Enthalpy changes for the binding of malonate, citrate, 1,2,3-propanetricarboxylate and 1,2,3,4-butanetetracarboxylate by fully methyl substituted linear polyammonium cations (with the general formula C3nNnH(8n + 2)n+, with n = 1,2,3) were determined calorimetrically. Enthalpy changes were also determined for the binding of malonate by unsubstituted polyammonium cations (with the general formula C2(n - 1)NnH(6n - 2)n+, n = 1...6). delta H0/kJ mol-1 values are always positive and strongly dependent on the charges involved in the formation reaction. Mean values for delta G0 and T delta S0 were obtained as a function of the charge product zeta = Zanion/ Zcation: -delta G0/kJmol-1 = (4.0 +/- 0.4) zeta, T delta S0/kJmol-1 = (5.9 +/- 0.1) zeta (substituted polyamines), and -delta G0/kJmol-1 = (3.5 +/- 0.2) zeta, T delta S0/kJmol-1 = (5.0 +/- 0.4) zeta (unsubstituted polyamines). For both classes of amines it was found that T delta S0 vs. delta G0 is linear with a correlation coefficient of r = 0.9618. Crude approximation gives -delta G0/kJmol-1 = (7.0 +/- 0.4) n-1, T delta S0/kJmol-1 = (10.0 +/- 0.8) n-1 for unsubstituted amines and -delta G0/kJmol-1 = (8.0 +/- 0.8) n-1, T delta S0/kJmol-1 = (11.8 +/- 2.0) n-1 (n = number of possible salt bridges, or single interactions) for substituted amines.