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VOL.

55, PAGES 497-505 (1961)

JOURNAL OF POLYMER SCIENCE

Thermodynamic Properties of Polystyrene and Styrene


R. W. WARFIELD and RiI. C. PETREE, U . S. Naval Ordnance Laboratory,
Silver Spring, Maryland

INTRODUCTION
The study of the specific heat C, and related thermodynamic functions
of a monomer and its solid polymer over a temperature range extending
down to absolute zero represents a fundamental approach toward understanding the structure and internal motion of a polymer. lcrom accurate
C, measurements on the monomer and its polymer the entropy, enthalpy,
and free energy can be calculated, as well as changes in these functions due
to glass transitions, melting, crystallization, and polymerization. Specific.
heat measurements made a t low temperatures are also useful in testing
the validity of various theoretical equations for the C, of linear polymer
chains, such as those advanced by Tarassov. More thermodynamic data
on bulk polymers are needed to establish the nature of the glassy and crystalline states and to explain the magnitude of the energy changes which
occur when polymers are heated or cooled, crystallized or melted.
Presented in this paper are calculated values of the entropy, enthalpy,
and Gibbs free energy for polystyrene and styrene. Xlm, the difference
C, - C, and the number of vibrating units per repeating unit of polystyrene are determined.

RESULTS
Specific Heats of Styrene and Polystyrene
The C, of polystyrene from (30K. to 195K. has recently betn determined by Sochava and Trapeznikova,2and Ucberreiter aiid Otto-I,aupenmuhlen3 have determined C, for polystyrene between 257K. and S9(iK
The C, of styrene has been determined by Iitzer and co-worktrs4 over the
temperature range 15K. to 300K. Thrse data are shown in lcigure 1
and in Tables I and 11. Sochava aiid Trapeznikova2 concluded that the
bulge between 60K. and 110K. in the plot of C, versus temperature
for polystyrene (Fig. 1) is due to the internal rotation of the phenyl ring
around the polymer chain axis.
Extrapolation of the C, data of Sochava aiid Trapeznikova%between
0K. and 60K. was made by means of a Tarassov function.

C,

2/dR(T/OT)
497

R. W. WARFIELD AND M. C . PETREE

498

where C, is the specific heat, R is the gas constant, T is the absolute temperature, and Or is the characteristic temperature, 160.8OK. as calculated
by Sochava and Trapeznikova.2 This function has been derived by
Tarassov' for the low temperature heat capacity of a chain structure by
TABLE I
Specific Heat, Entropy, Enthalpy, and Gibbs Free Energy of Styrene

Temp., "K.

Specific
Heat Cpa,
cal./g."

10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
I70
180
190
200
210
220
230
240
250
260
270
280
290
298.16
300

(0.002)
0.027
0.053
0.074
0 .o w
0.106
0.118
0.129
0.139
0.149
0.159
0.170
0.181
0.194
0.209
0.224
0.243
0.264
0.287
0.311
0.334
0.358
0.381
0.404
0.389
0.395
0.401
0.406
0.414
0.419
0.421

ST -

&OK,

cal./g. O

0.0022
0 .Ol60
0.0338
0,0524
0.0709
0.0886
0.1055
0.1217
0.1372
0 . I521
0.1666
0.1808
0.1947
0.2086
0.2225
0.2365
0.2508
0.2655
0.2806
0.2962
0.3121
0.3284
0.3450
0.3618
0.4814b
0.4986
0.5114
0.5259
0.54033
0.5518
0.5542

H , - HOOK.,
cal./g.
0.02
0.29
0.82
1.56
2.48
3.54
4.72
6.01
7.40
8.89
10.48
12.18
13.99
15.93
18.03
20.26
22.69
25.33
28.20
31.31
34.65
38.23
42.04
46.08
75.13"
79.08
83.09
87.15
91.29
94.71
95.50

-(FT F~K.),
cal./g.

0.002
0.030
0.194
0.536
1.07
1.78
2.67
3.73
4.95
6.32
7.85
9.52
11.32
13.27
15.36
17.58
19.95
22.46
25.11
27.93
30.89
34.02
37.31
40.75
45.22
50.04
54.99
60.10
65.40
69.81
70.76

Data of Pitzer et al.4


The entropy of fusion4is 0.104 cal./g.'
The heat of fusion4is 25.16 cal./g.

utilizing a one-dimensional function of the Debye type. The results


presented here aiid in other papers1z2indicate that the use of this function
to estimate C, a t low temperatures iiktroduces little error into entropy,
enthalpy, and free energy calculations.

TIIERMODYNAMICS OF POLYSTYRENE A N D STYREYE

499

TABLE I1
Specific Heat, Entropy, Enthalpy, and Giblrs Free Energy of Polystyrene

Temp., "K.
5
15
25
35
45
55
65
75
85
95
105
115
125
135
145
155
165
175
185
195
205
215
225
235
245
255
265
275
285
295
298.16
305
315
325
335
345
355
365
375
385
395

cal./g."

cal./g . O

(0.004)
(0.012)
(0.019)
(0.027)
(0.035)
0.058
0.081
0.090
0.095
0.100
0.106
0.113
0.122
0.131
0.140
0.150
0. 158
0.167
0.176
0.185
(0.195)"
(0.204)"
(0.214)"
(0.225)"
(0.237)"
(0.249)"
(0.261)"
(0.2i2)h
(0.285Ih
(0.297)b
( 0 .301)b
(0.310)b
(0.321)b
(0.333)b
(0.345)b
(0.357)b
(0.393)b
( 0 .423)h
(0 435)b
(0.447)b
(0.457)b

0.0092
0.0175
0.0252
0.0330
0.0408
0.0514
0.0639
0.0759
0.0871
0.0976
0.107'7
0.1175
0.12i3
0.13iO

0 1467
0.1564
0 1660
0 ,1756
0.1851
0.1946
0.2041
0.2136
0.2231
0.2327
0.2424
0.2522
0.2620
0.2719
0.2819
0.2920
0.2952
0.3022
0.3124
0.322i
0.3330
0.3434
0.3544
0.3660
0.3776
0.3892
0.4008

cal./g.
0.04
0.16
0.35
0.62
0.9i

1.55
2.36
3.26
4.21
5.21
6.27
7.40
8.62
9.93
11.33
12.83
14.41
16.08
17.84
19.69
21.64
23.68
25.82
28.07
30.44
32.93
35.54
38.26
41.11
44.08
45.04
47.18
50.39
53.72
57.17
GO. 74
64.67
68.90
73.25
7 7 .i 2
82.29

cal./g.

0.0060
0.1025
0.2800
0.5350
0.8660
1.277
1.794
2.433
3.194
4.062
5.039
6.113
7.293
8.565
9.942
11.41
12.98
14.65
16.40
18.26
20.20
22.24
24.38
26.61
28.05
31.38
33.89
36.51
39.23
42.06
42.08
44.99
48.02
51.16
54.39
57.73
61.14
64.69
68.35
72.12
16.03

Interpolated between the data of Sochava and Trapexnikova* (55-195K.) and that
of Ueberreiter and Otto-Laupenmuhlen3 (275-395K.).
bValues of specific heat in parentheses are those obtained by extrapolation (5-45'K 1
or by interpolation (275-395K.).

500

R. W. WARFIELD AND M. C. PETKEE

it! 020-

rJrJrJ7---,--u

:ir

60

120

,
/
A
_

160 200 210 280 320 360 400


TEMPERATURE PK)

Fig. 1. Specific heats C , of st.rrrene and polystyrene.

Entropy, Enthalpy, and Gibbs Free Energy


The values of the entropy, enthalpy, and Gihbs free energy of styrene
and polystyrene have been calculated from C, data by numerical integration, and are presented in Tables I and l I and in Figures 2, 3, and 4. The
values were obtained by evaluating the thermodynamic relations

320

TEMPERATURE

(OK)

Fig. 2. Entropy of styrene and polystyrene.

360

400

TkIERMODYNAMICS OF POLYSTYRtiNE AND STYIZLSNE

501

TEMPERATURE P'K)

Fig. 3. I*hthalpyof styrene and polystyrene.

80

160

240

TE M PE R ATU R E,

320

400

(OK1

Fig. 4. Free rnergy of styrene and pol\.styrene.

\\-here (Sr - & O K ) , ( H , - Hook;), and (F, - F o o I i ) are the entropy, ciithulpy, and Gibbs frre energy, rehpwtively, relative to the absolute zero of
t tmpernture.
Atactic polystyrene exhibits little teiideiicy to crystallize and would be

502

li. W. WARFIELD AND M. C. PETREE

expected to have a residual entropy a t O O K . A contribution of great


importance would be the determination of the C, of isotactic polystyrene of
known crystallinity. Such data might be analyzed to yield information
indicative of the absolute entropy of polystyrene.
The entropy of polystyrene a t 298.16"K. was found to be 30.70 cal./
mole' and that of styrene 57.39 cal./moleo. The entropy of polymerization was found by difference to be 26.69 cal./mole". These values are in
agreement with the corresponding values given by Dainton and Ivin,j
namely, 32.23, 57.16, and 24.93 cal./mole". Burnett6 gives the entropy of
polymerization as 27.9 cal./moleo.
The enthalpy of styrene a t 298.16OK. was found to be 94.71 cal./g.
(9850 cal./mole) and that of polystyrene 45.04 cal./g. (4684 cal./mole)
At the same temperature the Gibbs free energy of styrene and of polystyrene were -7260 cal./mole and -4470 cal./mole, respectively.
The molecular weight of the polystyrene used by Sochava and Trapeznikova2 is not known, while that used by Ueberreiter and Otto-Laupenmuhlen3 is given as 3650. However, Ueberreiter and Otto-Laupenmuhlen have noted that below the glass transition temperature, the C, is
almost independent of the molecular weight and is a result of transverse
vibrations. An increase in the specific heat of polystyrene occurs a t the
glass transition range a t about 355K.

The Function C,/T vs. 'I! for Polystyrene


Smith and Dole7 have pointed out that the function C,/T versus T ,
where T is absolute temperature, is a constant if the specific heat rises
linearly with T from a zero value a t absolute zero. The function C,/T
measures the rate a t which the entropy increases with temperature.

(dS/dT), = C,/T

(5)

Dole and Wunderlich8 have presented data on the function C,/T versus
temperature for a number of polymers and long-chain hydrocarbons over
various temperature ranges. The C,/T values for the hydrocarbons pass
through a maximum a t 60-70K., which according to Dole and Wunderlich, is to be expected theoretically if one or more modes of vibration having
the same frequency dominate in this temperature range. They further
suggest that the plots of C,/T versus temperature for polyethylene, polyethylene sebacate, and the polyamide 66 nylon should also exhibit maxima a t low temperatures. However, the lack of accurate low-temperature
C, data on these polymers prevented calculation of C,/T functions for
them.
The plot of C,/T versus temperature for polystyrene is shown in Figure
5. The C,/T values are presented on the basis of moles of repeating units.
Doleg has shown that this function is a sensitive indicator of the glass
transition temperature T , of polymers. This transition is shown clearly
in Figure 5 to occur over the range 350-365"k'.

TIIERMODYNAMICS O F POLYSTYRENE AND STYRENE

'k

50- 100

503

EO

-2.00 250 300 350 400


TEMPERATURE P K )

Fig. 5 . Specific heat function C,/T for polystyrene and polyethylene.

Also shown in Figure 5 is a plot of C,/T versus temperature for conventional polyethylene, taken from the C, data of Sochavalo for the range
17-60K., from Sochava and Trapeznikova" for the range 58-270K.,
from Dole and co-workers12 for the range 273-393K. A very slight increase is observed a t about 70K., as predicted by Dole and Wunderlich,g
and a large maximum is observed a t the melting point (380K.). The great
difference in the magnitudes of the function C,/T for polystyrene and polyethylene is due to the large difference in the molecular weights of the repeating units.
If the linear Tarassov function employed to estimate the specific heat is
correct, then the plot of C,/T versus T for polystyrene shown in Figure 5
should have zero slope. However, it will be observed that a maximum
occurs a t about 65'K. This suggests that to account for the interactions
between chains, a T 3term should be added to the Tarassov function at low
temperatures. Temperley13 has also concluded that the one-dimensional
specific heat theory must be combined with a three-dimensional Debye
spectrum proportional to T 3a t low temperatures. Tarassov' has recently
come to a similar conclusion and has proposed a two-parameter specific
heat equation which corresponds to the mathematical treatment of Stockmayer and Hecht. l4

Vibrating Units per Repeating Unit of Polystyrene


On the basis of a number of assumptions similar to those made by
who calculated the heat capacity per vibrating unit of polyethylene, it is
possible to estimate the number of classically vibrating units a t 273K. in
the polystyrene repeating unit -CH(C,H,) CH2-.
Three assumptions
are employed. The first is that the force constant of the C-H bond is so
great that the -CH2group will vibrate as a single unit; the second is
that every group in the chain can vibrate harmonically with two degrees of
freedom along mutually perpendicular axes transverse to the chain direction; and the third, that longitudinal or stretching vibrations are negligible a t 273K. If each vibrating unit vibrates with two degrees of free-

504

R. W. WARFIELD AND M. C. PETREE

dom, the expected specific heat would be 2R or 3.97 cal./moleo per vibrating unit. However, these considerations apply to C,,, not to C,.
C, can be calculated by means of the equation

where C, is the observed specific heat of polystyrene a t 273OI<., 28.1


cal./moleo; I'is the velocity of sound, 4'395 m./sec.15 d is the coefficient of
volume expansion, 2.33 X
per deg ;I6 and J is the mechanical equivalent of heat, 4.184 X lo7 ergs/cal.
is found to be 26.1 cal./moleo,
and C, - C, is thus 2.0 cal./moleo.
The number of vibrating units per repeating unit is found by dividing
C, by 2R, or 26.1 cal./moleo by 3.97 cal./moleo, which equals 6.57. This
implies that the pendent phenyl group is equivalent to four classically
vibrating units.

CONCLUSION
Styrene and polystyrene arc the only monomer-polymer pair for which
the C, data necessary for calculating the thermodynamic. functions are
available. Data on other systems would be of great utility for studying
the nature of the crystalline and amorphous btates, calculating kinetic
parameters for the polymerization process, studying the effects of various
degrees of crosslinking on the thcrmodj namir fun(~tions,
and investigating
the various theoretical equations for the specific heat of polymers. If data
were available on both the crystalline and amorphous forms of a polymer
the residual entropy might be determined.
The authors would like to express their appreciation to Dr. George T. Furukama of
the National Bureau of Standards for his helpful romnierits and to Mr. G. D. Blum for
checking the calculations.

References
1. Tarassov, V. V., Doklady Akad. .Yaiik S.S.S.IZ., 100, 307 (1955); J . Am. Chem.
SOC.,
80,5052 (1958).
2. Sochava, I. V., and 0. I). Trapeznikova, Vestnik Leningrad Univ., Ser. Piz. i
Khim., 13,No. 3,65 (1958);Cheni. Abslr., 53,4681(1959).
3. Ueberreiter, K., and E. Otto-Lauperimiihlen, 2. Naturforsch., 8a, 664 (1953).
4. Pitzer, K. S., L. Guttman, and E. F. Westrum, J . Am. Chenz. SOC.,68, 2209

(1946).
5. Ilainton, F. S., and K. J. Ivin, Qitart. Rev::., 12,76 (1958).
6. Burnett., G. M., Mechanism of P d y ~ i wIr'eactions, Interscience, New York, 1954,
p. 385.
7. Smith, C. W., and M. Dole, J . Polynier. Sci.,20, 37 (1956).
8. Dole, M., and B. Wunderlirh, .2falironrol. Cheni., 34,29 (1959).
9. Dole, M., Kolloid-Z., 165, 40 (1959).
10. Sochava, I. V., Doklady .-lkad. iVaiilc S.S.S.R., 130, 126 (19GO).
11. Sochava, I. V., and 0. 1.Trapeznikova, Dokladq Akad. Nauk S.S.S.R.. 113,
784 (1957).

THERMODYNAMICS OF POLYSTYRENE AND SI'YRENE

505

12. Dole, M., W. P. Hettinger, N. R. Larson, arid J. .4.\Vethingtori, J . C'hent. Phus.,


20,781 (1952).
13 Temperley, H. N. V., J . Research Natl. Bur. Standards, 56,55 (19%).
14. Stockmayer, W. H., and C. E. Hecht, J . Chetn. Phys., 21, 1954 (1953).
15. Krisnamurthi, M., and G. Sivarama-Sastry, Nature, 174,132 (1954).
16. Boyer, R. F., and R. S. Spencer, Advances in Colloid Science, Interscienre, Ken.
York, 1946, p. 125.

Synopsis
A Tarassov function has been used to estimate the specific heat of polystyrene between
0" and 60K. These data, together with published C, data, have been used to calculate
the entropy, enthalpy, and free energy of styrene and polystyrene from 0" to 298.16"K.
The entropy of polymerization of styrcne a t 298.16"K. was found to be26.69 cal./mole".
The thermodynamic function C,/T versus T as calculated for polystyrene, increases to a
maximum a t 65K. and then increases again a t the glass transition temperature. The
Tarassov function, which is shown to be useful in estimating the specific heat of amorphous polymers, should be combined with a T3 Debye function to yield more accurate
c, data a t low temperatures. The number of classically vibrating units per repeating
unit of polystyrene was found to be 6.57. The difference C, - C, i ~ a scalculated a t
273K. and found to be 2.0 cal./niole".

R6sum6
Une fonction de Tarassov a 6th utilisQepour estimer la chaleur spdcifique du polystyrbne entre zero a t 60K. Ces valeurs, en mBme temps que les valeurs de C, publiBee,
utilisees pour calculer les entropies, enthalpie et Qnergie libre du styrene et du
ont QtQ
polystyrbne de 0K. B 298.16"K. L'entropie de polym6risation du styrbne B 298.16"K.
est QgaleB 26.69 cal/deg.-mole. La fonction thermodynamique C,/T vs T , telle qu'elle
est calculee pour le polystyrhe, augmente jusqu'h un maximum B 65"K, puis
augmente de nouveau B la tempdrature de transition vitreuse. La fonction de Tarassov,
qu'on a montrd Btre utile pour estimer la chaleur spQcifique de polymhes amorphes
devrait Btre combinbe avec une fonction en T3 de Debye pour donner des valeurs plus
prhcises de C, aux basses tempQratures. Le nombre d'unitds vibrant classiquement par
uniti: de la chaine de polystryitne est de 6.57. C, - C, est calculi: B 273K. et est Bgal B
2.0 cal/deg.-mole.

Zusammenfassung
Zur Bestimmung der spezifischen Warme von Polystyrol zwischen 0" und 60K. wurde
eine Tarassovfunktion verwendet. Die Daten u-urden zusammen mit veroffentlichten
C,-Kerten zur Bcrechnung der Entropie, Enthalpie und freien Energie von Styrol und
Polystyrol im Bereich von 0" bis 298,16"K. verwendet. Die Polymerisationsentropie von
Styrol bei 298,16"K. wurde zu 26,69 cal/Grad.Mol bestimmt. Die fur Polystyrol
berechnete thermodynamische Funktion C,/T steigt als Funktion von T zu einem
Maximum bei 65K. und zeigt dann einen zweiten Anstieg bei der Glasumwandlungstemperatur. Es nird gezeigt, dass es gunstig ist, die fur die Berechnung der spezifischen
Warme amorpher Polymerer brauohbare Tarassovfunktion mit einer T3-Debyefunktion
zu kombinieren, um genauere C,-Werte fiir tiefe Temperaturen zu erhalten. Die Zahl
der klassischen Oszillatoren pro Grundeinheit wurde fur Polystyrol zu 6,57 bestimmt.
C, - C, wird fur 273C. berechnet und zu 2,O ral/Grad-Mol gefunden.

Received January 17,1961


Revised March 13, 1961