Abstract

In most thermodynamic treatments of aqueous reaction equilibria, the energetic contribution of the solvent is neglected or intentionally omitted. In the current work, water is treated as a co-reactant in the development of a general equation for binding equilibria that takes into account the unavoidable change in hydration that occurs when two solvated surfaces come into contact. The governing equation is supported by data obtained via isothermal titration calorimetry using the chelation of Ca2+ by EDTA as a model binding reaction. The desolvation free energy for formation of the EDTA/Ca2+ complex is unfavorable, as determined from the concentration dependence of the equilibrium “constant.” Results for dilute and crowded solutions are compared in order to assess the role of desolvation under conditions found in vivo.View Large Image | View Hi-Res Image | Download PowerPoint Slide

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