Vol 53, No 11 (2017)

The effect of components of the redox pair K₃[Fe(CN)₆]/K₄[Fe(CN)₆] on the dynamics of formation of octanethiol (OT) monolayers from aqueous thiol-containing solutions of 0.1 М NaClO₄ is studied by cyclic voltammetry (CVA). The formation of OT monolayers is shown to depend on the presence of ions of hexacyanoferrate(II)/(III) in solution. Being added to solution, the components of the [Fe(CN)₆]^3–/4– redox pair sharply increase the time of formation of the insulating monolayer OT films and make them less stable. The destabilizing and inhibiting action of [Fe(CN)₆]^3–/4– ions becomes stronger as their concentration in solution increases. The adsorption activity of individual components of the redox pair is assessed. The strong and approximately equal adsorption activity of ions [Fe(CN)₆]^3– and [Fe(CN)₆]^4– on gold in the presence of octanethiol is observed. At the same time, OT and the hexacyanoferrate(II)/(III) ions can be placed in the following row: OT > [Fe(CN)6]^3– ≈ [Fe(CN)₆]^4–. Recommendations are given on how to eliminate the interfering action of the K₃[Fe(CN)₆]/K₄[Fe(CN)₆] redox-pair ions when studying the insulating properties of thiol monolayers on gold.

For determination of nonionic surface-active substances (NSAS), in particular, polyoxyethylated nonylphenols, in aqueous solutions, the planar sensors are developed based on various carbon materials (graphite, carbon nanotubes). The effect of the nature and concentration of electroactive compounds (EAC), carbonaceous materials, plasticizers on the electroanalytical and performance characteristics of planar NSAS sensors is observed. It is shown that the planar electrodes can be used in determination of individual homologues of polyoxyethylated nonylphenols in the concentration interval from 1 × 10^–5 to 1 × 10^–2 М at pH 4–10 in model solutions, in small-volume samples, for determination of the content of surfactants in technological preparations, domestic chemistry products, and also in environmental monitoring of natural waters.

The effect of surfactants and carbon nanomaterials (CNMs) on the electroflotation extraction of the disperse phase of cobalt(II) and (III) hydroxides at pH 6 and pH 10 was studied. It is shown that at pH 6 in the absence of surfactants, the efficiency of cobalt extraction in various electrolytes is low and does not exceed 15–25%. In the surfactant–CNM–electrolyte system, the degree of extraction α increases in the chloride, nitrate, and sulfate solutions compared with the solutions containing no surfactants. The electroflotation extraction of cobalt was more efficient at pH 10: α reached 80–96% in the absence of surfactants, 70–97% in the surfactant–electrolyte system, and 60–97% in the surfactant–CNM–electrolyte system. The optimum conditions of the electroflotation extraction of cobalt hydroxides from solutions containing various inorganic electrolytes were determined. The effect of the sodium chloride content on the degree of cobalt extraction at pH 6 was studied. When the NaCl concentration increased from 0 to 10 g/L, the efficiency of cobalt extraction increased to 92%; when the flocculant was added and an additional stage of filtration was used, cobalt was extracted almost completely.

The results of studying characteristics of potentiometric DP-sensors (sensors with the Donnan potential as their analytical signal) are presented for alkaline solutions of a sulfur-containing amino acid with perfluorosulfonic cation exchange membranes subjected to thermal treatment and mechanical deformation at different relative humidity. Correlation between the distribution of sensitivity of DP-sensors towards cations and anions and diffusion permeability of membranes was found. A multisensor system including two DP-sensors based on membranes with optimized properties and a glass electrode for codetermination of potassium cations and amino acid anions and zwitterions in solutions at pH >7 are developed.