Effect of citrate impurities on the reference pH value of potassium dihydrogen buffer solution

Solutions of potassium dihydrogen citrate, KH₂C₆H₅O₇, exhibit reference pH values close to those of the primary standard pH buffer solutions of tartrate and phthate. Nevertheless, as opposed to all other recommended primary buffer standards, the citrate reagent is not commercially available as a standard reference material (SRM).In this work, experiments have been performed on solid reagent from different sources, which revealed the presence of the various citrate species in variable amounts. This may arise from the sensitivity of the system to the purification strategy, owing to the proximity of the acidity constants of the triprotic citric acid, H₃C₆H₅O₇.An experimental procedure has been developed which leads to a satisfactory preparation of the citrate reagent, to an extent that its solutions, independently of batch on supplier, exhibit reproducible pH values, in agreement with the conventionally assigned pH (S) = 3.776 at 25 °C for 0.05 m KH₂C₆H₅O₇.Comparison of expected and experimental values is used as a quantitative test for the quality of reagent, eventually indicating the need for purification according to recommendations.