Journal of Macromolecular Science, Part B

Physics

ISSN: 0022-2348 (Print) 1525-609X (Online) Journal homepage: http://www.tandfonline.com/loi/lmsb20

Heat capacities of solid polymers

B. Wunderlich & L. D. Jones

To cite this article: B. Wunderlich & L. D. Jones (1969) Heat capacities of solid polymers, Journal
of Macromolecular Science, Part B, 3:1, 67-79, DOI: 10.1080/00222346908217089

To link to this article: http://dx.doi.org/10.1080/00222346908217089

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 J. MACROMOL. SC1.-PHYS., B3(1), 67-79 (March, 1969)

Heat Capacities of Solid Polymers

B. WUNDERLICH and L. D. JONES
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Department of Chemistry
Rensselaer Polytechnic Institute
Troy, New York

Summary

The heat capacity of a solid polymer i s governed by the manner

in which the internal energy i s distributed over the various degrees
of freedom. If the internal energy manifests itself in harmonic os-
cillatory motions, the heat capacity is the sum of contributions of the
normal modes of motion. In practice, full frequency data a r e not
generally available f o r polymers. This paper proposes an empirical
method for determining the heat capacities of linear high polymers
by the addition of contributions from different chain segments. A
survey of heat capacity data for 30 linear high polymers and several
copolymer systems has revealed that additivity i s usually valid for
a temperature range from about 60°K to the glass-transition temper-
ature. A table of heat capacity contributions of a number of polymer
constituents is derived which permits the calculation of unknown heat
capacities to an accuracy of *5% o r better. In addition, ACp data for
the increase of the heat capacity a t the glass-transition temperature
were found to agree with the rule of constant heat capacity increase
per mole of 'bead" proposed 8 y e a r s ago.

INTRODUCTION

Recently an extensive review of heat capacities of linear high

polymers has been prepared [l]. The present paper describes some
new insights gained during the preparation of this review. In par-
ticular, correlations between frequency spectra and heat capacities
of solid polymers will be discussed and an empirical scheme for the
estimation of heat capacities will be proposed.

67
 68 B. WUNDERLICH AND L. D. JONES

THEORETICAL CALCULATION O F POLYMER HEAT CAPACITIES

Motion in the solid state consists mainly of vibrations of atoms

around their respective equilibrium positions. T h e s e vibrations a r e
usually assumed t o be harmonic oscillations. T h e harmonic approx-
imation allows the description of the s t a t e of motion in t e r m s of
normal modes. T h e molar heat capacity is simply the sum of the
contribution of all normal modes:

Cv = R E(O/T) (1)

E(B/T) r e p r e s e n t s the Einstein function which is the contribution of

a single vibration t o the heat capacity:
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E(O/T) = e z [ e x p ( e / ~ ) ] / [ l - exp(8/T)I2 (2)

0 r e p r e s e n t s the Einstein temperature and is defined by

0 = hw/k (3)

R , k, and h have the usual meaning, w is the frequency, and T is the

temperature. If the normal modes of vibration are known, it is a
simple m a t t e r t o evaluate the heat capacity with the help of Eq. (1).
T h e chemical s t r u c t u r e of a linear high polymer allows the sepa-
ration of the normal modes of vibration into two categories. T h e
f i r s t category is the group vibrations, and the second category the
skeletal vibrations. T h e skeletal vibrations can be looked upon as
vibrations of a chain of beads with the appropriate m a s s e s . T h e
group vibrations consist then of the normal modes of the detailed
s t r u c t u r e of the beads. T h e i r contribution t o heat capacity is given
by the sum o v e r the Einstein t e r m s for each normal mode [Eq. (2)]
multiplied by the number of beads. Much information on the group
vibration can be gained from the infrared absorption s p e c t r a and
from the study of low molecular weight model compounds. A series
of approximations h a s been proposed f o r the skeletal vibrations. A
f i r s t approximation is t o find the vibrational spectrum of the isolated
chain. F o r long wavelengths o r low frequencies it is possible t o ne-
glect the atomic s t r u c t u r e of the chain and u s e a continuum approxi-
mation which leads t o a constant frequency distribution. T h e s a m e
number of normal modes e x i s t s for every frequency chosen. T h e
maximum frequency w1 is in t h i s case chosen so that the total num-
b e r of normal modes corresponds t o the possible d e g r e e s of free-
dom. Instead of the sum of Eq. ( l ) ,one can write the integral:
 HEAT CAPACITIES O F SOLID POLYMERS 69

T h e t e r m in brackets is the one-dimensional Debye function and will

be abbreviated by the symbol D,:

Cv = 3RD,(fl,/T) (5)

T h e one-dimensional Debye function h a s been tabulated [2]. T h i s

approximation should work best for the heat capacity of isolated
chains at low temperatures and yields a linear temperature depen-
dence of the heat capacity up t o about T/B, = 0.1. As the wavelengths
of the vibrations become smaller and reach the o r d e r of magnitude
of the distance between atoms, the continuum approximation breaks
down. Calculation of the exact frequency spectrum of a string of
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beads, however, is not difficult. It leads to normal frequencies rep-

resented by

v= f v, sin(nL/N) L = 1, 2 , . ..,N (6)

Here v, is the maximum frequency and L represents a quantum num-

b e r running from 1 t o N, where N is the number of beads in the
chain, Knowing the proportionality between v and L , it is a simple
task to derive the frequency distribution:

At low frequencies Eq. (7) is nearly constant as expected; at high fre-

quencies the value of p(v) increases steeply i n contrast to the Debye
approximation.
Although the forces between chains within a crystal are relatively
weak, there is coupling between the vibrations of the different chains
for low frequencies. T h i s coupling has first been calculated on a
simplified polymer crystal structure by Stockmayer and Hecht [3].
More detailed calculations were given later by Genensky and Newel1
[ 4 ] . T h e introduction of force constants between chains for nearest
and next-nearest neighbors introduces three-dimensional coupling,
and as a result the heat capacity at the very low temperatures shows
a T 3 temperature dependence. The low-frequency results of the one-
dimensional Debye model are thus in e r r o r because of the coupling
between different chains. T h e high-frequency results, however, are
also in e r r o r because of the atomic nature of the chains. The one-
dimensional Debye function can produce a fit only in the middle fre-
quency (or temperature) region.
Tarasov h a s proposed t o describe the skeletal contribution to the
heat capacities of linear high polymers in a second approximation as
a sum of two contributions: one from the intermolecular vibrations,
 70 B. WUNDERLICH AND L. D. JONES

described by a three-dimensional Debye function D,; and the other

from the intramolecular vibrations, described by a one-dimensional
Debye function D, [5] :

The high- and low-temperature regions of the heat capacity are t o

be fitted separately t o one- and three-dimensional Debye functions.
Since the constant frequency distribution of the intramolecular vibra-
tions would be of use only a t the lower frequencies where it is re-
placed by the three-dimensional frequency distribution, the Tarasov
approximation must be looked upon as an empirical equation where
all frequencies beyond the intermolecular vibrations are averaged
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in t e r m s of a box frequency distribution. Because heat capacities

a r e relatively insensitive t o higher frequencies, the T a r a s o v approx-
imation has been used successfully for a number of polymers [ l ] .
Table 1 shows a collection of data f o r 9, and 0 , evaluated by the u s e
of Eq. (8).

TABLE 1
0, and O a for Skeletal Vibrations of Various Po l y m er sa

Polymeric selenium 370 97

Polyethylene 540 1.00 1.00 147
Polystyrene 230 0.50 0.43 41
Polypropylene 480 0.82 0.89 -
Polybutad i ene 580 -
Polyisoprene 580
Polytetrafluoro-
ethylene 270 0.53 0.50 46
Poly (vinylidene
chloride) 260 0.54 0.48 -
Poly (vinyl chloride) 350 0.67 0.65 175

'A = s q u ar e root of the r a t io of m a s s p e r backbone carbon to m a s s of CH,.

B = Ratio of 0, of the polymer in question to 0, of polyethylene.

T h e 8-values in Table 1 except f o r selenium are calculated for

two normal vibrations p e r chain atom, since the third is related t o
the C-C stretching vibrations and was shown f o r polyethylene [6] t o
consist of a narrow distribution which can be treated better with the
group vibrations.
 HEAT CAPACITIES O F SOLID POLYMERS 71

Vibrational frequencies are proportional to the square root of the

force constant and inversely proportional to the square root of the
m a s s . Comparing on this b a s i s 0-temperatures of polyethylene with
other polymers of identical backbone chain shows that the temper-
ature ratios are close to the ratio of the square root of m a s s e s , while
the 8, ratios are not. As a result one must conclude that,forexample,
the intermolecular forces which govern the value of 8, are much
stronger in polyethylene than in polytetrafluoroethylene. The 0,
values in turn are, as long as the carbon-carbon backbone is similar
in different polymers, largely determined by the m a s s per chain
atom. In t h i s dependence of 8, of carbon-carbon backbone polymers
on m a s s lies the justification of the addition scheme of heat capaci-
t i e s to be proposed below. 8, governs the skeletal heat capacity only
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at the lowest temperatures, while 8, determines the skeletal heat

capacity at higher temperatures. The group vibrations which make
up the rest of the heat capacity are additive by their very nature.
Strictly, this discussion applies only t o the heat capacity a t constant
volume. However, only at temperatures above room temperature
does the contribution of Cp - Cv become significant.

APPROXIMATION O F POLYMER HEAT CAPACITIES

F o r most polymers adetailed frequency spectrum [7-91 is not avail-

able. From the discussion of all data available to date [ l ] ,it be-
came clear that differences in conformation, crystallinity, and inter-
molecular forces of carbon backbone linear high polymers are only
of little importance above about 60%. They become important again
at the glass-transition temperature and above because of different
motion in amorphous and semicrystalline polymers [ l o ] . This leaves
a relatively large temperature range between 60°K and the glass-
transition temperature where the differences in heat capacity be-
tween polymers are largely determined by the differences in m a s s
p e r carbon-backbone atom and the difference in group vibrations, a
conclusion supported by the 8,-values of Table 1. Based on these
findings, it is proposed that heat capacities in this temperature
region can be derived by adding characteristic contributions arising
from the different chemical groups in the polymer molecule.
Table 2 lists an addition scheme for 30 polymers, t o be analyzed
in the next sections of t h i s paper. The polymers, their abbreviations,
and the addition schemes are listed. I stands f o r a CH, group in the
polymer backbone, 11 for a CH, group in the side chain, and I11 for a
CH, group which is part of a methyl group.
 72 B. WUNDERLICH AND L. D. JONES

TABLE 2
Addition Scheme f o r Heat Capacities
~

Polymer Abbreviation Addition s c h e m e

1. Polyethylene PE I
2. Polypropylene PP 21 + I11
3. Poly- 1-butene PB 21 + I1 + 111
4. Poly (4-methyl-1-pentene) PM P 21 + 211 + 2111
5. Polyisobutylene PIB 21 + 2111
6. Polystyrene PS 21 + CgHka
7. Polybutadiene PBD 21 + C2H2
8. Polyisoprene PIP 21 + 111 + CzH2
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9. Polyoxymethylene POM 1'0,

10. Penton P 31 + 0, + 2CH2CHCl
11. Poly (methyl methacrylate) PMMA 21 + 2111 + coo
12. Poly (methyl acrylate) PMA 21 + I11 + coo
13. Poly (methacrylic acid) PMAA 21 + I11 + coo
14. Polytetrafluoroethylene PTFE CF2
15. Nylon 6 N6 51 + CONH
16. Nylon 7 N7 61 + CONH
17. Propene polysulfone PPS 21 + I11 + s o 2
18. 1-Butene polysulfone BPS 21 + I1 + 111 + s o 2
19. 1-Hexene polysulfone HPS 21 + 311 + 111 + S O 2
20. Polvcarbonate PC I + 2111 + 2CgHab + Oa + COO
21. Poly (vinyl alcohol) PVA 21 + 0,
22. Polytrifluoroethylene PTrFE CF, + CHF
23. Poly (vinylidene chloride) PVCl I + CCI,
24. Polytetrahydrofuran PTHF 41 + Oa
25. Poly (vinyl chloride) PVC I + CHCl
26. Poly(2,6-dimethyl-1.4-
phenylene ether) PPO
27. Polyoxy ethylene POE
28. Polyoxypropylene POP
29. Deuteriopolyethylene DPE
30. Selenium SE

HEAT CAPACITY CONTRIBUTIONS

From the experimental data heat capacity contributions for the

different polymer segments were derived as follows: The heat capa-
city of completely crystalline polyethylene was taken as the contri-
bution of I. The contribution II has been calculated from the appro-
priate polymer combinations (see Table 2) of P B and PP, PMP and
PIB, and HPS and PPS. The internal error of 53 data points calcu-
 HEAT CAPACITIES O F SOLID POLYMERS 73

lated as RMS e r r o r of a single point was k0.12 cal deg-' mole-'. The
contribution III has been calculated combining data on the following
polymers and I and 11: PIP and PBD; PP and I; P B, I, and II; PMP,
I, and II. In t his case 60 data points had an e r r o r of *0.10 cal deg-l
mole-'. An increased e r r o r f or data from PZB can be t r a c e d t o the
change of excitation of the hindered rotation and vibration on changing
the st er i c hindrance of the methyl group [ l ] . For other entries a l l
possible combinations in Table 2 have been averaged. The estimated
e r r o r vari es mainly because of the quality of available heat capacity
data which is usually, despite the claim of authors, not much better
than *1 t o 38.If differences of large repeating units are necessary
t o evaluate small group heat capacity contributions, the e r r o r is ex-
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pected t o be gr eater accordingly. I t is estimated that most of the

heat capacity contributions calculated are good t o 5% of their abso-
lute value o r better. The r es ults of calculations were averaged where
possible and smoothed internally to within a sc a t t e r of 1%o r less.
Tables 3 and 4 display the results.

TABLE 3
Heat C a p a c i t y C o n t r i b u t i o n s
(in cal deg-' mole-')

T, 'K I I1 I11 CD2 CHF CF2 CHCI CCl, 0,

50 1.1 1.2 1.2 - 1.8 2.5 2.5 3.0 0.8

60 1.4 1.5 1.3 - 1.9 2.9 2.9 3.8 1.3
70 1.7 1.8 1.4 - 2.3 3.4 3.3 4.5 1.8
80 1.9 2.0 1.7 2.4 2.5 3.8 3.6 5.3 2.2
90 2.1 2.3 1.9 2.6 2.7 4.3 3.8 5.9 2.5
100 2.3 2.5 2.0 2.8 2.9 4.7 4.1 6.5 2.7
110 2.5 2.7 2.2 3.0 3.2 5.1 4.3 6.9 2.9
120 2.6 2.9 2.4 3.2 3.3 5.5 4.5 7.2 3.1
130 2.8 3.1 2.6 3.3 - 5.9 4.7 7.5 3.4
140 3.0 3.3 2.8 3.5 - 6.2 4.9 7.8 3.6
150 3.1 3.5 2.9 3.7 - 6.6 5.1 8.2 3.9
160 3.3 3.7 3.1 3.9 - 7.0 5.2 8.5 4.2
170 3.5 3.9 3.2 4.0 - 7.3 5.4 8.9 4.5
180 3.7 4.1 3.3 4.2 - 7.7 5.6 9.1 4.8
190 3.8 4.3 3.5 4.4 - 8.0 5.8 9.5 5.0
200 4.0 4.5 3.7 4.6 - 8.3 5.9 9.8 5.3
210 4.1 4.8 3.9 4.8 - 8.6 6.2 10.2 5.5
220 4.2 5.0 4.0 4.9 - 9.0 6.4 10.6 5.9
230 4.3 5.2 4.3 5.1 - 9.3 6.6 11.0 6.3
240 4.4 5.5 4.6 5.2 - 9.6 6.8 11.4 6.6
 74 B. WUNDERLICH AND L. D. JONES

TABLE 4
Heat Capacity Contributions
(in cal deg-' mole-')

50 2.1 - 3.0 1.6 1.3 2.4 4.5 4.0 - 2.6

60 3.0 - 3.5 1.7 1.4 2.6 4.9 4.4 - 3.0
70 3.7 3.9 4.0 1.8 1.5 2.9 5.3 4.8 5.0 3.5
80 4.2 4.4 4.6 2.0 1.6 3.2 5.8 5.2 7.3 3.8
90 4.8 4.8 5.1 2.2 1.7 3.5 6.2 5.6 8.1 4.1
100 5.3 5.1 5.6 2.3 1.7 3.8 6.8 6.1 8.9 4.4
110 5.7 5.5 6.0 2.5 1.8 4.1 7.2 6.6 9.5 4.6
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120 6.0 5.8 6.6 2.7 1.9 4.4 7.7 7.3 10.0 4.8
130 6.4 6.2 7.1 2.9 2.0 4.6 8.2 7.9 10.4 4.9
140 6.7 6.7 7.6 3.0 2.0 5.0 8.7 8.7 11.1 5.1
150 7.1 7.1 8.1 3.2 2.0 5.3 9.2 9.3 11.7 5.2
160 7.6 7.5 8.5 3.3 2.1 5.5 9.7 10.0 12.2 5.3
170 7.9 8.1 8.9 3.4 2.1 5.8 10.4 10.7 12.8 5.4
180 8.4 8.5 9.2 3.5 2.1 6.0 11.0 11.4 13.4 5.4
190 8.9 9.1 9.6 3.6 2.1 6.3 11.6 12.0 14.0 5.5
200 9.3 9.8 9.9 3.8 2.2 - 12.1 12.6 14.5 5.6
210 9.7 10.5 10.2 4.0 2.3 - 12.8 13.3 14.9 5.6
220 - 11.7 10.7 4.2 - - 13.8 - 15.4 5.7
230 - 12.8 11.1 4.6 - - 14.6 - - 5.7
240 - 13.9 11.4 4.9 - - 15.5 - - 5.8
~~

The CH, contributions I, 11, and 111 are seen t o be not very much
different. T h e reason f or t h i s must be that t he hindered oscillator-
r o tato r f o r side-group CH,'s makes up p a r t of the heat capacity lost
from the low-frequency skeletal vibrations of the chain. Also the
contribution of the et her oxygen 0, from P T H F and P O P listed in
Table 4 is quite s i m i l ar t o I. Its quite different contribution i n POM
and POE listed in Ob h a s been t r aced t o t h e skeletal torsional fre-
quency limit which is about twice as high as in polyethylene [1] ,
causing a lowering i n heat capacity. T h i s example indicates that the
additivity scheme is limited probably t o polymers with si m i l ar back-
bones because of a possible change i n skeletal vibrations. It can al so
be noted that the COO, CONH, and SO, contributions are not much
different f r o m one another. With only little l o s s i n accuracy these
seven different groups could thus be combined t o two contributions
only. Table 5 shows a n example of a comparison between m easured
and estimated heat capacities as well as a prediction of the presently
unknown heat capacities of Nylon 610 and poly(ethy1ene terephthalate),
 HEAT CAPACITIES O F SOLID POLYMERS 75

TABLE 5
Measured and Estimated Heat Capacities (in cal deg-' mole-')

Nylon'
PMPa HPSb
Temp., 610 PET,
'K Meas. Est. Meas. Est. Est. Est.

50 7.24 7.0 10.19 10.0 (21.4) (10.4)

60 8.69 8.4 12.24 12.1 (26.6) (13.3)
70 10.04 9.8 14.19 14.2 31.6 15.6
80 11.34 11.2 16.09 16.1 35.4 18.4
90 12.66 12.6 17.94 18.1 39.0 20.5
100 13.80 13.6 19.81 19.7 42.4 22.7
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110 14.89 14.8 21.61 21.3 46.0 24.3

120 15.97 15.8 23.38 22.9 48.0 25.8
130 16.99 17.0 25.09 24.6 51.6 27.5
140 18.00 18.2 26.71 26.3 55.4 29.3
150 18.99 19.0 28.28 27.7 57.6 31.0
160 19.94 20.2 29.77 29.3 61.2 32.9
170 20.93 21.2 31.6 30.8 65.2 34.5
180 21.94 22.2 32.6 32.2 68.8 36.5
190 22.93 23.2 34.0 33.6 71.4 38.4
200 23.96 24.4 35.4 35.1 75.6 40.1
210 24.95 25.6 36.8 36.7 78.4 41.7
220 26.00 26.4 38.3 38.1 82.2 (44.7)
230 27.01 27.6 39.9 39.6 85.8 (46.3)
240 28.08 29.0 41.3 41.3 89.4 (49.2)

aThe samples analyzed were largely isotactic, about 30% crystalline. The
glass transition was a t about 305'K. Data were obtained from F.E. Karasz,
H.E. Bair, and J.M. O'Reilly, Polymer, 8, 547 (1967), and T.P. Melia and
A. Tyson. Makromol. Chem., 109, 87 (1967).
bData by F. Dainton, D. Evans, F. Hoare, and T. Melia, Polymer, 3, 310
(1962).
'PET = poly (ethylene terephthalate) .
COPOLYMER HEAT CAPACITIES
Several s e r i e s of copolymers thought to be more or less random
.
have been investigated by measuring heat capacities [l] Since the
addition scheme proposed is applicable for different homopolymers,
it should apply even more to copolymers. Figure 1 shows a plot of
the heat capacity of styrene-butadiene copolymers calculated per
mole of average repeating unit using mainly data generated over the
years by the Bureau of Standards [l]. The deviation from strict
 76 B. WUNDERLICH AND L. D. JONES

additivity is 0 to - 4% below T g and 0 t o - 5% above Tg. These e r r o r

limits are l e s s than the uncertainty in the heat capacity in polybuta-
diene which h a s slightly different heat capacities in the cis and t r a n s
form. Averages have been used for the calculation of the copolymer
heat capacity.
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Tempwature ( * K 1
FIG. 1. Heat capacity of copolymers of s t y r en e and butadiene. The m o l e
percentage s t y r e n e i s written next to each c u r v e.

Another series of copolymers includes those of poly(ethy1ene

terephthalate-sebacate) investigated by Dole and Wunderlich [ l ].
T h i s series of copolymers is semicrystalline and data are available
mainly above the glass-transition temperature. Taking into account
the effects due t o melting and g l a s s transition, additivity s e e m s to
be preserved also. At 360"K, for example, the calculated 60/40 co-
polymer heat capacity is 91.5 cal deg" mole'', while the measured
value is 88.8 cal deg" mole"; the 80/20 copolymer shows calculated
and measured values at the s a m e temperature of 80.7 and 84.5 cal
deg" mole-', respectively.
The heat capacities of a series of poly(methy1 methacrylate-
methacrylic acid) copolymers have been represented by [l]

Cp = 26.5 + 0.14t - (6.2 + 0.05t)nx c a l deg-' mole"' (9)

where nx r e p r e s e n t s the mole fraction of methacrylic acid in the co-

polymer and t is the temperature in "C. Equation (9) r e p r e s e n t s all
available data t o f 2% between 50 and 100°C. At higher and lower
t e m p e r a t u r e s l a r g e r deviations seem t o be caused by a systematic
e r r o r in the data used in the derivation of Eq. (9).
Finally Table 6 shows calculated data f o r an ethylene propylene
copolymer compared to experimental data [ l ] .
 HEAT CAPACITIES O F SOLID POLYMERS 77

TABLE 6
Calculated and Measured Heat Capacities of a 31% Propylene
Copolymer of Ethylene and Propylene (in cal deg-’ mole-‘)

Glass Melt
T, ”K Cp (meas.) Cp (calc.) T, O K Cp (meas.) Cp (calc.)

80 4.33 4.33 260 16.4 16.0

100 5.28 5.27 280 16.5 16.7

120 6.20 6.11 300 16.6 17.0

140 7.10 6.91 320 16.8 17.6
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160 7.99 7.69

180 8.87 8.45

All copolymer data show that additivity of heat capacity holds in

the region below the glass-transition temperature. Only a slightly
increased e r r o r is found in the liquid region. The importance of
Tables 4 and 5 has increased through the study of copolymers, since
the unlimited variety of copolymer heat capacities can now be esti-
mated t o a fair degree of accuracy. It is expected that in the pre-
diction of heat capacities of copolymers f r om the homopolymers the
gr e ate s t use of the additivity method will be found since it is im-
possible t o meas ur e the heat capacity of all different copolymers.

ACp AT THE GLASS-TRANSITION TEMPERATURE

Previously [ll]it w as observed that the i ncrease in heat capacity
of many substances can be rationalized by dividing the molecules into
“beads” which are the basic units of major motion in the liquid phase.
Calculated p e r mole of “bead”, the heat capacity i ncrease heating
through the glass-transition t em per at ur e w as found to be 2.7 f 0.5
cal deg’’ mole-’ f or 41 gl as s es (rule of constant ACp). At that time
only few amorphous polymer heat capacities w ere known. Table 7
collects data on all measured polymers to date based on Ref. [l].
Th e r u le of constant ACp is found t o be observed as demonstrated
by the average value i n Table 7 which is 2.60, close to the previously
determined average. For the polymers which show deviations of
mo r e than *0.2, a case could even be made for a different bead as-
signment o r possible e r r o r i n heat capacity data.
Brown and Wall [12] have obtained additional ACp data for 17
fluorine-containing polymers and conclude that the rule of constant
ACp holds f o r these polymers.
 78 B. WUNDERLICH AND L. D. JONES

TABLE 7
ACp a t the Glass-Transition Temperature

AC No. of ACp / T,
Polymer c a l deg-lcole-' beads bead OK
-
Polytetrahydrofuran 13.24 5 2.65 187
Poly (propylene oxide) 7.66 3 2.55 198
Polyethylene 2.52 1 2.52 237
Polyisobutylene 5.40 2 2.70 198
Polyisoprene 7.48 3 2.49 196
Polycarbonate of bisphenol A 15.2 6 2.53 415
Poly (vinyl chloride) 4.44 2 2.22 350
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Poly (methyl methacrylate) 8.17 3 2.72 378

Poly(viny1 acetate) 9.99 4 2.50 312
Polystyrene 8.20 3 2.73 365
Poly (2,6-dimethyl-l, 4-
phenylene ether) 6.9 2 3.45 480
Poly (ethylene terephthalate) 15.42 7 2.20 340
Poly (4-methyl- 1-pentene) 8.05 3 2.68 305
Polypropylene 4.84 2 2.42 259
Average 2.60

CONCLUSION

In t h i s paper it has been shown that due t o the unique s t r u c t u r e of

linear high polymers t h e i r heat capacities can be predicted f r o m con-
tributions of their chain units over a relatively l a r g e temperature
range.
NOTE: At present afile of c u r r e n t heat capacities is maintained in
our laboratory. A copy can be obtained by writing t o the authors.

Acknowledgments

T h i s work h a s been supported by the National Aeronautics and

Space Administration and the National Science Foundation.

REFERENCES

[l] B. Wunderlich and H. Baur, F o r t s c h r . Hochpolymer. Forsch.

(1969),t o be published (preprints available from the author).
[2] B. Wunderlich,J. C h e m . P h y s . , 3 7 , 1207 (1962).
[3] W. H. Stockmayer and C . E. Hecht,J. C h e m . Phys., 21, 1954
(1953).
 HEAT CAPACITIES O F SOLID POLYMERS 79

[41 S. M. Genensky and G. F. Newell, J . Clzem. Phys., 26, 486

(1957).
[51 V. V. Tarasov and G. A. Yunitskii, Zh. Fiz. Khim,, 39, 2077
(1965)( s e e f o r earlier p a p e r s ) .
[61 B. Wunderlich, J . Chem. Phys., 37, 1207 (1962).
[7 I M. T a s u m i , J . Mol. Spectry., 9, 261 (1962);M. Shimanouchi,
ibid., 11, 422 (1963);T. Miyazawa, J. Chern. Phys., 35, 693
(1961).
[8I M. T a s u m i and T. Shimanouchi, J. Chem. Phys., 43, 1245 (1965).
[91 T . Kitagawa and T. Miyazawa, Rept. Progr. Polymer Phys.
Japan, 9, 175 (1966).
B. Wunderlich, J . Polymer Sci., C1, 41 (1963).
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B. Wunderlich, J . Phys. Chem., 64, 1052 (1960).

D. W. Brown and L. A. Wall, J . Polymer Sci., A-2, to be pub-
lished.

Received by editor September 25, 1968

Submitted f o r publication December 11, 1968