Preview

Measurement Standards. Reference Materials

Advanced search

Development of a Reference Material for Potassium Bromide Composition

https://doi.org/10.20915/2077-1177-2025-21-3-40-61

Abstract

To obtain reliable measurement results for the content of components in various materials, reference materials with certified content of the studied component are required. Elemental bromine, being a volatile and toxic liquid, is unsuitable as a source material for the preparation of a reference material for the chemical element bromine. The most optimal choice for the reference material is a bromine salt – potassium bromide.

The aim of the study is to develop a certified reference material for composition of potassium bromide based on the same high-purity salt with the certified characteristic «mass fraction of potassium bromide». The mass fraction of the main component in potassium bromide was measured using two methods: a direct method employing coulometric titration with corrections for interfering impurities determined by ion chromatography, and an indirect method based on the scheme of 100% minus the sum of impurities, taking into account their ionic forms.

It is shown that the direct and indirect methods for determining the mass fraction of potassium bromide yield consistent results: (99.871 ± 0.029) and (99.873 ± 0.017)%, respectively. Studies of homogeneity, as well as short-term and long-term stability, were conducted using the coulometric titration. A reference material for potassium bromide composition, GSO 12300-2023, was developed with an interval of certified values of the mass fraction of potassium bromide (99.5–100)% and an expanded uncertainty of the certified value of 0.05% at k=2. The certified value and expanded uncertainty of the mass fraction of potassium bromide for a batch of the reference material were (99.87 ± 0.05)%.

A distinctive feature of the indirect method for determining the mass fraction of potassium bromide implemented in this work is the construction of a chemical composition model of the analyzed object. This model is based on both a priori and experimental data and utilizes two fundamental principles when summing impurity contents: the condition of material (mass) balance and the principle of electroneutrality. The described indirect method is sufficiently universal. For high-purity salts, it enables achieving a relative expanded uncertainty (at k=2) of less than 0.02%. This method can be adopted in analytical practice for assessing the purity of other metal salts where high accuracy is required.

The developed certified reference material can be used to ensure the metrological traceability of measurement results in both titrimetry (precipitation titration) and elemental analysis. It can also be utilized for the preparation or control of certified values for reference materials of bromide ion solution composition, including those in multicomponent mixtures with other anions.

About the Authors

A. V. Sobina
UNIIM – Affiliated Branch of the D. I. Mendeleyev Institute for Metrology
Russian Federation

Alena V. Sobina – Cand. Sci. (Eng.), Head of the Laboratory of Physical and Chemical Methods for Metrological Certification of Reference Materials

4 Krasnoarmeyskaya st., Yekaterinburg, 620075



E. P. Sobina
UNIIM – Affiliated Branch of the D. I. Mendeleyev Institute for Metrology
Russian Federation

Egor P. Sobina – Dr. Sci. (Eng.), Director, UNIIM – Affiliated Branch, Head of the Laboratory for Metrological Assurance of Nano Industry, Spectral Methods of Analysis and Reference Materials

4 Krasnoarmeyskaya st., Yekaterinburg, 620075



A. Yu. Shimolin
UNIIM – Affiliated Branch of the D. I. Mendeleyev Institute for Metrology
Russian Federation

Alexandr Yu. Shimolin – Cand. Sci. (Eng.), Senior Engineer of the Laboratory of Physical and Chemical Methods for Metrological Certification of Reference Materials

4 Krasnoarmeyskaya st., Yekaterinburg, 620075

Researcher ID: Q‑5745–2017



References

1. Moody J. R., Greenberg R. R., Pratt K. W., Rains T. C. Recommended inorganic chemicals for calibration. Analytical Chemistry. 1988;60(21):1203A. https://doi.org/10.1021/ac00172a001

2. Máriássy M., Hanková Z., Hwang E., Lim Y., Pratt K. W., Hioki A. et al. Final report on key comparison CCQM-K96: Determination of amount content of dichromate. Metrologia. 2013;50(1A):08012. https://doi.org/10.1088/0026–1394/50/1A/08012

3. Liandi M. A., Bing W. U., Mariassy M., Pratt K. W., Hwang E., Manzano J. V. L. et al. CCQM-K48.2014: Assay of potassium chloride. Metrologia. 2016;53(1A):08012. https://doi.org/10.1088/0026–1394/53/1A/08012

4. Wu B., Sobina A., Recknagel S., Meinhardt R., Rivera-Sánchez G., Ortiz-Aparicio J. L. et al. Assay of sodium carbonate. Metrologia. 2023;60(1A):08004. https://doi.org/10.1088/0026–1394/60/1A/08004

5. Sobina A., Shimolin A., Sobina E., Tabatchikova T., Ortiz-Aparicio J. L., Velina J. et al. Report of the CCQM-K152. Assay of potassium iodate. Metrologia. 2020;58(1A):08005. https://doi.org/10.13140/RG.2.2.26310.09285

6. Kuselman I., Pennecchi F. R., da Silva R. J. N. B., Hibbert D. B. IUPAC/CITAC guide: Evaluation of risks of false decisions in conformity assessment of a multicomponent material or object (IUPAC Technical report). Pure and Applied Chemistry. 2020;92(1):113–154. https://doi.org/10.1515/pac 2019–0906

7. Pennecchi F. R., Kuselman I., Di Rocco A., Hibbert D. B., Sobina A., Sobina E. Specific risks of false decisions in conformity assessment of a substance or material with a mass balance constraint – A case study of potassium iodate. Measurement. 2021;173:108662. https://doi.org/10.1016/j.measurement.2020.108662

8. Vasil’ev V. P. Analytical chemistry: In 2 vol. of vol. 1. Gravimetric and titrimetric methods of analysis. Moscow: Vysshaia shkola; 2007. P. 287–289. (In Russ.).

9. Korostelev P. P. Preparation of solutions for chemical-analytical works: textbook. 2th ed. Moscow: Nauka; 1964. P. 173–174. (In Russ.).

10. Kreshkov A. P., Iaroslavtsev A. A. Course of analytical chemistry. Quantitative analysis: textbook. 5th ed. Moscow: Khimiia; 1982. P. 163–165. (In Russ.).

11. Lazukina O. P., Malyshev K. K., Volkova E. N., Churbanov M. F. Analysis of data on the impurity composition of samples of simple solids of the exhibition-collection of high-purity substances. Vysokochistye veshchestva. 1992;5–6:7–11. (In Russ.).

12. Malyshev K. K., Stepanov V. M. Statistical assessment of the total concentration of impurities based on incomplete analysis data using the example of Te, Mn, Al. Vysokochistye veshchestva. 1990;2:229–236. (In Russ.).

13. Balaram V. Recent developments in analytical techniques for characterization of ultra pure materials – An overview. Bulletin of Materials Science. 2005;28(4):345–348. https://doi.org/10.1007/BF02704247

14. Medvedevskikh S. V., Sobina E. P., Migal P. V., Goryaeva L. I., Gorbunova E. M., Tabatchikova T. N. et al. On the use of pure inorganic substances in metrology of analytical measurements. Measurement Standards. Reference Materials. 2014;3:58–67. (In Russ.).

15. Sobina E. P., Sobina A. V., Tabatchikova T. N. Method for determining the mass fraction of the main component in sodium chloride and potassium chloride salts. Patent RF, №  2686468, 2019. (In Russ.).

16. Sobina E. P., Sobina A. V., Shimolin A. Yu., Tabatchikova T. N., Lebedeva E. L., Migal’ P. V. et al. Application of direct and indirect methods for determining the mass fraction of the main component in flotation potassium chloride. Measurement Standards. Reference Materials. 2021;17(4):65–84. (In Russ.). https://doi.org/10.20915/2687 0886 2021 17 4 65 84

17. Sobina A. V., Sobina E. P., Shimolin A. Yu., Tabatchikova T. N. Development of a reference materials of potassium iodate composition: application of direct and indirect approaches to assessing salt purity. Zhurnal Analiticheskoi Khimii. 2024;79(1):61–20. (In Russ.). https://doi.org/10.31857/S0044450224010077

18. Huang T., Zhang W., Wang J. et al. Coulometric method with titratable impurity analysis and mass balance method: convert acidimetric purity to chemical purity for SI-traceable highest standard of qNMR (potassium hydrogen phthalate), and verified by qNMR. Analytical and Bioanalytical Chemistry. 2023;415:1445–1454. https://doi.org/10.1007/s00216–023–04532-x

19. Skutina A. V., Terentiev G. I. State primary standard of units of mass (mole) fraction and mass (molar) concentration of a component in liquid and solid substances and synthetic materials on the basis of coulometric titration. Izmeritelʹnaya Tekhnika. 2011;9:4–8. (In Russ.).

20. Prohaska T., Irrgeher J., Benefield J., Böhlke J. K., Chesson L. A., Coplen T. B. et al. Standard atomic weights of the elements 2021 (IUPAC Technical Report). Pure and Applied Chemistry. 2022;94(5):573–600. https://doi.org/10.1515/pac 2019–0603

21. Shimolin A. Yu. Metrological support for measurements of oxidizing and reducing agent content in high-purity substances and their solutions by coulometric titration with electrogenerated iodine. Cand. Sci. (Eng.). diss., VNIIM. Available at: https://www.vniim.ru/files/diss-shimolin.pdf [Accessed 5 June 2025]. (In Russ.).

22. Shimolin A. J., Sobina A. V., Zyskin V. M. Potassium iodate purity determination by high precision coulometric titration: New measurement procedure implementation. In: 2nd International Ural Conference on Measurements (UralCon), Chelyabinsk, Russia, 16–19 October 2017. IEEE, p. 311–315. https://doi.org/10.1109/URALCON.2017.8120729

23. Molloy J. L., Winchester M. R., Butler T. A., Possolo A. M., Rienitz O., Roethke A. et al. CCQM-K143 comparison of copper calibration solutions prepared by NMIs/Dis. Metrologia. 2020;58(1A):08006. https://doi.org/10.1088/0026–1394/58/1A/08006

24. Jingbo C., Liandi M., Naijie S., Yunqiao L., Yan C., Lijie D. CCQM-K161 anions in seawater. Metrologia. 2024;61(1A):08016. https://doi.org/10.1088/0026–1394/61/1A/08016.


Review

For citations:


Sobina A.V., Sobina E.P., Shimolin A.Yu. Development of a Reference Material for Potassium Bromide Composition. Measurement Standards. Reference Materials. 2025;21(3):40-61. (In Russ.) https://doi.org/10.20915/2077-1177-2025-21-3-40-61

Views: 11


ISSN 2687-0886 (Print)