Thermodynamics of Ag(I) Complex Formations with 2-Mercaptoimidazole in Water−Dimethyl Sulfoxide Solvents

Abstract

The stability of coordination compounds of metal ions with ligands is of fundamental importance for elaborating upon practical sensors for the detection and quantification of metal ions in environmental samples. In this work, the stability constants of silver(I) complexes with 2-mercaptoimidazole (2MI) in a mixed water–dimethyl sulfoxide (DMSO) solvent were determined at 298.15 K and 308.15 K. It was found that with increasing temperature, the stability of the complexes decreases. The dependence of lgβ1 on the water−DMSO solvent compositions has its minimum at a concentration of dimethyl sulfoxide of 0.1 mol. fr. To explain the effect of the solvent, the solvation characteristics of the reagents were analyzed. In this regard, the 2MI Gibbs energy of transfer from water to aqueous dimethyl sulfoxide solvents was determined, and the influence of the aqueous DMSO solvent on the thermodynamics of 2MI protonation was analyzed. The stabilization of the silver ion and 2MI during the transition from water to a water–DMSO solvent makes a negative contribution to the change in the Gibbs energy of complexation, while the solvation of a complex particle promotes the complex formation. As a result, the Gibbs energy transfer values are slightly increased. The results of these thermodynamic studies could be useful for the development of sensor materials based on mercaptoimidazoles.

Keywords

• complexation
• complex stability
• distribution coefficient
• inorganic ion sensors
• 1-methyl-2-mercaptoimidazole
• silver(I)