Counterion association to aqueous sodium dodecyl sulfate micelles in the presence of organic additives

Abstract

The effect of polar, nonpolar, and mixed polar-nonpolar additives on the counterion association, the structure, and the size of aqueous sodium dodecyl sulfate micelles has been examined by measuring the conductivity, the viscosity, and the electromotive force at 298.15 K. Octane does not affect the degree of counterion association, but the mobility of the micelles decreases. This is mainly due to an increased micellar volume. Small quantities of 1-butanol and 1-hexanol decrease the degree of counterion association. At higher hexanol molalities larger micellar aggregates, rod- or disk-like micelles are formed. Long-chained α,ω-alkanediols, 1,9-nonanediol and 1,10-decanediol, also reduce the degree of counterion association. The shorter diols apparently affect the micellar system mainly through their effect on the solvent. The effect of the mixed additives is intermediate to that of pure components. Changes in the aggregation number, the micellar radius, and the number of associated counterions have been estimated from the conductivity and electromotive force measurements. Addition of octane does not affect the degree of associated counterions, but the micellar aggregation number increases. Addition of hexanol lowers both the micellar aggregation number and the fraction of associated counterions.