Skip to main content
Log in

A study of interfacial adsorption isotherm at divided interface for novel macrocycles in solvent extraction

  • Original Article
  • Published:
Journal of Inclusion Phenomena and Macrocyclic Chemistry Aims and scope Submit manuscript

Abstract

A new aspect of liquid–liquid extraction by using the adsorption isotherm approach at divided interface was described. In order to explain complexation behavior of ligands, extraction of ions in the interfacial region of liquid–liquid phase can be modeled by Langmuir adsorption isotherm. A series of macrocycles of different ring sizes with different type of donor atoms has been synthesized and characterized by several spectroscopic techniques. Solvent extraction method was used to evaluate metal-ion binding properties of the macrocycles. The values of the extraction constants and the complex compositions were determined for the extracted complexes. Macrocycles 2 and 3 as extractant of silver cation from aqueous solution at different temperatures and concentrations was investigated. Kinetics and thermodynamic parameters of the interfacial adsorption were also investigated. The cation-binding affinity of macrocyclic ligand 2 among the other ligands for Ag+ over other cations in both organic solvents was found to be the highest. The Ag+ ion was extracted by 88.3 and 81.7 % to the dichloromethane and chloroform phase with macrocycle 2, respectively. The maximum metal ion adsorption capacity (28 %) was found for macrocycle 2 at 20 °C.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. Pedersen, C.J.: Cyclic polyethers and their complexes with metal salts. J. Am. Chem. Soc. 89, 7017–7036 (1967)

    Article  CAS  Google Scholar 

  2. Izatt, R.M., Bradshaw, J.S., Nielsen, S.A., Lamb, J.D., Christensen, J.J.: Thermodynamic and kinetic data for cation-macrocycle interaction. Chem. Rev. 85, 271–339 (1985)

    Article  CAS  Google Scholar 

  3. An, H., Bradshaw, J.S., Izatt, R.M.: Macropolycyclic polyethers (cages) and related compounds. Chem. Rev. 92, 543–572 (1992)

    Article  CAS  Google Scholar 

  4. Lindoy, L.F.: The chemistry of macrocyclic ligand complexes. Cambridge University Press, Cambridge (1989)

    Book  Google Scholar 

  5. Hancock, R.D., Martell, A.E.: Ligand design for selective complexation of metal ions in aqueous solution. Chem. Rev. 89, 1875–1914 (1989)

    Article  CAS  Google Scholar 

  6. Chartres, J.D., Davies, M.S., Lindoy, L.F., Meehan, G.V., Wei, G.: Macrocyclic ligand design: the interaction of selected transition and post-transition metal ions with a 14-membered N2S2-donor macrocycle. Inorg. Chem. Commun. 9, 751–754 (2006)

    Article  CAS  Google Scholar 

  7. Qiu, T., Xu, X., Liu, J., Qian, X.: Novel perfluoroalkyl phthalocyanine metal derivatives: synthesis and photodynamic activities. Dyes Pigments 83, 127–133 (2009)

    Article  CAS  Google Scholar 

  8. Banfi, S., Carous, E., Buccafurni, L.: Zinc phthalocyanines-mediated photodynamic therapy induces cell death in adenocarcinoma cells. J. Organomet. Chem. 692, 1269–1276 (2007)

    Article  CAS  Google Scholar 

  9. Guo, L., Meng, F.S., Gong, X.D., Xiao, H.M., Chen, K.C., Tian, H.: Synthesis and spectral properties of soluble trimethylsilyl substituted metal-phthalocyanines. Dyes Pigments 49, 83–91 (2001)

    Article  CAS  Google Scholar 

  10. Taner, B.: Novel vic-dioxime ligand containing calix[4]pyrolle moiety: synthesis, characterization, anion binding studies and complexation with Ni(II). J. Incl. Phenom. Macrocycl. Chem. 79, 75–81 (2014)

    Article  CAS  Google Scholar 

  11. Chand, R., Watari, T., Inoue, K., Kawakita, H., Luitel, H.N., Parajuli, D., Torikai, T., Yada, M.: Selective adsorption of precious metals from hydrochloric acid solutions using porous carbon prepared from barley straw and rice husk. Miner. Eng. 22, 1277–1282 (2009)

    Article  CAS  Google Scholar 

  12. Yordanov, A.T., Roundhill, D.M.: Solution extraction of transition and post-transition heavy and precious metals by chelate and macrocyclic ligands. Coord. Chem. Rev. 170, 93–124 (1998)

    Article  CAS  Google Scholar 

  13. Hassan, M.L., El-Wakil, N.A.: Heavy metal ion removal by amidoximated bagasse. J. Appl. Poly. Sci. 87, 666–670 (2003)

    Article  CAS  Google Scholar 

  14. Shin, K.Y., Hong, J.Y., Yang, J.: Heavy metal ion adsorption behavior in nitrogen doped magnetic carbon nanopatricles: isotherm and kinetic study. J. Hazard. Mater. 190, 36–44 (2011)

    Article  CAS  Google Scholar 

  15. Bose, P., Bose, M.A., Kumar, S.: Critical evolution of treatment strategies involving adsorption and chelation for waste-water containing copper, zinc and cyanide. Adv. Environ. Res. 7, 179–195 (2002)

    Article  CAS  Google Scholar 

  16. Çeçen, F., Semerci, N., Geyik, A.G.: Inhibition of respiration and distribution of Cd, Pb, Hg, Ag and Cr species in nitrifying sludge. J. Hazard. Mater. 178, 619–627 (2010)

    Article  Google Scholar 

  17. Kabay, N., Baygu, Y., Alpoguz, H.K., Kaya, A., Gök, Y.: Synthesis and characterization of porphyrazines as novel extractants for the removal of Ag(I) and Hg(II) from aqueous solution. Dyes Pigments 96, 372–376 (2013)

    Article  CAS  Google Scholar 

  18. Testard, F., Berthon, L., Zemb, T.: Liquid–Liquid extraction: an adsorption isotherm at divided interface? C. R. Chim. 10, 1034–1041 (2007)

    Article  CAS  Google Scholar 

  19. Chamupathi, V.G.: Role of the interface in metal solvent extraction kinetics. PhD Thesis, Department of Chemistry, The University of Arizona, Ann Arbor, (1987)

  20. Gokel, G.W., Korzeniowski, S.H.: Macrocyclic polyether syntheses. In: Hafner, K., et al. (eds.) Reactivity and Structure Concepts in Organic Chemistry, vol. 13. Springer-Verlag, Berlin (1982)

    Google Scholar 

  21. Cook, F.L., Caruso, T.C., Byrne, M.P., Bowers, C.W., Speck, D.H., Liotta, C.L.: Facile syntheses of 12-crown-4 and 15-crown-5. Tetrahedron Lett. 46, 4029–4032 (1974)

    Article  Google Scholar 

  22. Gök, H.Z., Farsak, B.: Synthesis, characterisation and aggregation properties of novel metal-free and metallophthalocyanines containing four 21-membered oxatetrathiadiaza macrocycles. J. Organomet. Chem. 735, 65–71 (2013)

    Article  Google Scholar 

  23. Gök, H.Z., Farsak, B.: Synthesis and spectral properties of novel metal-free and metallophthalocyanines bearing four 19-membered tetrathiadiaza macrocycles. J. Mol. Struct. 1054–1055, 25–31 (2013)

    Article  Google Scholar 

  24. Gök, H.Z., Farsak, B., Keleş, H., Keleş, M.: Novel metal-free and metallophthalocyanines containing four 21-membered pentathiadiaza macrocycles: synthesis, characterization, and study of aggregation properties. Turk. J. Chem. doi:10.3906/kim-1403-63

  25. Perrin, D.D., Armarego, W.L.F.: Purification of Laboratory Chemicals, 2nd edn. Pergamon Press, Oxford (1989)

    Google Scholar 

  26. Kantekin, H., Kılıçaslan, M.B., Ağın, F., Alp, H., Ocak, Ü.: New heavy metal ion-selective macrocyclic ligands with mixed-donor atoms and their extractant properties. J. Coord. Chem. 63, 1921–1932 (2010)

    Article  CAS  Google Scholar 

  27. Alp, H., Gök, H.Z., Kantekin, H., Ocak, Ü.: Synthesis and metal ion binding properties of thiaaza crown macrocycles. J. Hazard. Mater. 159, 519–522 (2008)

    Article  CAS  Google Scholar 

  28. Gök, H.Z., Ocak, Ü., Kantekin, H., Alp, H.: The synthesis and characterization of 22-membered diazapentathia macrocycles and investigation of their ion extraction capability from aqueous media. Transit. Met. Chem. 323, 1073–1078 (2007)

    Article  Google Scholar 

  29. Alp, H., Bıyıklıoğlu, Z., Ocak, M., Ocak, Ü., Kantekin, H., Dilber, G.: New heavy metal ion-selective macrocyclic ligands with nitrogen and sulfur donor atoms and their extractant properties. Sep. Sci. Technol. 42, 835–845 (2007)

    Article  CAS  Google Scholar 

  30. Bradshaw, J.S., Krakowiak, K.E., Izatt, R.M.: A simple crab-like cyclization procedure to prepare polyaza-crowns and cyclams with one or two unsubstituted macroring nitrogen-atoms or with a hydroxy group. J. Heterocycl. Chem. 26, 1431–1435 (1989)

    Article  CAS  Google Scholar 

  31. Yang, Z., Bradshaw, J.S., Zhang, X.X., Savage, P.B., Krakowiak, K.E., Dalley, N.K., Su, N., Todd Bronson, R., Izatt, R.M.: New tetrazacrown ethers containing two pyridine, quinoline, 8-hydroxyquinoline, or 8-aminoquinoline sidearms. J. Org. Chem. 64, 3162–3170 (1999)

    Article  CAS  Google Scholar 

  32. Izatt, R.M., Pawlak, K., Bradshaw, J.S.: Thermodynamic and kinetic data for macrocycle interaction with cations, anions, and neutral molecules. Chem. Rev. 95, 2529–2586 (1995)

    Article  CAS  Google Scholar 

  33. Saito, K., Taninaka, I., Murakami, S., Muromatsu, A.: Synthesis of thiacrown ether carboxylic acids and their characteristics as extractants for metal ions. Anal. Chim. Acta 299, 137–144 (1994)

    Article  CAS  Google Scholar 

  34. Corbitt, R.A.: The Standard Handbook of Environmental Engineering. McGraw-Hill, New York (1990)

    Google Scholar 

  35. Rudnicki, P., Hubicki, Z., Kołodyńska, D.: Evaluation of heavy metal ions removal from acidic waste water streams. Chem. Eng. J. 252, 362–373 (2014)

    Article  CAS  Google Scholar 

  36. Demir, H., Top, A., Balköse, D., Ülkü, S.: Dye adsorption behavior of luffa cylindrica fibers. J. Hazard. Mater. 153, 389–394 (2008)

    Article  CAS  Google Scholar 

  37. Tchakalova, V., Testard, F., Wong, K., Parker, A., Benczedi, D., Zemb, T.: Solubilization and interfacial curvature in microemulsions I interracial expansion and co-extraction of oil. Colloids Surf. A. 331, 31–39 (2008)

    Article  CAS  Google Scholar 

  38. Rattanaphani, S., Chairat, M., Bremner, B.J., Rattanaphani, V.: An adsorption and thermodynamic study of lac dyeing on cotton pretreated with chitosan. Dyes Pigments 72, 88–96 (2007)

    Article  Google Scholar 

  39. Zhou, W.J., Li, T.Y., Song, Q.X.: Investigation of the chelation of photochromic spiropyran with Cu(II). J. Photochem. Photobiol. A: Chem. 87, 37–42 (1995)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This study was supported in part by The Scientific and Technological Research Council of Turkey (TUBITAK) (Project No: TBAG-109T806). Technical assistance from Department of Chemistry in Karadeniz Technical University is gratefully acknowledged. Beyza Akan and Feyza Erdal (Department of Chemistry, Osmaniye Korkut Ata University) are also gratefully acknowledged for their assistance.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Halil Zeki Gök.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 1158 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gök, H.Z., Demir, H. A study of interfacial adsorption isotherm at divided interface for novel macrocycles in solvent extraction. J Incl Phenom Macrocycl Chem 81, 95–104 (2015). https://doi.org/10.1007/s10847-014-0438-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-014-0438-y

Keywords

Navigation