Binding of Ca²⁺ Ions to Alkylbenzene Sulfonates: Micelle Formation, Second Critical Concentration and Precipitation

Anionic surfactants, such as sodium linear alkylbenzene sulfonates (NaLAS), are utilized in various fields, including industry, household, and agriculture. The efficiency of their use in aqueous environments is significantly affected by the presence of cations, Ca²⁺ and Mg²⁺ in particular, as they can decrease the concentration of the surfactant due to precipitation. To understand cation-sulfonate interactions better, we study both NaLAS colloidal solutions in the presence of CaCl₂ and precipitates forming at higher salt concentrations. Upon addition of CaCl₂, we find the surface tension and critical micelle concentration of NaLAS to decrease significantly, in line with earlier findings for alkylbenzylsulfonates in the presence of divalent cations. Strikingly, an increase in the surface tension is discernible above 0.6 g L^-1 NaLAS, accompanied by the decrease of apparent micelle sizes, which in turn gives rise to transparent systems. Thus, there appears to be a second critical concentration indicating another micellar equilibrium. Furthermore, the maximum salt tolerance of the surfactant is 0.1 g L^-1 Ca²⁺, above which rapid precipitation occurs yielding sparingly soluble CaLAS₂∙2H₂O.