An experimental determination of the thermodynamic properties of H 2 O-CO 2 -NaCl fluids at high pressures and temperatures

Mathematics – Logic

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Understanding the role of fluids in geological processes requires a knowledge of the mixing properties of common geological fluids. A technique for experimentally determining activity coefficients for H 2 O in fluid mixtures at pressures and temperatures accessible to the internally heated pressure vessel (10 kbar, 1100°C) is presented which uses a new f H 2 O buffer. The f H 2 O buffer involves the simultaneous control of f O 2 (with Ni / NiO ) and f H 2 (with a hydrogen membrane), thereby buffering f H 2 O (or equivalently, a H 2 O through the reaction H 2 + 1/2 O 2 = H 2 O . After quenching the run, the sample is analyzed to determine the X H 2 O and, thus, the activity-composition relation for H 2 O ( a H 2 O - X H 2 O ). Reversals are obtained by simultaneously running capsules loaded with low and high X H 2 O , thereby allowing the equilibrium X H 2 O to be approached from both directions. Several experimental problems encountered during this study and their implications for the precise control of f H 2 in hydrothermal experiments are discussed. Data were collected primarily in the H 2 O-CO 2 system at 2 kbars, 550-850°C, and at 4 kbars, 650°C. At those conditions, the H 2 O-CO 2 system generally shows small positive deviations from ideality. These results are in good agreement with the predictions of the MRK equation of state of (1977) at low T ( T = 550° C ) and are in good agreement with the predictions of the MRK equation of state of And (1981) at higher temperatures. At two conditions (2 kbar, 750°C; 4 kbar, 650°C), negative deviations from ideality are indicated at high X H 2 O . Some data were also collected in the H 2 O-NaCl and H 2 O-CO 2 -NaCl systems. In the former, H 2 O shows small positive deviations from ideality at 2 kbars, 850°C, which increase with decreasing X H 2 O . In the H 2 O-CO 2 -NaCl system, isofugacity lines for H 2 O were measured. In the two-phase region, these lines represent tie lines and, thus can be used to constrain the phase relations in the system.

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