A review of the state of the art of electrochemical methods at the highest metrology level in national metrology institutes (NMIs) is given, with emphasis on standardization work (primary methods) in the fields of pH and electrolytic conductivity, as well as use of coulometry. Attention is also given to certain technical issues in the implementation of these methods.
The possible approaches to realising a link to the SI system and the status of primary direct methods in the traceability chain of chemical measurements are discussed. Some results obtained with the new coulometric standard system are presented.
In the 1990s the CCQM (Comité consultatif pour la quantité de la matière) defined the term 'primary method'. It also identified some methods that are considered to be primary. One of these methods is titrimetry. In this paper, the principle of titrimetry and two practical examples performed at the highest metrological level in the frame of key comparison CCQM-K8 are discussed. It is evident that titrimetry is a very powerful method leading to highly accurate results when performed correctly, and does not depend on whether the classical metrological approach or a new experimental design using modern laboratory technology is applied.
Key Comparison CCQM-K36.2016 was a follow-up comparison for K36 and provided updated support for the corresponding calibration and measurement capability (CMC) entries in the BIPM CMC database. It aimed to demonstrate the capabilities of the participating NMIs to measure electrolytic conductivity of aqueous electrolyte solutions in the conductivity range 0.15 S m−1 to 1.5 S m−1 and in the conductivity range 1.5 mS m−1 to 15 mS m−1. To this end electrolytic conductivity of a potassium chloride solution (nominal conductivity 0.5 S m−1) and of a HCl solution (nominal conductivity 5 mS m−1) had to be measured. 17 NMIs participated in the comparison. The key comparison reference value (KCRV) of the KCl solution was (0.50999 +/-0.00032) S m−1 and the KCRV of the HCl solution was (4.9877 +/-0.012) mS m−1. Both values were estimated from the medians of the results considered eligible for KCRV calculation. They were given with their expanded uncertainties (95% coverage). The majority of the 0.5 S m-1 results were consistent with the KCRV. Two institutes showed a small inconsistency, one outlier was observed. The conductivity of the HCl solution showed a small, but steady linear drift of 0.00006843 mS m−1 per day during the measurement period and was corrected for KCRV calculation. Some institutes reported unstable measurement conditions for this solution. The results of seven participants have been inconsistent with the KCRV. 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 (CIPM MRA).
The aim of this comparison was to demonstrate the capability of national metrology institutes to measure elemental mass fractions at a level of w(E) ≈ 1 g/kg as found in almost all mono-elemental calibration solutions. These calibration solutions represent an important link in traceability systems in inorganic analysis. Virtually all traceable routine measurements are linked to the SI through these calibration solutions. Every participant was provided with three solutions of each of the three selected elements chromium, cobalt and lead. This comparison was a joint activity of the Inorganic Analysis Working Group (IAWG) and the Electrochemical Analysis Working Group (EAWG) of the CCQM and was piloted by the Physikalisch-Technische Bundesanstalt (PTB, Braunschweig, Germany) with the help of the Bundesanstalt für Materialforschung und -prüfung (BAM, Berlin, Germany), the Centro Nacional de Metrología (CENAM, Querétaro, Mexico) and the National Institute of Standards and Technology (NIST, Gaithersburg, USA).A small majority of participants applied inductively coupled plasma optical emission spectrometry (ICP OES) in combination with a variety of calibration strategies (one-point-calibration, bracketing, calibration curve, each with and without an internal standard). But also IDMS techniques were carried out on quadrupole, high resolution and multicollector ICP-MS machines as well as a TIMS machine. Several participants applied titrimetry. FAAS as well as ICP-MS combined with non-IDMS calibration strategies were used by at least one participant. The key comparison reference values (KCRV) were agreed upon during the IAWG/EAWG meeting in November 2011 held in Sydney as the added element content calculated from the gravimetric sample preparation. Accordingly the degrees of equivalence were calculated. Despite the large variety of methods applied no superior method could be identified. The relative deviation of the median of the participants' results from the gravimetric reference value was equal or smaller than 0.1% (with an average of 0.05%) in the case of all three elements.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 (CIPM MRA).
The CCQM-K48 key comparison for determination of the purity of potassium chloride was organized jointly by the inorganic analysis and electrochemical analysis working groups of CCQM to test the abilities of the metrology institutes to measure the amount content of chloride in KCl. National Institute of Metrology P.R.China (NIM) acted as the coordinating laboratory of this comparison with SMU and NIST as co-coordinating laboratories. Seven NMIs participated in this key comparison. All participants used coulometry (except NMIJ which used gravimetry) and all of them analyzed the impurity bromine in the sample and made corrections. In general very good agreement of the results was observed. Some possible problems were highlighted.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).
The key comparison CCQM-K34 was organized jointly by the inorganic and electrochemistry working groups of the CCQM as a follow-up to the pilot study CCQM-P36 to test the abilities of the metrology institutes to measure the amount content of acid in solid weak acids. The Slovak Institute of Metrology acted as the coordinating laboratory, and seven NMIs expressed interest in participation. All participants used constant current coulometry at different levels of sophistication. In general very good agreement of the results was observed; some possible problems were highlighted.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.
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