RESUMO
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.
RESUMO
We report shear viscosity of heavy water supercooled 33K below its melting point, revealing a 15-fold increase compared to room temperature. We also confirm our previous data for the viscosity of supercooled light water and reach a better accuracy. Our measurements, based on the spontaneous Brownian motion of 350nm spheres, disagree at the lowest temperature with the only other available data, based on Poiseuille flow in a narrow capillary, which may have been biased by electro-osmotic effects. Here we provide a detailed description of the experiment and its analysis. We review the literature data about dynamic properties of water (viscosity, self-diffusion coefficient, and rotational correlation time), discuss their temperature dependence, and compare their decoupling in the two isotopes.
