Effects of pH and Surfactant Precipitation on Surface Tension and CMC Determination of Aqueous Sodium n-Alkyl Carboxylate Solutions

Aqueous solutions of sodium tetradecanoate (S14C) and sodium dodecanoate (S12C) were used to evaluate complicated precipitation phenomena and to monitor the effects of bulk pH adjustments on surface tension and critical micelle concentrations (CMC) determination from surface tension plots. Limited solubilities of pure sodium n-alkyl carboxylates in solution near the CMC have been reported previously many times. In this study, precipitation encountered with solutions prepared from vender-supplied S12C was eliminated through additional purification. As sodium alkyl carboxylates discussed in the literature are commonly used as received from the manufacture without additional purification, the wide range of reported CMC values as well as precipitation near the CMC for S12C are also likely due to impurities. However, complete solubility for S14C solution concentrations near the reported CMC values was not obtained through additional purification of purchased material. Hence, some CMC values reported in the literature for S14C should be reconsidered, as discontinuities in the slope of surface tension versus concentration plots are likely caused by the formation of a precipitate not micelle aggregation. In addition and in agreement with other studies, solution pH adjustments revealed a minimum surface tension for maximum solubility near the pK _a value for S14C.