The thermodynamics of extraction of some lanthanide ions and bismuth, aluminium, calcium and zinc ions from perchloric acid into solutions of dinonylnaphthalenesulphonic acid have been studied. Extraction of the trivalent ions is dominated by the entropy of complexing. Electrostriction of large complex micelles by the complexed ion is postulated in order to account for the entropy effect. In the case of divalent ions, the enthalpy of dehydration of the ion is more important. A strategy for improving the separation factors is proposed.