Equilibrium supercooled liquid's entropy and enthalpy in the Kauzmann and the third law extrapolations, and a proposed experimental resolution

Journal of Chemical Physics

Volumn 113, Issue 2, 2000, Pages 751-761

  Johari, G P ^a  

^a MCMASTER UNIVERSITY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

ENTHALPY; ENTROPY; EXTRAPOLATION; GIBBS FREE ENERGY; GLASS TRANSITION; INTERPOLATION; MATHEMATICAL MODELS; MELTING; SPECIFIC HEAT OF LIQUIDS; SUPERCOOLING; VAPOR PRESSURE; VITRIFICATION;

HEAT OF SOLUTION; KAUZMANN EXTRAPOLATIONS; MOLECULAR KINETICS; SUPERCOOLED LIQUID; TRIPHENYLETHENE;

LIQUIDS;

EID: 0034225045     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.481850     Document Type: Article

References (58)

1. W. Kauzmann, Chem. Rev. 43, 219 (1948).
2. J. H. Gibbs and E. A. DiMarzio, J. Chem. Phys. 28, 373,807 (1958).
3. J. H. Gibbs, in Modern Aspects of the Vitreous State, edited by J. D. McKenzie (Butterworths, London, 1960), Chap. 7.
4. P. J. Flory, J. Chem. Phys. 10, 51 (1942); 17, 223 (1949).
5. P. J. Flory, J. Chem. Phys. 10, 51 (1942); 17, 223 (1949).
6. M. L. Huggins, Ann. (N.Y.) Acad. Sci. 43, 1 (1942).
7. G. Adam and J. H. Gibbs, J. Chem. Phys. 43, 139 (1965).
8. H. Vogel, Phys. Z. 22, 645 (1921).
9. G. S. Fulcher, J. Am. Ceram. Soc. 8, 339 (1923).
10. G. Tammann and W. Hesse, Z. Anorg. Allg. Chem. 156, 245 (1926).
11. G. P. Johari, Philos. Mag. 41, 41 (1981).
12. I. Gutzow, in Amorphous Materials, edited by R. W. Douglas and W. Ellis (Wiley, London, 1972), p. 159; in Disordered Systems and New Materials, edited by M. Borissov, N. Kirov, and A. Vavrek (World Scientific, London, 1989), p. 11.
13. I. Gutzow, in Amorphous Materials, edited by R. W. Douglas and W. Ellis (Wiley, London, 1972), p. 159; in Disordered Systems and New Materials, edited by M. Borissov, N. Kirov, and A. Vavrek (World Scientific, London, 1989), p. 11.
14. I. Gutzow, in The Physics of Noncrystalline Solids, edited by G. H. Frischat (Trans. Tech. Publ. Aedermannsdorf, 1977), p. 356.
15. I. Gutzow and J. Schmelzer, The Vitreous State: Thermodynamics, Structure, Rheology and Crystallization (Springer, Heidelberg, 1995), p. 165-215.
16. I. Gutzow, Wiss. Z. Friedrich-Schiller-Univ. Jena, Math-Nat. 28, 243 (1979).
17. A. Milchev and I. Gutzow, J. Macromol. Sci., Phys. 21, 583 (1982).
18. A. Milchev, C. R. Acad. Bulg. Sci. 36, 1415 (1983).
19. H.-P. Wittmann, J. Chem. Phys. 95, 8449 (1991).
20. P. D. Gujrati, J. Phys. A 13, L437 (1980).
21. P. D. Gujrati and M. Goldstein, J. Chem. Phys. 74, 2596 (1981).
22. E. A. DiMarzio and A. J. M. Yang, J. Res. Natl. Inst. Stand. Technol. 102, 135 (1997).
23. F. H. Stillinger, J. Chem. Phys. 88, 7818 (1988).
24. F. E. Simon, Ergeb. Exakten. Naturwiss. 9, 244 (1930); Z. Anorg. Allg. Chem. 203, 219 (1931).
25. F. E. Simon, Ergeb. Exakten. Naturwiss. 9, 244 (1930); Z. Anorg. Allg. Chem. 203, 219 (1931).
26. Kauzmann [Chem. Rev. 43, 219,244 (1948)] had considered the possibility that a nonvitreous liquid can somehow pass continuously over into the crystalline state in a manner anologous to the liquifaction of gases above the critical temperature in a manner such as that described by F. E. Simon [Z. Anorg. Allg. Chem. 203, 219 (1931)], but found little justification for it since the entropy and enthalpy curves of the liquid seemed to extrapolate to the crystal values at different temperatures.
27. Kauzmann [Chem. Rev. 43, 219,244 (1948)] had considered the possibility that a nonvitreous liquid can somehow pass continuously over into the crystalline state in a manner anologous to the liquifaction of gases above the critical temperature in a manner such as that described by F. E. Simon [Z. Anorg. Allg. Chem. 203, 219 (1931)], but found little justification for it since the entropy and enthalpy curves of the liquid seemed to extrapolate to the crystal values at different temperatures.
28. See also F. E. Simon, Ergeb. Exakten. Naturwiss. 9, 244 (1930).
29. O. V. Mazurin, Steklovanie (Glass Transition) (Nauka, Leningrad, 1986), p. 101.
30. S. V. Nemilov, Glass Phys. Chem. 20, 367 (1994); 21, 379 (1995); 22, 326 (1996);
31. S. V. Nemilov, Glass Phys. Chem. 20, 367 (1994); 21, 379 (1995); 22, 326 (1996);
32. S. V. Nemilov, Glass Phys. Chem. 20, 367 (1994); 21, 379 (1995); 22, 326 (1996);
33. J. Non-Cryst. Solids 196, 352 (1996);
34. Glass Phys. Chem. 25, 377 (1999).
35. S. V. Nemilov, Thermodynamics and Kinetic Aspects of the Vitreous State (CRC, Boca Raton, 1995).
36. W. Oldekop, Glastech. Ber. 30, 8 (1957).
37. G. P. Johari, J. Chem. Phys. (in press).
38. R. Roy, J. Non-Cryst. Solids 3, 33 (1970).
39. G. P. Johari, J. Chem. Educ. 51, 23 (1974).
40. G. P. Johari and J. Perez, Mol. Phys. 83, 235 (1994); the first + sign in Eq. (2) should read negative.
41. J. Perez, Physique el Mecanique des Polymeres Amorphes (Tec & Doc, Lavoisier, 1992); see also English Translation (A. A. Balkama, 1998).
42. W. Schottky, Phys. Z. 23, 448 (1922).
43. B. Petroff, A. Milchev, and I. Gutzow, J. Macromol. Sci., Phys. 35, 763 (1996).
44. T. Hikima, N. Okamoto, M. Hanaya, and M. Oguni, J. Chem. Thermodyn. 30, 509 (1998).
45. pd In T integral from the data given in Table VI disagreed with the entropy value at high temperatures given in the same table. We have used the integrated value for our calculations.
46. J. F. Counsell, E. B. Lees, and J. F. Martin, J. Chem. Soc. A, 1819 (1968).
47. E. Grantscharova and I. Gutzow, J. Non-Cryst. Solids 81, 99 (1986).
48. G. Rehage, Ber. Bunsenges. Phys. Chem. 81, 969 (1977). Studies here refer to swollen or dissolved polymers, which formed a gel in the solvent.
49. G. Salvetti, E. Tognani, E. Tombari, and G. P. Johari, Thermochim. Acta 285, 243 (1996).
50. G. P. Johari, Thermochim. Acta 266, 31 (1995).
51. K. Hofer, J. Perez, and G. P. Johari, Philos. Mag. Lett. 64, 37 (1991).
52. G. P. Johari and G. Sartor, J. Phys. Chem. 101, 8331 (1997).
53. G. P. Johari and E. Whalley, J. Chem. Phys. 70, 2094 (1979).
54. D. J. Plazek, J. H. Magill, I. Echeverria, and I.-C. Chay, J. Chem. Phys. 110, 10445 (1999).
55. G. Sartor and G. P. Johari, J. Phys. Chem. B 103, 11036 (1999).
56. E. Donth, Glasubergang (Academie-Verlag, Berlin, 1981), p. 106, Fig. 22.
57. E. Donth, J. Phys. I France 6, 1189 (1996).
58. E. Kahle, M. Schulz, and E. Donth, J. Non-Cryst. Solids 238, 234 (1998).