A unified pH scale of absolute values (pHabs scale) enables the comparison of acidities in different solvents. To date, very few different experimental setups have been used for the measurement of values on this scale. The article describes the design and performance of the different symmetric cells used for unified pH measurement by several institutions. Well-established and reliable standard aqueous buffer solutions are the first step of method validation necessary to achieve a robust metrological level for more complex media. The pH of aqueous standard buffers was measured by differential potentiometry, where the potential between two glass electrodes is measured directly. All the tested electrochemical cells prove to be suitable for unified pH measurements. This validation highlights that the method is, to a large extent, independent of the used equipment, including the cell geometry. The inherent symmetry of the cell design helps to reduce the experimental workload and improve the accuracy of obtained results.

Measurement of pH in aqueous-organic mixtures with different compositions is of high importance in science and technology, but it is, at the same time, challenging both from a conceptual and practical standpoint. A big part of the difficulty comes from the fundamental incomparability of conventional pH values between solvents (spH, solvent-specific scales). The recent introduction of the unified pH (pHabs) concept opens up the possibility of measuring pH, expressed as pHabsH2O, in a way that is comparable between solvent, and, thereby, removing the conceptual problem. However, practical issues remain. This work presents the experience of the authors with measuring pHabsH2O values in mixtures of methanol, ethanol, and acetonitrile, with water, but without the presence of buffers or other additives. The aim was to assigned pHabsH2O values to solvent–water mixtures using differential potentiometry and the ‘pHabs-ladder’ method. Measurements were made of the potential difference between glass electrodes immersed in different solutions, separated by an ionic liquid salt bridge. Data were acquired for a series of solutions of varying solvent content. This work includes experiences related to: a selection of commercial electrodes, purity of starting material, and comparability between laboratories. Ranges of pHabsH2O values for selected compositions of solvent–water mixtures are presented.

The definition of pH, its measurement and standard buffers, is well developed in aqueous solutions. Its definition in solvents other than water has been elaborated for a couple of solvents and their mixtures with water. However, the definition of a universal pH scale spanning all solvents and phases, not to mention standard procedures of measurement, is still a largely uncharted territory. UnipHied is a European collaboration and has the goal of putting the theoretical concept of an earlier introduced (2010) unified pHabs scale on a metrologically well-founded basis into practice. The pHabs scale enables the comparability of acidity between different phases. This article draws the connection of the concepts of unified acidity and secondary pH measurement.

No abstract

Main text This key comparison CCQM-K19.2018, as a repetition of the previous study CCQM-K19 from 2005, was performed to evaluate the degree of equivalence of measurement procedures of participating National Metrology Institutes (NMIs) and Designated Institutes (DIs) for the determination of pH of borate buffer solutions. The nominal pH value of the buffer was 9.2 at 25 °C and the suggested measurement temperatures were 5 °C, 15 °C, 25 °C, 37 °C and 50 °C. Good agreement of the results is demonstrated by most participants. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).