The solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0 and 90°C, and an evaluation of the aqueous model for the system CaCO3-CO2-H2O

Calculations based on approximately 350 new measurements (Ca_T-PCO₂) of the solubilities of calcite, aragonite and vaterite in CO₂-H₂O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants K_C, K_A, and K_V respectively, for the reaction CaCO₃(s) = Ca²⁺ + CO²⁻₃: 

 where T is in ^oK. At 25°C the logarithms of the equilibrium constants are −8.480 ± 0.020, −8.336 ± 0.020 and −7.913 ± 0.020 for calcite, aragonite and vaterite, respectively.

The equilibrium constants are internally consistent with an aqueous model that includes the CaHCO⁺₃ and CaCO⁰₃ ion pairs, revised analytical expressions for CO₂-H₂O equilibria, and extended Debye-Hückel individual ion activity coefficients. Using this aqueous model, the equilibrium constant of aragonite shows no PCO₂-dependence if the CaHCO⁺₃ association constant is between 0 and 90°C, corresponding to the value logK_Cahco⁺3 = 1.11 ± 0.07 at 25°C. The CaCO⁰₃association constant was measured potentiometrically to be  between 5 and 80°C, yielding logK_CaCO⁰3 = 3.22 ± 0.14 at 25°C.

The CO₂-H₂O equilibria have been critically evaluated and new empirical expressions for the temperature dependence of K_H, K₁ and K₂ are , and logK₂ = −107.8871 − 0.03252849T + 5151.79/T + 38.92561 logT − 563713.9/T² which may be used to at least 250°C. These expressions hold for 1 atm. total pressure between 0 and 100°C and follow the vapor pressure curve of water at higher temperatures.

Extensive measurements of the pH of Ca-HCO₃ solutions at 25°C and 0.956 atm PCO₂ using different compositions of the reference electrode filling solution show that measured differences in pH are closely approximated by differences in liquid-junction potential as calculated by the Henderson equation. Liquid-junction corrected pH measurements agree with the calculated pH within 0.003-0.011 pH.

Earlier arguments suggesting that the CaHCO⁺₃ ion pair should not be included in the CaCO₃-CO₂-H₂O aqueous model were based on less accurate calcite solubility data. The CaHCO⁺₃ ion pair must be included in the aqueous model to account for the observed PCO₂-dependence of aragonite solubility between 317 ppm CO₂ and 100% CO₂.

Previous literature on the solubility of CaCO₃ polymorphs have been critically evaluated using the aqueous model and the results are compared.