Retention patterns of alkali and alkaline earth metal cations on a carboxylic cation exchanger

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Abstract

The chromatographic retention features of alkali and alkaline earth metal cations on poly(styrene-divinylbenzene) cation exchangers with grafted carboxylic groups were investigated. It was found that the retention of metal cations with the same charge is directly proportional to their polarizability. The retention patterns of metal and ammonium cations were studied in relation to the nature and concentration of the eluent, and the contribution of secondary processes to retention and peak shape was determined. It was shown that increasing eluent concentration improves the symmetry of chromatographic peaks. Van’t Hoff dependencies were constructed, and the enthalpy values (ΔH°) of adsorption were calculated. It was noted that column efficiency increases with temperature. The possibility of simultaneous determination of alkali, alkaline earth metal, and ammonium cations by ion chromatography using carboxylic cation exchangers and two variants of conductometric detection was demonstrated. Practical applications of the sorbents are discussed.

About the authors

P. N. Nesterenko

Department of Chemistry, Lomonosov Moscow State University

Email: p.nesterenko@phys.chem.msu.ru
Moscow, Russia

M. S. Timina

Department of Chemistry, Lomonosov Moscow State University

Email: p.nesterenko@phys.chem.msu.ru
Moscow, Russia

S. V. Krasheninina

Department of Chemistry, Lomonosov Moscow State University

Email: p.nesterenko@phys.chem.msu.ru
Moscow, Russia

A. N. Stavrianidi

Department of Chemistry, Lomonosov Moscow State University

Email: p.nesterenko@phys.chem.msu.ru
Moscow, Russia

N. B. Rozhmanova

Department of Chemistry, Lomonosov Moscow State University

Author for correspondence.
Email: p.nesterenko@phys.chem.msu.ru
Moscow, Russia

References

  1. Nesterenko P.N. Ion chromatography / Liquid Chromatography: Fundamentals and Instrumentation. V. 1. 3rd Ed. Oxford: Elsevier, 2023. P. 465.
  2. Шпигун O.A., Золотов Ю. А. Ионная хроматография и ее применение в анализе вод. М: МГУ, 1990. 198 c.
  3. Haddad P.R., Nesterenko P.N., Buchberger W. Recent developments and emerging directions in ion chromatography // J. Chromatogr. A. 2008. V. 1184. P. 456.
  4. Нестеpенко П.Н., Пирогов А.В., Шпигун O.A. Современные системы разделения для ионной хроматографии // Заводск. лаборатория. 2003. T. 69. № 3. C. 10.
  5. Нестеpенко П.Н., Кебец П.А., Сочилина К.О. Применение микросферического сульфированного сверхсшитого полистирола в ионной хроматографии // Журн. аналит. химии. 2003. T. 58. № 5. C. 523. (Nesterenko P.N., Kebets P.A., Sochilina K.A. Use of microspherical sulfonated hypercrosslinked polystyrene in ion chromatography // J. Anal. Chem. 2003. V. 58. № 5. P.467.)
  6. Sato H. Isocratic elution of sodium, ammonium, potassium, magnesium and calcium ions by ion-exchange chromatography // J. Chromatogr. 1989. V. 469. P. 339.
  7. Potts M.E., Stillian J.R. Monitoring of inorganic and organic cations using on-line ion chromatography // J. Chromatogr. Sci. 1988. V. 26. № 7. P. 315.
  8. Hajós P. Histidine as a dipolar eluent component in cation chromatography. // J. Chromatogr. A. 1997. V. 789. P. 141.
  9. Small H., Miller T.E. Indirect photometric chromatography // Anal. Chem. 1982. V. 54. № 3. P. 462.
  10. Sherman J.H., Danielson N.D. Comparison of inorganic mobile phase counterions for cationic indirect photometric chromatography // Anal. Chem. 1987. V. 59. № 3. P.490.
  11. Campbell D.L., Stillian J., Carson S., Joyce R., Heberling S. Separation and detection of group I and II cations by ion chromatography // J. Chromatogr. 1991. V. 546. P. 229.
  12. Rocklin R.D., Rey M.A., Stillian J.R., Campbell D.L. Ion chromatography of monovalent and divalent cations // J. Chromatogr. Sci. 1989. V. 27. № 8. P. 474.
  13. Kolla P., Koehler J., Schomburg G. Polymer-coated cation-exchange stationary phases based on silica // Chromatographia. 1987. V. 23. № 7. P. 465.
  14. Nair L.M., Saari-Nordhaus R., Anderson Jr J.M. Ion chromatographic separation of transition metals on a polybutadiene maleic acid-coated stationary phase // J. Chromatogr. A. 1994. V. 671. P. 43.
  15. Кузьмина K.A., Нестеренко П.Н. Синтез и хроматографические свойства карбоксильных катионообменников на основе алкилсиликагелей, динамически модифицированных гидролизованным малеинизированным льняным маслом // Вестн. Моск. ун-та. Сер. 2. Химия. 2005. Т. 46. № 6. С. 406. (Kuz’mina К.А., Nesterenko P.N. Synthesis and chromatographic characteristics of carboxylic cation exchangers based on alkyl silica gels modified dynamically with hydrolyzed maleinized linseed oil // Moscow Univ. Chem. Bull. 2006. V. 60. № 6. P. 26.)
  16. Nesterenko P.N. Chapter 3. Stationary phases for ion separations / Ion-Exchange Chromatography and Related Techniques / Eds. Nesterenko P.N., Poole C.F., Sun Y. Oxford: Elsevier, 2024. P. 49.
  17. NIST Critically selected stability constants of metal complexes dstsbase. Version 8.0. 2004.
  18. Лисичкин Г.В., Фадеев А.Ю., Сердан A.A., Нестеренко П.Н., Мингалев П.Г., Фурман Д.Б. Химия привитых поверхностных соединений. М.: Физматлит, 2003. 592с.
  19. Элефтеpов A.И., Нестеpенко П.Н., Шпигун O.A. Одновpеменное ионохpоматогpафическое опpеделение щелочных и щелочноземельных металлов. Использование катионообменника с пpивитыми диаминокаpбоксильными гpуппами // Журн. аналит. химии. 1996. T. 51. № 10. C. 1064. (Elefterov A.I., Nesterenko P.N., Shpigun O.A. Simultaneous ion-chromatographic determination of alkali and alkaline-earth metals: Use of a cation exchanger with bonded diaminocarboxylic groups // J. Anal. Chem. 1996. V. 51. № 10. P. 972.)
  20. Elefterov A.I., Kolpachnikova M.G., Nesterenko P.N., Shpigun O.A. Ion-exchange properties of glutamic acid-bonded silica // J. Chromatogr. A. 1997. V. 769. P. 179.
  21. Nesterenko P.N., Nesterenko E.P. Hydrophobicity of polymer based anion-exchange columns for ion chromatography // Heliyon. 2021. V. 7. Article e07290.
  22. Jensen D., Weiss J., Rey M.A., Pohl C.A. Novel weak acid cation-exchange column // J. Chromatogr. 1993. V. 640. P. 65.
  23. Shaw M.J., Nesterenko P.N., Dicinoski G.W., Haddad P.R. Retention characteristics of lanthanide ions on a mixed phosphonic acid – carboxylic acid cation exchanger // Aust. J. Chem. 2003. V. 56. P. 201.
  24. Shaw M.J., Nesterenko P.N., Dicinoski G.W., Haddad P.R. Selectivity behaviour of a bonded phosphonate–carboxylate polymeric ion exchanger for metal cations with varying eluent compositions // J. Chromatogr. A. 2003. V. 997. P. 3.
  25. Al-Jadaan S.A.N. Determination of some lanthanides ion coeluent with the transient metals by ion chromatography // Res. J. Pharm. Biol. Chem. Sci. 2014. V. 5. № 6. P. 860.
  26. Schipplick L., Kahler P., Seubert A. Combination of atom transfer radical polymerization and alkyne-azide click-chemistry for the synthesis of phosphonic acid cation exchange materials // J. Chromatogr. A. 2025. V. 1743. Article 465675.
  27. Rey M.A., Pohl C.A. Novel cation-exchange stationary phase for the separation of amines and of six common inorganic cations // J. Chromatogr. A. 1996. V. 739. P. 87.
  28. Chong J., Hatsis P., Lucy C.A. High-speed ion chromatographic separation of cations at elevated temperatur. // J. Chromatogr. A. 2003. V. 997. P. 161.
  29. Hatsis P., Lucy C.A. Evaluation of column temperature as a means to alter selectivity in the cation exchange separation of alkali metals, alkaline earth metals and amine. // Analyst. 2001. V. 126. № 12. P. 2113.
  30. Li Y., Nesterenko P. N., Stanley R., Paull B., Macka M. Comparison of cation-exchange capillary columns used for ion chromatographic separation of biogenic amine // J. Chromatogr. A. 2018. V. 1571. P. 193.
  31. Rey M.A., Pohl C.A., Jagodzinski J., Kaiser E.Q., Riviello J.M. A new approach to dealing with high-to-low concentration ratios of sodium and ammonium ions in ion chromatography // J. Chromatogr. A. 1998. V. 804. № 1-2. P. 201.
  32. Pohl C., Rey M., Jensen D., Kerth J. Determination of sodium and ammonium ions in disproportionate concentration ratios by ion chromatography // J. Chromatogr. A. 1999. V. 850. P. 239.
  33. Schmitt M., Egorycheva M., Frerichs D., Fiedler S., Graumann P.L., Seubert A. Factors affecting mixed-mode retention properties of cation-exchange stationary phases // J. Chromatogr. A. 2023. V. 1695. Article 462790.
  34. Nesterenko P.N. Ion exchange. Overview / Encyclopedia of Analytical Science. 3rd Ed. / Eds. Worsfold P., Poole C., Townshend A., Miró M. Oxford: Academic Press, 2019. P. 204.
  35. Кебец П.А., Кузьмина К.А., Нестеpенко П.Н. Теплоты адсорбции катионов металлов на силикагеле с ковалентно закрепленной полиаспарагиновой кислотой // Журн. физ. химии. 2002. T. 76. № 9. C. 1639. (Kebets P.A., Kuz’mina K.A., Nesterenko P.N. The heats of adsorption of metal cations on silica gel with covalently fixed polyaspartic acid // Russ. J. Phys. Chem. A. 2002. V. 76. № 9. P. 1481.)
  36. Kondratjonok B., Schwedt G. Isocratic simultaneous ion chromatography of alkali, alkaline earth and other metal ions // Fresenius J. Anal. Chem. 1988. V. 332. № 4. P. 333.
  37. Morris J., Fritz J.S. Ion chromatography of metal cations on carboxylic acid resins // J. Chromatogr. 1992. V. 602. № 1-2. P. 111.
  38. Jones P., Nesterenko P.N. Use of complexing reagents as additives to the eluent for optimization of separation selectivity in high-performance chelation ion chromatography // J. Chromatogr. A. 2008. V. 1213. P. 45.
  39. Шапошник В.А. Электростатическая теория селективности ионообменников // Сорбционные и хроматографические процессы. 2020. T. 20. № 1. C. 48.
  40. Stahlberg J. Retention models for ions in chromatography // J. Chromatogr. A. 1999. V. 855. P. 3.
  41. Rey M.A. High-capacity cation-exchange column for enhanced resolution of adjacent peaks of cations in ion chromatography // J. Chromatogr. A. 2001. V. 920. P. 61.
  42. Thomas D.H., Rey M., Jackson P.E. Determination of inorganic cations and ammonium in environmental waters by ion chromatography with a high-capacity cation-exchange column // J. Chromatogr. A. 2002. V. 956. P. 181.
  43. Bashir W., Tyrrell E., Feeney O., Paull B. Retention of alkali, alkaline earth and transition metals on an itaconic acid cation-exchange column – Eluent pH, ionic strength and temperature effects upon selectivity // J. Chromatogr. A. 2002. V. 964. P. 113.
  44. Nesterenko P.N., Zhukova O.S., Shpigun O.A., Jones P. Synthesis and ion-exchange properties of silica chemically modified with aminophosphonic acid // J. Chromatogr. A. 1998. V. 813. P. 47.
  45. Nesterenko P.N., Shaw M.J., Hill S.J., Jones P. Aminophosphonate-functionalized silica: A versatile chromatographic stationary phase for high-performance chelation ion chromatography // Microchem. J. 1999. V. 62. P. 58.
  46. Nesterenko P.N., Jones P. Recent developments in the high-performance chelation ion chromatography of trace metals // J. Sep. Sci. 2007. V. 30. № 11. P. 1773.
  47. Kim J.H., Lee J.H. Simultaneous determination of six cations in mineral water by single-column ion chromatography // J. Chromatogr. A. 1997. V. 782. P. 140.
  48. Nesterenko P. N., Fedyanina O. N., Volgin Y. V., Jones P. Ion chromatographic investigation of ion-exchange properties of microdisperse sintered nanodiamonds // J. Chromatogr. A. 2007. V. 1155. P. 2.
  49. Zachariadis G.A., Lyratzi A.I., Stratis J.A. Ion chromatographic method for the determination of cations of group IA and IIA in water samples, pharmaceuticals and energy drinks by non-suppressed conductometric detection // Cent. Eur. J. Chem. 2011. V. 9. № 5. P. 941.
  50. Kolpachnikova M.G., Penner N.A., Nesterenko P.N. Effect of temperature on retention of alkali and alkaline-earth metal ions on some aminocarboxylic acid functionalised silica based ion exchangers // J. Chromatogr. A. 1998. V. 826. P. 15.
  51. Kebets P.A., Nesterenko E.P., Nesterenko P.N., Alpert A.J. Ion-chromatography performance of polyaspartic acid bonded silica with various pore size at different ionic strength and column temperature // Microchim. Acta. 2004. V. 146. № 2. P. 103.
  52. Dimitrov V., Komatsu T. Correlation among electronegativity, cation polarizability, optical basicity and single bond strength of simple oxides // J. Solid State Chem. 2012. V. 196. P. 574.
  53. Питьевая вода. Гигиенические требования к качеству воды централизованных систем питьевого водоснабжения. Контроль качества. СанПиН 2.1.4.1074-01. 2001.

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