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At present, the National Metrology Institute of Japan provides six national primary pH buffers under the Japan Calibration Service System. Each batch of these buffers is certified by the primary pH method using a Harned cell. On the basis of these primary buffers, the designated laboratories supply the secondary and working pH standards using a high-precision pH meter. This paper provides an estimate of the batch-to-batch reproducibility of the primary pH standard production based on the history of the certification of primary carbonate buffers in NMIJ. This buffer, which was chosen as the subject of the study because of the relative difficulty of its measurements (and thus a greater dispersion of results), is nominally the 0.025 mol kg−1 equimolal solution of disodium carbonate and sodium hydrogen carbonate. As its pH value is significantly affected by the purity of the reagents used, the evaluation of their source materials is made by both pH measurements and acidimetric gravimetric back titrations. Considering the experimentally determined pH reproducibility of ca. 0.010, potential risks to the pH accuracy are discussed when using recipe-based carbonate pH standards. [ABSTRACT FROM AUTHOR]