The Unified Redox Scale for All Solvents: Consistency and Gibbs Transfer Energies of Electrolytes from their Constituent Single Ions

Abstract

We have devised the unified redox scale EabsH2O, which is valid for all solvents. The necessary single ion Gibbs transfer energy between two different solvents, which only can be determined with extra‐thermodynamic assumptions so far, must clearly satisfy two essential conditions: First, the sum of the independent cation and anion values must give the Gibbs transfer energy of the salt they form. The latter is an observable and measurable without extra‐thermodynamic assumptions. Second, the values must be consistent for different solvent combinations. With this work, potentiometric measurements on silver ions and on chloride ions show that both conditions are fulfilled using a salt bridge filled with the ionic liquid [N2225][NTf2]: if compared to the values resulting from known pKL values, the silver and chloride single ion magnitudes combine within a uncertainty of 1.5 kJ mol−1 to the directly measurable transfer magnitudes of the salt AgCl from water to the solvents acetonitrile, propylene carbonate, dimethylformamide, ethanol, and methanol. The resulting values are used to further develop the consistent unified redox potential scale EabsH2O that now allows to assess and compare redox potentials in and over six different solvents. We elaborate on its implications.

Improved pH measurement of mobile phases in reversed-phase liquid chromatography

“…The more advanced measurement method 15 employed in this work uses a novel ionic liquid salt bridge (ILSB) with triethylamylammonium bis((trifluoromethyl)sulfonyl)imide [N 2225 ][NTf 2 ]. Because of the high similarity of the involved ions – both by mobilities and solvation Gibbs energies in a wide variety of solvents – this IL has been demonstrated to effectively cancel the LJP out within standard deviation of 6.3 mV, corresponding to 0.11 pH units, 16–19 thus, significantly simplifying the measurement and decreasing the uncertainty of the obtained w abs pH values. The ILSB approach can be used with essentially any solvent or mixture.…”

“…Some earlier published values were remeasured to compare the previous values obtained with LJP estimation 14 to the more accurate values obtained with the new method utilising the specially designed ILSB, which enables cancellation of LJP. 19 In addition, the new w abs pH measurement approach was applied with a double junction combined pH electrode to demonstrate the easy applicability of the method adaption by practitioners in routine laboratories.…”