International Journal of Thermophysics

, Volume 25, Issue 4, pp 1025–1036 | Cite as

Reaction Kinetics and Critical Phenomena: Saponification of Ethyl Acetate at the Consolute Point of 2-Butoxyethanol + Water

  • Y. W. Kim
  • J. K. Baird


The rate of sponification of ethyl acetate by sodium hydroxide was measured near the consolute point of the liquid mixture, 2-butoxyethanol + water. At temperatures far below the lower critical solution temperature, Tc, the apparent rate constant obeyed the Arrhenius equation. In the one-phase region just beneath Tc, the rate constant decreased below the Arrhenius background, indicating critical slowing down. Because the kinetics of this reaction are second order, the net reaction rate depends upon both (∂ΔG/∂ξ)e and (∂ΔG/∂ξ)e, where Δ G is the Gibbs free energy difference between products and reactants, ξ is the extent of reaction, and subscript “e” refers to chemical equilibrium. On the basis of the Principle of Universality, it is argued that as the temperature approaches Tc, both of these thermodynamic derivatives should go to zero, and the net reaction rate should slow down as is actually observed.

2-butoxyethanol critical slowing down kinetics saponification water 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    A. Findlay, A.N. Campbell, and N.O. Smith, The Phase Rule, 9th Ed. (Dover Publications, New York, 1951), Chapt.6.Google Scholar
  2. 2.
    J.C. Clunie and J.K. Baird, Fluid Phase Equilib. 150-151:549 (1998).Google Scholar
  3. 3.
    J.K. Baird and J.C. Clunie, J.Phys.Chem.A 102:6498 (1998).Google Scholar
  4. 4.
    E.S. Gould, Mechanism and Structure in Organic Chemistry (Holt, Rinehart, and Winston, New York, 1959)Chaps.8 and 9.Google Scholar
  5. 5.
    Y.W. Kim and J.K. Baird, Int.J.Thermophys. 22:1449 (2001).Google Scholar
  6. 6.
    Y.W. Kim and J.K. Baird, J.Phys.Chem. 107:8435 (2003).Google Scholar
  7. 7.
    J.K. Baird, J.Chem.Educ. 76:1146 (1999).Google Scholar
  8. 8.
    R.G. Griffiths and J.C. Wheeler, Phys.Rev.A 2:1047 (1970).Google Scholar
  9. 9.
    Y.W. Kim.Dissertation, University of Alabama in Huntsville (2000).Google Scholar
  10. 10.
    C.-H. Shaw and W.I. Goldburg, J.Chem.Phys. 65:4906 (1976).Google Scholar
  11. 11.
    J.F. Counsell, D.H. Everett, and R.J. Munn, Pure Appl.Chem.. 2:335 (1961).Google Scholar
  12. 12.
    J.C. Wheeler and R.G. Petschek, Phys.Rev.A 28:2442 (1983).Google Scholar
  13. 13.
    J. March, Advanced Organic Chemistry, 4th Ed. (John Wiley, New York, 1992), pp.298–305.Google Scholar
  14. 14.
    C.A. VanderWerf, Acids, Bases, and the Chemistry of the Covalent Bond (Reinhold Publishing Corp., New York, 1961).Google Scholar
  15. 15.
    S.C. Greer and M.R. Moldover, Annu.Rev.Phys.Chem. 32:233 (1981).Google Scholar
  16. 16.
    J.V. Sengers and J.M.H. Levelt-Sengers, Annu.Rev.Phys.Chem. 37:189 (1986).Google Scholar
  17. 17.
    J.K. Baird and Y.W. Kim, J.Phys.Chem. 107:10241 (2003).Google Scholar

Copyright information

© Plenum Publishing Corporation 2004

Authors and Affiliations

  • Y. W. Kim
    • 1
  • J. K. Baird
    • 1
  1. 1.Department of ChemistryUniversity of Alabama in HuntsvilleHuntsvilleU.S.A

Personalised recommendations