Thermodynamics of ionic solid solutions: III. An addendum

In two earlier papers (C.A. 117:259320(1;121:19411y) the activity coefficients of the salts in binary solid solutions at 25‡C for 38 salt pairs, in which the members of each pair differ with respect to only one kind of ion, were determined. While the activity data are correct, the conclusions regarding deviations from ideality for eight of these pairs, namely those in which there are two moles of replaceable ion per mole of salt, require modification in order to be consistent with ideal entropies of mixing. By changing the formulation of the component salts to one-half of what is usual, the inconsistencies disappear. This half-mole approach, applied to the salt pairs CU_1/2(NH₄/K)SO₄-3H₂O, Mg_1/2NH₄(SO₄/ CrO₄)-3H₂O, Mg_1/2NH₄(SeO₄/SO₄)-3H₄O, Mg_1/2NH₄(SeO₄/CrO₄)-3H₄O, Mg_1/2 (K/NH₄)SeO₄-3H₂O, (NH₄/K)(SO₄)_1/2, and Ba_1/2(ClO₃/BrO₃)-1/2 H₂O shows that these solid solutions exhibit positive, not negative, deviations from ideality at 25‡C. Only the system Pb_1/2(C1/Br) still deviates negatively.