Skip to main content

Advertisement

SpringerLink
Log in

Volumetric Study of Aqueous Solutions of Polyethylene Glycol as a Function of the Polymer Molar Mass in the Temperature Range 283.15 to 313.15 K and 0.1 MPa

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

Abstract

Density measurements were made for binary aqueous solutions of polyethylene glycol at seven temperatures: 283.15, 288.15, 293.15, 298.15, 303.15, 308.15, and 313.15 K. Polyethylene glycol samples with nominal average molar masses of 3000 g⋅mol−1 (PEG 3000), 6000 g⋅mol−1 (PEG 6000), 10000 g⋅mol−1 (PEG 10000) and 20000 g⋅mol−1 (PEG 20000) were used. These results were used to determine the specific volumes of solutions with solute-to-solvent mass ratios (mass of the solute/mass of the solvent) in the range 0.0546 to 1.4932 for PEG 3000, from 0.0553 to 1.4986 for PEG 6000, from 0.0552 to 1.2241 for PEG 10000, and from 0.0530 to 1.2264 for PEG 20000. The differences between the specific volume of a solution and the specific volume of the pure solvent, at a given temperature, were represented by a virial-type equation in terms of solute concentration. The first-order coefficient of the expansion is the partial specific volume of the solute at infinite dilution. The higher-order coefficients are related to the contribution of pairs, triplets, and higher-order solute aggregates, according to the Constant-Pressure Solution Theory. The functional dependence of the virial coefficients upon temperature is discussed in terms of solute-solute and solute-solvent interactions. The effect of the PEG molar mass on the partial specific volume of solute at infinite dilution, as well as the contributions of pairs of solute molecules to the solution volume, are also investigated. The apparent specific volume, apparent specific expansibility, apparent specific expansibility at infinite dilution and virial coefficients of the apparent specific expansibility are also presented.

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

Similar content being viewed by others

References

  1. Saeki, S., Kuwahara, N., Nakata, M., Kaneko, M.: Upper and lower critical solution temperatures in poly(ethylene glycol) solutions. Polymer (Guildf.) 17, 685–689 (1976). doi:10.1016/0032-3861(76)90208-1

    Article  CAS  Google Scholar 

  2. Albertsson, P.-Å.: Partition of Cell Particles and Macromolecules, 3rd edn. Wiley-Interscience, New York (1986)

    Google Scholar 

  3. Venohr, H., Fraaije, V., Strunk, H., Borchard, W.: Static and dynamic light scattering from aqueous poly(ethylene oxide) solutions. Eur. Polym. J. 34, 723–732 (1998). doi:10.1016/S0014-3057(97)00159-6

    Article  CAS  Google Scholar 

  4. Dormidontova, E.E.: Role of competitive PEO-water and water-water hydrogen bonding in aqueous solution PEO behavior. Macromolecules 35, 987–1001 (2002). doi:10.1021/ma010804e

    Article  CAS  Google Scholar 

  5. Franks, F., Pedley, M., Reid, D.S.: Solute interactions in dilute aqueous solutions. Part. 1 — Microcalorimetric study of the hydrophobic interaction. J. Chem. Soc., Faraday Trans. I 72, 359–367 (1976). doi:10.1039/f19767200359

    Article  CAS  Google Scholar 

  6. Kirinčič, S., Klofutar, C.: A volumetric study of aqueous solutions of poly(ethylene glycol)s at 298.15 K. Fluid Phase Equil. 149, 233–247 (1998). doi:10.1016/S0378-3812(98)00369-0

    Article  Google Scholar 

  7. Cruz, R.C., Martins, R.J., Cardoso, M.J.E.M., Barcia, O.E.: Volumetric study of aqueous solutions of poly(ethylene glycol) from 283.15 to 313.15 K and at 0.1 MPa. J. Appl. Polym. Sci. 91, 2685–2689 (2004). doi:10.1002/app.13451

    Article  CAS  Google Scholar 

  8. Rudan-Tasic, D., Klofutar, C.: Apparent molar volume and apparent molar refraction of mono-, di-, tri-, and tetra(oxyethylene) glycol in aqueous, 1,4-dioxane, and benzene solutions at 298.15 K. Monatsh. Chem. 134, 1185–1193 (2003). doi:10.1007/s00706-003-0052-y

    CAS  Google Scholar 

  9. Rudan-Tasic, D., Klofutar, C.: Apparent specific volume and apparent specific refraction of some poly(oxyethylene) glycols in 1,4-dioxane and benzene solutions at 298.15 K. Monatsh. Chem. 135, 1209–1224 (2004). doi:10.1007/s00706-004-0211-9

    Article  CAS  Google Scholar 

  10. Leslie, T.E., Lilley, T.H.: Aqueous-solutions containing amino-acids and peptides. 20. Volumetric behavior of some terminally substituted amino-acids and peptides at 298.15 K. Biopolymers 24, 695–710 (1985). doi:10.1002/bip.360240409

    Article  CAS  Google Scholar 

  11. Tawfik, W.Y., Teja, A.S.: The densities of polyethylene glycols. Chem. Eng. Sci. 44, 921–923 (1989). doi:10.1016/0009-2509(89)85265-0

    Article  CAS  Google Scholar 

  12. Hill, T.L.: Theory of solutions. I. J. Am. Chem. Soc. 79, 4885–4890 (1957). doi:10.1021/ja01575a016

    Article  CAS  Google Scholar 

  13. Hill, T.L.: Theory of solutions. II. Osmotic pressure virial expansion and light scattering in two component solutions. J. Chem. Phys. 30, 93–97 (1959). doi:10.1063/1.1729949

    Article  CAS  Google Scholar 

  14. Hill, T.L.: Thermodynamics for Chemists and Biologists. Addison-Wesley, Boston (1968)

    Google Scholar 

  15. Hill, T.L.: An Introduction to Statistical Thermodynamics. Dover, New York (1986)

    Google Scholar 

  16. Wurzburger, S., Sartorio, R., Guarino, G., Nisi, M.: Volumetric properties of aqueous solutions of polyols between 0.5 and 25 °C. J. Chem. Soc., Faraday Trans. I 84, 2279–2287 (1988). doi:10.1039/f19888402279

    Article  CAS  Google Scholar 

  17. Lide, D.R.: Handbook of Chemistry and Physics, 76th edn. CRC, Boca Raton (1995)

    Google Scholar 

  18. Nelder, J.A., Mead, R.: A simplex method for function minimization. Comput. J. 7, 308–313 (1965)

    Google Scholar 

  19. Himmelblau, D.M.: Applied Nonlinear Programming. McGraw-Hill, New York (1972)

    Google Scholar 

  20. Millero, F.J., Ward, G.K., Chetirkin, P.: Partial specific volume, expansibility, compressibility, and heat capacity of aqueous lysozyme solutions. J. Biol. Chem. 13, 4001–4004 (1976)

    Google Scholar 

  21. Shekaari, H., Mansoori, Y., Sadeghi, R.: Density, speed of sound, and electrical conductance of ionic liquid 1-hexyl-3-methyl-imidazolium bromide in water at different temperatures. J. Chem. Thermodyn. 40, 852–859 (2008). doi:10.1016/j.jct.2008.01.003

    Article  CAS  Google Scholar 

  22. Poling, B.E., Prausnitz, J.M., O’Connell, J.P.: The Properties of Gases and Liquids, 5th edn. McGraw-Hill, New York (2001)

    Google Scholar 

  23. Flory, P.J.: Principles of Polymer Chemistry, 5th impression. Cornell University Press, Ithaca (1966)

    Google Scholar 

  24. Sarazin, D., Francois, J.: Apparent specific volumes of polymers in dilute solutions. Polymer (Guildf.) 24, 547–552 (1983). doi:10.1016/0032-3861(83)90103-9

    Article  CAS  Google Scholar 

  25. Savage, J.J., Wood, R.H.: Enthalpy of dilution of aqueous mixtures of amides, sugars, urea, ethylene glycol, and pentaerythritol at 25 °C: Enthalpy of interaction of the hydrocarbon, amide, and hydroxyl functional groups in dilute aqueous solutions. J. Solution Chem. 5, 733–750 (1976). doi:10.1007/BF00643457

    Article  CAS  Google Scholar 

  26. Jolicoeur, C., Lacroix, G.: Thermodynamic properties of aqueous organic solutes in relation to their structure. Part III. Apparent molal volumes and heat capacities of low molar mass alcohols and polyols at 25 °C. Can. J. Chem. 54, 624–630 (1976). doi:10.1139/v76-089

    Article  CAS  Google Scholar 

  27. Perron, G., Desnoyers, J.E.: Heat capacities and volumes of interaction between mixtures of alcohols in water at 298.15 K. J. Chem. Thermodyn. 13, 1105–1121 (1981). doi:10.1016/0021-9614(81)90009-4

    Article  CAS  Google Scholar 

  28. Hepler, L.G.: Thermal expansion and structure in water and aqueous solutions. Can. J. Chem. 47, 4613–4617 (1969). doi:10.1139/v69-762

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Laboratório de Físico-Química de Líquidos e Eletroquímica, Departamento de Físico-Química, Instituto de Química, Universidade Federal do Rio de Janeiro, Centro de Tecnologia, Bloco A, sala 411, Cidade Universitária, CEP 21949-900, Rio de Janeiro, RJ, Brasil

    Raphael da C. Cruz, Rosana J. Martins, Márcio J. E. de M. Cardoso & Oswaldo E. Barcia

  2. Departamento de Físico-Química, Instituto de Química, Universidade Federal Fluminense, Outeiro de São João Batista s/nº, CEP 24020-150, Niterói, RJ, Brasil

    Raphael da C. Cruz & Rosana J. Martins

Authors
  1. Raphael da C. Cruz
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Rosana J. Martins
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Márcio J. E. de M. Cardoso
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Oswaldo E. Barcia
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Raphael da C. Cruz.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Cruz, R.d.C., Martins, R.J., Cardoso, M.J.E.d.M. et al. Volumetric Study of Aqueous Solutions of Polyethylene Glycol as a Function of the Polymer Molar Mass in the Temperature Range 283.15 to 313.15 K and 0.1 MPa. J Solution Chem 38, 957–981 (2009). https://doi.org/10.1007/s10953-009-9388-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-009-9388-1

Keywords

Search

Navigation