Evidence of liquid water formation during methane hydrates dissociation below the ice point

Dissociation of small methane hydrate samples formed from water droplets of size 0.25-2.5 mm has been investigated below the ice melting point in the temperature range of 240-273 K, where the self-preservation effect is observed for bulk hydrates. The experiments included optical microscopy observations combined with P-T measurements of the dissociation conditions for the methane hydrates. For the first time, the formation of supercooled liquid water during the hydrate dissociation was reliably detected in the temperature range of 253-273 K. The formation of the liquid phase was visually observed. The induction time of the ice nucleation for the metastable liquid water depended from the dissociation temperature and a size of water droplets formed during the hydrate dissociation. It was found that in the temperature range of 253-273 K values of the dissociation pressure for the small hydrate samples fall on the extension of the water-hydrate-gas equilibrium curve into the metastable region where supercooled water exist. The average molar enthalpy of 51.7 kJ/mol for the dissociation of the small methane hydrate samples in the temperature range of 253-273 K was calculated using Clausius-Clapeyron equation. This value agrees with the enthalpy of dissociation of bulk methane hydrates into water and gas at temperatures above 273 K.