Standard systems for measurement of pKs and ionic mobilities. 1. Univalent weak acids

Determination of pK values of weak bases and acids by CZE has already attracted big attention in current practice and proved to offer the advantage of being applicable for mixtures of analytes. The method is based on the measurement of mobility curves plotting the effective mobility vs. the pH of the background electrolyte, and following computer-assisted regression involving corrections for ionic strength and temperature. To cover the necessary range of pH for a given case, both buffering weak acids and bases are used in one set of measurements, which requires implementing computations of individual ionic strength corrections for each pH value. It is also well known that some components of frequently used background electrolytes may interact with the analytes measured, on forming associates or complexes. This obviously deteriorates the reliability of the resulting data. This contribution brings a rational approach to this problem and establishes a standard system of anionic buffers for measurements of pKs and mobilities of weak acids, where the only counter cation present (besides H(+)) is Na(+). In this way, the risk of formation of complexes or associates of analytes with counter ions is strongly reduced. Moreover, the standard system of anionic buffers is selected in such a way that it provides, for an entire set of measurements, constant and accurately known ionic strength and the operational conditions are selected so that they provide constant Joule heating. Due to these precautions only one correction for ionic strength and temperature is needed for the obtained set of experimental data. This considerably facilitates their evaluation and regression analysis as the corrections need not be implemented in the computation software. The reliability and the advantages of the proposed system are well documented by experiments, where the known problematic group of phenol derivatives was measured with high accuracy and without any notice of anomalous behaviour.