Lando Gabriele, Bretti Clemente, Cardiano Paola, Irto Anna, Milea Demetrio, De Stefano Concetta
Department of Chemical, Biological, Pharmaceutical and Environmental Sciences, University of Messina, Viale Ferdinando Stagno d'Alcontres, 31, I-98166 Messina, Italy.
Molecules. 2025 Mar 27;30(7):1497. doi: 10.3390/molecules30071497.
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 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 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.
本研究对酒石酸在包括氯化钠、氯化钾、四甲基氯化铵和四乙基碘化铵在内的各种离子介质水溶液中的质子化行为进行了详细的热力学研究。具体而言,在288.15至310.15 K的温度范围和0.1至1.0 mol dm的离子强度下进行电位测量,以确定不同离子介质中的化学计量质子化常数。通过Δ法获得了酒石酸盐与碱金属阳离子之间弱络合物的形成情况。此外,使用德拜-休克尔方程和特定离子相互作用理论(SIT)对数据进行建模,从而能够计算标准热力学参数并评估质子化常数对离子强度的依赖性。此外,还将酒石酸的质子化行为与结构相关的酸(如丙二酸和中草酸)的质子化行为进行了比较,从而深入了解分子结构在酸解离中的作用。结果强调了熵贡献在质子化过程中的重要作用,并为在广泛实验条件下酒石酸的热力学性质提供了一个全面的模型。