Indirect Potentiometric pH Detection of Weak Acids with Absolute Quantitation by a Theoretical Approach

A fast response potentiometric flow-through pH sensor was applied for organic acid determination. The analyte response with the pH sensor was obtained by eluent pH modification following ion exclusion chromatography with HClO₄ as an eluent. The response characteristics depend on the adjusted baseline pH. The baseline pH adjustment was successfully done with an ammonia permeation device without solution mixing, which may cause analyte dilution, dispersion, and mixing noise. After pH adjustment, the pH response was universal to the equivalent of introduced analyte acids because the pH response was obtained by the titration of the permeant ammonia by the analytes. The average of limit of detections (S/N = 3) was 0.06 mM for seven target organic acids. Furthermore, the pH response follows the theoretical pH calculation with the concentrations of the eluent, pH modifier, and analyte. Thus, the analyte concentration in the sample can be theoretically calculated from the pH response without calibration by the analyte standard. Predicted concentrations of injected standards were within 5% of the actual standard concentration. Additionally, analysis of real samples was performed and compared with the conventional post-column reaction with a bromothymol blue (BTB) method. The results obtained with the present system (absolute quantification with theoretical calculation) and conventional BTB method agreed within 10% of errors.