water systems. While this study does not prove the two-state theories for water, it indicates that a high level of tetrahedral structure of water is not in agreement with water's anomalous properties when used in thermodynamic models. |
| Keywords: | thermodynamic models molecular simulations SAFT structural fluctuations water |