A UNIVERSAL REDUCED GLASS TRANSITION

TEMPERATURE FOR LIQUIDS*

Although one generally identifies the glass transition temperature T, with
polymeric materials, it is less well known that low-molecular-weight liquids,
i.e., water, toluene, anisole, etc., also exhibit a glass transition temperature
under certain conditions.
In recent years, considerable data for the dependence of the glass transi-
tion temperature on the molecular structure for low-molecular-weight liquids
has been published. For example, a cursory search of the literature has yield-
ed T, data for some 64 such liquids and other data undoubtedly exists as well
(1,2). With these data, it was of interest to determine whether the reduced
glass transition temperature of Boyer (3) is a universal constant as proposed.
Boyer (3) observed that a reduced glass transition temperature, defined by

Tg* = T,/T, (1)

where T, is the melting point, was independent of the chemical structure of

the molecule. Subsequently, he showed that symmetric molecules were char-
acterized by Tg* = 1/2 while for unsymmetric molecules Tg* = 2/3. However,
late work by Lee and Knight (4) has shown that for 138 polymers, T,* was
not constant but varied rather widely.
The purpose of this article is to point out that a characteristic temperature
ratio rT, defined by

where T, is the melting point and Tb is the boiling point and both measured
at atmospheric pressure, is a universal constant independent of the molecular
structure of liquid. The average value of rT obtained using data for some 65
liquids is 1.15.
Of the parameters appearing in the expression, both the melting point T,
and the glass transition temperature T, can generally be obtained experimen-
tally irrespective of the molecular weight of the liquid. However, this is not
true for the remaining parameter, the boiling point, which at the present time
can only be obtained directly for liquids of low molecular weight. Although
methods exist for the estimation of Tb for liquids using various schemes such
as those based on additive atomic and group contributions (5), such is not the

*This article represents the results of one phase of research carried out at
the Jet Propulsion Laboratory, California Institute of Technology, under Con-
tract No. NAS 7-100 sponsored by the National Aeronautics and Space Ad-
ministration.

Journal of Polymer Science: Polymer Letters Edition, Vol. 17, 719-722 (1979)
0 1979 John Wiley & Sons, Inc. 0360-6384/79/0017-0719$01.00
720 POLYMER LETTERS EDITION

TABLE I
Selected Properties of Various Liquids

Hydrocarbons

Liquid Tm
- -
Tb
T9 O K Tm OK T b 'K
T' 9 T9 Ref.

1. ?-methyl propane 79.5 119.5 333.4 1.10 1.50 4.20 1

2. 2-niethylbutane 68.2-69 113.3 306 1.12 1.64 4.43 1
3. 2-methylhexane 88 153.6 365 1.15 1.75 4.15 1
4. 2-methyl-2-butene 73 149 311.4 1.20 2.04 4.27 1
5. methyl cyclonexane 85-87 146.6 373.3 1.13 1.71 4.34 1
6. ethyl cyclohexafle 98 141.3 404.9 1.09 1.44 4.13 1
7. isopropyl cyclohexane I08 183.3 427.6 1.14 1.70 3.96 1
8. butyl cyclohexane 119 198.4 454 1.14 1.69 3.82 1
9. 4-methyl cyclohexene 94 157.6 375.7 1.14 1.68 4.00 1
10. benzene 131 278.5 353.3 1.30 2.13 2.70 1
11. toluene 115-117 178 383 1.13 1.53 3.30 1
12. ethylbenzene 111-115.7 179.1 409.2 1.13 1.57 3.53 ;
13. propylibenzene 125.5-127.5 173.6 432.3 1.09 1.38 3.43 1
14. butylbenzene 125-129.6 191.8 456.3 1.11 1.50 3.58 1
15. tert-butylbenrene 140-142 214.9 442.1 1.13 1.52 3.14 1
16. pentylbenzene 135-1 37 198.1 478.5 1.11 1.46 3.52 1
17. hexyl benzene 140.4 206.2 500 1.11 1.46 3.56 1
18. pent-1-ene 80.9 135 303 1.14 1.67 3.75 1
19. pent-2-ene 80 134 304 1.14 1.68 3.86 2
20. hex-1-ene 83 175 336.5 1.22 2.11 4.05 2
21. hept-1-ene 91 163 366.6 1.16 1.79 4.03 2

Alcohols

-
Tnl -
Tb
Liquid T9 O K Tm 'K Tb 'K T
PT T9 Ref.

22. Methanol 102.6-110 175.2 337.6 1 .16 1.65 3.19 1

23. Ethanol 97.2-100 155.7 351.5 1.14 1.58 3.57 1
24. propanol 98-109 146.6 370.1 1.09 1.42 3.58 1
25. isopropanol 125 184 355.3 1.12 1.47 2.84 2
26. butanol 111-118 183.6 390.3 1.14 1.60 3.39 1
27. isobutanol 116 184 373 1.14 1.59 3.22 2
28. pentanol 120 194.7 411.2 1.14 1.62 3.42 2
29. isopentanol 125 223 372.4 1.20 1.78 2.97 2
30. hexanol 125 221.4 430.2 1.17 1.77 3.44 2
31. heptdnol 123 238.4 449 1.20 1.94 3.65 2
32. phenol 198-206 314 455 1.17 1.55 2.25 1
33. benzyl alcohol 171-171.9 257.7 478.2 1.13 1.50 2.79 1
34. cyclohexanol 161 297 434.5 1.22 1.85 2.70 1
35. e t h y l e n e glycol 154.2-155 255.6 470.2 1.14 1.66 3.03 1
36. glycerin 189.5-190.9 291.2 563 1.13 1.53 2.96 1
37. water 136-139 273 373 1.27 1.98 2.72 1

case for the high-molecular-weightpolymers. At the present time and until

such methods are developed for polymers, rT is restricted to application to
low-molecular-weightliquids.
The single exception to this situation is polyethylene. Using boiling point
data for the low-molecular-weightalkanes, Van Nes and Van Westen (6) have
POLYMER LETTERS EDITION 721

TABLE I (continued from previous page)

Halides

-m 'b
Liquid Tg 'K Tm OK Tb O K
k:
T
9 5 Ref.

38. bury1 c h l o r i d e 93 141.7 341 1.11 1.52 3.67 2

39. isobutyl chloride 88 141.7 341 .3 1 .13 1 .61 3.88 2
40. buty bromide 92 160.6 374.6 1.15 1.75 4.07 2
41. i s o b u t y l bromide i00 161 364.5 1.13 1.61 3.85 2
42. butyl iodide 105 169.5 404 1.13 1.61 3.85 2
43. i s o p e n t y l bromide 135 161.1 393 i ,11 1.53 3.74 2
44. hexyl c h l o n d e 110 190 405.4 1 .15 1.73 3.69 2
45. hexyl bromide 115 188 429 1.13 1.64 3.73 2
46. chiorobenzene 126-128 228 405 1.19 1.80 3.19 1
47. bromobenzene 135-138 242.4 428 1.19 1.78 3.14 1
48. stannic chloride 130 240 387.1 1.21 1.85 2.98 i
49. methylene c h l o r i d e 99-103.1 176.3 313.1 1.18 1.75 3.10 1
50. chloroform 105.9-114 209.5 334 1.22 1.90 3.04 1
51. carbon t e t r a c h l o r i d e 129-130.6 250.2 349.8 1.25 1.94 2.70 1

Miscellaneous

'm
- -
Liquid T9 'K Tm 'K Tb OK P T T Ref.

52. acetaldehyde 82 149.5 294 1.18 1.82 3.59 1

53. acetonitrile 93 232 355 1.28 2.50 3.82 1
54. ether 87-92.5 156.7 307.6 1.17 1.74 3.42 I
55. acetone 93-100 178 329.5 1.19 1.85 3.38 1
56. dimethylformamide 129 21 2 426 1.15 1.64 3.30 1
57. dimethylacetamide 150 291.6 462.1 1.23 1.94 3.08 1
58. dimethyesulfone 190 383 51 1 1.28 2.02 2.69 1
59. pyridine 11 6-1 28 231.3 388.7 1.21 1.90 3.19 1
60. anisole 122 235.7 428 1.21 1.93 3.51 1
61. benzaldehyde 146.5-1 49 247 452.5 1.17 1.67 3.08 1
62. aniline 188.9-192 266.8 457.4 1.12 1.40 2.39 i
63. nitrobenzene 161 244.6 374.3 1.16 1.52 2.33 1
64. butronitrile iio i77 414 1.13 1.61 3.76 2
65. diethylmaionate 153 223.2 472 1.11 1.46 3.09 2

Polymer

66. polyethylene 183-1937 409.5~ 10866 ;.17 2.18 5.78

been able to estimate the limiting boiling point of the alkane of infinite mo-
lecular weight. Using their result, Tb = 1086 K for polyethylene. It may be
mentioned that the same estimation procedure yielded for an alkane of infi-
nite molecular weight a limiting melting point of 41 1 K which compares very
favorably with the melting point of 409.5 K obtained experimentally for poly-
ethylene (7). This close correspondence lends confidence to the value of Tb
estimated for polyethylene.
Table I lists such data for liquids as has been collected. For each liquid,
there is listed the T,, as well as values of T, and Tb. As can be seen the
722 POLYMER LETTERS EDITION

values of rT are very close to the average value of 1.15 . Column 6 lists the
reciprocal of the Boyer characteristic temperature and, as may be seen, these
values vary widely. Were the Boyer suppositions correct, the values in this
column should be either 1.5 if the molecule is asymmetric or 2.0 if the mole-
cule is unsymmetric. Values of the ratio of Tb/T, vary widely depending on
the chemical nature of the molecule. The final entry in Table I is for poly-
ethylene where the rT value for this polymer is the same as that for low-mo-
lecular-weight liquids.
It is of interest to note that eq. (2) can be used to estimate the T, of a
liquid of interest provided both T, and Tb are known or are estimatable.

References

(1) C. A. Angell, J. M. Sare, and E. J. Sare, J. Phys. Chem., 82, 2622

(1978).
(2) M. R. Carpenter, D. B. Davies, and A. J. Matheson, J. Chem. Phys., 46,
2451 (1967).
(3) R. F. Boyer, 2nd Int. Conf. Phys. Chem. Paris, June 6, 1952; J. Appl.
Phys., 25, 825 (1954).
(4) W. A. Lee and G. J. Knight, Br. Polym. J., 2, 73 (1970).
(5) R. H. Perry, C. H. Chilton, and S . D. Kirkpatrick, Eds., “Chemical En-
gineers Handbook,” McGraw-Hill, New York, 1963.
(6) K. Van Nes and H. A. Van Western, “Aspects of the Constitution of
Mineral Oils,” Elsevier, New York, 1951, p. 96.
(7) J. Brandrup and E. H. Immergut, Eds., “Polymer Handbook,” Intersci-
ence, New York, 1975.

R. F. Fedors

Jet Propulsion Laboratory

California Institute of Technology
Pasadena, California 9 1 103

Received May 29, 1979