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The aqueous reactions H++OH−=H2O at 325°C and Na++OH−= NaOH(aq) at 250–325°C, were studied using a flow calorimeter. Heats of mixing of aqueous NaOH and HCl solutions were measured at 325°C. The enthalpy of water formation (ΔH=95.9 kJ-mol−1, valid at 12.4 MPa and infinite dilution) was obtained at this temperature from the heat of mixing data but differs significantly from that calculated from the Marshall-Franck equation. This calorimetric ΔH at 325°C was used in combination with literaturelog K and ΔH values at lower temperatures to derive equations representinglog K, ΔH, ΔS, and ΔCp for the formation of water from 250 to 325°C. Heats of dilution of aqueous NaOH solutions were measured at 250, 275, 300, and 325°C. Log K, ΔH, and ΔS for the formation of NaOH(aq) were determined at these temperatures from the fits of the calculated and measured heats while ΔCp values were calculated from the variation of ΔH with temperature. No previous experimental results have been reported for the formation of NaOH(aq). The isocoulombic reaction principle is tested using thelog K values obtained in this study. The plot oflog K vs. 1/T for the isocoulombic reaction NaOH(aq) +H+=H2O+Na+ is approximately linear.

The phase equilibrium CO2(g)=CO2(aq) and the aqueous reactions CO32-+H+=HCO3-, HCO3-+H+=CO2(aq)+H2O, and Na++CO32-=NaCO3- were studied from 225 to 325°C using a flow calorimetric technique. Heats of mixing of gaseous CO2 with liquid H2O and with aqueous NaOH solutions were measured at these temperatures. Log K, ?H, ?S, and ?Cp values were determined for these reactions from the heat of mixing data. Equations for these thermodynamic quantities valid at infinite dilution (I=0) and 12.4 MPa are given as a function of temperature from 225 to 325°C. The log K and ?H values agree well with literature values at these temperatures for the first and third reactions, but not for the second reaction. No previous results have been reported for the fourth reaction at high temperatures. The isocoulombic reaction principle is tested using the log K values determined in this study. This principle is found to be valid for the reactions where each charge on one side of the equation is balanced on the other side by a charge of the same sign and magnitude, but not for the reaction where two single negative charges (HCO3- and OH-) are balanced by one double negative charge (CO32-).