A mixture of anionic and amphoteric surfactants is composed of three components at intermediate pH levels: anionic, cationic (protonated amphoteric), and zwitterionic (unprotonated amphoteric). Knowledge of the composition of each surfactant in both monomer and micellar forms (monomer-micelle equilibrium) is important in applications using this mixture. Hydrogen ion titration of the mixed surfactant solution as a function of surfactant composition is combined with the pseudophase separation model and regular solution theory for the three-surfactant mixture to calculate the concentration of each surfactant in monomer and in micelle forms at different pH levels. The specific systems studied here contain sodium dodecyl sulfate (SDS) and dimethyldodecylamine oxide (DDAO), which are used in a wide range of consumer products. The degree of protonation of monomeric DDAO is not affected by the presence of SDS, indicating an insignificant formation of ion pairs between these monomers. However, the presence of SDS in micelles shifts the micellar pK a of DDAO protonation significantly and the method used here allows the quantification of partial fugacities of each individual surfactant in micelle form. The composition in the monomer phase at each pH will aid in understanding and predicting solution compositions corresponding to anionic/amphoteric surfactant precipitation boundaries, which is the focus of the subsequent paper in this series.

Dissolution of calcium salt of a long chain fatty acid or soap scum is a major challenge for hard surface cleaners since soap scum forms when soap is exposed to hard water and has very low water solubility. In this paper, the aqueous equilibrium solubility of calcium octadecanoate (or calcium stearate) was measured as a function of pH as well as chelating agent (ethylenediaminetetraacetate disodium salt) and surfactant concentrations. Anionic, nonionic, and amphoteric surfactants were studied. The highest soap scum solubility was observed at high pH with an amphoteric surfactant. Under this condition, the chelant effectively binds calcium, and the stearate anion forms mixed micelles well with the amphoteric surfactant, which is in zwitterionic form at high pH.

The equilibrium solubilities of two model soap scums [calcium stearate and magnesium stearate: Ca(C18)2 and Mg(C18)2] were measured in aqueous solutions containing three different types of surfactants: methyl ester sulfonate (MES) as an anionic; alcohol ethoxylate (EO9) as a nonionic; and dimethyldodecylamine oxide (DDAO) as an amphoteric with and without a chelating agent [disodium ethylenediaminetetraacetate (Na2EDTA)]. The solubility of calcium soap scum was generally higher than that of magnesium soap scum, the exception being some DDAO systems. The use of the DDAO surfactant with the Na2EDTA chelating agent at high pH gives the highest solubilities of both studied soap scums. The soap scum solubility is on the order of 2,000 times that in water at high pH. The DDAO is the most effective surfactant under all conditions. The MES is more effective than the EO9 at low pH with the opposite trend observed at high pH. The synergism from added chelant is generally greater at higher pH and is greatest for DDAO followed by EO9.

Use of amphoteric and anionic surfactants is very common in practical formulations such as shampoos and hand dishwashing products. Precipitation of mixtures of dimethyldodecylamine oxide (DDAO) as an amphoteric surfactant and sodium dodecyl sulfate (SDS) as an anionic surfactant were studied at different pH levels. The DDAO is a pH-sensitive surfactant and its protonation can be expressed in terms of a pK a similar to an acid dissociation constant. The protonated form of DDAO carries a positive charge and precipitates with the oppositely charged SDS. Therefore, precipitation phase boundaries are pH dependent due to the varying degree of DDAO protonation. By combining the use of regular solution theory and the pseudophase separation model to describe micellar mixing nonidealities with the precipitate solubility product constant and the protonation dissociation constant, a model to predict the precipitation phase boundary is presented here. The model agrees well with experimental phase boundaries at different pH levels.

One synergism of using surfactant mixtures is the reduction in the equilibrium extent of and rate of precipitation. The overall time required for calcium-induced precipitation of mixed sodium dodecyl sulfate (SDS) and sodium octylbenzene sulfonate (SOBS) over a particular range of ratios has been found to increase dramatically when compared to either SDS or SOBS alone. In this study, light transmission and isoperibol calorimetry were used to measure the delay in the precipitation reaction, while scanning electron and optical micrographs of crystals formed give insight into the precipitation mechanism. The smaller the difference in the supersaturation ratio of the two precipitating surfactants, the longer the induction time is. The delay in the extent of precipitation is due to the interruption of crystal formation from dissimilar precipitating surfactants.