Phase Behavior of Aqueous Na-K-Mg-Ca-CI-NO3 Mixtures: Isopiestic Measurements and Thermodynamic Modeling

A comprehensive model has been established for calculating thermodynamic properties of multicomponent aqueous systems containing the Na{sup +}, K{sup +}, Mg{sup 2+}, Ca{sup 2+}, Cl{sup -}, and NO{sub 3}{sup -} ions. The thermodynamic framework is based on a previously developed model for mixed-solvent electrolyte solutions. The framework has been designed to reproduce the properties of salt solutions at temperatures ranging from the freezing point to 300 C and concentrations ranging from infinite dilution to the fused salt limit. The model has been parameterized using a combination of an extensive literature database and new isopiestic measurements for thirteen salt mixtures at 140 C. The measurements have been performed using Oak Ridge National Laboratory's (ORNL) previously designed gravimetric isopiestic apparatus, which makes it possible to detect solid phase precipitation. Water activities are reported for mixtures with a fixed ratio of salts as a function of the total apparent salt mole fraction. The isopiestic measurements reported here simultaneously reflect two fundamental properties of the system, i.e., the activity of water as a function of solution concentration and the occurrence of solid-liquid transitions. The thermodynamic model accurately reproduces the new isopiestic data as well as literature data for binary, ternary and higher-order subsystems. Because of its high accuracy in calculating vapor-liquid and solid-liquid equilibria, the model is suitable for studying deliquescence behavior of multicomponent salt systems

High temperature water adsorption on The Geysers rocks

In order to measure water retention by geothermal reservoir rocks at the actual reservoir temperature, the ORNL high temperature isopiestic apparatus was adapted for adsorption measurements. The quality of water retained by rock samples taken from three different wells of The Geysers geothermal reservoir was measured at 150{sup degree}C, 200{sup degree}C, and 250{sup degree}C as a function of pressure in the range 0.00 {<=}p/p{sub degree} {<=} 0.98, where p{sub degree} is the saturated water vapor pressure. Both adsorption (increasing pressure) and desorption (decreasing pressure) runs were made in order to investigate the nature and the extent of the hysteresis. Additionally, low temperature gas adsorption analyses were performed on the same rock samples. Nitrogen or krypton adsorption and desorption isotherms at 77 K were used to obtain BET specific surface areas, pore volumes and their distributions with respect to pore sizes. Mercury intrusion porosimetry was also used to obtain similar information extending to very large pores (macropores). A correlation is sought between water adsorption, the surface properties, and the mineralogical and petrological characteristics of the solids

Measurements of water vapor adsorption on The Geysers rocks

One of the goals of this project is to determine the dependence of the water retention capacity of the rocks as a function of temperature. The results show a significant dependence of the adsorption and desorption isotherms on the grain size of the sample. The increase in the amount of water retained with temperature observed previously between 90 and 30{degrees}C for various reservoir rocks from The Geysers may be due to the contribution of slow chemical adsorption and may be dependent on the time allowed for equilibration. In contrast with the results of Shang, some closed and nearly closed hysteresis loops on the water adsorption/desorption isotherms were obtained in this study. In these cases the effects of activated processes were not present, and no increase in water adsorption with temperature was observed

Water adsorption at high temperature on core samples from The Geysers geothermal field

The quantity of water retained by rock samples taken from three wells located in The Geysers geothermal field, California, was measured at 150, 200, and 250 C as a function of steam pressure in the range 0.00 {le} p/p{sub 0} {le} 0.98, where p{sub 0} is the saturated water vapor pressure. Both adsorption and desorption runs were made in order to investigate the extent of the hysteresis. Additionally, low temperature gas adsorption analyses were made on the same rock samples. Mercury intrusion porosimetry was also used to obtain similar information extending to very large pores (macropores). A qualitative correlation was found between the surface properties obtained from nitrogen adsorption and the mineralogical and petrological characteristics of the solids. However, there was no direct correlation between BET specific surface areas and the capacity of the rocks for water adsorption at high temperatures. The hysteresis decreased significantly at 250 C. The results indicate that multilayer adsorption, rather than capillary condensation, is the dominant water storage mechanism at high temperatures

Direct Measurements of Pore Fluid Density by Vibrating Tube Densimetry

The densities of pore confined fluids were measured for the first time by means of vibrating tube densimetry VTD . A custom built high pressure, high temperature vibrating tube densimeter was used to measure the densities of propane at subcritical and supercritical temperatures between 35 and 97 C and carbon dioxide at supercritical temperatures between 32 and 50 C saturating hydrophobic silica aerogel 0.2 g cm3, 90 porosity synthesized inside Hastelloy U tubes. Additionally, supercritical isotherms of excess adsorption for CO2 and the same porous solid were measured gravimetrically using a precise magnetically coupled microbalance. Pore fluid densities and total adsorption isotherms increased monotonically with increasing density of the bulk fluid, in contrast to excess adsorption isotherms, which reached a maximum and then decreased toward zero or negative values above the critical density of the bulk fluid. The isotherms of confined fluid density and excess adsorption obtained by VTD contain additional information. For instance, the maxima of excess adsorption occur below the critical density of the bulk fluid at the beginning of the plateau region in the total adsorption, marking the end of the transition of pore fluid to a denser, liquidlike pore phase. Compression of the confined fluid significantly beyond the density of the bulk fluid at the same temperature was observed even at subcritical temperatures. The effect of pore confinement on the liquid amp; 8722;vapor critical temperature of propane was less than amp; 8764;1.7 K. The results for propane and carbon dioxide showed similarity in the sense of the principle of corresponding states. Good quantitative agreement was obtained between excess adsorption isotherms determined from VTD total adsorption results and those measured gravimetrically at the same temperature, confirming the validity of the vibrating tube measurements. Thus, it is demonstrated that vibrating tube densimetry is a novel experimental approach capable of providing directly the average density of pore confined fluids, and hence complementary to the conventional gravimetric or volumetric piezometric adsorption techniques, which yield the excess adsorption the Gibbsian surface exces