Tensammetry with accumulation on the hanging mercury drop electrode : Part 3. The behaviour of triton X-100 in mixtures with PEG-9000

The behaviour of Triton X-100, which can be present in monomeric or associated form, and its mixtures with PEG-9000, which does not undergo association, is described. The tensammetric curve of Triton X-100 alone shows one or two peaks at negative potentials, depending on the concentration of Triton X-100, i.e., on the presence of associated forms. For <2 mg l^?1, there is one broad peak, related to monomers of Triton X-100. The calibration plot for this peak is sigmoidal but its rising section (0.05–0.20 mg l^?1) is approximately linear. The calibration curve of the second, much narrower, peak related to associated forms of Triton X-100, grows parabolically with increasing concentration of Triton X-100. The behaviour of a mixture of PEG-9000 with a larger amount of Triton X-100 is similar to the behaviour of a model mixture of components with sufficiently different properties (e.g., PEG 1500/PEG 9000). The peak for PEG-9000, the stronger surfactant, is relatively less affected by a large amount of Triton X-100. Even this effect can be decreased by using a suitable preconcentration potential (?1.45 V vs. SCE) so that PEG-9000 can be determined in the presence of a 1000-fold amount of Triton X-100. Both peaks of Triton X-100 are greatly decreased by the presence of PEG-9000 and the broad peak can be completely suppressed. Triton X-100 cannot be determined accurately in the presence of unknown amounts of PEG-9000.