Phase relations in the system NaCl-KCl-H 2 O II: Differential thermal analysis of the halite liquidus in the NaCl-H 2 O binary above 450°c

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Thermal analysis of the halite liquidus in the system NaCl-H 2 O has been conducted for NaCl mole fractions ( X NaCl ) greater than 0.25 ( i.e. , > 50 wt. % NaCl) at pressures between 0.3 and 4.1 kb and temperatures greater than 450°C. The position of the liquidus was located by differential thermal analysis (DTA) of cooling scans only, as heating scans did not produce definitive DTA peaks. The dP/dT slope of the liquidus is positive and steep at high pressures, but at high X NaCl , and pressures below 0.5 kb it appears to reverse slope and intersects the three-phase curve (liquid-halite-vapour) at a shallow angle. However, due to the complex nature of the DTA signal when P <- 0.5 kb, there is considerable doubt about exactly what event has been recorded in the experiments conducted at these low pressures. The solubility of halite can be expressed as a function of the mole-fractional-based activity of NaCl in the liquid phase ( L ) in temperature (T, °K) and pressure (P, bars) In NaCl ( L . T . P ) = -19.884 - 0.001275 T - 1388/ T + 3.2305 In ( T ) - 0.07574 PT Our liquidus data (based on 10 compositions) above 500 bars for these brines were combined with this equation to generate activity coefficients of NaCl which were fit within their experimental uncertainties to the following one parameter Margules equation In NaCl ( L . T . P ) = (0.7268 - 695.7/ T - 0.1217 PT )(1 - X NaCl ) 2 . Concentrated solutions of NaCl show negative deviations from ideality which rapidly increase in magnitude with decreasing X NaCl .

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