izmertechИзмерительная техникаIzmeritel`naya Tekhnika0368-10252949-5237ФГУП "ВНИИФТРИ"10.32446/0368-1025it.2024-8-56-68izmertech-2227Research ArticleФИЗИКО-ХИМИЧЕСКИЕ ИЗМЕРЕНИЯPHYSICOCHEMICAL MEASUREMENTSИзмерение чистоты органических веществ: общие подходы и разработка оптимальной процедуры исследований чистого органического веществаMeasuring the purity of organic chemicals: general approaches and development of an appropriate procedure for research of pure organic chemicalshttps://orcid.org/0000-0003-1032-5653МихееваА. Ю.MikheevaA. Yu.

Алёна Юрьевна Михеева, Кандидат хим. наук, Ведущий научный сотрудник, Зам. руководителя НИО государственных эталонов в области органического и неорганического анализа

Санкт-Петербург

a.mikheeva@vniim.ruВсероссийский научно-исследовательский институт метрологии им. Д. И. МенделееваРоссияD. I. Mendeleev All-Russian Institute for MetrologyRussian Federation2024300920247385668Copyright © ФГУП "ВНИИФТРИ", 20242024ФГУП "ВНИИФТРИ"ФГУП "ВНИИФТРИ"https://www.izmt.ru/jour/about/submissions#copyrightNoticehttps://www.izmt.ru/jour/article/view/2227

Отмечена востребованность чистых веществ в различных отраслях народного хозяйства, науки и промышленности, а также необходимость чистых веществ для решения метрологических задач в области органического анализа, где чистое органическое вещество является основой формирования цепи метрологической прослеживаемости к Международной системе единиц. Рассмотрены международно признанные подходы к измерению чистоты чистых органических веществ, обеспечивающие прослеживаемость аттестованного (сертифицированного) значения чистоты вещества к основным единицам Международной системы единиц – молю и килограмму. Обуждены особенности использования прямых и косвенного методов измерений чистоты органических веществ, а также конкретные аналитические техники и процедуры, которые можно использовать для этой цели. Подчёркнуто, что определение чистоты органического вещества в большинстве случаев – непростая аналитическая и метрологическая задача, что требует применения релевантных инструментальных методов и создания на их основе оптимальной процедуры измерений, которая гарантирует всестороннее изучение органического вещества и позволяет достичь требуемой точности значения аттестованной характеристики. Отмечено, что с учётом колоссального разнообразия органических соединений определение чистоты вещества никогда не будет стандартизированной процедурой.

Pure materials are in demand in many sectors of the national economy, including the metrological service. High purity organic material is the ultimate source of metrological traceability in organic analysis to the basic units of the International System of Units (SI). This article presents the general approaches to determining the mass fraction of the main component in pure organic chemicals, which provide a traceable connection between the certified value of substance purity and the basic SI units - mass (kilogram) and amount of substance (mole), the features of using direct and indirect measurement approaches are considered, specific analytical methods that can be used for this purpose are discussed. Determining the purity of an organic material in most cases is not a plain analytical and metrological task. Solving this issue requires the relevant instrumental methods and appropriate measurement procedure, which is able to provide a comprehensive study of organic matter and guarantee the necessary accuracy of the certified value. Taking in consideration the vast diversity of organic chemicals, the determination of the purity of organic substances will never be a standardized procedure.

чистые органические веществаколичество веществамольметрологическая прослеживаемостьосновной компонентпримесные компонентыpure organic compoundsamount of substancemolemetrological traceabilitymain componentimpurity componentsThe author declares that no funds, grants, or other support were received during the preparation of this manuscript.ReferencesМеждународная система единиц (СИ). Международное бюро мер и весов, Федеральное агентство по техническому регулированию и метрологии (Росстандарт). Перевод Н. А. Александровой и др. Изд. 9-е. Санкт-Петербург (2019).The International System of Units (SI). 9th edition 2019, Bureau International des Poids et Mesures, V3.01 (2024).Основы аналитической химии. В 2 т. Под ред. Золотова Ю. А. Академия, Москва (2012).Osnovy analiticheskoj himii. Ed. Zolotov Yu. A., in 2 vol. Akademiya, Moscow (2012). (In Russ.)Аналитическая химия и физико-химические методы анализа. В 2 т. Под ред. Ищенко А. А. Академия, Москва (2010).Analiticheskaya himiya i fiziko-himicheskie metody analiza. Ed. Ishenko A. A., in 2 vol. Akademiya, Moscow (2010). (In Russ.)Pharmaceutical Analysis. Eds. Lee D. C, Webb M. L. Blackwell, Oxford (2003).Pharmaceutical Analysis. Eds. Lee D. C, Webb M. L. Blackwell, Oxford (2003).Analytical Techniques in the Pharmaceutical Science. Eds. Muellertz A. et al. Springer, N.Y. (2016).Analytical Techniques in the Pharmaceutical Science. Eds. Muellertz A. et al. Springer, N.Y. (2016).Handbook of isolation and characterization of impurities in pharmaceuticals. Eds. Ahuja S., Alsante K. M. Elsevier, San Diego (2003).Handbook of isolation and characterization of impurities in pharmaceuticals. Eds. Ahuja S., Alsante K. M. Elsevier, San Diego (2003).Duewer D. L., Parris R. M., White V. E., May W. E. An approach to the metrologically sound traceable assessment of the chemical purity of organic reference materials. NIST Special Publication, (1012), 55 (2004).Duewer D. L., Parris R. M., White V. E., May W. E. An approach to the metrologically sound traceable assessment of the chemical purity of organic reference materials. NIST Special Publication, (1012), 55 (2004).Westwood S., Choteau T., Daireaux A., Josephs R. D., Wielgosz R. I. Mass balance method for the SI value assignment of the purity of organic compounds. Analytical Chemistry, 85, 3118–3126 (2013). https://doi.org/10.1021/ac303329kWestwood S., Choteau T., Daireaux A., Josephs R. D., Wielgosz R. I. Mass balance method for the SI value assignment of the purity of organic compounds, Analytical Chemistry, 85, 3118–3126 (2013). https://doi.org/10.1021/ac303329kWestwood S., Lippa K., Shimuzu Y. et al. Methods for the SI-traceable value assignment of the purity of organic compounds (IUPAC Technical Report), Pure and Applied Chemistry, 95(1), 1–77 (2023). https://doi.org/10.1515/pac-2020-0804Westwood S., Lippa K., Shimuzu Y. et al. Methods for the SI-traceable value assignment of the purity of organic compounds (IUPAC Technical Report), Pure and Applied Chemistry, 95(1), 1–77 (2023). https://doi.org/10.1515/pac-2020-0804Katrice A. Lippa, David L. Duewer, Michael A. Nelson et al. The role of the CCQM OAWG in providing SI traceable calibrators for organic chemical measurements. Accreditation and Quality Assurance, 24, 407–415. (2019). https://doi.org/10.1007/s00769-019-01407-6Katrice A. Lippa, David L. Duewer, Michael A. Nelson et al. The role of the CCQM OAWG in providing SI traceable calibrators for organic chemical measurements, Accreditation and Quality Assurance, 24, 407–415. (2019). https://doi.org/10.1007/s00769-019-01407-6Зенкевич И. Г. Алгоритмы определения газохроматографических индексов удерживания. Сравнительная характеристика. Лаборатория и производство, (5), 50–64 (2019). https://doi.org/10.32757/2619-0923.2019.5.9.50.64Zenkevich I. G. Algorithms for determining gas chromatographic retention indices. comparative characteristics. Laboratoriya i proizvodstvo, (5), 50–64 (2019). (In Russ.) https://doi.org/10.32757/2619-0923.2019.5.9.50.64Васильева И. А. Алгоритмы повышения точности определения индексов удерживания в газовой хроматографии с программированием температуры: дисс. канд. хим. наук, СпбГУ, Санкт-Петербург (2003).Vasilieva I. A. Algorithms for improving the accuracy of determination of retention indices in gas chromatography with temperature programming: diss. PhD of Chemical Sciences, SpbGU, Saint Petersburg (2003).Тахистов В. В., Пономарев Д. А. Органическая масс-спектрометрия. ВВМ, Санкт-Петербург (2005).Takhistov V. V., Ponomarev D. A. Organicheskaya mass-spektrometriya. VVM, Saint-Petersburg (2005). (In Russ.)Лебедев А. Т. Масс-спектрометрия в органической химии. Изд. 2-е. Техносфера, Москва (2015).Lebedev А. Т. Mass-spektrometriya v organicheskoj himii, 2nd edition, Tekhnosfera, Moscow (2015). (In Russ.)Carlos Cobas. NMR signal processing, prediction, and structure verification with machine learning techniques. MRC, 58(6), 512–519 (2020). https://doi.org/10.1002/mrc.4989Carlos Cobas. NMR signal processing, prediction, and structure verification with machine learning techniques. MRC, 58(6), 512–519 (2020). https://doi.org/10.1002/mrc.4989Mikhail Elyashberg. Identification and structure elucidation by NMR spectroscopy. TrAC Trends in Analytical Chemistry, 69, 88–97 (2015). http://dx.doi.org/10.1016/j.trac.2015.02.014Mikhail Elyashberg. Identification and structure elucidation by NMR spectroscopy. TrAC Trends in Analytical Chemistry, 69, 88–97 (2015). http://dx.doi.org/10.1016/j.trac.2015.02.014B. Zghari, P. Doumenq, A. Romane, A. Boukir. GC-MS, FTIR and 1H, 13C NMR structural analysis and identification of phenolic compounds in olive mill wastewater extracted from oued oussefrou effluent (Beni Mellal-Morocco). Journal of Materials and Environmental Sciences, 8(12), 4496–4509 (2017). https://doi.org/10.26872/jmes.2017.8.12.475B. Zghari, P. Doumenq, A. Romane, A. Boukir. GC-MS, FTIR and 1H, 13C NMR structural analysis and identification of phenolic compounds in olive mill wastewater extracted from oued oussefrou effluent (Beni Mellal-Morocco). Journal of Materials and Environmental Sciences, 8(12), 4496–4509 (2017). https://doi.org/10.26872/jmes.2017.8.12.475Jinzhe Zhang, Kei Terayama, Masato Sumita et al. NMR-TS: de novo molecule identification from NMR spectra. Science and Technology of Advanced Materials, 21(1), 552–561 (2020). https://doi.org/10.1080/14686996.2020.1793382Jinzhe Zhang, Kei Terayama, Masato Sumita et al. NMR-TS: de novo molecule identification from NMR spectra. Science and Technology of Advanced Materials, 21(1), 552–561 (2020). https://doi.org/10.1080/14686996.2020.1793382Tsutomu Miura. Purity determination of high-purity BeO using gravimetric analysis with stepwise conversions of weighing form of Be. Talanta, 9, 100307 (2024). https://doi.org/10.1016/j.talo.2024.100307Tsutomu Miura. Purity determination of high-purity BeO using gravimetric analysis with stepwise conversions of weighing form of Be, Talanta, 9, 100307 (2024). https://doi.org/10.1016/j.talo.2024.100307Beck C. M. Toward a revival of classical analysis. Metrologia, 34(1), 19–30, (1997). https://doi.org/10.1088/0026-1394/34/1/4Beck C. M. Toward a revival of classical analysis. Metrologia, 34(1), 19–30, (1997). https://doi.org/10.1088/0026-1394/34/1/4Vetter T. W. Gravimetric Analysis of Sodium in Serum. CCQM Primary Methods Symposium: How Far Does the Light Shine? 4–5 April 2000, BIPM, Sèvres, France.Vetter T. W. Gravimetric Analysis of Sodium in Serum. CCQM Primary Methods Symposium: How Far Does the Light Shine? 4–5 April 2000, BIPM, Sèvres, France.Стромберг А. Г., Семченко Д. П. Физическая химия. Высшая школа, Москва (2001).Stromberg A. G., Semchenko D. P. Fizicheskaya himiya. Vysshaya shkola, Moscow (2001). (In Russ.)Хеммингер В., Хене Г. Калориметрия. Теория и практика. Перевод с английского О. Б. Саламатиной. Химия, Москва (1989).Hemminger V., Hene G., Kalorimetriya. Teoriya i praktika, translation from English by O. B. Salamatina, Himiya, Moscow (1989). (In Russ.)Máriássy M. Coulometry for Purity Determination. CCQM Primary Methods Symposium: How Far Does the Light Shine? 4–5 April 2000, BIPM, Sèvres, France.Máriássy M. Coulometry for Purity Determination. CCQM Primary Methods Symposium: How Far Does the Light Shine? 4–5 April 2000, BIPM, Sèvres, France.Термический анализ на практике. Советы и рекомендации. Справочник. Под ред. Мелани Нийман и редакционной коллегии подразделения Materials Characterization Group, Меттлер, Толедо (2021).Thermal Analysis in Practice. Tips and Tricks. Handbook. Edited by Melanie Nijman and the Editorial Board of the Division Materials Characterization Group, Mettler Toledo (2021).Альмяшев В. И., Василевская А. К., Кириллова С. А. и др. Комплексный термический анализ. Лема, Санкт-Петербург (2017).Al'myashev V. I., Vasilevskaya A. K., Kirillova S. A. et al. Kompleksnyj termicheskij analiz. Lema, Saint-Petersburg (2017). (In Russ.)Ishikawa K., Hanari N., Shimizu Y. et al. Mass balance method for purity assay of phthalic acid esters: development of primary reference materials as traceability sources in the Japan Calibration Service System. Accreditation and Quality Assurance, 16, 311–322 (2011). https://doi.org/10.1007/s00769-011-0767-0Ishikawa K., Hanari N., Shimizu Y. et al. Mass balance method for purity assay of phthalic acid esters: development of primary reference materials as traceability sources in the Japan Calibration Service System. Accreditation and Quality Assurance, 16, 311–322 (2011). https://doi.org/10.1007/s00769-011-0767-0Westwood S. et al. Mass fraction assignment of Bisphenol-A high purity material. Metrologia, 58(1A), 08015 (2021). https://doi.org/10.1088/0026-1394/58/1A/08015Westwood S. et al. Mass fraction assignment of Bisphenol-A high purity material. Metrologia, 58(1A), 08015 (2021). https://doi.org/10.1088/0026-1394/58/1A/08015Weber M., Hellriegel C., Rück A. et al. Using high-performance quantitative NMR (HP-qNMR®) for certifying traceable and highly accurate purity values of organic reference materials with uncertainties <0.1 %. Accreditation and Quality Assurance, 18, 91–98 (2013). https://doi.org/10.1007/s00769-012-0944-9Weber M., Hellriegel C., Rück A. R. et al. Using high-performance quantitative NMR (HP-qNMR®) for certifying traceable and highly accurate purity values of organic reference materials with uncertainties <0.1 %. Accreditation and Quality Assurance, 18, 91–98 (2013). https://doi.org/10.1007/s00769-012-0944-9Bharti S. K., Roy R. Quantitative 1H NMR spectroscopy. TrAC Trends in Analytical Chemistry, 35, 5–26 (2012). https://doi.org/10.1016/j.trac.2012.02.007Bharti S. K., Roy R. Quantitative 1H NMR spectroscopy. TrAC Trends in Analytical Chemistry, 35, 5–26 (2012). https://doi.org/10.1016/j.trac.2012.02.007Blaza Toman, Michael A Nelson and Katrice A Lippa. Chemical purity using quantitative 1H-nuclear magnetic resonance: a hierarchical Bayesian approach for traceable calibrations, Metrologia, 53, 1193–1203 (2016). doi:10.1088/0026-1394/53/5/1193Blaza Toman, Michael A Nelson and Katrice A Lippa. Chemical purity using quantitative 1H-nuclear magnetic resonance: a hierarchical Bayesian approach for traceable calibrations, Metrologia, 53, 1193–1203 (2016). doi:10.1088/0026-1394/53/5/1193Takeshi Saito, Taichi Yamazaki, Masahiko Numata. Quantitative NMR as a Versatile Tool for the Reference Material Preparation. Magnetochemistry, 7(1), 15 (2021). https://doi.org/10.3390/magnetochemistry7010015Takeshi Saito, Taichi Yamazaki, Masahiko Numata. Quantitative NMR as a Versatile Tool for the Reference Material Preparation. Magnetochemistry, 7(1), 15 (2021). https://doi.org/10.3390/magnetochemistry7010015Takeshi Saito, Taichi Yamazaki, Masahiko Numata. Development of nuclear magnetic resonance as a tool of quantitative analysis for organic materials. Metrologia, 56(5), 054002 (2019). https://doi.org/10.1088/1681-7575/ab348dTakeshi Saito, Taichi Yamazaki, Masahiko Numata. Development of nuclear magnetic resonance as a tool of quantitative analysis for organic materials. Metrologia, 56(5), 054002 (2019). https://doi.org/10.1088/1681-7575/ab348dWeber M., Hellriegel C., Rueck A. et al. Method development in quantitative NMR towards metrologically traceable organic certified reference materials used as 31P qNMR standards. Analytical and Bioanalytical Chemistry, 407, 3115–3123 (2014). https://doi.org/10.1007/s00216-014-8306-6Weber M., Hellriegel C., Rueck A. et al. Method development in quantitative NMR towards metrologically traceable organic certified reference materials used as 31P qNMR standards. Analytical and Bioanalytical Chemistry, 407, 3115–3123 (2014). https://doi.org/10.1007/s00216-014-8306-6Okaru A. O., Brunner T. S., Ackermann S. M. et al. Application of 19F NMR spectroscopy for content determination of fluorinated pharmaceuticals, Journal of Analytical Methods in Chemistry, 9206297 (2017). https://doi.org/10.1155/2017/9206297Okaru A. O., Brunner T. S., Ackermann S. M. et al. Application of 19F NMR spectroscopy for content determination of fluorinated pharmaceuticals. Journal of Analytical Methods in Chemistry, 9206297 (2017). https://doi.org/10.1155/2017/9206297Rigger R., Rück A., Hellriegel C. et al. Certified reference material for use in 1H, 31P, and 19F quantitative NMR, ensuring traceability to the International System of Units, Journal of AOAC International, 100(5), 1365–1375 (2017). https://doi.org/10.5740/jaoacint.17-0093Rigger R., Rück A., Hellriegel C. et al. Certified reference material for use in 1H, 31P, and 19F quantitative NMR, ensuring traceability to the International System of Units, Journal of AOAC International, 100(5), 1365–1375 (2017). https://doi.org/10.5740/jaoacint.17-0093Nelson M. A., Waters J. F., Toman B. et al. A New Realization of SI for Organic Chemical Measurement: NIST PS1 Primary Standard for Quantitative NMR (Benzoic Acid), Analytical Chemistry, 90, 10510–10517 (2018). https://doi.org/ 10.1021/acs.analchem.8b02575Nelson M. A., Waters J. F., Toman B. et al. A New Realization of SI for Organic Chemical Measurement: NIST PS1 Primary Standard for Quantitative NMR (Benzoic Acid). Analytical Chemistry, 90, 10510–10517 (2018). https://doi.org/ 10.1021/acs.analchem.8b02575Westwood S. et al. Final report on key comparison CCQM-K55.b (aldrin): An international comparison of mass fraction purity assignment of aldrin. Metrologia, 49, 08014 (2012). https://doi.org/10.1088/0026-1394/49/1A/08014Westwood S. et al. Final report on key comparison CCQM-K55.b (aldrin): An international comparison of mass fraction purity assignment of aldrin. Metrologia, 49, 08014 (2012). https://doi.org/10.1088/0026-1394/49/1A/08014Naoki Saito, Yuko Kitamaki, Satoko Otsuka et al. Extended internal standard method for quantitative 1H NMR assisted by chromatography (EIC) for analyte overlapping impurity on 1H NMR spectra. Talanta, 184, 484–490 (2018). https://doi.org/10.1016/j.talanta.2018.03.003Naoki Saito, Yuko Kitamaki, Satoko Otsuka et al. Extended internal standard method for quantitative 1H NMR assisted by chromatography (EIC) for analyte overlapping impurity on 1H NMR spectra. Talanta, 184, 484–490 (2018). https://doi.org/10.1016/j.talanta.2018.03.003Jeremy E. Melanson, Marie-Pier Thibeault, Bradley B. Stocks, et al. Purity assignment for peptide certified reference materials by combining qNMR and LC-MS/MS amino acid analysis results: application to angiotensin II. Analytical and Bioanalytical Chemistry, 410, 6719–6731 (2018), https://doi.org/10.1007/s00216-018-1272-7Jeremy E. Melanson, Marie-Pier Thibeault, Bradley B. Stocks, et al. Purity assignment for peptide certified reference materials by combining qNMR and LC-MS/MS amino acid analysis results: application to angiotensin II. Analytical and Bioanalytical Chemistry, 410, 6719–6731 (2018), https://doi.org/10.1007/s00216-018-1272-7Wei Zhang, Ting Huang, Hongmei Li et al. Determination of avermectins by the internal standard recovery correction – high performance liquid chromatography – quantitative Nuclear Magnetic Resonance method. Talanta, 172, 78–85 (2017). https://doi.org/10.1016/j.talanta.2017.04.080Wei Zhang, Ting Huang, Hongmei Li et al. Determination of avermectins by the internal standard recovery correction – high performance liquid chromatography – quantitative Nuclear Magnetic Resonance method. Talanta, 172, 78–85 (2017). https://doi.org/10.1016/j.talanta.2017.04.080Михеева А. Ю., Крылов А. И., Будко А. Г. Алгоритм определения чистоты органических веществ, пригодных к выделению или очистке методом перегонки. Эталоны. Стандартные образцы, 18(2), 5–18 (2022). https://doi.org/10.20915/2077-1177-2022-18-2-5-18Mikheeva A. Yu., Krylov A. I., Budko A. G. Algorithm for determining the purity of organic substances suitable for isolation or purification by distillation. Measurement Standards. Reference Materials, 18(2), 5–18 (2022). (In Russ.) https://doi.org/10.20915/2077-1177-2022-18-2-5-18King B. Review of the potential of titrimetry as a primary method. Metrologia, 34(1), 77–82 (1997). https://doi.org/10.1088/0026-1394/34/1/11King B. Review of the potential of titrimetry as a primary method. Metrologia, 34(1), 77–82 (1997). https://doi.org/10.1088/0026-1394/34/1/11Сакодынский К. И. и др. Аналитическая хроматография. Химия, Москва (1993).Sakodynskiy K. I. i dr. Analiticheskaya hromatografiya. Himiya, Moscow (1993). (In Russ.)Столяров Б. В., Савинов И. М., Витенберг А. Г. и др. Практическая газовая и жидкостная хроматография. СПбГУ, Санкт-Петербург (2002).Stolyarov B. V., Savinov I. M., Vitenberg A. G. et al. Prakticheskaya gazovaya i zhidkostnaya hromatografiya. SPbGU, Saint Petersburg (2002). (In Russ.)Руденко Б. А., Руденко Г. И. Высокоэффективные хроматографические процессы. В 2-х томах. Наука, Москва (2003).Rudenko B. A., Rudenko G. I. Vysokoeffektivnye hromatograficheskie processy. V 2-h tomah. Nauka, Moscow (2003). (In Russ.)Шатц В. Д. Высокоэффективная жидкостная хроматография. Книга по требованию, Санкт-Петербург (2012).Shats V. D. Vysokoeffektivnaya zhidkostnaya hromatografiya. Kniga po trebovaniyu, Saint Petersburg (2012). (In Russ.)Сычев К. С. Практическое руководство по жидкостной хроматографии. Техносфера, Москва (2010).Sychev K. S. Prakticheskoe rukovodstvo po zhidkostnoj hromatografii. Tekhnosfera, Moscow (2010). (In Russ.)Михеева А. Ю., Будко А. Г., Крылов А. И. Алгоритм определения чистоты чистых органических веществ фталатов косвенным методом массового баланса. Эталоны. Стандартные образцы, 18(3), 41–55 (2022). https://doi.org/10.20915/2077-1177-2022-18-3-41-55Mikheeva A. Yu., Budko A. G., Krylov A. I. Algorithm for determining the purity of pure organic substances phthalates by an indirect mass balance method. Measurement Standards. Reference Materials, 18(3), 41–55 (2022). (In Russ.) https://doi.org/10.20915/2077-1177-2022-18-3-41-55

The authors declare that there are no conflicts of interest present.