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. (7th February 2018)

• Record Type: Journal Article
• Authors: Ermantraut, Andreas; Radtke, Valentin; Gebel, Niklas; Himmel, Daniel; Koslowski, Thorsten; Leito, Ivo; Krossing, Ingo
• Is Part Of: Angewandte Chemie. Volume 130:Number 9(2018)
• Page Start: 2372
• Page End: 2376
• Publication Date: 2018-02-07
• Subjects: Flüssigkeitsgrenzpotential -- Ionen -- Ionische Flüssigkeiten -- Lösungsmitteleffekte -- Thermodynamik; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201707334
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: An important intermediate goal to evaluate our concept for the assumption‐free determination of single‐ion Gibbs transfer energies Δ tr G°(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.