5376 J. Phys. Chem.

1983, 87, 5376-5380

sorption of molecularly adsorbed CO occurs at tempera-
tures between 350 and 450 K. But the CO desorbing at
higher temperatures originates from a surface reaction
between chemisorbed carbon and oxygen. Thus, the
coexistence of carbon and oxygen adatoms during our
thermodynamic studies cannot be excluded. To examine
this aspect, we evaluated the equilibrium
0(a) + CO(g) * C02(g)
based on chemisorbed oxygen atoms as the only oxygen-
containing surface species (Figure 2). Thus, from the ex-
perimentally determined partial pressures of C02 and CO
in equilibrium with surface oxygen, we constructed the
isostere presented in Figure 8. It is of interest that the
data can be represented by a single isostere, independent
of surface oxygen coverage.
The heat of reaction (eq 3) is calculated to be -56.8
kJ-moT1 at 600 K, compared to -48.5 kJ-mol'1 for the
reaction involving bulk nickel oxide
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
However, oxygen atoms chemisorbed on Ni exhibit a very
low chemical potential relative to bulk NiO. At half-cov-
erage the entropy of formation of adsorbed oxygen at 600
K is 110 J-mol-1-K"1, about one-hald the value of gaseous
atomic oxygen.
In conclusion, the chemical potential of surface carbon
at low coverage on Ni is considerably higher than that of
(3) graphite. The entropy of formation of the carbon adatoms
calculated from the partial molar entropy of adsorption
suggests the bonding of carbon atoms to Ni with weak
interactions between carbon atoms until high surface
coverages are attained. A diagram showing the various
energy levels of the adsorbed carbon species is presented
in Figure 9. With a heat of segregation of 50 kJ-mol"1 **for
carbon dissolved in Ni, the carbon surface states observed
in our study should be accessible from the bulk phase.
Acknowledgment. We thank our colleagues B. J. Wood,
K. M. Sander, and J. G. McCarty for profitable discus-
sions, and D. R. Sheridan for the TPSR measurements.

NiO(s) + CO(g) *± Ni(s) + C02(g) (4) Support of this study by the National Science Foundation
is gratefully acknowledged.
(18) P. W. Wentrcek, J. G. McCarty, C. M. Ablow, and H. Wise, J. Registry No. Ni, 7440-02-0; C02, 124-38-9; CO, 630-08-0;
Catal., 61, 232 (1980). carbon, 7440-44-0; atomic oxygen, 17778-80-2.
Downloaded via Lorena Meneses on March 18, 2021 at 15:02:09 (UTC).

Activation Energies and Frequency Factors for the Dehydrochlorination of Poly(vinyl

chloride) from the Arrhenius Equation

Joseph D. Danforth* and James Indiver!

Department of Chemistry, Grlnnell College, Grlnnell, Iowa S0112 (Received: January 19, 1983; In Final Form: April 22, 1983)

Reproducible values for the activation energies and frequency factors of five samples of PVC having chain lengths
in the range of 634-1381 were obtained from rates at 180 and 190 °C by using the Arrhenius equation. Although
there was a threefold variation in rates among the samples, all activation energies were 28-29 kcal/mol and
the frequency factors were uniform at 108-109 s'1. In order for the Arrhenius equation to give reproducible
and meaningful values, it was necessary to assure that only the temperature induced changes in the rates. The
dehydrochlorination reaction was acceleratory. Unless special care was taken in the rate measurements, the
changes in rate as a function of time would be superimposed upon the changes in rate caused by the change
in the temperature to give erroneous activation energies.

Introduction
Activation energies for the dehydrochlorination of
poly(vinyl chloride) under a variety of conditions have been
listed in a review article by Ayrey and co-workers.1 Values
ranged from 24 to 33 kcal-mol for dry polymer in inert
atmospheres. Activation energies from thermal gravimetric
methods in the range of 35-50 kcal/mol were reported.
Liteanu and co-workers2 treated thermogravimetric data
for a substituted PVC by an Arrhenius type model. Fre-
quency factors and activation energies varied excessively
with the extent of conversion. Garn3 observed similar
erratic behavior of frequency factors and activation en-
ergies when the Arrhenius equation was applied to reac-
tions on heterogeneous catalysts.
(1) G. Ayrey, B. C. Head, and R. C. Poller, J. Polym. ScoMacromol.
Rev. 8 1-49 (1974).
(2) V. Liteanu, A. Cs. Biro, and I. A. Schneider, J. Thermal Anal., 18,
227 (1980).
(3) Paul D. Garn, “Thermal Analysis”, Vol. 1, Proceedings, Fourth
International Conference on Thermal Analysis, Heyden, London, 1974,
p 25-32.
Our work on five samples of PVC has shown that the
Arrhenius equation can be applied properly only when the
rates observed at different temperatures are a function of
temperature alone and that they do not include rate
changes introduced because of the acceleratory charac-
teristics of the reaction.
Under isothermal conditions the rate of hydrogen
chloride evolution is slow at the beginning, then increases,
passes through a maximum, and decreases as the sample
is depleted.4 Rate of hydrogen chloride evolution mea-
sured during the acceleratory period will increase with each
measurement due to the acceleratory nature of the reaction
and these increases in rate will be superimposed upon rate
changes induced by temperature changes. A reverse con-
tribution to rates will occur during deceleration where each
rate measured after a previous rate will be lower than it
should be due to temperature changes alone. There is no
equation based on a single rate constant that correctly
(4) Joseph D. Danforth, Joel Spiegel, and John Bloom, J. Macromol.
Sci., Chem., 17, 1107-27 (1982).

0022-3654/83/2087-5376$01.50/0 © 1983 American Chemical Society

Dehydrochlorination of Poly(vlnyl chloride) The Journal of Physical Chemistry, Vol. 87, No. 26, 1983 5377

Figure 1. Photograph of a predegradation record; 69.1 mg of PVC (DP

1272) at 220 °C.

represents the changes in rate as a function of the extent Figure 2. Rates of Degradation as a Function of a at 190 °C: (·)
of degradation. The magnitude of rate changes caused by DP 634, (O) DP 684, ( ) DP 1272, (A) DP 1381. All samples pre-
the acceleratory behavior of the reaction may exceed rate degraded at 235 °C.
changes caused by changes in the temperature and lead
to excessive variations in the apparent activation energies. TABLE I: Source and Available Ch aracteristics
Because of our knowledge of the kinetics of PVC de- of PV C Samples
hydrochlorination, it was possible to measure reaction rates degree no. av wt. av
at conditions where the changes in rate depended only on polymn source mol wt mol wt
the temperature. Under these conditions all samples of 634 SPP° 39 600 77 300
PVC gave essentially the same activation energy and had 684 BEG6 42 700
a relatively narrow range of values for the frequency fac- 917 SPP 57 300 122 300
tors. 1272 BFG 79 500
1381 SPP 86 300 193 600
Experimental Section Scientific Polymer Products, Inc. 6
B. F. Goodrich.
The apparatus used for the precise measurement of the
rates of HC1 evolution at a constant temperature has been peratures of 220, 225, and 235 °C the; reaction begins slowly
described.6-9 At 60-s intervals helium carrier gas sweeps since hydrogen chloride which is essential for the initiation
through the reaction chamber carrying product gas through of the zip reaction must form from a few zip chains already
a chromatographic column (12 in. length of l/% in. diameter present or by slow degradation from the so-called “weak
stainless steel tubing packed with 80-100 mesh Porapak linkages” that have been postulated.5 The zip kinetics
Q (Waters Assoc.)) into a detector cell (Gow-Mac 10-952 which have been developed for the dehydrochlorination
No. 03310 J-WX) the impulse from which gives a peak on of PVC apply only to the situation in which degradation
a recorder (Sargent Welch Model SGR). Each peak area occurs at a constant pressure of hydrogen chloride.4
was measured by the recorder integrator. The sum of all A photograph of a typical predegradation record is
peak areas including a calculated peak area for hydrogen shown in Figure 1. DP1272 (69.1 mg) was preheated at
chloride remaining in the sample when degradation ceased 235 °C for 3 min with no detectable loss in weight and then
was divided into individual peak areas and the cumulative allowed to degrade isothermally at 220 °C until 21.2 mg
sum of peak areas to give, respectively, /60 s and a as of HC1 had been evolved. The degradation was carried
a function of time, a is the fraction dehydrochlorinated. beyond the time at which the maximum rate had been
Samples (60-90 mg) in a quartz crucible (3 mm i.d., 1.75 attained. The sudden change in peak height at the 40th
in. long) with a loose glass wool plug at the top were in- peak was caused by a change in attenuation. Peak areas
troduced to a stainless steel reaction chamber which could corrected for changes in attenuation increased regularly.
be maintained at any desired temperature by a West SCR The integrator tracings appear below each peak area and
stepless controller. The glass wool plug assured that he- the observed areas, though not legible on the photograph,
lium carrier gas swept out only hydrogen chloride over- were recorded for each peak.
flowing the crucible and did not dilute the hydrogen When predegraded samples are further degraded at 190
chloride atmosphere above the sample. The volume of °C, there is a range of degradation beyond the maximum
hydrogen chloride in the free space of the crucible was rate where the degradation rate decreases regularly with
negligible in comparison with the volume of hydrogen increasing percentage degradation. Figure 2 shows plots
chloride being produced. All samples melted and degraded of rate, /60 s, as a function of percentage degradation
during predegradation leaving a black porous solid on at 190 °C for four samples of PVC. Straight lines have
which the critical rate measurements were made. been drawn through the regions where the rate decreased
In this work the helium gauge pressure was 15 lb/in.2 regularly with increasing percentage degradation. Al-
so the hydrogen chloride pressure above the samples was though predegraded samples evolved copious amounts of
approximately 30 lb/in,2. Even at predegradation tem- hydrogen chloride at 190 °C, samples that had not been
predegraded evolved only traces of hydrogen chloride
under these same conditions.
(5) R. G. Parker, “PVC Stabilization: The Why and How”, Summer
Conference in Polymer Science and Technology, New Paltz, NY, 1977. Degradation rates at 180 and 190 °C for five PVC sam-
(6) Joseph D. Danforth and T. Takeuchi, J. Polymer Sci., Polym. ples described in Table I were determined after prede-
Chem. Ed., 11, 2091-8 (1973).
(7) Jospeh D. Danforth, U.S. Patent 3431077, March 4, 1969.
gradation at 220, 225, or 235 °C to a percentage degrada-
(8) Joseph D. Danforth and J. Dix, Inorg. Chem., 10, 1623 (1971). tion that was just beyond that observed at the maximum
(9) Joseph D. Danforth and J. Dix, «7. Am. Chem. Soc., 93, 6843 (1971). degradation rate. The predegraded samples were then
5378 The Journal of Physical Chemistry, Vol. 87, No. 26, 1983 Danforth and Indiveri

TABLE II: Rates, /s, for Samples of PVC at Designated Vallies'1 Used To Calculate Activation Energies and Frequency
Factors from the Arrhenius Equation
/s
run sample0 TDb °C TD x 104c 190j X 10s
d *
190„ X10s 190 interp X 10s f 180 X 10s g
2D53 634 225 4.38 (48.1)h 4.78 (57.2) 3.88
(66.9) 4.10 (60.9) 2.24 (60.9)
2D50 634 225 6.05 (47.2) 4.60 (47.2) 3.40
(74.0) 4.25 (67.6) 2.05 (67.6)
2D51 634 225 4.88(50.8) 4.22 (64.1) 2.87
(71.9) 3.61 (67.6) 1.73 (67.6)
2D58 634 220 3.74 (41.0) 4.28 (50.0) 3.38
(58.8) 3.85 (54.3) 2.02(54.3)
2D43 634 225 6.40 (43.0) 3.70 (63.6) 2.68
(72.9) 3.19 (68.3) 1.70 (68.3)
2D41 634 225 7.12 (43.1) 4.70 (59.0) 3.80
(71.0) 4.28 (64.5) 2.25 (64.5)
2D59 684 220 6.58 (41.0) 5.80 (63.8) 3.28
(72.6) 4.80 (68.3) 2.30 (68.3)
2D49 684 225 7.22 (49.0) 4.68(67.9) 2.92
(78.1) 3.76 (73.0) 1.93 (73.0)
2D47 684 225 5.33 (42.2) 4.12
(66.5) 2.92
(77.1) 3.48 (71.6) 1.90 (71.6)
2D46 684 225 5.42 (52.9) 4.67
(68.5) 2.65
(72.9) 3.64 (73.0) 1.77 (73.0)
2D24 684 225 7.88 (49.1) 6.17
(69.2) 3.48
(77,7) 4.83 (73.5) 2.35 (73.5)
2D23 684 225 7.02 (42.8) 5.48
(67.0) 3.41
(75.4) 4.37 (71.5) 2.32(71.5)
2D 57 917 220 6.00 (38.4) 5.95
(60.3) 4.35
(72.4) 5.09 (66.6) 2.75 (66.6)
2D16 917 225 10.2 (53.8) 6.57
(70.1) 3.18
(77.7) 4.57 (74.6) 2.27 (74.6)
2D17 917 225 10.0 (60.5) 4.63
(75.5) 2.88
(81.4) 3.71 (78.6) 1.82 (78.6)
2D61 1272 220 1.85 (40.1) 2.38
(55.8) 2.03
(61.0) 2.21 (58.4) 1.15 (68.4)
2D39 1272 235 7.55 (54.4) 2.68
(65.6) 2.33
(71.1) 2.53 (68.0) 1.29 (68.0)
2D38 1272 235 7.00 (44.9) 2.30
(60.2) 1.91
(66.1) 2.11 (62.5) 1.11 (62.5)
2D37 1272 235 8.05 (50.2) 2.67
(66.8) 2.37
(73.1) 2.55 (69.3) 1.29 (69.3)
2D36 1272 235 8.51 (49.7) 3.32
(63.3) 2.70
(71.0) 3.10 (66.0) 1.54 (66.0)
2D28 1272 225 4.77 (45.2) 3.85
(64.6) 2.65
(72.0) 3.32 (67.8) 1.62 (67.8)
2D54 1381 235 7.19 (41.0) 3.62
(59.5) 2.67
(67.6) 3.15 (63.0) 1.62 (63.0)
2D34 1381 235 7.28 (46.4) 1.93
(66.3) 1.62
(70.5) 1.83 (67.7) 0.88 (67.7)
2D33 1381 235 7.28 (43.7) 2,55
(62.8) 1.87
(69.4) 2.30 (65.2) 1.11 (65.2)
2D31 1381 235 7.48 (41.4) 2.85
(64.3) 1.70
(73.2) 2.15(70.5) 1.05 (70.5)
b
“
Degree of polymerization. Temperature of predegradation. c Maximum rate at Td/190i, first 190. e
190n, second
190. ' Interpolated 190 °C. g Rate at 180 °C. b a values at which rate was observed are in parentheses.

degraded at 190 °C until a regular and slowly decreasing

rate was attained. At this point three to five rate mea-
surements were averaged and recorded as the rate at 190¡
for an average value of the percentage degradation. The
change in percentage degradation during rate measure-
ments at 180-190 °C rarely exceeded 1.0% of the total
degradation. The temperature was then lowered to 180
°C, allowed to line out, and the average rate and average
value of percent degradation again determined. The tem-
perature was then raised to 190 °C where the average rate,
190n, and the average percent degradation was again ob-
tained.
The values of rate as /s for 190: and 190n were plotted
as a function of percentage degradation and the interpo-
lated rate for 190 °C at the percent degradation at which
the 180 °C measurement had been made was obtained.
The interpolated rates at 190 °C and the observed rates
at 180 °C were used to calculate correct activation energies.
In order to calculate frequency factors it was assumed that
the rate constant was equal to the observed rate expressed
as the fraction of a chain degrading per second. Three to
six separate determinations of activation energy and fre-
quency factor were made for each PVC sample and
standard deviations are calculated and recorded for each
activation energy in Table IV.
Activation energies were calculated from rates, /dt,
using the In (rate) vs. 1/T relationship. Only when the
fraction of degrading chains remained constant could the
observed rates be taken to represent the rate constants for
the zero-order reaction of unzipping. Frequency factors
were calculated from these rate constants according to the
Arrhenius equation, k = exp(-£A/R).
Figure 3 is a photograph of the run sheet on which rates
at 190¡, 180 °C, and 190¡i for sample DP 1272 were mea-
sured after the predegradation at 220 °C shown in Figure
1. Peaks at 180 °C appearing during the central portion
of the photograph actually have about half the areas of the
peaks at 190 °C but appear larger due to a twofold change
in attenuations. Peak areas, sample weights, and weight
Figure 3. Photograph of run sheet for 2D61B. DP 1272 predegraded
at 220 °C. Peaks at 60-s intervals. Change in attenuation between
peaks 28 and 29 and between 59 and 60. Left to right: rates at 190,,
180, and 190,, taken as average of peaks 22-26, 51-55, and 74-78.
Peaks at 180 °C appear doubled by change in attenuation.
losses during predegradation and rate determination at
180-190 °C were entered into a computer program which
gave a printout of rates at 60-s intervals
as a function of
time and corresponding values of percent degradation.
Degradation rates at the maximum predegradation rate,
190I; 180,190n, and the interpolated degradation rate at
190 °C are recorded in Table II. The percentage degra-
dation at which each rate was determined is entered in
parentheses following the rate. The correct activation
energies and frequency factors were calculated from rates
190, interpolated and 180 °C. Upper limit activation en-
ergies were calculated from the maximum rates during
predegradation and the rate, 190^ The upper limit can
be specified because in the deceleratory portion of the
degradation the 190j rate will always be significantly lower
than it would be from changes in temperature alone be-
cause of the deceleratory nature of the reaction. The lower
than expected rate at the lower temperature will always
give activation energies and frequency factors larger than
the correct values.
Dehydrochlorination of Poly(vlnyl chloride) The Journal of Physical Chemistry, Vol. 87, No. 26, 1983 5379

TABLE III: Upper Limit, Lower Limit, and Correct fraction of producing zip chains remains constant, all five
Activation Energy PVC samples have correct activation energies of 28-29
activation energy, kcal/mol and frequency factors in the range 108-109 s"1.
kcal/mol The rates of degradation of the individual samples, how-
deg upper lower ever, varied at least threefold. When rates at different
run polymn limit0 limit6 correct0 temperatures were used to calculate activation energies
2D53 25.2
without assuring a constant fraction of producing chains,
634 29.3 22.9
2D50 634 33.8 21.1 30.4 upper limit activation energies for individual runs ranged
2D51 634 32.1 21.1 30.7 from 29 to 40 kcal/mol and lower limit activation energies
2D58 634 32.8 21.5 26.9 ranged from 15 to 25 kcal/mol. Although these calculated
2D43 634 37.3 19.0 26.2 upper and lower limit activation energies vary excessively
2D41 634 35.6 21.9 30.7 among themselves, the standard deviations for the average
2D59 684 36.7 14.8 28.0 values of individual samples are not significantly different
2D49 684 35.8 17.3 27.8
2D47 684 33.5 17.9 26.4 from the standard deviations observed for the correct
2D46 684 32.1 16.8 30.1 values.
2D24 684 33.4 16.4 30.0
2D23 684 33.4 16.1 26.4 Discussion
2D57 917 35 19.1 25.7 The information reported in this paper appears to be
1D16 917 35.9 14.1 29.2 significant for at least two reasons: First, our knowledge
2D 17 917 40.2 19.1 29.7 of the degradation characteristics of PVC is increased.
2D61 1272 31.0 24.7 29.7
2D39 1272 34.7 23.9 28.1 Second, limitations are suggested for the proper application
2D38 1272 35.5 22.7 26.9 of the Arrhenius equation to the degradation of PVC and,
2D37 1272 35.4 16.9 28.4 presumably, to other acceleratory degradations, as well.
2D36 1272 33.7 23.4 29.2 Similar limitations would be expected to apply to any
2D28 1272 33.0 20.5 29.9 reaction for which the reaction rate as a function of time
2D54 1381 31.1 20.8 27.7 cannot be accurately expressed in terms of a simple rate
2D34 1381 37.7 25.4 30.4
2D33 1381 34.8 21.8 30.4 equation containing a single rate constant.
2D31 1381 34.0 20.1 29.9 In order to understand why precautions were taken to
assure that rates used to calculate activation energies were
0 ’
Rate at maximum predegradation/190,. 1
180/190,,. measured under conditions of constant a, an understand-
0
190 interpolated/180.
ing of the kinetic model that has been assumed to repre-
TABLE IV: Average Values of Activation Energies,0 sent the zipper mechanism is essential. In the zipper
Their Standard Deviations, and Ranges of Frequency mechanism it is assumed that zip chains are initiated at
Factors for the Correct Values of the Activation Energy relatively few positions along a PVC chain. Once a zip
correct value 190
chain is initiated, it unzips at a constant rate. Since the
interpolated/180 hydrogen chloride involved in initiation is negligible when
compared to the hydrogen chloride evolved in the zip re-
log lower limit
action, the rate of hydrogen chloride evolution represents
upper limit range of 180/190n
deg max rate/190 exponent, activation only the zip reaction.10 The changes in rate occurring from
polymn act energy act energy s'1 energy the beginning to the end of a degradation are caused by
634 33.5 2.8 7-10 changes in the fraction (number) of zip chains. Zip chains
± 28.3 ± 2.3 21.3 ± 1.3
are initiated and during the acceleratory phase, the hy-
684 34.2 ± 1.7 28.1 ± 1.6 8-9 16.6 ± 1.1
917 37.0 ± 2.8 28.2 ± 2.2 7-9 17.4 ± 2.9 drogen chloride production from newly initiated zip chains
1172 33.9 ± 1.7 28.4 ± 1.3 8-9 22.0 ± 2.9 adds to that of already producing chains and the rate
1381 34.4 ± 2.7 29.5 ± 1.3 8-9 22.0 ± 1.5 increases. At the maximum rate the first started zip chains
0
kcal/mol. have completely degraded and beyond this time more zip
chains are terminating than are starting. The fraction of
Lower limit activation energies were calculated from degrading chains decreases during the deceleratory phase
rates at 180 °C and 190n. The rate observed at 190n will of the degradation. Even though the rate, da/df, changes
be less than it should be because of deceleration and the from the beginning to the end of a degradation, the zip rate
calculated activation energies will be too low. per producing chain remains constant. The rate changes
Upper limit, lower limit, and correct activation energies are caused entirely by changes in the fraction of degrading
for individual runs are summarized in Table III. The chains.
frequency factors for the correct values have also been On the basis of this model, da/dt at any degree of
reported. Average values of activation energies for each degradation is a direct measure of the constant zip rate
sample and their standard deviations are recorded in Table for whatever fraction (or number) of chains is producing
IV. The range of frequency factor associated with the at that time and at that value of a. Activation energies
correct value of the activation energy is also included in for the zip reaction could be obtained from any position
Table IV. along the acceleratory curve if the rates at the different
Each activation energy and frequency factor is calculated temperatures were measured under conditions where the
from a run having 30-80 peaks in the predegradation and fraction of degrading chains remained constant.
60-120 peaks at 180-190 °C. A computer program lists A convenient range for measuring chains is represented
for each peak area the value of a, the time, and the rate by the straight line portions of the degradation curves
as /60 s. Values in the tables were calculated from this shown in Figure 2. In this region the rate is a straight line
very large amount of original data. function of a. Rates 190i, 180, and 190n can be measured
and the interpolated rate can be estimated at 190 °C at
Results the value of a where the rate at 180 °C was obtained.
When precautions are taken to assure that rates at 180
and 190 °C are measured under conditions where the (10) Joseph D. Danforth, J. Macromol. Set., Chem., 19, 897 (1983).
5380 The Journal of Physical Chemistry, Vol. 87, No. 26, 1983
When this is done the interpolated rate at 190 °C will
represent the same fraction of chains that were producing
at 180 °C. Activation energies based on rates having a
constant fraction of producing chains are recorded as
correct activation energies in Tables III and IV.
The calculation of a valid frequency factor requires a
correct evaluation of the rate constant. Since the zip re-
action is zero order, (da/dt)„ = K, there is justification for
assuming that the rate constant is equal to the rate at a
constant fraction of producing chains. Certainly, the units,
fraction per second, are appropriate. The equality of rate
and rate constant is expected for zero-order reactions but
is not entirely proper in this situation for the following
reason. On the basis of the assumed mechanism the ob-
served degradation rate, da/dt, at any time will equal the
intrinsic degradation rate times the fraction of chains
degrading. For any given position on the degradation curve
da/dt is a constant, but only when the fraction of de-
grading chains is 1.0 will the observed rate equal the rate
constant. Thus K is really kF where k is the true rate
constant and F is the fraction of producing chains. The
fraction of producing chains has been estimated to fall in
the range of 0.5 to 0.7 under the conditions where the rate
measurements have been made. These values of F imply
that the rate constants obtained by assuming that the rate
equals the rate constant will never be in error by a factor
greater than 2. When frequency factors are expressed in
the range 108-109 s™1, the error introduced by assuming the
equality of rate and rate constant is negligible.
The uniform values of activation energies and the rel-
atively small variations in the values of the frequency
factors for five samples of PVC that exhibit significant
differences in their degradation behaviors gives credence
to the assumptions of the kinetic model and to the pro-
cedure whereby activation energies were determined.
The values of activation energy are in reasonable
agreement with those reported by Crosato-Arnaldi and
co-workers11 under vacuum and by Thallmaier and Braun12
in a stream of nitrogen. Under vacuum or in a stream of
nitrogen, hydrogen chloride would be effectively removed
so that it could not initiate new chains. It seems probable
that these literature activation energies were measured
under conditions where the number of chains unzipping
did not change significantly over the time period during
which the rates were observed.
On the other hand, activation energies of 38-51 kcal/mol
reported by Bataille and Van13 would be expected because
of the way the rates were measured. In the normal op-
eration of DTG, DTA, and TGA a sample is subjected to
increasing temperatures and reaction rates estimated from
the rates of weight loss or changes in some other param-
eter. If we start with a fresh sample the rate at the higher
temperature will be greater than the rate due to the in-
crease in temperature because of the acceleratory nature
of the reaction. A higher than normal rate at the high
temperatures will always give incorrect and abnormally
high values of the activation energy.
Activation energies reported in the literature show a
significant variation in values under conditions where the
individual values appear to be reproducible. It seems
appropriate to consider our upper and lower limit activa-
tion energies to demonstrate how reproducible but in-
correct values of activation energy can be obtained when
(11) A. Crosato-Arnaldi, G. Palma, and G. Talamini, Mater. Plast.
Elastomeri., 32, 50 (1966).
(12) M. Thallmaier and D. Braun, Makromol. Chem., 108, 241 (1967).
(13) P. Bataille and B. T. Van, J. Polym. Sci., Part A-l, 10, 1097
(1972).
Danforth and Indiveri
proper precautions are not taken to assure that the rates
at two different temperatures are compared at a constant
fraction of degrading chains. Activation energies are
normally obtained by the Arrhenium equation from rate
constants obtained from plots of rate as a function of a
at several different temperatures. At different tempera-
tures the fraction of chains initiating per second will
change significantly. For comparable values of a at dif-
ferent temperatures, there will be different fractions of
degrading chains contributing to the observed rates. The
calculated activation energies and frequency factors may
be reproducible but they will not be correct unless com-
parisons of rate are made at a constant fraction of pro-
ducing chains.
It is possible to establish a range of values which must
include the correct activation energy. The maximum
degradation rates at 220, 225, or 235 °C can be used in
conjunction with the rates at 190j to calculate the upper
limits of the activation energy. Upper limit activation
energies recorded in Table III range from 29.3 to 40.2
kcal/mol and are uniformly higher than the correct acti-
vation energy of 28-29 kcal/mol. The higher values of the
activation would be expected because the fraction of chains
producing at the maximum rate and higher temperature
will be larger than the fraction of chains producing at'190i.
In Table III under the column heading, lower limit, are
recorded activation energies calculated from rates observed
at 180 °C and 190n under conditions where the fraction
of chains producing hydrogen chloride is decreasing be-
tween rate measurements. The rates at 180 °C represent
a higher fraction of producing chains than the rates at 190n
and the activation energies are lower than expected. The
range of lower limit activation energies was 14.1-25.4
kcal/mol. Although activation energies for the different
samples displayed considerable variation, the average ac-
tivation energies of each sample had standard deviations
that were not appreciably different from the standard
deviations observed for the correct values. Thus carefully
controlled experiments can give reproducible and precise
values of activation energies that are incorrect.
Preexponential factors associated with upper limit and
lower limit activation energies ranged from 102 to 1015 s"1.
The extreme variations of rate as a function of time il-
lustrated in Figure 1 makes it unlikely that any meaningful
function can be found to express rate changes as a function
of time or a. There may be ranges in acceleratory deg-
radations where a conventional rate behavior can be es-
timated but the rate constants so obtained must always
be of questionable significance. Unless rates can be cor-
rectly expressed as a function of time by using a single rate
constant, activation energies and frequency factors from
the Arrhenium equation are likely to be in error. The
techniques described in this paper illustrate how correct
activation energies and frequency factors can be deter-
mined for acceleratory degradations where there is no
meaningful equation describing rate as a function of time
or a.
It is probably not important whether the activation
energy for the dehydrochlorination of PVC is 24, 28, or 32
kcal/mol. It does seem important to understand the
mechanism of dehydrochorination and to demonstrate that
the Arrhenius equation applies to acceleratory degrada-
tions when proper precautions are taken in the measure-
ment of rates.
Acknowledgment. Acknowledgment is made to the
donors of the Petroleum Research Fund, administered by
the American Chemical Society, for support of this work.
Registry No. Poly(vinyl chloride) (homopolymer), 9002-86-2.