The association reactions involving counterions, Na+ and Mg2+, and micelles composed of the anionic surfactant, dodecylsulfate (DS), were investigated in ultrafiltration experiments. To access the data, an innovative model was developed that considered specific counterion binding within a Stern layer, with binding constant dependent upon the electrical potential as derived by the Poisson-Boltzmann equation and with calculation of the cmc as a function of counterion binding (or association). The experimental and model results both show that magnitude of counterion binding is greater for divalent species, Mg2+, than that for the monovalent species, Na2+. However, high concentration of Na+ compete for surface area diminishing the ability of the DS to bind either divalent species. At experimental conditions from 0 to 100 mM NaCl addition, the binding ratio (BR) varied only from 0.58 to 0.63. The optimum binding constants, KMg and KNa, were determined to be 0.4 and 1.0 L mol−1, respectively, for the model. The experimental data and model calculated results were generally in good agreement.

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