The purpose of the work is to show how to employ the experimental data from geocryology and soil physics for thermodynamic calculations of gas hydrate phase equilibria by taking into account pore water behavior in sediments. In fact, thermodynamic calculation is used here to determine the amount of non-clathrated pore water content in sediments in equilibrium with gas and hydrate phases. A thermodynamic model for pore water behavior in sediments is developed. Taking into account the experimental water potential data, the model calculations show good agreement with the experimentally measured unfrozen water content for different pressure and temperature conditions. The proposed thermodynamic model is applied for calculations of three-phase equilibria: multicomponent gas phase (methane, natural gas, etc.) – pore water in clay, sand, loamy sand, etc. – bulk (or pore) hydrate. As a result, correlations have been established between unfrozen and non-clathrated water content in natural sediments.

The equilibrium “pore water in sediment–gas hydrate-former–bulk gas hydrate” was experimentally studied. This residual pore water corresponds to a minimal possible amount of water in the sediment, which is in thermodynamic equilibrium with both gas and the bulk hydrate phase. This pore water can be defined as non-clathrated water by analogy to unfrozen water widely used in geocryological science. The amount of non-clathrated water depends on pressure, temperature, type of sediment, and gas hydrate former. The presence of residual pore water influences the thermodynamic properties of hydrate-saturated samples. The paper’s purpose is to describe a new experimental method for determining the amount of non-clathrated water in sediments at different pressure/temperature conditions. This method is based on measuring the equilibrium water content in an initially air-dried sediment plate that has been placed in close contact with an ice plate under isothermal, hydrate-forming gas pressure conditions. This method was used to measure the non-clathrated water content in kaolinite clay in equilibrium with methane hydrate and CO2 hydrate at a temperature of –7.5o C in a range of gas pressures from 0.1 to 8.7 MPa for methane and from 0.1 to 2.5 MPa for CO2. Experimental data show that at the fixed temperature the non-clathrated water in hydrate-containing sediments sharply reduces when gas pressure increases. The experiment demonstrates that the non-clathrated water content strongly depends on temperature, the mineral structure of sediment, and the hydrate-forming gas.

The equilibrium “pore water in sediment–gas hydrate-former–bulk gas hydrate” was experimentally studied. This residual pore water corresponds to a minimal possible amount of water in the sediment, which is in thermodynamic equilibrium with both gas and the bulk hydrate phase. This pore water can be defined as non-clathrated water by analogy to unfrozen water widely used in geocryological science. The amount of non-clathrated water depends on pressure, temperature, type of sediment, and gas hydrate former. The presence of residual pore water influences the thermodynamic properties of hydrate-saturated samples. The paper’s purpose is to describe a new experimental method for determining the amount of non-clathrated water in sediments at different pressure/temperature conditions. This method is based on measuring the equilibrium water content in an initially air-dried sediment plate that has been placed in close contact with an ice plate under isothermal, hydrate-forming gas pressure conditions. This method was used to measure the non-clathrated water content in kaolinite clay in equilibrium with methane hydrate and CO2 hydrate at a temperature of –7.5o C in a range of gas pressures from 0.1 to 8.7 MPa for methane and from 0.1 to 2.5 MPa for CO2. Experimental data show that at the fixed temperature the non-clathrated water in hydrate-containing sediments sharply reduces when gas pressure increases. The experiment demonstrates that the non-clathrated water content strongly depends on temperature, the mineral structure of sediment, and the hydrate-forming gas.