Hindawi Publishing Corporation

International Journal of Chemical Engineering

Volume 2012, Article ID 782346, 8 pages
doi:10.1155/2012/782346

Research Article
Enthalpy-Entropy Compensation in Polyester
Degradation Reactions
Adam Al-Mulla
Chemical Engineering Department, Kuwait University, P.O. Box 5969, 13060 Safat, Kuwait
Correspondence should be addressed to Adam Al-Mulla, a.almulla1@ku.edu.kw
Received 22 May 2012; Accepted 28 July 2012
Academic Editor: Adrian Schumpe
Copyright 2012 Adam Al-Mulla. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
In an earlier work the author had studied the degradation kinetics of polyethylene terephthalate (PET), polytrimethylene
terephthalate (PTT), and polybutylene terephthalate (PBT) under nonisothermal conditions in air and N2 at heating rates of
5, 10, 15, and 20 C/min. In this paper the kinetic degradation parameters of PET, PTT, and PBT were estimated using the CoatsRedfern method for two dierent weight loss regions ranging from 28% (Zone I) and 840% (Zone II). A comparative analysis
of the enthalpy-entropy compensation eect for these polyesters in air and N2 is presented. A linear relationship was found to exist
between entropy and enthalpy values. The following criteria were applied to establish an enthalpy-entropy compensation eect and
to check the presence of an isokinetic temperature: (a) Exners plot of log k3T1 versus log k3T2 , and (b) Krug et al. linear regression
of H versus G. By the use of the latter two methods, varying isokinetic temperatures were obtained. These temperatures were
not in the range of the experimental work conducted, indicating that these systems do not display compensation phenomena.

1. Introduction
Kinetic studies carried out on similar compounds with a
correctly chosen mechanism function f () ( is the weight
fraction of material decomposed at temperature T and time
t) exhibit a linear relationship between the logarithm of the
preexponential factors and activation energies known as the
compensation eect [15]. Several theories and explanations
for such compensation behavior have been put forth [68].
In the case of thermal decomposition of solids, the
existence of the compensation eect permits certain conclusions concerning the decomposition mechanism and thermal
characteristics of the compounds under investigation. The
changes of Gibbs energy (G), enthalpy (H), and entropy
(S) for the degradation reactions can be obtained by
studying the kinetics of the thermal decomposition of solid
compounds with nonisothermal heating using the thermogravimetric (TG) curves and a correct algebraic expression
of the conversion function, f ().
The reaction mechanism for polymer degradation is
a very complex chain mechanism that includes initiation,
propagation, and termination reactions. Normally, two types
of reaction models, the first order f ()1 = (1 ) and the

second order f ()2 = (1 )2 , are used for the thermal

degradation studies of polymers.
The author has previously reported [5] the kinetic
parameters characterizing the degradation of PET, PTT, and
PBT in air and N2 using data from nonisothermal thermogravimetry and the calculation procedure of Coats and
Redfern [5].
The aim of this work was to obtain the thermodynamic
parameters, S, H, and G, relating to the degradation
of PET, PTT, and PBT and to determine whether the false
compensation eect (presence of an isokinetic temperature)
observed in the previous work can also be noticed when the
thermodynamic parameters (enthalpy-entropy relationship)
are used to check the compensation eect. Plots of S and
H were used to confirm this result.

2. Theoretical Background
Mathematical analysis was performed on the TG data using
the integral method of Coats and Redfern, [9] which has been
used successfully for studies on the kinetics of decomposition
of solid substances [1014]. The activation energy (E) and

International Journal of Chemical Engineering

the preexponential factor (A) for the degradation of PET,

PTT, and PBT have been previously calculated from the TG
curves.
Degradation of polymers can be described with chemical
reactions of dierent rate constants [15]. Because the molecular weight of a chain reduces continuously throughout
a process the dependence of chain length becomes weak.
Therefore the dependence of rate constant of degradation on
molecular weight is normally observed at moderate values
of molecular weight [16]. Breakdown of the chain molecules
leads to an increase of the number of molecules and a
decrease of the length, thus altering the dependence of the
system free energy on the molecular length [16, 17].
Kinetics of a degradation process can be described by the
theory of activated complexes [18, 19]. On assuming that
the system equilibrium can be achieved faster at given composition of solution, than the ongoing degradation process
the constant rate of reaction can be defined by free energies
of formation of initial chain and activated complex by [20
22]:
k=

xekB T
S
E
exp
,
exp
h
R
RT

(2)

where A is the preexponential factor, E is the activation

energy, T is the temperature, and R is the universal gas
constant.
Taking into account the preexponential constant A, the
following expression is obtained:
A=

xekB T
S
,
exp
h
R

(3)

and S can be calculated as follows:



S = R ln A

ln xekB T
,
h

(4)

where A is the preexponential factor in the Arrhenius equation. Because

E = H + RT.

(5)

The change of the enthalpy H and Gibbs free energy G

can be calculated using the following equation:
G = H TS.

3.2. Polymer Degradation. To determine the kinetic degradation parameters, all the polymers were subjected to TGA.
The decomposition temperatures for PET, PTT, and PBT
were measured using an SDT 2960 simultaneous DSCTGA instrument supplied by TA Instruments Ltd. The TGA
machine was calibrated using ASTM method, E 1582-93,
standard practice for calibration of temperature scale for
thermogravimetry (ASTM, 1993). The heating rates chosen
were 5, 10, 15, and 20 C/min, and the temperature range
scanned was 30 to 700 C. The weight loss of the polymers
was determined by loading 7-8 mg into a platinum crucible
and heating it at one of the rates chosen under a steady flow
of air and nitrogen (20 mL/min). The output signals from the
TA 2960 analyzer were fed to a computer interface, where the
data was stored.

4. Results and Discussion

RT

3.1. Materials. PET, PTT, and PBT with number average

molecular weight (Mn) = 20,000, 28,000, and 26,000 used
here was a product of Century Enka. Ltd. (India).

(1)

where k is the degradation rate constant, x is a transmission

coecient (unity for monomolecular reactions), kB is the
Boltzmann constant, h is the corresponding Plancks constant, e = 2.7183 is the Neper number, and S is the change
of entropy for the active complex formation [23]. Equation
(1) is based on the basic Arrhenius equation:
k = Ae

3. Experimental

(6)

S, H, and G were calculated at T = T p (T p is the dierential peak temperature. This temperature characterizes the
highest rate of the process).

PET, PTT, and PBT were analyzed using a dierential scanning calorimeter (DSC) to determine its melting point. The
melting points were found to be 254, 240, and 227 C, respectively. Dierential thermal analysis (DTA) of the thermograms for PET, PTT, and PBT revealed that the maximum
weight loss temperature for degradation occurred at around
40% weight loss [5]. Initial weight loss till around 2 weight
percent was not considered since it could be due to volatilization of low molecular weight compounds present in the
polymers.
The thermograms for all the three polymers had two
linear regions (28% (Zone 1) and 840% (Zone 2)) having
correlation coecient (r) above 0.99 was found for all the
three polymers. Figure 1 indicates the linear region obtained
for zone 1 (28%) which corresponds to the horizontal portion of the degradation curve, while Figure 2 indicates the
linear region for zone 2 which corresponds to the vertical
portion of the thermogram covering the range 840%. The
maximum rate of weight loss temperature (T p ) (peak of differential thermal analysis (DTG) curve) was obtained from
the thermogravimetric data using the manufacturer thermal
analysis software.
The Coats Redfern (CR) integral method was used in
the previous work [5] to estimate the degradation kinetic
parameters ln A and E. The CR equation is given as follows:


ln

g()
T2


=

AR
E

,
E
RT

(7)

where is the heating rate and the other parameters are the
same as those found in the equations above.
First order ( f ()1 = (1 )) and a second order ( f ()2 =
(1 )2 ) models, the integral forms of which are g()1 =
[ ln(1 )] and g()2 = [(1 )1 1], [23] were fitted
to the Coats-Redfern (7) to obtain the activation energy (E)

3
100

98

98

96

96

94
100

92

80

90
88

88
600
800
1000
Temperature (K)

620

640

100
80

40

400

600

92
90

60

20

86

94

Weight (%)

Weight (%)

100

Weight (%)

Weight (%)

International Journal of Chemical Engineering

660

680

700

720

40
20
400

86

1200

60

600

740

600
800
Temperature (K)

620

640

Temperature (K)
5 C/min
10 C/min

1000

660
680
Temperature (K)

5 C/min
10 C/min

15 C/min
20 C/min
(a) PET

700

720

15 C/min
20 C/min
(b) PTT

100
98

94
92

100
80

90
88

Weight (%)

Weight (%)

96

86
600

60
40
20
400

600
800
Temperature (K)

620

1000

640
660
680
Temperature (K)

5 C/min
10 C/min

700

720

15 C/min
20 C/min
(c) PBT

Figure 1: Plot of weight loss (28% conversion range) as a function of temperature for polyester degradation in air atmosphere (zone 1).

and the preexponential factor for degradation of these

polyesters. The E and A for the two dierent g() functions
were calculated at constant heating rates by fitting ln g()/T 2
versus 1/T plots. It was observed that when g()1 was used
for the Arrhenius parameter estimation in the CR equation,
correlation coecient values greater than 0.99 was obtained
(Figure 3). When g()2 was used in the CR equation, the
plots obtained had a correlation coecient less than 0.97.
Figure 4 is a plot indicating the poor fit.
Figures 5 and 6 indicate that linear plots obtained
between ln A and E using Arrhenius equation. It has correlation coecients greater than 0.99 for all the polyesters
degraded in air and N2 . In some systems, [24, 25] it has been
observed that the activation energy varies under dierent
measuring conditions. It is also found that the variation in
activation energy is accompanied by a change in A that is;
a large activation energy is accompanied by a large preexponential factor and vice versa, a phenomena often referred to
as compensation eect.

The frequency factor (A) given in (3) contains an entropy

term (exp S/R). The values of A will reflect in a specific way
on the change of entropy for the formation of degradation
products from the solid polymer. The enthalpy-entropy and
free energy values computed using (3), (5), and (6) are
reported in Table 1. It is noted that higher E has low entropy
values. The S values are also found to be negative. As
anticipated, the graphical representation of the dependence
between the values of S and E for the polyesters studied
shows a linear relationship for all the systems (Figures 7 and
8). Another obvious relationship found from these plots is
the existence of a linear relationship between S and E which
implies a direct proportionality between these two quantities.
The E values thus have an eect on the values of the change
in entropy. As the value of E increases, the value of S was
also found to increase for all the polyesters. The relationships
observed can be interpreted, first, as a proof that the activated
complex (before forming gaseous products) had a less organized structure and the rearrangements taking place were

International Journal of Chemical Engineering

100

100
100

100
80

60

Weight (%)

80

90
40

Weight (%)

Weight (%)

Weight (%)

80

90

20
0
400

600

70

800
1000
Temperature (K)

1200

80

60
40
20
0
400

600
800
Temperature (K)

70

1000

60

60

50

50
600

650

700

750

800

850

600

900

650

Temperature (K)
5 C/min
10 C/min

700
750
800
Temperature (K)

5 C/min
10 C/min

15 C/min
20 C/min
(a) PET

850

900

15 C/min
20 C/min
(b) PTT

100
100

80

80
Weight (%)

Weight (%)

90

60
40
20
0
400

70

600
800
Temperature (K)

1000

60

50
600

650

700

750

800

850

900

Temperature (K)
5 C/min
10 C/min

15 C/min
20 C/min
(c) PBT

Figure 2: Plot of weight loss (840% conversion range) as a function of temperature for polyester degradation in N2 atmosphere (zone 2).

accompanied by an increase in the entropy of the system. The

degrees of freedom of the unstable activated complex formed
before degradation into gaseous products were more than
the degrees of freedom of the parent polyester. The slopes
and the intercepts of the lines observed in Figures 7 and 8
were found to be not identical, possibly indicating that there
could be dierent dissimilar chemical processes. Figures 7
and 8 show that the value of S for PET was higher than that
for PTT and PBT, possibly implying that the corresponding
activated complexes for PET degradation have a lower degree
of arrangement (higher entropy) than the initial state.
According to the theory of the activated complex, [26] thermal degradation of PBT and PTT may be interpreted as a
fast reaction, while thermal degradation of PET is a slow
reaction. The correlation coecient (r) values of the latter

plots werefound to be greater than 0.99. In deducing the

compensation eect from temperature dependent data, the
temperature dependence of a suitable kinetic parameter, k,
is analyzed by making Arrhenius plots of ln k versus 1/T.
The slope and intercept of the resulting plots are reprocessed
in the light of the theory of formation of an active complex
[20] to yield estimates of enthalpy and entropy. The values
of enthalpy and entropy given in Table 1 tells us about the
changes in the internal structure or organization during the
degradation process. The majority of the researchers have
concluded that thermodynamic compensation in any chemical reaction occurs because of the linear relationship of the
enthalpy-entropy plot, which is supported by the high correlation coecient [24]. Plotting enthalpy against entropy
yields a compensation plot, typically a straight line when

International Journal of Chemical Engineering

Table 1: Kinetic characteristics of dierent polyesters.

5
10
Zone 1
15
20
5
10
Zone 2
15
20

Tp
648
669
674
682
771
793
800
807

5
10
Zone 1
15
20
5
10
Zone 2
15
20

Tp
652
663
670
676
767
790
805
808

PBT-N2
E
S
270 0.015
278 0.011
295 0.005
281 0.010
253 0.016
273 0.012
295 0.008
266 0.013
PBT-AIR
E
S
304 0.031
390 0.015
382 0.017
407 0.012
184 0.036
207 0.021
196 0.027
179 0.042

G
275
280
292
283
258
276
294
270

H
265
273
289
276
246
266
288
259

5
10
15
20
5
10
15
20

Tp
673
693
718
726
799
822
834
848

G
318
395
388
410
205
216
212
205

H
298
385
376
402
178
200
190
172

5
10
15
20
5
10
15
20

Tp
657
671
679
686
763
787
803
823

PTT-N2
S
0.022
0.022
0.025
0.025
0.027
0.022
0.021
0.031
PTT-AIR
E
S
328 0.045
397 0.033
411 0.030
389 0.037
274 0.040
300 0.036
296 0.036
280 0.039
E
439
450
429
429
310
370
379
290

G
448
458
441
441
326
381
389
309
G
352
413
426
408
298
321
318
305

H
433
444
423
423
304
363
372
283
H
323
391
405
383
268
293
289
273

5
10
15
20
5
10
15
20

Tp
695
710
717
725
901
972
949
973

5
10
15
20
5
10
15
20

Tp
701
706
719
725
901
905
928
950

PET-N2
E
S
483 0.169
494 0.148
480 0.174
475 0.182
459 0.031
470 0.029
443 0.036
430 0.042
PET-AIR
E
S
397 0.168
463 0.151
446 0.157
402 0.167
309 0.029
391 0.019
432 0.013
382 0.021

G
594
593
599
601
480
490
470
463

H
477
488
474
469
452
462
435
422

G
509
564
552
517
328
401
436
393

H
391
457
440
396
302
383
424
374

: heating rate ( C/min), T p : peak degradation temperature ( C), E: activation energy (kJ/mol), S: change in entropy (kJ/mol), G: change in free energy
(kJ/mol), H: change in enthalpy (kJ/mol).

15.2

13.5

15.4

ln((1 (1 )1 /T 2 )

ln((1 (1 )1 /T 2 )

14
14.5
15
15.5
16

15.6
15.8
16
16.2
16.4
16.6
16.8
17

16.5

0.0014

0.00145

0.0015
1/T (K1 )

0.00155

0.0016

PBT
PTT
PET

Figure 3: Plot of ln[1 (1 )1 ]/ T 2 versus 1/T for dierent

polyesters degraded in air atmosphere (zone 1).

the compensation eect is noted in the system under investigation. The name compensation eect refers to the idea
that variations in enthalpy that accompany variations in
temperature where molecular level splitting of the polymer
occurs during degradation are compensated for by variations in change in enthalpy. Figures 9 and 10 show variation
of enthalpy as a function of entropy. As seen in Table 1 values
of enthalpy and entropy is aected by varying heating rates.

0.0013

0.0014

0.0015
1/T (K1 )

0.0016

PBT
PTT
PET

Figure 4: Plot of ln[1 (1 )1 ]/ T 2 versus 1/T for dierent

polyesters degraded in N2 atmosphere (zone 1).

Free energy values are also found to be varying. This type

of behavior might be an indication that enthalpy-entropy
compensation eect does not operate in such systems [27].
According to Exner [28], a criterion for the existence of
a compensation eect is the linear relationship of kinetic
constants at two temperatures:
log k3T1 = b log k3T2 + const,

(8)

International Journal of Chemical Engineering

35

0.02
0

30

0.02
0.04

S (kJ/mol K)

ln(A )

25
20
15
10

0.06
0.08
0.1
0.12
0.14

5
0
280

0.16
0.18

300

320

340

360 380 400

E (kJ/mol)

420

440

460

280 300 320 340 360 380 400 420 440 460 480
E (kJ/mol)

480

PBT
PTT
PET

PBT
PTT
PET

Figure 5: Plot indicating a linear relationship between ln A versus

E for dierent polyesters degraded in air atmosphere (zone 1).

Figure 7: Plot indicating a linear relationship of S versus E for

dierent polyesters degraded in air atmosphere (zone 1).
0.005

31

0.01

30
S (kJ/mol K)

0.015

ln(A )

29
28
27

0.02
0.025
0.03
0.035
0.04

26

0.045

200

25
200

250

300

350

400

450

E (kJ/mol)

Figure 6: Plot indicating a linear relationship between ln A versus

E for dierent polyesters degraded in N2 atmosphere (zone 2).

where k3T1 and log k3T2 are kinetic constants at two dierent
temperatures T1 and T2 .
The slope b is related to the isokinetic temperature ()
by the following equation:
b1
bT1 T2

(T1 > T2 ).

300

350
400
E (kJ/mol)

450

500

PBT
PTT
PET

PBT
PTT
PET

= T1 T2

250

500

(9)

The values of log k3T1 and log k3T2 were determined from
the experiments. A plot of log k3660 k versus log k3680 k for PBT
in N2 atmosphere (zone 1) is indicated in Figure 11. The
dependence of both the temperatures for this plot was found

Figure 8: Plot indicating a linear relationship of S versus E for

dierent polyesters degraded in N2 atmosphere (zone 2).

to be linear with an r value of 0.99 and slope (b) equal to

0.852 0.156. Estimations were also conducted for log k3620 k
versus log k3630 k and b value was found to be 0.842 0.2 with
an r of 0.99. Even though a good r was obtained for both the
plots, the isokinetic temperature for both the temperature
ranges (660680 K and 620630 K) were obtained as 990 K
150 K and 1010 K 210 K which indicated that an
isokinetic temperature obtained using (9) does not lie in the
experimental range studied. The author in an earlier work
[5] tried to employ the criterion used by Peterson and Kevan
[29] to check the presence of compensation eect. In this
work ln k verses 1/T was plotted to check the presence of
compensation eect operating in these system. An isokinetic

International Journal of Chemical Engineering

7
6

480
460

440

400

log(k3 )T1

H (kJ/mol)

420

380
360

10

12

340
14

320
300
280
0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02

16
20

18

16

S (kJ/mol K)

14
log(k3 )T2

12

10

PBT-N2 -ZONE 1

PBT
PTT
PET

Figure 11: Plot of log k3660 versus log k3680 for PBT in N2 atmosphere
(zone 1).

Figure 9: Plot of change in enthalpy as a function of change in

entropy for the degradation of dierent polyesters in air atmosphere
(zone 1).

500
450
H (kJ/mol)

500

H (kJ/mol)

400

400
350
300

300
250
200
200

200

100
0.045 0.04 0.035 0.03 0.025 0.02 0.015 0.01 0.005

S (kJ/mol K)

Figure 10: Plot of change in enthalpy as a function of change in

entropy for the degradation of dierent polyesters in N2 atmosphere
(zone 2).

temperature (temperature at which all the lines concur to

a single point) was not obtained in these plots proving the
absence of compensation eect.
Another plot (Figure 12) was made to check the variation
of H as a function of G [30]. A linear relationship with a
slope was obtained. The slope is related to the isokinetic
temperature () by the following equation:
Thm
 ,
1 1/

300

350

400

450

500

550

PBT
PTT
PET

Figure 12: Plot of enthalpy change as a function of free energy

change for dierent polyesters in N2 atmosphere (zone 2).

PBT
PTT
PET

250

(10)

where Thm is the harmonic mean of experimental temperatures. The value of was obtained from the plot of enthalpy
and free energy and the corresponding value of were
obtained from (10). In this case was found to be 1089 K
120 K, which is not within the limits of the temperature
range conducted in this study, thus proving that compensation eect does not exist in the degradation of PET, PBT, and
PTT.

5. Conclusions
The Coats-Redfern equation was used to calculate the values
of activation energy and the preexponential factor (A) for
the nonisothermal degradation of PET, PTT, and PBT in
N2 and air atmospheres. A linear dependence was found by

8
plotting ln A and activation energy. A linear relationship was
also found to exist between changes in entropy and enthalpy
of activation for the degradation of these polyesters. These
dependences are related to the assumption that the kinetic
degradation mechanisms of these polyesters could be identical. The negative values of entropy show that the degradation
activated complex is a more organized structure than the
initial polymer structure. The slopes and the intercepts of the
lines for the plot of entropy versus activation energy were
found to be not identical, possibly indicating that there
could be dierent dissimilar chemical processes occurring on
degradation.
The positive values of free energy and enthalpy indicate
that the polyester degradation process is a nonspontaneous
reaction.

Acknowledgment
The principal author is grateful to the Research Department
of Kuwait University for providing funds from Project
EC01/08 for performing this research work.

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International Journal of Chemical Engineering

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