Journal of Thermal Analysis and Calorimetry

, Volume 111, Issue 1, pp 891–896 | Cite as

The thermodynamics study on the dissolution mechanism of cellobiose in NaOH/urea aqueous solution

  • Xiaojun Zhao
  • Yuting Chen
  • Xinwei Jiang
  • Yuhan Shang
  • Long Zhang
  • Qing Gong
  • Haibo Zhang
  • Zhiyong Wang
  • Xiaohai Zhou


NaOH/urea aqueous solution is a novel, green solvent for cellulose. To explain why cellulose just be dissolved in this solvent under −13 °C, we studied and discussed the dissolving process of cellobiose in water, urea solution, NaOH solution and NaOH/urea aqueous solution. Dissolving cellobiose in water and the urea solution absorb heat, which is an entropy-driven process. Dissolving cellobiose in NaOH solution and mixed NaOH/urea solution is exothermic, which is an enthalpy-driven process. OH plays an important role in the dissolving process by forming a hydrogen-bonding complex. From the thermodynamic point of view, negative entropy can well interpret why cellulose must be dissolved in cold NaOH/urea aqueous solution.


Solution enthalpy Cellobiose Urea solution NaOH/urea aqueous solution 



This study was supported by the National Basic Research Program of China (973 Program, 2010CB732203).


  1. 1.
    Cai J, Zhang L, Liu S, Liu Y, Xu X, Chen X, Chu B, Guo X, Xu J, Cheng H, Han CC, Kuga S. Dynamic self-assembly induced rapid dissolution of cellulose at low temperatures. Macromolecules. 2008;41:9345–51.CrossRefGoogle Scholar
  2. 2.
    Cai J, Zhang L. Unique gelation behavior of cellulose in NaOH/urea aqueous solution. Biomacromolecules. 2006;7:183–9.CrossRefGoogle Scholar
  3. 3.
    Cai J, Zhang L, Zhou J, Qi H, Chen H, Kondo T, Chen X, Chu B. Multifilament fibers based on dissolution of cellulose in NaOH/urea aqueous solution: structure and properties. Adv Mater. 2007;19:821–5.CrossRefGoogle Scholar
  4. 4.
    Qi H, Chang C, Zhang L. Properties and applications of biodegradable transparent and photoluminescent cellulose films prepared via a green process. Green Chem. 2009;11:177–84.CrossRefGoogle Scholar
  5. 5.
    Luo X, Liu S, Zhou J, Zhang L. Properties of films composed of cellulose nanowhiskers and a cellulose matrix regenerated from alkali/urea solution. J Mater Chem. 2009;19:3538–45.CrossRefGoogle Scholar
  6. 6.
    Chang C, Peng J, Zhang L, Pang D. Strongly fluorescent hydrogels with quantum dots embedded in cellulose matrices. J Mater Chem. 2009;19:7771–6.CrossRefGoogle Scholar
  7. 7.
    Liu S, Zhang L, Zhou J, Xiang J, Sun J, Guan J. Fiberlike Fe2O3 macroporous nanomaterials fabricated by calcinating regenerate cellulose composite fibers. Chem Mater. 2008;20:3623–8.CrossRefGoogle Scholar
  8. 8.
    Botti A, Bruni F, Imberti S, Ricci MA, Soper AK. Ions in water: the microscopic structure of concentrated NaOH solutions. J Chem Phys. 2004;120:10154–62.CrossRefGoogle Scholar
  9. 9.
    Botti A, Bruni F, Imberti S, Ricci MA, Soper AK. Solvation shell of OH ions in water. J Mol Liq. 2005;117:81–4.CrossRefGoogle Scholar
  10. 10.
    Woutersen S, Emmerichs U, Bakker HJ. Femtosecond Mid-IR pump-probe spectroscopy of liquid water: evidence for a two-component structure. Science. 1997;278:658–60.CrossRefGoogle Scholar
  11. 11.
    Bakker HJ, Nienhuys HK. Delocalization of protons in liquid water. Science. 2002;297:587–90.CrossRefGoogle Scholar
  12. 12.
    Nienhuys HK, Lock AJ, Santen RA, Bakker HJ. Dynamics of water molecules in an alkaline environment. J Chem Phys. 2002;117:8021–9.CrossRefGoogle Scholar
  13. 13.
    Omta AW, Kropman MF, Woutersen S, Bakker HJ. Negligible effect of ions on the hydrogen-bond structure in liquid water. Science. 2003;301:347–9.CrossRefGoogle Scholar
  14. 14.
    Chen B, Ivanov I, Park JM, Parrinello M, Klein ML. Solvation structure and mobility mechanism of OH: a Car–Parrinello molecular dynamics investigation of alkaline solutions. J Phys Chem B. 2002;106:12006–16.CrossRefGoogle Scholar
  15. 15.
    Chen B, Park JM, Ivanov I, Tabacchi G, Klein ML, Parrinello M. First-principles study of aqueous hydroxide solutions. J Am Chem Soc. 2002;124:8534–5.CrossRefGoogle Scholar
  16. 16.
    Tuckerman ME, Marx D, Parrinello M. The nature and transport mechanism of hydrated hydroxide ions in aqueous solution. Nature. 2002;417:925–9.CrossRefGoogle Scholar
  17. 17.
    Ludwig R. New insight into the transport mechanism of hydrated hydroxide ions in water. Angew Chem Int Ed. 2003;42:258–60.CrossRefGoogle Scholar
  18. 18.
    Ludwig R. Water: from clusters to the bulk. Angew Chem Int Ed. 2001;40:1808–27.CrossRefGoogle Scholar
  19. 19.
    Frank HS, Franks F. Structural approach to the solvent power of water for hydrocarbons; urea as a structure breaker. J Chem Phys. 1968;48:4746.CrossRefGoogle Scholar
  20. 20.
    Wetlaufer DB, Malik SK, Stoller L, Coffin RI. Nonpolar group participation in the denaturation of proteins by urea and guanidinium salts. Model compound studies. J Am Chem Soc. 1964;86:508–14.CrossRefGoogle Scholar
  21. 21.
    Finer EG, Franks F, Tait MJ. Nuclear magnetic resonance studies of aqueous urea solutions. J Am Chem Soc. 1972;94:4424–9.CrossRefGoogle Scholar
  22. 22.
    Adams R, Balyuzi HHM, Burge RE. X-ray diffraction studies of aqueous solutions of urea. Appl Crystallogr. 1977;10:256–8.CrossRefGoogle Scholar
  23. 23.
    Hoccart X, Turrel G. Raman spectroscopic investigation of the dynamics of urea–water complexes. J Chem Phys. 1993;99:8498–503.CrossRefGoogle Scholar
  24. 24.
    Keuleers R, Rousseau B, Alsenoy CV, Desseyn HO. Vibrational analysis of urea. J Phys Chem A. 1999;103:4621–30.CrossRefGoogle Scholar
  25. 25.
    Kresheck GC, Scheraga HA. The temperature dependence of the enthalpy of formation of the amide hydrogen bond: the urea model. J Phys Chem. 1965;69:1704–6.CrossRefGoogle Scholar
  26. 26.
    Stokes RH. Thermodynamics of aqueous urea solutions. Aust J Chem. 1967;20:2087–100.CrossRefGoogle Scholar
  27. 27.
    Kuharski RA, Rossky PJ. Molecular dynamics study of solvation in urea water solution. J Am Chem Soc. 1984;106:5786–93.CrossRefGoogle Scholar
  28. 28.
    Kuharski RA, Rossky PJ. Solvation of hydrophobic species in aqueous urea solution: a molecular dynamics study. J Am Chem Soc. 1984;106:5794–800.CrossRefGoogle Scholar
  29. 29.
    Jakli G, van Hook WA. Isotope effects in aqueous systems. 12. Thermodynamics of urea-h4/water and urea-d4/water-d2 solutions. J Phys Chem. 1981;85:3480–93.CrossRefGoogle Scholar
  30. 30.
    Lee C, Stahlberg EA, Fitzgerald G. Chemical structure of urea in water. J Phys Chem. 1995;99:17737–41.CrossRefGoogle Scholar
  31. 31.
    Cai J. Dissolution of cellulose in alkali hydroxide/urea aqueous systems, structure and properties of new materials based on them. Doctor degree thesis, Wuhan University. 2006.Google Scholar
  32. 32.
    Piekarski H, Nowicka B. Calorimetric studies of interactions of some peptides with electrolytes, urea and ethanol in water at 298.15 K. J Therm Anal Cal. 2010;102:31–6.CrossRefGoogle Scholar
  33. 33.
    Cooper A. Microcalorimetry of heat capacity and volumetric changes in biomolecular interactions—The link to solvation? J Therm Anal Cal. 2011;104:69–73.CrossRefGoogle Scholar
  34. 34.
    Wang CX, Song ZH, Xiong WG, Qu SS. Development of an isoperibol reaction calorimeter. Acta Phys Chim Sinica. 1991;7:586–8.Google Scholar
  35. 35.
    Cox JD. Recommended reference materials for the realization of physicochemical properties. Pure Appl Chem. 1974;40:399.Google Scholar
  36. 36.
    Roy C, Budtova T, Navard P, Bedue O. Structure of cellulose-soda solutions at low temperatures. Biomacromolecules. 2001;2:687–93.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2012

Authors and Affiliations

  • Xiaojun Zhao
    • 1
    • 2
  • Yuting Chen
    • 1
  • Xinwei Jiang
    • 1
  • Yuhan Shang
    • 1
  • Long Zhang
    • 1
  • Qing Gong
    • 1
  • Haibo Zhang
    • 1
  • Zhiyong Wang
    • 1
  • Xiaohai Zhou
    • 1
  1. 1.College of Chemistry and Molecular ScienceWuhan UniversityWuhanPeople’s Republic of China
  2. 2.Department of Chemistry and Chemical EngineeringAnkang UniversityAnkangPeople’s Republic of China

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