The Ideal Ionic Liquid Salt Bridge for Direct Determination of Gibbs Energies of Transfer of Single Ions,Part II: Evaluation of the Role of Ion Solvation and Ion Mobilities

An important intermediate goal to evaluate our concept for the assumption‐free determination of single‐ion Gibbs transfer energies Δ_trG°(i, S₁→S₂) is presented. We executed the crucial steps a) and b) of the methodology, described in Part I of this treatise, exemplarily for Ag⁺ and Cl^‐ with S₁ being water and S₂ being acetonitrile. The experiments showed that virtually all parts of the liquid junction potentials (LJPs) at both ends of a salt bridge cancel, if the bridge electrolyte is an “ideal” ionic liquid, that is, one with nearly identical diffusion of anion and cation. This ideality holds for [N₂₂₂₅]⁺[NTf₂]^‐ in the pure IL, but also in water and acetonitrile solution. Electromotive force measurements of solvation cells between S₁ and S₂ demonstrated Nernstian behavior for Ag⁺ concentration cells and constant like cell potentials for solutions with five tested Ag⁺ counterions.