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Impurity Induced Slowing oF Nucleation in Emulsified Liquids

  • Amy Herhold (a1), Deniz Ertaş (a1), Alex J. Levine (a1) and H. E. King (a1)


We report detailed nucleation studies on the liquid -to -solid transition of hexadecane using nearly monodisperse hexadecane -in -water emulsions. A careful consideration of the kinetics of isothermal and nonisothermal freezing show deviations from predictions of classical nucleation theory, if one assumes that the emulsion droplet population is homogeneous. Similar deviations have been observed previously [3]. As an explanation, we propose a novel argument based on the dynamic generation of droplet heterogeneity mediated by mobile impurities. This proposal is in excellent agreement with existing data.



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[1] Vonnegut, B., J. Colloid Sci. 3, p. 563 (1948).
[2] Turnbull, D., J. Chem. Phys. 20, p. 411 (1952).
[3] Turnbull, D. and Cormia, R. L., J. Chem. Phys. 34, p. 820 (1961).
[4] Kelton, K. F., Solid State Physics 45, p. 75 (1991).
[5] Perepezko, J. H., Materials Science and Engineering A 226–228, p. 374 (1997).
[6] Perepezko, J. H., Materials Science and Engineering 65, p. 125 (1984).
[7] Bibette, J., J. Colloid Interface Sci. 147, p. 474 (1991).
[8] Kandori, K., Kishi, K. and Ishikawa, T., Colloids and Surfaces 55, p. 73 (1991).
[9] Kandori, K., Kishi, K. and Ishikawa, T., Colloids and Surfaces 61, p. 269 (1991).
[10] Uhlmann, D. R., Kritchevsky, G., Straff, R. and Scherer, G., J. Chem. Phys. 62, p. 4,896 (1975).
[11] Oliver, M. J. and Calvert, P. D., J. Crystal Growth 30, p. 343 (1975).
[12] McClements, D. J.; Dickinson, E. and Povey, M. J. W., Chem. Phys. Lett. 172, p. 449 (1990).
[13] Dickinson, E., Kruizenga, F.-J., Povey, M. J. W. and Molen, M. v. d., Col. and Surf. A 81, p. 273 (1993).
[14] Dickinson, E., Goller, M. I., McClements, D. J., Peasgood, S. and Povey, M. J. W., J. Chem. Soc. Faraday Trans. 86, p. 1,147 (1990).
[15] Dickinson, E., McClements, D. J. and Povey, M. J. W., J. Colloid Interface Sci. 142, p. 103 (1991).
[16] Turnbull, D. and Spaepen, F., J. Polym. Sci., Polym. Symp. 63, p. 237 (1978).
[17] Small, D. M., The Physical Chemistry of Lipids: From Alkanes to Phospholipids,\Plenum Press, New York, 1986.
[18] Nakayama, H., Shinoda, K. and Hutchinson, E., J. Phys. Chem. 70, p. 3,502 (1966).
[19] Hato, M. and Shinoda, K., J. Phys. Chem. 77, p. 378 (1973).
[20] Shao, H., Ph.D Thesis, X-ray Scattering Study of Structures and Phase Transitions of Normal Alkanes, The Ohio State University, 1995.
[21] Turnbull, D. and Fisher, J. C., J. Chem. Phys. 17, p. 71 (1949).
[22] Wu, D., Solid State Physics 50, p. 37 (1996).
[23] We neglect the difference in specific heats Cp between the liquid and solid phases in this case.
[24] Turnbull, D., Contemp. Phys. 10, p. 473 (1969).
[25] At typical crystal growth velocities of meters per second, the time lag between nucleation and completion of growth in a single emulsion droplet is on the order of a microsecond. Even though these materials form plate-like structures during freezing which suggests slower growth along certain crystallographic directions, the ratio of the slow rate to the fast one would have to be less than 10–6 to have an effect on the experiments.
[26] Sirota, E. B., Langmuir 14, p. 3,133 (1998).
[27] Sirota, E. B. and Herhold, A. B., Science (to be published.)
[28] Siano, D. B., J. Chem. Educ. 49, p. 755 (1972).
[29] The standard deviation for the emulsion droplet volume distribution is about 0.3.
[30] Lifshitz, E. M. and Pitaevskii, L. P., Statistical Physics, 3rd Edition, Part 1, Pergamon Press, New York, 1980, Chap. 9.
[31] Ertaş, D., Herhold, A., Levine, A. J., and King, H. E. Jr., in preparation.
[32] Kurz, J. L., J. Phys. Chem. 66, p. 2,239 (1962); M. Muramatsu and M. Inove, J. Colloid Interface Sci. 55, p. 80 (1976).

Impurity Induced Slowing oF Nucleation in Emulsified Liquids

  • Amy Herhold (a1), Deniz Ertaş (a1), Alex J. Levine (a1) and H. E. King (a1)


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