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Updated: Jun 26, 2025

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Published on: July 19, 2019
Isotope effect on the anomalies of water: A corresponding states analysis
Frédéric Caupin1, Pierre Ragueneau1, Bruno Issenmann1
1Institut Lumière Matière, Université Claude Bernard Lyon 1, CNRS, Institut Universitaire de France, F-69622 Villeurbanne, France.
Abstract:
Light and heavy water show similar anomalies in thermodynamic and dynamic properties, with a consistent trend of anomalies occurring at higher temperatures 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 that leads to the collapse of thermodynamic data. The ratio between the 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.
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