From the Chemistry Research Department, Naval Ordnance Laboratory,

White Oak, Silver Spring, Maryland, U.S.A.

Thermodynamic Properties of Polyethylene

By R. W. WARFIELDand M. C. PETREE

(Eingegangen am 2. Oktober 1961)

SUMMARY:
The entropy, enthalpy, and GIBBS' free energy of conventional high pressure poly-
ethylene have been calculated over the range 0"to 315 "K. The use of a linear TARASSOV
function to estimate the specific heat of polyethylene is discussed. The thermodynamic
function Cp/T versus T has been calculated and exhibits an increase a t 60°K. due to
interactions between polymer chains. An approximation is made of the number of vibrat-
ing units per repeating unit a t 273 OK. Cp-C, is calculated a t 273 "K. and found to be
0.082 cal./deg. g.

ZUSAMMENFASSUNG:
Die Entropie, Enthalpie und die GIBBSsche freie Energie des iiblichen Hochdruck-Poly-
athylens wurde fiir den Bereich von 0 bis 315 "K berechnet. Die Benutzung der linearen
TARAssOv-Funktion fur die Bestimmung der spezifischen W P m e des Polylthylens wird
erortert. Die thermodynamische Funktion Cp/T gegen T wurde errechnet und zeigt a d
Grund der Zwischenwirkungen zwischen den Polymerketten einen Anstieg bei 60 "K. Die
Zahl der Schwingungseinheiten pro CH,-Gruppe ist bei 273°K ann5hernd 1,23. Der
Cp-C,-Wert betragt bei 273 "K 0,0082 ca1iGrad.g.

Introduction

The study of specific heat, C,, and related thermodynamic functions

of a polymer over a temperature range extending t o absolute zero repre-
sents a fundamental approach toward understanding the structure and
internal motions of a polymer. From accurate C, measurements entropy,
enthalpy, and free energy can be calculated, as well as changes in these
functions due t o increasing or decreasing temperature, glass transitions,
melting, crystallization and annealing. Specific heat measurements made
a t low temperatures are also useful in testing the validity of various
theoretical equations for the Cv of linear polymer chains, such as those
advanced by TARASSOV~).

113
 R. W. WARFIELDand M. C. PETREE

Additional thermodynamic data on bulk polymers are needed t o

elucidate the nature of the glassy and crystalline states and t o explain
t h e magnitude of t h e energy changes which occur when polymers are
heated or cooled, crystallized or melted. The literature contains very little
information of this type. DOLEand WUNDERLICH~) have estimated t h e
absolute entropies for a few polymers, PAUKOV and co-workers3), using
Cp data have calculated t h e entropies a t 298.16 OK. of E-caprolactam and
poly-E-caprolactam and WARFIELDand PETREE 4, have calculated t h e
thermodynamic functions of polystyrene over t h e range 0 t o 300°K.
Presented in this paper are calculated values of the entropy, enthalpy,
and GIBBS'free energy for conventional high pressure polyethylene. These
calculations are based upon published C, data over the range 17 t o 320 OK.
A TARASSOV function was employed t o estimate the specific heat between
0 t o 265 OK., and the usefulness of this function is considered in relation
t o t h e vibrational spectrum of linear polymers. The difference, CP-& is
also calculated as is the number of classically vibrating units per repeat-
ing unit of polyethylene.

The Specijic Heat of Polyethylene

Polyethylene, which is the simplest existing .organic polymer, has
strong primary bonds along t h e main chain and relatively weak inter-
molecular interactions between chains. The specific heat of polyethylene
is of particular interest because of t h e absence of pendent groups along
t h e chain and because specific heat a t low temperatures results primarily
from transverse and longitudinal vibrations of the polymer. chains 5).
Specific heat of conventional polyethylene has recently been deter-
mined b y SOCHAVA~) between 17 and 60 OK., b y SOCHAVA and TRAPEZNI-
K O V A ~ )between 58 and 270 OK., and by DOLEand co-workers 7, between
253 and 473 OK. The experimental values are given in Table 1 and plotted
in Fig. 1. The specific heat between 0 and 17°K. was obtained b y extra-
polating t o absolute zero a plot of C,/T versus T2 of the experimental data
between 17 t o 30°K. Inspection of Fig. 1 reveals t h a t t h e specific heat
increases with temperature in a n approximately linear manner over the
temperature range 0 t o about 240 OK. Above 240 OK. t h e specific heat
exhibits a n increase, which is probably associated with t h e motion of
chain segments in t h e amorphous regions of the polymer5,').

The Tarassov Spec;& Heat Function

TARASSOV has considered t h e structure of linear polymer chains and
has derived equations utilizing a one-dimensional function of the DEBYE

114
 Thermodynamic Properties of Polyethylene

Table 1. Heat capacity, entropy, enthalpy, and GIBBS' free energy of polyethylene

Temp. Heat capacitya) C, ST-SO "K. H.rHo"K. -(FT-Fo OK.)

(OK.) (cal./deg. g.) (cal./deg. 9.) (ca1.k.) (ca1.k.)

I10 (0.008) 0.0046 0.020 0.003

20 0.0173 0.0115 0.120 0.053
30 0.0384 0.0228 0.398 0.172
40 0.0597 0.0369 0.889 0.403
50 0.0806 0.0526 1.592 0.775
60 0.0999 0.0691 2.497 1.304
70 0.1185 0.0861 3.599 1.998
80 0.1340 0.1030 4.862 2.863
90 0.1480 0.1196 6.270 3.896
100 0.1615 0.1360 7.823 5.097
110 0.1739 0.1520 9.505 6.455
120 0.1858 0.1677 11.306 7.980
130 0.1972 0.1830 13.226 9.649
140 0.2081 0.1980 15.250 11.480
150 0.2210 0.2128 17.393 13.463
160 0.2319 0.2274 19.650 15.597
170 0.2438 0.2418 22.026 17.871
180 0.2552 0.2561 24.521 20.297
190 0.2660 0.2702 27.124 22.863
200 0.2790 0.2841 29.846 25.554
210 0.2919 0.2980 32.698 28.392
220 0.3069 0.3119 35.685 31.374
230 0.3235 . 0.3259 38.837 34.491
240 0.3426 0.3401 42.165 37.759
250 0.3644 0.3545 45.705 41.148
260 0.3887 0.3693 49.468 44.704
270 0.4151 0.3845 53.484 48.409
273.15 (0.430) 0.3898 54.89 49.69
280 (0.455) 0.4012 57.84 52.48
290 (0.493) 0.4170 62.61 56.23
300 (0.540) 0.4349 67.88 60.41
310 (0.591) 0.4540 73.70 64.76
320 (0.653) 0.4743 80.10 69.30
a) Data of S O C H A V A ~ )(17 to 55"K.), SOCHAVA and TRAPEZNIKOVA5) (60 to 265°K.) and
interpolated from that of DOLEet aL7) (275 to 315 OK.).

type, t o describe t h e temperature dependence of specific heat1). This use

of a single parameter or linear TARASSOV function is based on the assump-
tion t h a t strong covalent bonds are present along the polymer chain a n d
t h a t there are relatively weak interactions between chains. It is also
assumed t h a t the chain atoms vibrate transversely and have only 2/3 of t h e

115
 R. W. WARFIELDand M. C. PETREE

0.701 A L 1 I I I I

$ 0.60-o DATA OF SOCHAVA ET AL

6- AND DOLE ETAL
W

-I
0.50-
a 1

z: HEAT I
n
v,
1

"0 50 100 200 250 300

150 350 400
TEMPERATURE ( O K )
Fig. 1. Specilic heat of polyethylene

t o t a l vibrational degrees of freedom. Functions of the TARASSOV type have

been applied t o a number of polymeric materials with considerable suc-
cess. For example, TARASSOV~) has calculated the C, of polytetrafluoro-
ethylene a t low temperatures and obtained results t h a t agree very closely
with the observed C, as determined b y FURUKAWA and co-workerss).
WARFIELDand P E T R E E 4 ) have employed a linear TARASSOV function t o
estimate the low temperature C, of polystyrene.
Based upon these considerations the specific heat of polyethylene can
be estimated b y means of the TARASSOV function:

C, - 2/3 xaR
T
-
@T

where C, is the specific heat, R is t h e gas constant, T is t h e absolute

temperature and @T is t h e TARASSOV characteristic temperature, 577 OK.,
as calculated b y SOCHAVA and TRAPEZNIKOVA~~). Previous studies 438910)

have indicated t h a t t h e use of this function a t low temperatures will

introduce little error into entropy, enthalpy, and free energy calculations.
Since the TARASSOV function is a generalized DEBYEfunction, t h e value
of t h e TARASSOV characteristic temperature, @T = 577 O K . , can be checked
t o a first approximation b y the LINDEMANN melting formulall), Eq. 2.

116
 Thermodynamic Properties of Polyethylene

where OD is the DEBYEcharacteristic temperature, TM is the observed

melting point, 384"K., M is the molecular weight, and v is t h e specific
volume, 1.06 ml./g.12).Taking K t o be 115 (as suggested by BLACK MAN^^))
OD is found t o be 591 which is in satisfactory agreement with the OT
value.
A comparison of t h e observed and calculated specific heats is shown on
Fig. 1. It will be noted t h a t reasonably good agreement between experi-
mental and theoretical results is obtained between 45 and 115°K. A t
higher temperatures the agreement is only fair. At temperatures less t h a n
45 OK. the interactions between polymer chains become significant and
give rise t o a state in which specific heat can be more accurately described
b y a three-dimensional DEBYEcontinuum of acoustic frequencies13). A
T3 component should thus be combined with the one-parameter (linear)
TARASSOV function in this temperature region 14).
A similar conclusion t o t h e above has been made by TARASSOV~) who
has recently proposed a two-parameter function. It appears that, while'a
one-parameter TARASSOV function can be employed t o yield reasonably

0 i
I
0.0121 1

/
/
/

0
0 100 200 300 400 500 600 700 800 900
(TEMPERATURE, "K l2
Fig. 2. Specific heat function, C,/T vs. T2 for polyethylene

117
 and M. C. PETREE
R. W. WARFIELD

accurate values if only transverse vibrations are occurring, modifications

of the function are necessary a t low temperatures where chain interactions
are significant.
Satisfactory estimates of the low temperature specific heat over small
temperature ranges can be obtained b y extrapolating t o absolute zero a
plot of C,/T versus T2as is shown in Fig. 2. However, when the tempera-
ture range is broader t h a n 15 t o 20" K. it appears t h a t a TARASSOV func-
tion should be employed4y8).
STOCKMAYER and HECHT 13) have developed a mathematical treatment

of t h e specific heat of chain polymeric crystals which corresponds t o the

two-parameter equation given b y TARASSOV~). STARKWEATHER15), using
the:same data on the specific heat of polyethylene as is used in this paper,
has recently shown the validity of t h e theory of STOCKMAYER and HECHT.
WARFIELD and PETREE 16) have recently shown t h a t the STOCKMAYER-
HECHTtheory can be applied t o amorphous chain polymers in a similar
manner as STARKWEATHER has applied t h e theory t o crystalline polymers.

W
W
I I I I
IX
L
0 50 100 150 200 250 300
TEMPERATURE, (OK).
Fig. 3. Thermodynamic functions of polyethylene

118
 Thermodynamic Properties of Polyethylene

Entropy, Enthalpy, and Gibbs' Free Energy Calculations

From C, data values of entropy, enthalpy, and GIBBS' free energy of
polyethylene have been calculated a t ten-degree increments b y numerical
integration and are presented in Table 1 and on a composite plot in Fig. 3.
The values were obtained b y evaluating the thermodynamic relations

H, - HOoK = 1
0
CpdT (4)

where (ST-SWK), (HT-HwK), and (FT-Fo~K) are the entropy,

enthalpy, and GIBBS' free energy relative t o absolute zero.
While the temperature dependence of the crystallinity of high pressure
polyethylene is not known, the amount of crystallinity is about 50 yo a t
300"K., depending somewhat on its previous thermal history. It must
therefore be assumed t h a t there will be residual entropy a t 0°K. A
contribution of great importance would be t o determine the C, of poly-
ethylene samples of known crystallinity. Such d a t a could yield informa-
tion of the absolute entropy of polyethylene.
At 273.15 "K. the entropy of polyethylene was calculated t o be 0.3898
cal./deg. g., the enthalpy, 54.89 cal./g. and the GIBBS' free energy -49.69
cal. /g. Data on the thermodynamic functions of polymers are very limited,
b u t the calculated entropy value of 0.3898 cal./g. a t 273.15"K. for high
pressure polyethylene can be compared with the estimated value of
about 0.36 cal./deg. g. for low pressure highly crystalline polyethylene as
given graphically b y DOLE and WUNDERLICH~).
The specific heat of linear thermoplastic polymers does not appear t o
exhibit any significant differences due t o molecular weight providing that
the average molecular weight is greater t h a n about 20,000. The molecular
weight of polyethylene used b y S O C H A V Aand ~ ) b y SOCHAVA and TRA-
PEZNIKOVA5) is unknown. DOLEand co-workers7)gave 30,000 as the mo-
lecular weight of some of polyethylene they used.
It was found t h a t the plots of the thermodynamic functions change
with temperature in a manner similar t o those of polystyrene4).

119
 R. W. WARFIELD
and M. C. PETREE

The Function Cp/ T versus T for Polyethylene

SMITHand DOLEI')have pointed out that the function C,/T versus the
absolute temperature is a constant if the specific heat rises linearly with T
from a zero value a t absolute zero. The function Cp/T measures the rate
at which the entropy increases with temperature.

DOLE^^) has shown that this function is a sensitive method to locate the
glass transition. DOLEand WUNDERLICH~) have presented data on the
function Cp/T versus T for a number of polymers and long chain hydro-
carbons over various temperature ranges. The Cp/T values for the hydro-
carbons pass through a maximum a t 60-70°K. which is t o be expected
theoretically if one or more modes of vibration having the same frequency
dominate in this temperature range. DOLEand WUNDERLICH~) suggest
that the Cp/T versus T plot for polyethylene, should exhibit a maximum
a t low temperatures.
WARFIELD and P E T R E E 4 ) . have shown that a Cp/T versus T plot for
polystyrene exhibits a maximum of about 60°K. and clearly shows the
glass transition occurring over the range 350 t o 365 O K .

70 I I I I

60 - A POLYTETRAFLUOROETHYLENE
n
0
50-
50
o!
(3
W
n 40
40-
W

g 30
\
30-
d
0,20
0-20-
!-
k
0
10 0 POLYETHYLENE

Q I I 1

0 50 100 150 200 250 300 350 4

TEMPERATURE, (OK)
Fig. 4. Specific heat function, C, /Tfor polyethylene and polytetrafluoroethylene

120
 Thermodynamic Properties of Polyethylene

A plot of C,/T versus T for polyethylene and for polytetrafluoroethylene

is shown in Fig. 4. Data for polyethylene are those previously used in this
paper while the polytetrafluoroethylene data are those on the annealed
polymer of FURUKAWA and co-workers9) for t h e temperature ranges 0 t o
280 O K . and 310 t o 365 OK. Data of MARX and DOLE^^) were used between
285 to 307 OK. As is shown in Fig. 4 polyethylene exhibits a small increase
a t about 60°K. as predicted b y DOLE and WUNDERLICH~). Polytetra-
fluoroethylene on the other hand exhibits a small increase a t 35 OK., then
slowly decreases until about 270 OK. where the characteristic double first
order transitions are observed a t 292 and 301 "K. These double transitions,
which are clearly resolved in Fig. 4 are associated with changes in the
crystal structure 9).
If the single parameter (linear) TARASSOV function employed t o estimate
the specific heat was highly accurate, then the plots of C,/T versus T in
Fig. 4 should be constant. However, both polymers exhibit maximum
values a t low temperatures due t o interactions between the chains. As
previously noted these interactions can best be described by a three-
dimensional DEBYEcontinuum of acoustic frequencies.

Vibrating Units per Repeating Unit of Polyethylene

Based on a number of assumptions similar t o those made by DOLEIQ,
who calculated t h e heat capacity per vibrating unit of polyethylene, it is
possible t o estimate t h e number of classically vibrating units a t 273 OK.
in the polyethylene repeating unit -CH,-. Three assumptions are em-
ployed. The first is t h a t the force constant of the C-H bond is so great
t h a t the -CH,- group will vibrate as a single unit; the second is t h a t
every group in t h e chain can vibrate harmonically with two degrees of
freedom along mutually perpendicular axes transverse t o t h e chain
direction ; and the third is t h a t longitudinal or stretching vibrations are
negligible a t 273 O K . If each vibrating unit vibrates with two degrees of
freedom, t h e expected specific heat would be 2 R or 3.97 cal./deg. mole
per vibrating unit. However these considerations apply t o C,, not C,.
The number of vibrating units per repeating unit is found b y dividing
C,, the heat capacity a t constant volume, by 2 R. C, can be calculated by
means of Eq. 7

r 1 1
c, = c, TV2d2

121
 R. W. WARFIELDand M. C. PETREE

where C, is the observed heat capacity of polyethylene a t 273"K.,

0.430 cal./deg. g. or 6.02 cal./deg. mole; V is t h e sound velocity, 2260 m.1
sec. 20) ; d is the cubic coefficient of expansion, 5.5 .lo-4 per deg. 21) ; and J
is t h e mechanical equivalent of heat, 4.184.107 erg/cal. C, is found t o be
4.87 cal./deg. mole and Cp-Cv is 0.082 cal./deg. g. or 1.15 cal./deg. mole.
Based on these values t h e number of vibrating units is 1.23.

V. V. TARASSOV, Doklady Akad. Nauk, S.S.S.R. 100 (1955) 307; J. h e r . chem. SOC.
80 (1958) 5052.
*) M. DOLEand B. WUNDERLICH, Makromolekulare Chem. 34 (1959) 29.
3, I. R. PAUKOV, V. P. KOLESOV,and S. M. SKURATOV, Doklady Akad. Nauk, S.S.S.R.
126 (1959) 325.
4, R. W. WARFIELDand M. C. PETREE, J. Polymer Sci., 53 (1961).
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' fM. DOLE,W. P. HETTINGER, N. R. LARSON,and J. A. WETHINGTON, J. chem. Physics
20 (1952) 781.
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1176.
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(1952) 273.
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i. khim. No. 3 (1958) 65; C.A. 53 (1959) 4881.
M. BLACKMAN, in: Handbuch der Physik, Bd. VII, Teil 1, Springer-Verlag, Berlin-Got-
tingen-Heidelberg 1955, S. 325.
12) E. A. COLEand D. R. HOLMES, J. Polymer Sci. 46 (1960) 245.
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14) H. N. V. TEMPERLEY, J. Res. Nat. Bur. Standards 56 (1956) 55.
15) H. W. STARKWEATHER, J. Polymer Sci. 45 (1960) 525.
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l 8 ) M. DOLE, KoUoid-Z. 165 (1959) 40.
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R. A. V. RAFF,and J. B. ALLISON,Polyethylene, Interscience Publ., Inc., New York,

1956.

122