Valentine A. Nazarov

A new sulfate-selective electrode and its use in analysis

The improvement of the steric accessibility of exchange centers of higher quaternary ammonium salts (QAS) by replacing several long-chain alkyl substituents at the nitrogen atom with methyl groups enhanced the selectivity of ion-selective electrodes (ISEs) based on the specified ion exchangers for the SO42− ion up to six orders of magnitude in the presence of singly charged anions. This can be qualitatively explained by the specific features of ion pair formation between quaternary ammonium cations and singly and doubly charged anions. The effect of the steric accessibility of the QAS exchange center on the selectivity of ISEs is partially retained in the presence of a neutral anion carrier, hexyl p-trifluoroacetylbenzoate (HTFAB), which is used for enhancing the selectivity for the sulfate ion in the presence of singly charged anions. A sulfate-selective electrode with a reasonable selectivity for practical purposes was proposed. It is based on the HTFAB-higher QAS ion pair bearing three methyl substituents at the nitrogen atom. The ISE was used in the analysis of natural water.

Improved Separate Solution Method for Determination of Low Selectivity Coefficients

Simple, fast, and theoretically substantiated experimental method for determination of improved selectivity coefficients is proposed. The method is based on the well-known fact that low selectivity coefficients determined by the separate solution method (SSM) are time-dependent and, upon our finding, this dependence is a well-defined linear function of time raised to the certain negative power. In particular, the selectivity coefficients obtained for equally charged primary and foreign ions by SSM linearly depend on time to the minus one-fourth. It was found that extrapolation of experimental data using this function to the intersection with Y axes gives reliable values of rather low selectivity coefficients (down to n × 10(-7)), which strongly differ from those measured using SSM and correspond well with the values obtained using the modified separate solution method (MSSM) proposed by Bakker. At the same time, the new method is free of one very essential limitation inherent to MSSM, namely, it is applicable after the conditioning of electrodes in the primary ion solution and can be repeated many times.

Ibuprofen-selective electrode on the basis of a neutral carrier, N-trifluoroacetylbenzoic acid heptyl ester

An ibuprofen-selective electrode on the basis of a composition of an anion exchanger, 2,3,4-tris(dodecyloxy)benzyltrimethylammonium with a neutral carrier, N-trifluoroacetylbenzoic acid heptyl ester, is proposed. It exhibits good selectivity, a wide pH-range, and a low limit of detection. A procedure for the determination of ibuprofen in tablets is developed.

Potentiometric selectivity coefficients: Problems of experimental determination

The main problems arising in the determination of selectivity coefficients of ion-selective electrodes using the methods recommended by IUPAC are considered. A method for the determination of the limiting (thermodynamically justified) selectivity coefficients based on the analysis of the time dependence of the selectivity coefficients found experimentally using the separate solutions method is justified theoretically and experimentally. It has been demonstrated that the proposed method ensures the reliable determination of low values of selectivity coefficients (as low as n × 10−6). The criteria of the applicability of the proposed method are formulated and a particular algorithm of its implementation is proposed.

The influence of the plasticizer nature on the selectivity of ion-selective electrodes to physiologically active amine cations: Regularities and abnormalities

The influence of the nature of plasticizer in the membrane of an ion-selective electrode (ISE) on its selectivity to cations of more than 20 physiologically active amines (PAA) is studied. It is found that an increase in the basicity of the plasticizer leads to a sharp increase in the membrane selectivity to PAA cations with lower degrees of the substitution of the salt-forming nitrogen atom, and also to PAA cations with nonionic polar groups capable of forming hydrogen bonds with Lewis bases. PAA cations forming intermolecular hydrogen bonds are an exception. The effect of the nature of the ion exchanger on the selectivity to PAA cations is strongest when plasticizers with low basicity are used; the selectivity of membranes with plasticizers of high basicity does not depend on the nature of the ion exchanger. For ISEs based on the neutral carrier dibenzo-18-crown-6 (DB-18-C-6), the best selectivity to primary amine cations in comparison to secondary and tertiary ones is achieved using plasticizers with low basicity.

Determination of fluoride ions by titration with aluminum chloride to a preset potential

A procedure is proposed for determining fluoride ions based on titration with an aluminum chloride solution to a fixed potential. The procedure allows for the significant reduction of the determination error for fluoride ions due to the error of measuring the potential in comparison with direct potentiometry. The applicability of the procedure is confirmed by the results of determining fluoride ions in mixtures modeling the composition of Poles’e fluorinated cooking salt.