Skip to main content
SpringerLink
Log in

Kinetics of a Hydrolysis Reaction in an Oil/Water Microemulsion System Near the Critical Point

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

Abstract

We have constructed the pseudoternary phase diagram of surfynol465 + n-butanol + cyclohexane + H2O with k m = 2 (where k m is the weight ratio of surfynol465 to n-butanol) by the water titration method. Electrical conductivity measurements were employed to investigate the microstructures of the single-phase region. In the oil/water microemulsion region, we have measured the hydrolysis reaction rate of 2-bromo-2-methylpropane near and far away from the critical point. It was found that the Arrhenius equation was valid for correlating experimental measurements far away from the critical point but a significant acceleration effect exists near the critical point, which is not consistent with thermodynamic interpretation of Griffiths and Wheeler.

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

Similar content being viewed by others

References

  1. Cai, H., An, X., Liu, B., Qiao, Q., Shen, W.: Critical behavior of DMA + AOT + n-octane nonaqueous microemulsion with the molar ratio (ω = 2.66) of DMA to AOT. J. Solution Chem. 39, 718–726 (2010)

    Article  CAS  Google Scholar 

  2. Chen, Z., Liu, S., Huang, M., Yin, T., Wang, H., Shen, W.: Densities, heat capacities and asymmetric criticality of coexistence curves for binary mixtures {dimethyl adipate + n-heptane or n-octane}. J. Solution Chem. 42, 1816–1836 (2013)

    Article  CAS  Google Scholar 

  3. Domańska, U., Królikowska, M., Walczak, K.: Density, viscosity and surface tension of binary mixtures of 1-butyl-1-methylpyrrolidinium tricyanomethanide with benzothiophene. J. Solution Chem. 43, 1929–1946 (2014)

    Article  Google Scholar 

  4. Ouerfelli, N., Kouissi, T., Zrelli, N., Bouanz, M.: Competition of viscosity correlation equations in isobutyric acid + water binary mixtures near and far away from the critical temperature. J. Solution Chem. 38, 983–1004 (2009)

    Article  CAS  Google Scholar 

  5. Dilip, M., Bridges, N.J., Rodríguez, H., Pereira, J.F.B., Rogers, R.D.: Effect of temperature on salt–salt aqueous biphasic systems: manifestations of upper critical solution temperature. J. Solution Chem. 44, 454–468 (2015)

    Article  CAS  Google Scholar 

  6. Wheeler, J.C.: Singularity in the degree of dissociation of isobutyric acid, water solutions at the solution point. Phys. Rev. A 30, 648–649 (1984)

    Article  CAS  Google Scholar 

  7. Milner, S.T., Martin, P.C.: Critical slowing of chemical reactions. Phys. Rev. A 33, 1996–2002 (1986)

    Article  CAS  Google Scholar 

  8. Greer, S.C.: Chemical reactions and phase transitions. Int. J. Thermophys. 9, 761–768 (1988)

    Article  CAS  Google Scholar 

  9. Gitterman, M.: Phase equilibria and critical phenomena in closed reactive systems. J. Stat. Phys. 58, 707–748 (1990)

    Article  Google Scholar 

  10. Wheeler, J.C., Petschek, R.G.: Anomalies in chemical equilibria near critical points of dilute solutions. Phys. Rev. A 28, 2442–2448 (1983)

    Article  CAS  Google Scholar 

  11. Procaccia, I., Gitterman, M.: Slowing down of chemical reactions near thermodynamic critical points. Phys. Rev. Lett. 46, 1163–1165 (1981)

    Article  CAS  Google Scholar 

  12. Snyder, R.B., Eckert, C.A.: Chemical kinetics at a critical point. AIChE J. 19, 1126–1133 (1973)

    Article  CAS  Google Scholar 

  13. Kim, Y.W., Baird, J.K.: Reaction kinetics and critical phenomena: saponification of ethyl acetate at the consolute point of 2-butoxyethanol + water. Int. J. Thermophys. 25, 1025–1036 (2004)

    Article  CAS  Google Scholar 

  14. Clunie, J.C., Baird, J.K.: Suppression of the rate of hydrolysis of t-amylchloride at the consolute composition of isobutyric acid + water. Fluid Phase Equilib. 150, 549–557 (1998)

    Article  Google Scholar 

  15. Baird, J.K., Clunie, J.C.: Critical slowing down of chemical reactions in liquid mixtures. J. Phys. Chem. A 102, 6498–6502 (1998)

    Article  CAS  Google Scholar 

  16. Hu, B.C., Baird, J.K.: Reaction k and critical phenomena: iodination of acetone in isobutyric acid + water near the consolute point. J. Phys. Chem. A 114, 355–359 (2010)

    Article  CAS  Google Scholar 

  17. Kim, Y.W., Baird, J.K.: Kinetics of SN1 reactions in binary liquid mixtures near the critical point of solution. J. Phys. Chem. A 107, 8435–8443 (2003)

    Article  CAS  Google Scholar 

  18. Specker, C.D., Ellis, J.M., Baird, J.K.: Chemical dynamics and critical phenomena: electrical conductivity and reactivity of benzyl bromide in triethylamine + water near its consolute point. Int. J. Thermophys. 28, 846–854 (2007)

    Article  CAS  Google Scholar 

  19. Kim, Y.W., Baird, J.K.: Effect of the consolute point of isobutyric acid + water on the rate of an SN1 hydrolysis reaction. Int. J. Thermophys. 22, 1449–1461 (2001)

    Article  CAS  Google Scholar 

  20. Kim, Y.W., Baird, J.K.: Reaction kinetics and critical phenomena: rates of some first order gas evolution reactions in binary solvents with a consolute point. J. Phys. Chem. A 109, 4750–4757 (2005)

    Article  CAS  Google Scholar 

  21. Yin, H., Du, Z., Zhao, J., Shen, W.: Kinetics of the oxidation of iodide ion by persulfate ion in the critical water/bis(2-ethylhexyl) sodium sulfosuccinate/n-decane microemulsions. J. Phys. Chem. A 118, 10706–10712 (2014)

    Article  CAS  Google Scholar 

  22. Du, Z., Mao, S., Chen, Z., Shen, W.: Kinetics of the reaction of crystal violet with hydroxide ion in the critical solution of 2-butoxyethanol + water. J. Phys. Chem. A 117, 283–290 (2013)

    Article  CAS  Google Scholar 

  23. Wang, J., Chen, Y., Shi, B., Xie, Y., Cao, Y., Liu, Y., Zhang, S.: Kinetics of an SN1 reaction in triethylamine + D2O near the consolute point. J. Mol. Liq. 177, 313–316 (2013)

    Article  CAS  Google Scholar 

  24. Ullah, I., Baloch, M.K., Ullah, I.: Apparent solubility of ibuprofen in dimethyl dodecyl ammonium-propane sulfonate, DDAPS, micelles, DDAPS/butanol mixtures and in oil-in-water microemulsions stabilized by DDAPS. J. Solution Chem. 42, 657–665 (2013)

    Article  CAS  Google Scholar 

  25. Wang, J., Dan, Y., Yang, Y., Wang, Y., Hu, Y., Xie, Y.: The measurements of coexistence curves and critical behavior of a binary mixture with a high molecular weight polymer. J. Mol. Liq. 161, 115–119 (2011)

    Article  CAS  Google Scholar 

  26. Clausse, M., Zradba, A., Nicolas-Morgantini, L.: In: Rosano, H.L., Clausse, M. (eds.) Microemulsions Systems, p. 387. Marcel Dekker, New York (1987)

    Google Scholar 

  27. Griffiths, R.B., Wheeler, J.C.: Critical points in multicomponent systems. Phys. Rev. A 2, 1047–1064 (1970)

    Article  Google Scholar 

  28. Hao, Z.G., Yin, H.D., Zheng, P.Z., Zhao, J.H., Shen, W.G.: Critical anomalies of two SN1 hydrolysis reactions in critical binary solutions. J. Phys. Chem. A 119, 8784–8791 (2015)

    Article  CAS  Google Scholar 

  29. Telgmann, T., Kaatze, U.: Monomer exchange and concentration fluctuations in poly(ethylene glycol) monoalkyl ether/water mixtures toward a uniform description of acoustical spectra. Langmuir 18, 3068–3075 (2002)

    Article  CAS  Google Scholar 

  30. Mirzaev, S.Z., Behrends, R., Heimburg, T., Haller, J., Kaatzea, U.: Critical behavior of 2,6-dimethylpyridine–water: measurements of specific heat, dynamic light scattering, and shear viscosity. J. Chem. Phys. 124, 144517-1–144517-6 (2006)

    Article  Google Scholar 

  31. Bunker, C.E., Sun, Y.P.: Evidence for enhanced bimolecular reactions in supercritical CO2 at near-critical densities from a time-resolved study of fluorescence quenching of 9,10-bis(phenylethynyl)anthracene by carbon tetrabromide. J. Am. Chem. Soc. 117, 10865–10870 (1995)

    Article  CAS  Google Scholar 

  32. Ferry, J.L., Fox, M.A.: Temperature effects on the kinetics of carbonate radical reactions in near-critical and supercritical water. J. Phys. Chem. A 103, 3438–3441 (1999)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by The National Natural Science Foundation of China (Nos. 21363007, 21361009 and 21175033), and the Natural Science Foundation of Hubei Province (No. 2012FFC02401).

Author information

Authors and Affiliations

  1. Department of Chemistry, Hubei University for Nationalities, Enshi, 445000, Hubei, China

    Ya Yang, Jing Jin, Jinshou Wang, Zhen Shi & Shenghui Zhang

  2. Key Laboratory of Biologic Resources of Protection and Utilization of Hubei Province, Enshi, 445000, Hubei, China

    Jinshou Wang

Authors
  1. Ya Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jing Jin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jinshou Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Zhen Shi
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Shenghui Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jinshou Wang.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yang, Y., Jin, J., Wang, J. et al. Kinetics of a Hydrolysis Reaction in an Oil/Water Microemulsion System Near the Critical Point. J Solution Chem 45, 702–711 (2016). https://doi.org/10.1007/s10953-016-0467-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-016-0467-9

Keywords

Search

Navigation