Rigorous pH measurement in non-aqueous solution: measurement method and reference values in ethanol

Anal Bioanal Chem. 2024 Jan;416(2):461-465. doi: 10.1007/s00216-023-05043-5. Epub 2023 Nov 25.

Abstract

The recently introduced unified pH ([Formula: see text]) concept enables rigorous pH measurements in non-aqueous and mixed media while at the same time maintaining comparability to the conventional aqueous pH scale. However, its practical application is hindered by a shortage of reference [Formula: see text] values. In order to improve this situation, the European Metrology Research Project (EMPIR) UnipHied ("Realisation of a UnipHied pH scale") launched an interlaboratory comparison among highly experienced electrochemistry expert laboratories to assign the first such reference [Formula: see text] values by adopting an extensive statistical treatment of the reported measurement data: to phosphate buffer in water-ethanol mixture (50 wt% of ethanol) and ammonium formate buffer in pure ethanol. Two different measurement setups - one capable of being easily adopted in industrial applications - have been used to demonstrate the robustness of [Formula: see text] measurement. This is an important step towards wider adoption of the [Formula: see text] concept in practice, like liquid chromatography, biofuels analysis and electrocatalysis.

Keywords: Commercial glass electrodes; Differential potentiometry; Interlaboratory comparison; Non-aqueous buffer; Reference values; Unified pH scale.