Some Aspects of the Liquid Water Thermodynamic Behavior: From The Stable to the Deep Supercooled Regime

Abstract

Liquid water is considered to be a peculiar example of glass forming materials because of the possibility of giving rise to amorphous phases with different densities and of the thermodynamic anomalies that characterize its supercooled liquid phase. In the present work, literature data on the density of bulk liquid water are analyzed in a wide temperature-pressure range, also including the glass phases. A careful data analysis, which was performed on different density isobars, made in terms of thermodynamic response functions, like the thermal expansion <inline-formula><math display="inline"><semantics><msub><mi>&alpha;</mi><mi>P</mi></msub></semantics></math></inline-formula> and the specific heat differences <inline-formula><math display="inline"><semantics><mrow><msub><mi>C</mi><mi>P</mi></msub><mo>&minus;</mo><msub><mi>C</mi><mi>V</mi></msub></mrow></semantics></math></inline-formula>, proves, exclusively from the experimental data, the thermodynamic consistence of the liquid-liquid transition hypothesis. The study confirms that supercooled bulk water is a mixture of two liquid &ldquo;phases&rdquo;, namely the high density (HDL) and the low density (LDL) liquids that characterize different regions of the water phase diagram. Furthermore, the <inline-formula><math display="inline"><semantics><mrow><msub><mi>C</mi><mi>P</mi></msub><mo>&minus;</mo><msub><mi>C</mi><mi>V</mi></msub></mrow></semantics></math></inline-formula> isobars behaviors clearly support the existence of both a liquid&ndash;liquid transition and of a liquid&ndash;liquid critical point.