Skip to main content
Log in

Thermodynamic Data for the Formation of 1:1 and 2:1 Complexes of α,ω-Diamino Dihydrochlorides with 18-Crown-6 in Aqueous Solution

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

Calorimetric titrations are used to study the interactions between the crown ether 18-crown-6 and several α,ω-diamino dihydrochlorides in aqueous solution. These complexes are formed by ion-dipole interactions between the positively charged nitrogen atoms and the oxygen donor atoms of the crown ether. Depending on the experimental conditions, the formation of 1:1 or 2:1 complexes (ligand:diamines) can be studied. The solvation of the ligand and the amines are responsible for the observed thermodynamic values. The number of water molecules released during the reaction were calculated from the determined reaction entropies. Formation of 1:1 complexes distorts the solvation shell around the molecules. As a result, the number of solvent molecules released during the formation of the 2:1 complexes is slightly smaller than the number released from formation of the 1:1 complex. No experimental evidence is observed for the formation of complexes between one crown ether and two protonated amino groups.

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.

Similar content being viewed by others

References

  1. Lehn, J.-M.: Supramolecular Chemistry. VCH, Weinheim (1995)

    Google Scholar 

  2. Vögtle, F.: Supramolekulare Chemie. Teubner, Stuttgart (1989)

    Google Scholar 

  3. Balzani, V., De Cola, L.: Supramolecular Chemistry. Kluwer Academic, Dordrecht (1992)

    Google Scholar 

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

    Article  CAS  Google Scholar 

  5. Pedersen, C.J., Frensdorff, H.K.: Macrocyclic polyethers and their complexes. Angew. Chem. Int. Ed. 11, 16–25 (1972)

    Article  CAS  Google Scholar 

  6. Izatt, R.M., Pawlak, K., Bradshaw, J.S., Bruening, R.L.: Thermodynamic and kinetic data for macrocycle interaction with cations and anions. Chem. Rev. 91, 1721–2085 (1991)

    Article  CAS  Google Scholar 

  7. 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 

  8. Reinhoudt, D.N., van Veggel, F.C.J.M.: Complexation of neutral molecules by synthetic hosts. Pure Appl. Chem. 65, 965–969 (1993)

    Article  CAS  Google Scholar 

  9. Cram, D.J., Troeblood, K.N.: Host-Guest Complex Chemistry Macrocycles. Springer, New York (1985)

    Google Scholar 

  10. Buschmann, H.-J., Mutihac, L., Jansen, K.: Complexation of some amine compounds by macrocyclic receptors. J. Incl. Phenom. Macrocycl. Chem. 39, 1–11 (2001)

    Article  CAS  Google Scholar 

  11. Buschmann, H.-J., Mutihac, L.: Complex formation between the macrocyclic ligand 18-crown-6 and unprotonated amines in methanol. Thermochim. Acta 237, 203–206 (1994)

    Article  CAS  Google Scholar 

  12. Buschmann, H.-J., Schollmeyer, E., Mutihac, L.: The complexation of amino acids by crown ethers and cryptands in methanol. J. Incl. Phenom. Macrocycl. Chem. 30, 21–28 (1998)

    Article  CAS  Google Scholar 

  13. Buschmann, H.-J., Schollmeyer, E., Mutihac, L.: The complexation of the ammonium ion by 18-crown-6 in different solvents and by noncyclic ligands, crown ethers and cryptands in methanol. Supramol. Sci. 5, 139–142 (1998)

    Article  CAS  Google Scholar 

  14. Christensen, J.J., Ruckman, J., Eatough, D.E., Izatt, R.M.: Determination of equilibrium constants by titration calorimetry. Part I. Introduction to titration calorimetry. Thermochim. Acta 3, 203–218 (1972)

    Article  CAS  Google Scholar 

  15. Eatough, D.J., Christensen, J.J., Izatt, R.M.: Determination of equilibrium constants by titration calorimetry. Part II. Data reduction and calculation techniques. Thermochim. Acta 3, 219–232 (1972)

    Article  CAS  Google Scholar 

  16. Eatough, D.J., Izatt, R.M., Christensen, J.J.: Determination of equilibrium constants by titration calorimetry. Part III. Application of method to several chemical systems. Thermochim. Acta 3, 233–246 (1972)

    Article  CAS  Google Scholar 

  17. Buschmann, H.-J.: A comparison of different experimental techniques for the determination of the stabilities of polyethers, crown ethers and cryptand complexes in solution. Inorg. Chim. Acta 195, 51–60 (1992)

    Article  CAS  Google Scholar 

  18. Eatough, D.J., Christensen, J.J., Izatt, R.M.: Experiments in Thermometric Titrimetry and Titration Calorimetry. Brigham Young University Publications, Provo (1973)

    Google Scholar 

  19. Buschmann, H.-J., Schollmeyer, E.: A test reaction from macrocyclic chemistry for calorimetric titrations. Thermochim. Acta 333, 49–53 (1999)

    Article  CAS  Google Scholar 

  20. Buschmann, H.-J., Mutihac, L., Schollmeyer, E.: Complex formation of crown ethers with the cucurbit[6]uril-spermidine and cucurbit[6]uril-spermine complex in aqueous solution. J. Incl. Phenom. Macrocycl. Chem. 53, 85–88 (2005)

    Article  CAS  Google Scholar 

  21. Buschmann, H.-J., Schollmeyer, E.: Influence of the solvation upon the reaction of α-cyclodextrin with carboxylic acids, their methyl esters, and their sodium salts in aqueous solution studied by calorimetric measurements. J. Solution Chem. 34, 731–737 (2005)

    Article  CAS  Google Scholar 

  22. Buschmann, H.-J., Mutihac, L., Schollmeyer, E.: The formation of amino acid and dipeptide complexes with α-cyclodextrin and cucurbit[6]uril in aqueous solutions studied by titration calorimetry. Thermochim. Acta 399, 203–208 (2003)

    Article  CAS  Google Scholar 

  23. Patil, K., Dagade, D.: Studies of activity coefficients for ternary systems: water + 18-crown-6 + alkali chlorides at 298.15 K. J. Solution Chem. 32, 951–966 (2003)

    Article  CAS  Google Scholar 

  24. Kumbhar, R.R., Dagade, D.H., Terdale, S.S., Patil, K.J.: Thermodynamic equilibrium constant studies on aqueous electrolyte (alkaline earth chlorides) solutions containing 18-crown-6 at 298.15 K. J. Solution Chem. 36, 259–273 (2007)

    Article  CAS  Google Scholar 

  25. Tomar, P.A., Kolhapurkar, R.R., Dagade, D.H., Patil, K.J.: Equilibrium constant studies for complexation between ammonium ions and 18-crown-6 in aqueous solution at 298.15 K. J. Solution Chem. 36, 193–209 (2007)

    Article  CAS  Google Scholar 

  26. Bondi, A.A.: Physical Properties of Molecular Crystals, Liquids and Glass. Wiley, New York (1968)

  27. Buschmann, H.-J., Schollmeyer, E.: The interpretation of thermodynamic data for the complex formation of cations with crown ethers and cryptands. Part I: The reaction entropy. J. Incl. Phenom. Macrocycl. Chem. 38, 85–97 (2000)

    Article  CAS  Google Scholar 

  28. Nagano, O., Kobayashi, A., Sasaki, Y.: The crystal structure of the ammonium bromide complex of 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6), C12H24O6⋅NH4Br⋅2H2O. Bull. Chem. Soc. Jpn. 51, 790–793 (1978)

    Article  CAS  Google Scholar 

  29. Pears, D.A., Stoddart, J.F., Fakley, M.E., Atlwood, B.L., Williams, D.J.: Ammonium chloride complexes with 18-crown-6. Acta Crystallogr. C44, 1426–1430 (1988)

    CAS  Google Scholar 

  30. Buschmann, H.-J., Mutihac, L., Schollmeyer, E.: Simple molecular architecture using alkylamines, α-cyclodextrin and 18-crown-6 in aqueous solution. Supramol. Chem. 17, 447–451 (2005)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Hans-Jürgen Buschmann.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ocak, M., Buschmann, HJ. & Schollmeyer, E. Thermodynamic Data for the Formation of 1:1 and 2:1 Complexes of α,ω-Diamino Dihydrochlorides with 18-Crown-6 in Aqueous Solution. J Solution Chem 37, 595–601 (2008). https://doi.org/10.1007/s10953-008-9263-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-008-9263-5

Keywords

Navigation