Unusual Phase Behavior of Confined Heavy Water

TL;DR

This study investigates the anomalous phase behavior of heavy water confined in nanoporous silica, revealing a potential transition from second-order to first-order phase transitions and suggesting a tricritical point at specific temperature and pressure.

Contribution

It provides the first neutron scattering measurements of confined heavy water's density over a wide T-P range, uncovering unusual phase transition features.

Findings

Observation of a density kink below a certain pressure

Hysteresis in density profiles above the critical pressure

Evidence suggesting a tricritical point at Pc ≈ 1500 bar, Tc ≈ 210 K

Abstract

Many of the anomalous properties of water are amplified in the deeply supercooled region. Here we present neutron scattering measurements of the density of heavy water confined in a nanoporous silica matrix MCM-41-S (\approx15 {\AA} pore diameter), namely, the equation of state {\rho}(T,P), in a temperature-pressure range, from 300 K to 130 K and from 1 bar to 2900 bar, where bulk water will crystalize. A sudden change of slope in the otherwise continuous density profile (a "kink") is observed below a certain pressure Pc; however, this feature is absent above Pc. Instead, a hysteresis phenomenon in the density profiles between the warming and cooling scans becomes prominent above Pc. Hence, the data can be interpreted as a line of apparent 2nd-order phase transition at low pressures evolving into a line of 1st-order phase transition at high pressures. If so, the existence of a "tricritical point" at Pc \approx 1500 bar, Tc \approx 210 K becomes another possible scenario to explain the exceptionally rich phase behavior of low-temperature confined water.