Presence of hydrophobic groups may modify the specific ion effect in aqueous polyelectrolyte solutions.

Enthalpies of dilution of aqueous solutions of aliphatic 6,12- and 12,12-ionene bromides and fluorides and enthalpies of mixing with low molecular-weight salts, such as sodium fluoride and bromide, are determined. In the second part of the study, the various x,y-ionenes (x, y are numbers of methylene groups between the adjacent charges) with fluoride, bromide, and iodide counterions are mixed with aqueous sodium sulfate solution. The polyelectrolytes examined in this part of the work are 3,3-, 6,9-, 6,12-, and 12,12-ionenes. A comparison with theoretical results, based on the Poisson-Boltzmann cell model, is presented. The theory predicts for the enthalpy of dilution to be exothermic and the enthalpy of mixing endothermic, while experiments show that signs of the heat effects depend on the nature of the counterion of the added salt, as also on the hydrophobicity (numbers x, y of methylene groups) of the ionene. We show that the salts when ordered by heat effects produced by mixing of NaF and NaBr with 3,3-, 6,9-, or 6,12-ionene fluorides and bromides follow the opposite ordering than in the case when the same alkali halide salts are mixed with more hydrophobic 12,12-ionene salts. The results for the enthalpy of mixing of ionenes under study with Na2SO4 follow the same order as obtained for monovalent salts.