Solvent‐Governed Standard Potentials of the K/K ⁺ Redox Couple

ABSTRACT

We determine the solvent dependence of the K/K ⁺ redox couple using a dual‐phase thermodynamic cycle combined with ab initio cluster–continuum calculations. The computed solvation free energies Δ G *(K ⁺ ( s )) show reasonable agreement with available reference data and provide model‐dependent estimates of E ⁰ (K/K ⁺ ( s )) for solvents where direct measurements are unavailable. Donor‐number analysis shows no universal DN–Δ G *(K ⁺ ( s )) relationship across the chemically diverse solvent set, although the limited ether subset exhibits a steeper apparent dependence than the non‐ether solvents. Given the small ether dataset and the structural sensitivity of the model‐derived values, this separation is interpreted as a preliminary tendency rather than a predictive family‐specific correlation. These results clarify the origin of solvent‐controlled redox thermodynamics and provide a standard‐state thermodynamic reference for comparing intrinsic solvent effects in potassium‐metal electrolytes.