A Comprehensive Equilibrium Analysis of Tartronate with Proton and Major Cations in Natural Fluids

This study presents a detailed thermodynamic investigation on the protonation behavior of tartronic acid in aqueous solutions of various ionic media, including sodium chloride, potassium chloride, tetramethylammonium chloride, and tetraethylammonium iodide. Specifically, potentiometric measurements were performed at temperatures ranging from 288.15 to 310.15 K and ionic strengths between 0.1 and 1.0 mol dm^-3 to determine stoichiometric protonation constants in different ionic media. The formation of weak complexes between tartronate and alkaline metal cations was obtained by means of the Δ<i>pK</i> method. Moreover, data were modeled using the Debye-Hückel equation and Specific Ion Interaction Theory (SIT), allowing for the calculation of standard thermodynamic parameters and the assessment of the dependence of protonation constants on ionic strength. Additionally, the protonation behavior of tartronic acid was compared with that of structurally related acids, such as malonic and mesoxalic acids, providing insights into the role of molecular structure in acid dissociation. The results emphasize the significant role of entropic contributions in the protonation process and provide a comprehensive model for the thermodynamic properties of tartronic acid across a wide range of experimental conditions.