Thermodynamics of brine-salt equilibria -- II. The system NaCl-KCl-H 2 O from 0 to 200°C

Details Thermodynamics of brine-salt equilibria -- II. The system NaCl-KCl-H 2 O from 0 to 200°C Thermodynamics of brine-salt equilibria -- II. The system NaCl-KCl-H 2 O from 0 to 200°C

Oct 1976

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1976gecoa..40.1211w&link_type=abstract

Geochimica et Cosmochimica Acta, vol. 40, Issue 10, pp.1211-1220

Physics

Scientific paper

Thermodynamic functions describing salt solubilities and activities in the system NaCl-KCl-H 2 O have been obtained over the temperature range 0-200°C using existing isopiestic and solubility data. The two-parameter equation used previously at 25°C was sufficient to characterize the activity coefficient of the aqueous binary systems from infinite dilution to saturation, and the mixing behavior could be described by Harned's Rule over this temperature range. Activity coefficients have been calculated for NaCl-KCl-H 2 O mixtures as a function of temperature using the expression: log ± A = - A I /(1+å B I ) + B . I + AB I . Calculated solubility curves are in good agreement with the experimental data up to 200°C and estimates of H 0 ( sat ) and C 0 p ( sat ) calculated from the first and second temperature derivatives of log K are consistent with measured standard state enthalpies and heat capacities for both NaCl and KCl. The absolute value of the mixing parameters, AB , decrease with increasing temperature and approach zero for both salts in the vicinity of 200°C. The excess free energy of mixing thus approaches zero and may be due to the transition from a dissociated electrolyte solution to one in which associated ions or molecular species are beginning to dominate over `free' ions. The mixing parameter decreases more rapidly for KCl than for NaCl and suggests that KCl-rich systems become associated at lower temperatures than NaCl-rich systems.

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