Search

CCQM-K9.2 was performed supplementary to the key comparison CCQM-K9 on the pH determination of a phosphate buffer with nominal pH ~ 6.9 (at 25 ?C). The sample composition was very similar in both comparisons. Only the source of the starting material used for sample preparation was different. The comparison was restricted to the use of the primary method for pH (Harned cell measurement) as defined in the IUPAC Recommendations [2]. The measurement temperatures were 15 ?C, 25 ?C, 37 ?C. CCQM-K9.2, CCQM-K.9 and the first supplementary comparison CCQM-K9.1 [5] are activities of the Electrochemical Working Group (EAWG) of the CCQM. All three comparisons were coordinated by the PTB, Germany. The Danish Primary Laboratory (DPL) successfully took part in the CCQM-K9. Meanwhile the primary set-up for pH in Denmark moved from DPL affiliated to Radiometer Medical to DFM, Denmark. The subsequent comparison allows assessing the degree of equivalence for the measurement of pH at DFM after the move. Due to the interest of other laboratories in demonstrating their progress in pH measurements on the primary level the CCQM-K9.2 supplementary comparison was extended to other participants than DFM, namely NMIJ, VNIIFTRI, INMETRO and CMI. The reported quantity for CCQM-K9.2 was not the pH of the sample but the acidity function at zero chloride molality (see chapter 12). To calculate the pH value from the acidity function it is necessary to know the ionic strength of the sample buffer solution, which was undisclosed by the coordinator. With the exception of the Czech Metrology Institute, CMI, good agreement in the determined acidity function is found between the participants. The results reported by DFM and by PTB agree within their measurement uncertainty at all measurement temperatures. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

A comparison of the primary methods for pH measurement of Russia and Germany was carried out. Three buffer solutions: potassium tetraoxalate, 0.05 mol/kg, potassium hydrogen phthalate, 0.05 mol/kg and disodium tetraborate decahydrate, 0.01 mol/kg, prepared from materials of the All-Russian Research Institute for Physical, Technical and Radio-Technical Measurements (VNIIFTRI) and Merck KGaA, Germany, were used. The pH values obtained at 25 °C in this comparison agree within an expanded uncertainty of 0.004 for the borate and oxalate buffers and 0.005 for the phthalate buffer (k = 2).

The EUROMET project 696, a trilateral comparison between PTB, Germany, LNE, France and VNIIFTRI, Russia was performed in order to demonstrate and document the capability of the participants to measure the pH of a phthalate buffer by the primary measurement procedure for pH. Good agreement of the reported results was observed. The sample was very similar to the one used in the comparison CCQM-K17. PTB acts as pilot laboratory in CCQM-K17 and in EUROMET 696. This comparison allows one to link the results obtained by LNE to the CCQM-K17 key comparison through the degree of equivalence of PTB. On the other hand, the discrepancy between measured pH values at the VNIIFTRI and PTB for the same type of buffer solution decreased, as compared with a bilateral comparison in 1997. Main text. To reach the main text of this paper, click on Final Report. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the Mutual Recognition Arrangement (MRA).

The second key comparison for the quantity pH, CCQM-K17, was carried out to assess the degree of equivalence of the national primary measurement procedures used to determine the pH of primary standard buffer solutions. The CCQM-K17 comparison allows estimations of the capability of ten national metrology institutes (NMIs) to determine the pH of a phthalate buffer of unknown concentration at different temperatures. The key comparison was co-ordinated by the CCQM Working Group on Electrochemical Analysis and piloted by the Physikalisch-Technische Bundesanstalt (PTB) with assistance from the National Institute of Standards and Technology (NIST) and the Slovak Institute of Metrology (SMU). The measurement results of the NMIs agreed not at the same level as for the first key comparison on pH CCQM-K9. The results obtained by seven of the eleven participants agree very well within the uncertainty stated by the participants. Four participants obtained results somewhat lower. The two groups of results are most obviously evident at a measurement temperature of 37 °C. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the Mutual Recognition Arrangement (MRA).