Activity-based analysis of potentiometric pH titrations

The discrepancy between concentrations and activities is a predicament well known to the analytical chemist. Because of the difficulty of determining activity coefficients, the standard technique for quantitative equilibrium studies is to work under a particular ‘constant ionic strength’ by adding an excess of an inert salt. Under such conditions, activity coefficients are approximately constant and can be taken into the equilibrium constants which are defined for the chosen ionic strength (I). Here we propose a fundamentally different approach. Throughout the numerical analysis of the titration data, activity coefficients for all individual species are approximated by well-known equations based on the work of Debye-Hückel. The computational analysis of the measurements strictly obeys the law of mass conservation and obeys the law of mass action only approximately. The main novelty is that now the addition of inert salts is no longer required and measurements are done at minimal I. Consequently, the thermodynamic equilibrium constants are now determined much more robustly based on experiments taken at low I. The approach has been tested and validated with the two very well investigated 3-protic phosphoric and citric acids. In summary: the technique of artificially keeping ionic strength constant has been replaced by improved computational analysis. [Display omitted] •Analysis of potentiometric pH titrations using the law of mass action, based on activities not concentrations.•This avoids the necessity of maintaining constant ionic strength.•This, in turn, avoids the addition of ‘inert’ salts, which usually are not completely inert.•Thermodynamically correct equilibrium constants are determined without the investigation of ionic strength dependences.•The overall result is a substantial saving in experimental effort, time and chemicals.