Activity coefficients and thermodynamic parameters for RbCl/CsCl + amide (acetamide, propanamide, and n-butanamide) + water system at 298.15 K

Electromotive force (emf) of the chemical cell without liquid-junction K-ISE | RbCl/CsCl ( mE) | ISE-Cl and K-ISE | RbCl/CsCl (mE), amide (mN) | ISE-Cl, have been measured at 298.15 K, where mE = (0.005 to 0.5) mol kg− 1 and mN= (0.05 to 3.0) mol kg− 1. The activity coefficients of RbCl/CsCl in amide (acetamide, propanamide, and n-butanamide) + water mixture can be obtained from these electromotive force data and in the mean time the Gibbs free energy interaction parameters of RbCl/CsCl + amide pair in water, gEN, as well as the salt constant, kS, can be evaluated. The results show that both gEN > 0, kS > 0 at 298.15 K, and all the activity coefficients of electrolyte in amide + water mixture increase with increasing the mN, but it is a little complicated for the dependence of activity coefficients on mE. These thermodynamic parameters were discussed in terms of a model of the structural interaction and electrostatic interaction and the dependence of them on the number of carbon atoms in amide as well as the radius of metal ions were interpreted by the group additivity principle.