Unravelling Anion Solvation in Water‐Alcohol Mixtures by Single Entity Electrochemistry. Issue 7 (19th January 2022)

• Record Type: Journal Article
• Authors: Saw, En Ning; Kanokkanchana, Kannasoot; Amin, Hatem M. A.; Tschulik, Kristina
• Is Part Of: ChemElectroChem. Volume 9:Issue 7(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-01-19
• Subjects: Ion solvation -- Nanoelectrochemistry -- Nano impact electrochemistry -- Solvent mixtures -- Viscosity of alcohol water mixtures; Electrochemistry -- Periodicals; 541.37
• DOI: 10.1002/celc.202101435
• Languages: English
• ISSNs: 2196-0216

Abstract

Abstract: Single entity electrochemistry is employed to gain insights into ion solvation in solvent mixtures. To this end, the time required for the oxidation of individual indicator nanoparticles to sparingly soluble products is used to probe ionic diffusion, and hence gain new insights into the solvation properties of solvent mixtures. Herein, water‐ethanol or water‐methanol mixtures of different compositions are analyzed following this new approach, using silver nanoparticle oxidation in the presence of chloride and iodide as a complementary indicator reaction. For increasing concentrations of the bulkier alcohol molecules in the mixtures with water, an increasing content of alcohol molecules in the halide's solvation shell is detected by the observation of hindered halide diffusion. The extent of this solvent replacement is shown to scale with the charge density of the ions and the experimental results are rationalized with respect to literature‐derived thermodynamic data, highlighting the ability of single entity electrochemistry to explore solvation in solvent mixtures. Abstract : Solvation in solvent mixtures : Single nanoparticle electrochemistry is utilized to probe the diffusion/solvation of ions. At high overpotential, the time needed for the full oxidation of a single nanoparticle depends on the halide diffusion, which is related to the solvation of the halides. The duration of individual nanoparticle full oxidation is measured in different solvent mixtures to unravel the effect of the latter on halide solvation.