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

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.

Evaluation and validation of detailed and simplified models of the uncertainty of unified [Formula: see text] measurements in aqueous solutions.

The use of the unified pH concept, [Formula: see text] , applicable to aqueous and non-aqueous solutions, which allows interpreting and comparison of the acidity of different types of solutions, requires reliable and objective determination. The [Formula: see text] can be determined by a single differential potentiometry measurement referenced to an aqueous reference buffer or by a ladder of differential potentiometric measurements that allows minimisation of inconsistencies of various determinations. This work describes and assesses bottom-up evaluations of the uncertainty of these measurements, where uncertainty components are combined by the Monte Carlo Method (MCM) or Taylor Series Approximation (TSM). The MCM allows a detailed simulation of the measurements, including an iterative process involving in minimising ladder deviations. On the other hand, the TSM requires the approximate determination of minimisation uncertainty. The uncertainty evaluation was successfully applied to measuring aqueous buffers with pH of 2.00, 4.00, 7.00, and 10.00, with a standard uncertainty of 0.01. The reference and estimated values from both approaches are metrologically compatible for a 95% confidence level even when a negligible contribution of liquid junction potential uncertainty is assumed. The MCM estimated pH values with an expanded uncertainty, for the 95% confidence level, between 0.26 and 0.51, depending on the pH value and ladder inconsistencies. The minimisation uncertainty is negligible or responsible for up to 87% of the measurement uncertainty. The TSM quantified measurement uncertainties on average only 0.05 units larger than the MCM estimated ones. Additional experimental tests should be performed to test these uncertainty models for analysis performed in other laboratories and on non-aqueous solutions.

Unified pH Measurements of Ethanol, Methanol, and Acetonitrile, and Their Mixtures with Water.

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.

Molecular scale characterization of the titania-dye-solvent interface in dye-sensitized solar cells.

Charge separation at the dye/titania interface in dye sensitized solar cells is strongly influenced by the thickness and homogeneity of the sensitizing dye layer, as this controls the potential drop across the interface, and the probability of an excited electron being transferred from the dye to the titania. In this study we use atomic force microscopy and the depth profiling method neutral impact collision ion scattering spectroscopy (NICISS) to investigate the thickness and homogeneity of N719 dye adsorbed to titania before and after rinsing with pure acetonitrile. Both experimental methods show that the dye layers are closed but inhomogeneous. Inhomogeneity is more pronounced for unrinsed samples.