Calculation of the thermodynamic and geochemical consequences of nonideal mixing in the system H2O-CO2-NaCl on phase relations in geologic systems: Equation of state for H2O-CO2-NaCl fluids at high pressures and temperatures |
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| Authors: | Teresa Suter Bowers Harold C Helgeson |
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| Institution: | Department of Geology and Geophysics, University of California, Berkeley, California 94720 U.S.A. |
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| Abstract: | Fluid inclusion analyses leave little doubt that solutions containing large concentrations of H2O, CO2, and electrolytes are involved in a wide range of geologic processes. Although the miscibility gap in the system H2O-CO2 occurs only at low temperatures, experimental data reported by Takenouchi and Kennedy (1965) and Gehrig (1980) indicate that the addition of 6 weight percent NaCl relative to H2O + Nacl extends the region of immiscibility in the system H2O-CO2-NaC] to ≥700°C at 500 bars and mole fractions of CO2 (XCO2) ? 0.1. In contrast, addition of 20 weight percent NaCl relative to H2O + NaCl at 700°C and 500 bars expands the miscibility gap to XCO2 ? 0.2. At 2000 bars, addition of 20 and 35 weight percent NaCl relative to H2O + NaCl causes the miscibility gap to extend to ~500° and ~700°C, respectively, at . The existence of the immiscible region in this high-pressure/temperature environment has a profound effect on temperatures of equilibration for metamorphic mineral assemblages (Bowers and Helgeson, 1983). To determine the extent to which nonideality in the ternary system affects these equilibria, the modified Redlich-Kwong (MRK.) equation of state was fit to pressure-volume-temperature data taken from Gehrig (1980) along pseudobinaries for which is constant. Fugacity coefficients of the components were then generated from the fugacity coefficient analog of the MRK equation of state and these coefficients were used together with solubility data to determine the compositions of the coexisting immiscible phases. The tie lines connecting the coexisting phases shift in orientation from nearly parallel to the H2O-CO2 binary at low temperatures to almost perpendicular to this binary at high temperatures. |
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