Direct Potentiometric Sensing of Anion Concentration (Not Activity)

Potentiometric probes used in direct potentiometry are attractive sensing tools. They give information on ion activities, which is often uniquely useful. If, instead, concentrations are desired as sensor output, the ionic strength of the sample must be precisely known, which is often not possible. Here, for the first time, direct potentiometry can be made to report concentrations, rather than activities. It is demonstrated for the detection of monovalent anionic species by using a self-referencing Ag/AgI pulstrode as the reference element instead of a traditional reference electrode. This reference pulstrode releases a discrete quantity of iodide ions from the electrode and the resulting reference potential varies with the activity coefficient of iodide. The effects of activity coefficient on the indicator and reference electrode are therefore compensated and the observed cell potential may now be described in a Nernstian manner against anion concentration, rather than activity. Theoretical simulations and experimental results support the validity of this approach. For most monovalent anions of practical relevance, the potential difference between this approach and from a traditional activity coefficient calculation is less than 0.5 mV. The concept is validated with an all-solid-state nitrate sensor as well as a commercial fluoride-selective electrode, giving Nernstian responses in different ionic strength backgrounds against concentration without the need for correcting activity coefficients or liquid junction potentials.