Isotope effect on the anomalies of water: a corresponding states analysis
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arXiv
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| Auteurs principaux: | , , |
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| Format: | Preprint |
| Publié: |
2021
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| _version_ | 1866914796196069376 |
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| author | Caupin, Frédéric Ragueneau, Pierre Issenmann, Bruno |
| author_facet | Caupin, Frédéric Ragueneau, Pierre Issenmann, Bruno |
| contents | Light and heavy water show similar anomalies in thermodynamic and dynamic properties, with a consistent trend of anomalies occurring at higher temperature in heavy water. Viscosity also increases faster upon cooling in heavy water, causing a giant isotope effect, with a viscosity ratio near 2.4 at 244 K. While a simple temperature shift apparently helps in collapsing experimental data for both isotopes, it lacks a clear justification, changes value with the property considered, and requires additional ad hoc scaling factors. Here we use a corresponding states analysis based on the possible existence of a liquid-liquid critical point in supercooled water. This provides a coherent framework which leads to the collapse of thermodynamic data. The ratio between dynamic properties of the isotopes is strongly reduced. In particular, the decoupling between viscosity $η$ and self-diffusion $D$, measured as a function of temperature $T$ by the Stokes-Einstein ratio $Dη/T$, is found to collapse after applying the corresponding states analysis. Our results are consistent with simulations and suggest that the various isotope effects mirror the one on the liquid-liquid transition. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2112_09010 |
| institution | arXiv |
| publishDate | 2021 |
| record_format | arxiv |
| spellingShingle | Isotope effect on the anomalies of water: a corresponding states analysis Caupin, Frédéric Ragueneau, Pierre Issenmann, Bruno Chemical Physics Other Condensed Matter Light and heavy water show similar anomalies in thermodynamic and dynamic properties, with a consistent trend of anomalies occurring at higher temperature in heavy water. Viscosity also increases faster upon cooling in heavy water, causing a giant isotope effect, with a viscosity ratio near 2.4 at 244 K. While a simple temperature shift apparently helps in collapsing experimental data for both isotopes, it lacks a clear justification, changes value with the property considered, and requires additional ad hoc scaling factors. Here we use a corresponding states analysis based on the possible existence of a liquid-liquid critical point in supercooled water. This provides a coherent framework which leads to the collapse of thermodynamic data. The ratio between dynamic properties of the isotopes is strongly reduced. In particular, the decoupling between viscosity $η$ and self-diffusion $D$, measured as a function of temperature $T$ by the Stokes-Einstein ratio $Dη/T$, is found to collapse after applying the corresponding states analysis. Our results are consistent with simulations and suggest that the various isotope effects mirror the one on the liquid-liquid transition. |
| title | Isotope effect on the anomalies of water: a corresponding states analysis |
| topic | Chemical Physics Other Condensed Matter |
| url | https://arxiv.org/abs/2112.09010 |