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.