The acid/base properties, critical micelle concentrations (cmcs), and pH-dependent solubility of five synthetic tetraacids have been studied at several ionic strengths (20-600 mM NaCl) and in the pH range of 1.5-11 using high precision potentiometric titrations, tensiometer measurements, and UV spectroscopy, respectively. The molecular weight of the tetraacids ranged between 478 and 983 g/mol. The potentiometric titration data was evaluated in terms of thermodynamic equilibrium models, developed in the light of relevant solubility data, Langmuir monolayer compressions and cmc of the different tetraacids. The results indicate that for two of the tetraacids, called BP5 and BP7, two chemical forms fully dominate the speciation of the monomers; the insoluble fully protonated form, and the soluble fully deprotonated form. The partly protonated species, only play a very minor role in the speciation of these tetraacids. For the other tetraacids the results are more complicated; for the smallest tetraacid, called BP1, all species seem to play important roles, and for the most hydrophobic, BP10, the formation of micelles and aggregates severely complicates the evaluation of the speciation. For the tetraacid BP3 one of the partly deprotonated forms seems to be important, thus confirming the structure to properties relationship. In spite of the complicated micelle formation chemistry, and although not actually measured, the acid/base properties for the monomers of BP10 were interpreted by means of surface charge densities of the micellar aggregates. The modeling indicates an increase of the aggregation number of the micelle upon acidification, a result of formation of mixed micelles incorporating the fully protonated and deprotonated species. An intrinsic pK(a) of 5.4 for BP5 was used to model the monomer pK(a) of BP10, and corresponded well with a monolayer acidity constant pK(s)(a) of 5.5 obtained from surface collapse pressures of Langmuir monolayers as a function of pH.
2010. Vol. 26, no 3, 1619-29 p.