Exploration of the phase diagram of liquid water in the low-temperature metastable region using synthetic fluid inclusions

Qiu, Chen; Krüger, Yves; Wilke, M.; Marti, D.; Ricka, Jaroslav; Frenz, Martin (2016). Exploration of the phase diagram of liquid water in the low-temperature metastable region using synthetic fluid inclusions. Physical Chemistry Chemical Physics, 18(40), pp. 28227-28241. Royal Society of Chemistry 10.1039/C6CP04250C

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We present new experimental data of the low-temperature metastable region of liquid water derived from high-density synthetic fluid inclusions (996-916 kg m-3) in quartz. Microthermometric measurements include: (i) prograde (upon heating) and retrograde (upon cooling) liquid-vapour homogenisation. We used single ultrashort laser pulses to stimulate vapour bubble nucleation in initially monophase liquid inclusions. Water densities were calculated based on prograde homogenisation temperatures using the IAPWS-95 formulation. We found retrograde liquid-vapour homogenisation temperatures in excellent agreement with IAPWS-95. (ii) Retrograde ice nucleation. Raman spectroscopy was used to determine the nucleation of ice in the absence of the vapour bubble. Our ice nucleation data in the doubly metastable region are inconsistent with the low-temperature trend of the spinodal predicted by IAPWS-95, as liquid water with a density of 921 kg m-3 remains in a homogeneous state during cooling down to a temperature of -30.5 °C, where it is transformed into ice whose density corresponds to zero pressure. (iii) Ice melting. Ice melting temperatures of up to 6.8 °C were measured in the absence of the vapour bubble, i.e. in the negative pressure region. (iv) Spontaneous retrograde and, for the first time, prograde vapour bubble nucleation. Prograde bubble nucleation occurred upon heating at temperatures above ice melting. The occurrence of prograde and retrograde vapour bubble nucleation in the same inclusions indicates a maximum of the bubble nucleation curve in the ϱ-T plane at around 40 °C. The new experimental data represent valuable benchmarks to evaluate and further improve theoretical models describing the p-V-T properties of metastable water in the low-temperature region.

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