Skip to main content
SpringerLink
Log in

Dehydration of a polyether type extraction agent and of the corresponding K+ complex: insights into liquid-liquid extraction mechanisms by quantum chemical methods

  • Original Paper
  • Published:
Journal of Molecular Modeling Aims and scope Submit manuscript

Abstract

In this paper we report a quantum chemical study performed at the B3LYP/6-311G++(d,p) level of theory on structural and energetic aspects of the sequential dehydration of a tetra-hydrated polyethylene-glycol type podand (1,2-bis-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy}-benzene, hereafter b33) and its complex with the K+ cation. Thermodynamical parameters were determined by hessian quantum calculations performed using a self-consistent reaction field (SCRF) method, taking into account solvent (dichloromethane) effects. The results allowed the estimation of dehydration enthalpies, entropies and free energies for the hydrated free b33 podand and its corresponding K+ cation complex in dichloromethane. The low absolute values found for the dehydration free energies as well as the structural features found for the optimized structures and the corresponding basis superposition calculated interaction energies, support the hypothesis of an interfacial complexation type mechanism governing the assisted extraction of K+ from an aqueous toward an organic phase, in liquid/liquid extraction.

Stereo-view of the optimized structures of [Kb33(H2O)n]+ complexes with n=0,1,2,3 and 4

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Valente M, Sousa SF, Magalhães AL, Freire C (2010) Crown-ether type podands as alkali metal cation extractants: influence of the number of oxygens in the chain. J Solution Chem 39:1230–1242. doi:10.1007/s10953-010-9579-9

    Article  CAS  Google Scholar 

  2. Frensdorff HK (1971) Stability constants of cyclic polyether complexes with univalent cations. J Am Chem Soc 93:600–606. doi:10.1021/ja00732a007

    Article  CAS  Google Scholar 

  3. Pedersen CJ (1967) Cyclic polyethers and their complexes with metal salts. J Am Chem Soc 89:7017–7036. doi:10.1021/ja01002a35

    Article  CAS  Google Scholar 

  4. Rose L, Jenkins ATA (2007) The effect of the ionophore valinomycin on biomimetic solid supported lipid DPPTE/ECP membranes. Bioelectrochemistry 70:387–393. doi:10.1016/j.bioelechem.2006.05.009

    Article  CAS  Google Scholar 

  5. Huczynski A, Ratajczak-Sitarz M, Katrusiak A, Brzezinski B (2007) Molecular structure of the 1:1 inclusion complex of monesin A sodium salt with acetonitrile. J Mol Struct 832:84–89. doi:10.1016/j.molstruc.2006.07.043

    Article  CAS  Google Scholar 

  6. Moyer BA, Bonnensen PV, Custelcean R, Delmau LH, Hay BP (2005) Strategies for using host-guest chemistry in extractive separations of ionic guests. Kem Ind 54:65–87. doi:10.1002/chin.200531276

    CAS  Google Scholar 

  7. Starks CM, Liotta CL (1994) Halpern M phase-transfer catalysis, fundamentals, applications and industrial perspectives. Chapman & Hall, New York, ISBN 0-412-04071-9

    Google Scholar 

  8. Kakutani T, Nishiwaki Y, Osakai T, Senda M (1986) On the mechanism of transfer of sodium ion across the nitrobenzene/water interface facilitated by Dibenzo-18-crown-6. Bull Chem Soc Jpn 59:781–788. doi:10.1246/bcsj.59.781

    Article  CAS  Google Scholar 

  9. Schmickler W (1999) A model for assisted ion transfer across liquid | liquid interfaces. J Electroanal Chem 460:144–148. doi:10.1016/S0022-0728(98)00367-2

    Article  CAS  Google Scholar 

  10. Osakai T, Ogata A, Ebina K (1997) Hydration of ions in organic solvent and its significance in the gibbs energy of ion transfer between two immiscible liquids. J Phys Chem B 101:8341–8348. doi:10.1021/jp971773l

    Article  CAS  Google Scholar 

  11. Osakai T, Ebina K (1998) Non bornian theory of the gibbs energy of ion transfer between two immiscible liquids. J Phys Chem B 102:5691–5698. doi:10.1021/jp9814193

    Article  CAS  Google Scholar 

  12. Chang T-M, Dang LX (2006) Recent advances in molecular simulations of ion solvation at liquid interfaces. Chem Rev 106:1305–1322. doi:10.1021/cr0403640

    Article  CAS  Google Scholar 

  13. Chorny I, Benjamin I (2005) Hydration shell exchange dynamics during ion transfer across the liquid/liquid interface. J Phys Chem B 109:16455–16462. doi:10.1021/jp051836x

    Article  CAS  Google Scholar 

  14. Rose D, Benjamin I (2009) Free energy of transfer of hydrated ion clusters from water to an immiscible organic solvent. J Phys Chem B 113:9296–9303. doi:10.1021/jp903286d

    Article  CAS  Google Scholar 

  15. Valente M, Sousa SF, Magalhães AL, Freire CA (2010) Comparative molecular dynamics study on the complexation of alkali metal cations by a poly-ethylene-glycol type podand in water and in dichloromethane. J Mol Struct (THEOCHEM) 946:77–82. doi:10.1016/j.theochem.2009.10.025

    Article  CAS  Google Scholar 

  16. Valente M, Sousa SF, Magalhães AL, Freire C (2011) Complexation of alkali metal cations by crown-ether type podands with applications in solvent extraction: insights from quantum calculations. J Mol Model 17:3275–3288. doi:10.1007/s00894-011-1004-9

    Article  CAS  Google Scholar 

  17. Valente M, Sousa SF, Magalhães AL, Freire C (2010) Factors influencing the binding of a potassium cation to a polyethylene-glycol type podand in liquid-liquid extraction—a molecular dynamics study. Theor Chem Acc 127:681–687. doi:10.1007/s00214-010-0778-7

    Article  CAS  Google Scholar 

  18. Valente M, Sousa SF, Magalhães AL, Freire C (2012) Transfer of the K+ cation across a water/dichloromethane interface: a steered molecular dynamics study with implications in cation extraction. J Phys Chem B 116:1843–1849. doi:10.1021/jp210786j

    Article  CAS  Google Scholar 

  19. Valente M, Sousa SF, Magalhães AL, Freire C (2012) Decomplexation and complexation of alkali metal cations by a crown-ether-type podand in dichloromethane: a steered molecular dynamics study. Theor Chem Acc 131:1171–1177. doi:10.1007/s00214-012-1171-5

    Article  Google Scholar 

  20. Stephenson MJ, Holmes SM, Dryfe RAW (2004) A novel approach to the elucidation of facilitated ion transfer mechanisms at the liquid/liquid interface. Electrochem Commun 6:294–298. doi:10.1016/j.elecom.2004.01.004

    Article  CAS  Google Scholar 

  21. Tsai R-S, Fan W, El Tayar N, Carrupt P-A, Testa B, Kier LB (1993) Solute—water interactions in the organic phase of a biphasic system. 1. Structural influence of organic solutes on the “water-dragging” effect. J Am Chem Soc 115:9632–9639. doi:10.1021/ja00074a031

    Article  CAS  Google Scholar 

  22. Fan W, Tsai R-S, El Tayar N, Carrupt P-A, Testa B (1994) Solute—water interactions in the organic phase of a biphasic system. 2. Effects of organic phase and temperature on the “water-dragging” effect. J Phys Chem 98:329–333. doi:10.1021/j100052a054

    Article  CAS  Google Scholar 

  23. Bushmann H-J, Mutihac R-C, Schollmeyer E (2010) Interactions between crown ethers and water, methanol, acetone, and acetonitrile in halogenated solvents. J Solution Chem 39:291–299. doi:10.1007/s10953-010-9499-9

    Article  Google Scholar 

  24. Kikuchi Y, Arayashiki Y, Anada T (2001) Hydration to Benzo-15-crown-5, Benzo-18-crown-6 and the Benzo-18-crown-6-potassium ion complex in low-polar organic solvents. Anal Sci 17:421–424. doi:10.2116/analsci.17.421

    Article  CAS  Google Scholar 

  25. Gaussian 09, Revision A.1, Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ, (2009) Gaussian Inc., Wallingford CT

  26. Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652. doi:10.1063/1.464913

    Article  CAS  Google Scholar 

  27. Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789. doi:10.1103/PhysRevB.37.785

    Article  CAS  Google Scholar 

  28. Sousa SF, Fernandes PA, Ramos MJ (2007) General performance of density functionals. Phys Chem A 111:10439–10452. doi:10.1021/jp0734474

    Article  CAS  Google Scholar 

  29. Cossi M, Rega N, Scalmani G, Barone V (2003) Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model. J Comput Chem 24:669–681. doi:10.1002/jcc.10189 (and references therein)

    Article  CAS  Google Scholar 

  30. Boys SF, Bernardi F (1970) The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors. Mol Phys 19:553–566. doi:10.1080/00268977000101561

    Article  CAS  Google Scholar 

  31. Laage D, Hynes JT (2006) A molecular jump mechanism of water reorientation. Science 331:832–835. doi:10.1126/science.1122154

    Article  Google Scholar 

  32. Mootz D, Albert A, Schaefgen S, Staeben D (1994) Hydrates of weak and strong bases. 12. 18-crown-6 and water: crystal structure of a binary hydrate. J Am Chem Soc 116:12045–12046. doi:10.1021/ja00105a052

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work has been supported by Fundação para a Ciência e a Tecnologia through Grant No. Pest-C/EQB/LA0006/2011.

Author information

Authors and Affiliations

  1. Requimte—Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, Rua Campo Alegre s/n, 4169-007, Porto, Portugal

    Mário Valente, Sérgio Filipe Sousa, Alexandre L. Magalhães & Cristina Freire

Authors
  1. Mário Valente
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sérgio Filipe Sousa
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Alexandre L. Magalhães
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Cristina Freire
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Alexandre L. Magalhães or Cristina Freire.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Valente, M., Sousa, S.F., Magalhães, A.L. et al. Dehydration of a polyether type extraction agent and of the corresponding K+ complex: insights into liquid-liquid extraction mechanisms by quantum chemical methods. J Mol Model 18, 4909–4915 (2012). https://doi.org/10.1007/s00894-012-1491-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00894-012-1491-3

Keywords

Search

Navigation