The Binding Characteristics of Conventional and α,ω-Type Ionic Surfactant Mixtures to Polyion

The binding isotherms of decyltrimethylammonium bromide (DeTAB) to poly(potassium vinyl sulfate) were determined potentiometrically in mixed solutions with N,N,N,N′,N′,N′-hexamethyl-1,20-icosanediammonium dibromide (ETMAB) and 1,1′-1,20-icosanediylbispyridinium dibromide (EPB). In both systems, an addition of the α,ω-type surfactant causes a remarkable decrease in the slope of the binding isotherm of DeTA+. In addition, the binding isotherm tended to shift regularly to a low concentration range with increasing concentration of the α,ω-type surfactant. A regular solution treatment of the mixed clusters on the polyion chain suggests that substantially all of the added α,ω-type ions bind to the polyion under our experimental conditions. The observed binding isotherms can well be reproduced with interchange energies of −0.6 kT for DeTA+–ETMA2+ and −1.6 kT for DeTA+–EP2+ pairs in the mixed clusters, respectively.