Physical Nature of Relaxation Time in Aqueous Alcoholic Solutions

  • Yu. M. Stula I.I. Mechnikov National University of Odessa
Keywords: relaxation kinetics, aqueous alcoholic solution, formation of new-phase nuclei, dissipation of new-phase nuclei, self-diffusion coefficient of molecules from the nucleus surface


The kinetics of relaxation processes in aqueous alcoholic solutions has been studied. A model
for the nonequilibrium state of those solutions is proposed, in which the slowest relaxation
process is associated with the destruction of new phase nuclei. The process of their destruction
is described in the framework of both the Lagrangian formalism with low dissipation and the
nucleation theory. The self-diffusion coefficients of molecules from the nucleus surface are
calculated and used to estimate the lifetime of nuclei and its dependence on the nucleus size. A
relation between the diffusion coefficient of nuclei in the nucleus-size space and the coefficient
of molecular self-diffusion from the nucleus surface is found. A comparison with available
experimental data is made.


  1. V.E. Chechko. Light scattering of aqueous glycerol solutions. Ukr. J. Phys. 46, 920 (2001) (in Ukrainian).

  2. V.E. Chechko, V.Ya. Gotsulskiy, V.G. Zaremba. On the nature of relaxation processes in dilute water-glycerol solutions, J. Mol. Liq. 105/2, 211 (2003).

  3. F. Vuks, M.B. Vinnichenko. Refractometric studies of the structure of aqueous tertiary-butyl-alcohol solutions, Fiz. Zhidk. Sost. 14, 63 (1986) (in Russian).

  4. S. Banerjee, J. Furtado, B. Bagchi. Fluctuating microheterogeneity in water–tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies. J. Chem. Phys. 140, 194502 (2014).

  5. D. Subramanian, M.A. Anisimov. Resolving the mystery of aqueous solutions of tertiary butyl alcohol. J. Phys. Chem. 115, 9179 (2011).

  6. G.P. Roshchina. Research of fluctuations in non-aqueous electrolyte solutions by light scattering. Ukr. Fiz. Zh. 9, 512 (1964) (in Russian).

  7. V.E. Chechko, T.V. Lokotosh, N.P. Malomuzh, V.G. Zaremba, V.Ya. Gotsul'sky. Clusterization and anomalies of fluctuations in water-alcohol solutions of low concentrations. J. Phys. Stud. 7, 175 (2003).

  8. V.Ya. Gotsulskiy, V.E. Chechko, Yu.A. Melnik. The origin of light scattering by aqueous solutions of alcohols in vicinities of their singular points. Ukr. J. Phys. 60, 782 (2015) (in Ukrainian).

  9. L.A.Bulavin,V.Ya.Gotsulskii,N.P.Malomuzh,V.E.Chechko. Relaxational and equilibrium properties of dilute aqueous alcohol solutions. Izv. Ross. Akad. Nauk Ser. Khim. 4, 851 (2016) (in Russian).

  10. F. Franks, D.J.G. Ives. The structural properties of alcohol water mixtures. Quater. Rev. Chem. Soc. 20, 1 (1966).

  11. V.E. Chechko, V.Ya. Gotsulskii, M.P. Malomuzh. Characteristic features of the temperature and concentration dependences of the contraction of aqueous ethanol solutions. Zh. Fiz. Khim. 87, 10 (2013) (in Russian).

  12. M.S. Ghoraishi, J.E. Hawk, A. Phani, M.F. Khan, T. Thundatb. Clustering mechanism of ethanol-water mixtures investigated with photothermal microfluidic cantilever deflection spectroscopy. Sci. Rep. 6, 23966 (2016).

  13. L.D. Landau, E.M. Lifshitz. Fluid Mechanics (Pergamon Press, 1993).

  14. J. Frenkel. Kinetic Theory of Liquids (Dover, 1955).

  15. M. Volmer, Kinetik der Phasenbuildung (Steinkopff, 1939).

  16. Ya.B. Zel'dovich. The theory of the interaction of an atom and a metal. Zh. ` Eksp. Teor. Fiz. 12, 525 (1942) (in Russian).

  17. R. Ghosh, B. Bagchi. Enhanced density fluctuations in water-ethanol mixtures at low ethanol concentrations: Temperature dependent studies. J. Phys. Chem. 120, 12568 (2016).

  18. L.A. Bulavin, A.V. Chalyi, O.I. Bilous. Anomalous propagation and scattering of ultrasound in 2-propanol water solution near its singular point. J. Mol. Liq. 235, 24 (2017).

  19. L.A. Bulavin, O.I. Belous, O.S. Svechnikova. Amomalous ultrasound attenuation near the critical point of n-pentanol-nitromethane solutions stratification. Ukr. J. Phys. 61, 375 (2016).
How to Cite
Stula, Y. (2018). Physical Nature of Relaxation Time in Aqueous Alcoholic Solutions. Ukrainian Journal of Physics, 63(2), 138.
Physics of liquids and liquid systems, biophysics and medical physics