Prediction of Activity Coefficients for Uni-univalent Electrolytes in Pure Aqueous Solution

Parameter‐free activity coefficient equations were tested in addition to those containing one, two, three or four electrolyte‐dependent parameters with the experimental activity coefficients obtained from the literature data for aqueous solutions of the following electrolytes at 298.15 K: KCl, NaCl, RbCl, KBr, RbBr, CsBr, KI, RbI, KNO3, and KH2PO4. The experimental activity coefficients of each electrolyte considered can be reproduced within the uncertainty of the measurements up to the molality of the saturated solution by using a three‐parameter equation of the extended Hückel type. The best Hückel equations are given for all electrolytes in question. The results from the present studies reveal that the parameter‐free equations can be reliably used in thermodynamic studies only for very dilute electrolyte solutions. On the other hand, in most cases, a good agreement with the experimental data is obtained with the one‐parameter equations of Bromley [14] and Kusik and Meissner [13], with the two‐parameter equation of Bretti et al. [15], and with the three‐ or four‐parameter equation of Hamer and Wu [19] in addition to the three‐parameter Pitzer equation [23], with almost all parameter values suggested in the literature. In several cases, these equations seem to apply to much higher molalities than those used in the parameter estimations. Therefore, the best of these equations may have important applications in calculations associated with the dissolution and crystallization processes of these salts. The activity coefficients equations in the literature are tested with activity coefficients obtained by using the best extended Hückel equations for KCl, NaCl, RbCl, KBr, RbBr, CsBr, KI, RbI, KNO3, and KH2PO4 solutions at 298.15 K. These Hückel equations probably reproduce the best thermodynamic data from solutions of these electrolytes within experimental error up to the molality of the saturated solutions.