Study Behavior Non Arrhenius 1 or Kinetic Expressions

STUDY OF THE BEHAVIOR OF NON-ARRHENIUS
FIRST ORDER KINETIC EXPRESSIONS

by
RAMON J. FLORES DOMINGUEZ. B.S. in Ch.E.
A THESIS
IN
CHEMICAL ENGINEERING
Submitted to the Graduate Faculty
of Texas Tech University in
Partlal Fulfinment of
the Requirements for
the Degree of
MASTER OF SCIENCE
IN
CHEMICAL ENGINEERING
Approved
May, 1988
ACKNOWLEDGEMENTS
I would like to express my gratitude to my advisor Dr. E. Fischer

for his guidance through this work and for his
that led me to the completion of the M.S. degree.
help and suggestions

I would
also
like
to express my gratitude to Dr. R. R. Rhinehart for his suggestions and

for being an active member of my committee.
This work
Dominguez, my
is
dedicated to my parents, R.
grandfathers, R.
J. Flores and A. A.
Dominguez and E. Lozano, and to my
brother, R. J. Flores, for their constant support and inspiration.

I would like to thank my friends, especially
always
H.
took the time to listen and make suggestions.
A.
Garza, who
I am especially
thankful to E. D. de Larralde for her help and encouragement.
11
TABLE OF CONTENTS
ACKNOWLEDG EMENT S
ii
LIST OF TABLES
LIST OF FIGURES
vi
NOMENCLATURE
I.
II.
III.
IV.
viii
INTRODUCTION
LITERATURE REVIEW
COATS AND REDFERN TECHNIQUE
10
3.1
Derivation of the CR Technique
10
3.2
N\americal Determination of Kinetic Parameters

Using the CR Technique
13
THE BEHAVIOR OF FIRST ORDER GAUSSIAN DISTRIBUTED

KINETICS
18
4.1
Introduction
18
4.2
Derivation of Gaussian Distributed Model
18
4.3
V.
Numerical Approximation for the Gaussian

Model
COMPARISON AMONG TECHNIQUES TO RETRIEVE KINETIC
21
PARAMETERS FROM THERMOGRAVIMETRY DATA
34
5.1 Introduction
34
5.2
Perturbed Data
34
5.3
Coats and Redfern Technique
36
5.4 Modified Coats and Redfern Technique I
36
5.5
Modified Coats and Redfern Technique II
38
5.6
Chen-Nuttal Equation
39
111
VI.
VII.
5.7
Reich and Stivala Equation
39
5.8
Horowitz and Metzger Equation
40
5.9
One-Way Analysis of Variance
49
TEMPERATURE DEPENDENT RATE CONSTANTS IN

NON-ISOTHERMAL FIRST ORDER REACTIONS
60
6.1 Introduction
60
6.2
Theory
61
CONCLUSIONS
72
7.1
72
Recommendations
LITERATURE CITED
73
IV
LIST OF TABLES
Table
Page
Results from Integration of Equation (3.4) Used in the

Coats and Redfern Method to Calculate Kinetic
Parameters
14
Linear Regression Results Obtained by Using the Coats

and Redfern Technique on the Data Given in Table 1
17
Comparison Between the Selected Set of Parameters Used

in the Integration of Equation (4.3), and the Predicted
Values Obtained With a Linear Regression With Equation
(4.20)
23
Coefficients for Equations (14a) and (14b)
Roots of the Hermite Pol^momial of Order 5, and Weight

Factors for the Gauss-Hermite Quadrature
28
Selected Values of E and \Q/P to be Used for the

Integration of Equation (3.4)
35
Values of Seed to be Used With the Random Number

Generator
37
Comparison of Results by Different Methods Using

Theoretical Data From Gear's Integration
42
Comparisons of the Results of Different Methods for

Perturbed Theoretical Data by Using Random Number
Generator for Parameters E-20,000 ko/)9-lE5
43

Generator for Parameters E-30,000 ko/i9-lE6
44

Generator for Parameters E-60,000 ko/)9-lE3
45

Generator for Parameters E-10,000 ko/;9-lE7
46
One Way Analysis of Variance for Perturbed Data of

the Following Parameters E-20,000 ko/)3-lE5
51
7
8
9
10
11
12
13
24
14
15
16

the Following Parameters E-30,000 ko/^-lE6
52

53

54
17
Scheffe's Test for the Data in Table 13
56
18
57
19
58
20
21

Selected Parameters Used in the Integration of
Equation (6.11)
59
22
23
24
64
Results From the Integration of Equation (6.11)

Case When b-0
65

Case When b1
66
Results From the Integration of Equation(6.11)

Case When b-1/2
67
25
Results From the Integration of Equation (6.11) Using a

Modified Coata and Redfern Equation Case When b1
70
26
Results From the Integration of Equation (6.11) Using a

Modified Coats and Redfern Equation Case When b-1/2
71
VI
LIST OF FIGURES
Figure
Page
Coats and Redfern plot for the data in Table 1
15
Comparison between the values of conversion versus

temperature predicted using Coats and Redfern, the
method proposed and numerical integration of the
Arrhenius expression
25
Coats and Redfern plot of concentration versus

temperature profiles obtained with Gaussian distributed
kinetics for E-20,000 ko/i9-10,000 and different values
of standard deviation
30

temperature profiles obtained with Arrhenius type
expressions for E-20,000 and different values of
Ô/P (different heating ramps)
31

temperature profiles obtained with Gaussian distributed
kinetics for E-20,000 a=10% and different values of
ko/i8 (different heating ramps)
32
Perturbation of theoretical data using random number

generator
47
Coats and Redfern plot for the data in Figure 6
48
Coats and Redfern plot for the three cases of b

studied
68
vii
NOMENCLATURE
reactant concentration, concentration units
product concentration, concentration units
parameters defined in Equations (14a) and (14b)
activation energy, kcal/gmol
EQ
mean value of activation energies
Arrhenius frequency factor
Gauss-Hermite polynomial order
ideal gas constant, 1.9872 kcal/gmol K
temperature of the reacting system, K
time
fractional conversion of A
weight factors for Gauss-Hermite Quadrature
Greek Symbols
yS
heating ramp, k/time
standard deviation, kcal/gmol
heat input to the reacting system
roots of Gauss-Hermite polynomial
Subscripts
CR
Coats and Redfern values
ith fraction of the raaterial
initial value
viii
CHAPTER I
INTRODUCTION
The values of kinetic parameters of a given chemical reaction are

normally
from
experimental
data
of
reactions
under
isothermal
conditions; however, recently numerous investigators in the

thermal
analysis have attempted
to obtain
kinetic
field
of
parameter values
from non-isothermal methods such as dynamic thermogravimetric analysis

(TGA),
and programmed heating.
system
temperature is
In the dynamic
increased at
TGA experiment,
a predetermined
rate,
and
the
the
change of a solid reactant mass is monitored by measuring
its
weight
loss
of
kinetic
as
the
parameters
evolved gas
escapes.
from a constant
The
determination
heating rate in
the TGA analysis
can be
done using the Coats and Redfern method (1964), and many investigators
have tried to compare their experimental results with
since
it is much
simpler and easier
to use than
that
technique
the ones found
in
literature.
One
of
behavior
has
be
the
objectives of this work is to study the dynamic TGA
of a reactant system with Gaussian distributed kinetics.
It
been shown that a complicated reaction such as coal pyrolysis can

viewed
statistical
view
as
set
Gaussian
of
distribution
can provide valuable
reaction.
Hermite
independent
In this work
chemical reactions
of activation
insight into the

a
quadrature, will be
energies, and this
overall kinetics of
numerical integration
used with a
having
technique,
modified Coats and
the
GaussRedfern
equation to analyze dynamic TGA behavior of the
Gaussian
distributed
model.
Another
random
used
important
aim of
data error contained

to determine kinetic
this work is
in data^
In
to study the
this work, errors
parameters by several
of variance, will be applied
effect of
methods.
to establish if there
will be
Analysis
is a significant
difference on the prediction of the activation energy by the different

methods used in this work.
The
is
last objective of this work is to investigate whether
there
a method to detect a temperature dependency of the form koT"e'^/^^
in the activation energy of a first order reaction using the Coats and
Redfern method.
CHAPTER II
LITERATURE REVIEW
Thermogravimetric
analysis (TGA) has come into wide use recently
since it has many advantages over conventional isothermal
methods
of
generating
number
of
kinetic
expression
parameters;
and
investigators have demonstrated its usefulness. Following is
brief
description of these methods.

Van
Kreveleen
integrating
plot
of
(1951)
the rate equation.
the
data, from
described
This
which
the
this technique requires the
approximate
means
technique resulted in a
activation energy
exponential factor can be easily obtained.

by
an
of
linear
and the pre-
To obtain a reaction order
plotting of various functions
of the
sample weight until a linear relationship is obtained.

Later,
these
other investigators developed different methods,
techniques
differentiations
involve
either
graphical
of the thermographical data.
or
Some of
numerical
These differentiation
procedures are cumbersome and result in large errors when
the
curves
have high slopes.

Freeman and Carroll (1958) derived an equation for non-reversible
reactions in which the rate dependent parameters, such
energy
and
order
experimental
of
curve.
reaction,
To apply
may
this
be
as
calculated from
method to
raethod.
developing a
The
technique which
solution
can
be
replaced the
obtained
single
differential thermal
analysis data, they expanded the derivation of Borchardt

(1957),
activation
either
and
trial and
Daniels
error
graphically
or
analytically.
However,
as
stated
earlier,
this raethod requires
numerical or graphical differentiations which result in large errors.

The equation proposed is:
-E A(l/T)
ALn(dx/dt)
R A Ln(x)
_ ^
^^ i)
A Ln(x)
Where:
X - mole fraction of reactant
E activation energy
R = gas constant
T - absolute temperature
n - order of reaction
A = differential
The
derivation
expression
for
the
of
the above
rate
of
equation
is
based on
the
rate
disappearance
of
reactant
and
then
an
approximation which
differentiating with respect to dx/dt, x and T.

Horowitz
allowed
Metzger
determination
reactions.
and
and
(1963) developed
of
the
kinetic
parameters
for
pyrolysis
The assumptions made are that no intermediates are formed
that the products of
definition
the reaction escapes immediately,
of a reference temperature,
that the rate equation can be integrated.
then the
leads to an approximation
so
For gas phase reactions the
equation is:
Ln
l-(l-x)^-"
1-n
Where
Ln
koRT
L /9E
-,2
s
L + L_
RTs
RTs^
(2.2)
ko = frequency factor
fi - heating ramp
Tg = reference temperature
6 = characteristic temperature
In this method, a plot of the solid weight fraction
temperature
energy.
is plotted, the slope
of this plot gives
left
versus
the activation
The main purpose of this method was to develop an approximate
integral method which would provide a simpler and easier way to obtain
kinetic parameters.
Coats
and
approximation
prior
Redfern
(1964)
to calculate kinetic
knowledge of the
developed
another
parameters.
value of the
mathematical
In this
order of reaction
technique a
is required.
The equation is:

Ln
"l-(l-x)l--^"l
= Ln
(l-n)T2
Ln
The
koR(l-2RT)
. /3E
Ln(l-x)
Ln
RT
koR(l-2RT)
. )3E
RT
(2.3)
(n^l)
(2.4)
(n=l)
slope of the plot of weight fraction left versus the inverse
of temperature gives the activation energy and the intercept gives the
value of the pre-exponential factor.
A more detailed
description
of
this method will be discussed in detail in later chapters.

MacCallum
and Tanner (1970) proposed
to calculate kinetic parameters.
another empirical equation
They believe that
the
substitution
for the rate constant in a decomposition reaction can only be made for
an equation involving an isotherraal rate.
follows
The equation is
listed
as
LoglO
l-d-x)!-^" = Logio^ - 0.485E0-^35

1-n
^R
0.449 + 0.217E*103"
(2.5)
Gorbachev (1975) proposed another technique and the equation is
Ln
g(x)
-LnO - L
+ 2
fi
RT
The
(2.6)
RT
solution of the equation above is possible only by trial and
error treatment
Reich and Stivala (1980) proposed another equation
kinetic
parameters.
This equation calculates
pairs of given values of 1-x and T.
1-(1-Xi)l--" Ti+1I2l
Ln
Ll-(l-Xi+i)
1 J J
The equation is given as:
E 1
R T^
of
the
reaction and
the
calculate
values of E/R for two
(2.7)
Ti+lJ
This method provides an iterative technique for

order
to
activation
determining
energy by
varying
the
the
reaction order until the intercept is closest to zero.

Chen and Nuttal (1980) derived an equation as follows:
1-x - EXP
ko
RT2
. /3 E+2RT
EXP
E
RT
(2.8)
An
slope
iterative regression analysis
will allow calculation
of the
and intercept; the iteration first requires a guess value of E,
with which one can compute E and k^ until a tolerance is achieved.

The
literature
references
on
combustion
and
pyrolysis
to pyrolytic reaction models based on
Gaussian distribution of activation energies.

used
to describe the pyrolysis of coal
Pitt
(1962)], oil
[Lewellen, et al.
contains many
the concept of a
Such models
have been
[Anthony and Howard
shale [Campbell, et al.
(1980)],
and
(1976),
cellulose
(1977)].
Pitt dealt with the evolution of volatile products from coal, and
suggested that coal be a mixture of many components
independently,
which
decomposed
and the decompositions have a wide range of activation
energies based on a large number of simplifying assumptions.

Anthony
parallel
(1976) dealt with coal pyrolysis as a set of independent
reactions
activation energies.
having
Gaussian
distribution of
The equation he derived is as follows:
f expjlOp
1-x
a statistical
exp(-E/RT) dT^ f(E) dE
(2.9)
'^ )9 J T O
where:
f(E) - :^
exp
Efforts
(E-Eo)2"
(2.10)
2(7-
have been made to integrate this reaction model, such as
Suuberg (1983) , and Nuttal (1983) but they are not accurate
not
shown
the behavior
experimental conditions.
of
this
reacting
system
for
and have
different
8
In this work, the numerical tchnique of Gauss-Hermite quadrature
and
a modified Coats and
Redfern equation will be
used to integrate
the Gaussian distributed model.

Several
Redfern
techniques
are available
equation, such as the
to
integrate the
predictor corrector method and
more
suitable
statistic
These
for our
problem.
library (IMSL) has
methods find an
these techniques,
Gear's stiff methods (bdf) are
The international
the algorithms for
approximation to the
basic
methods
are
of
implicit
mathematics and
the above methods.
solution of a
initial value ordinary differential equations of the

The
and
Euler, Runge-Kutta, Adams family, and
the backward difference formula (bdf) methods. Of

Adams
Coats
form y'=f(x,y).
linear multistep
implicitness of the basic formula requires that the
system of
type.
algebraic
The
systera
of equations be solved at each step. A variety of corrector iteration

methods
and
are available for this, more details about these
algorithms
(1971)].
are
available
in
the
technical
techniques
literature
[Gear
During this work the above bdf algorithras will be used.
The Coats and Redfern equation will be solved numerically for the
cases
when the Arrhenius expression is supposed to have a temperature
dependence
of
literature
the
form;
that Varhegyi
T'êxp [ -E/RT] .
(1977)
used
Pade
It was found
in the
approximations
and
linearization of the Coats and Redfern equation to solve the Arrhenius

expression but the expressions derived contain significant
to
linearization.
interpolation
House
(1980) used
erapirical
error
due
relationships but
has to be made in the tables given in his work and this
leads to error.
solved
In this work the Coats and Redfern equation will be
with the Gear's
package, a very
eliminate truncation error.
accurate method that
should
CHAPTER III
COATS AND REDFERN TECHNIQUE
3.1 Derivation of the CR Technique

To
the
understand this work better
theory behind the Coats
it is a necessity
to understand
and Redfern equation. For
a first order
reaction, the rate of disappearance of A may be expressed as follows:
A(s)
B(g)
(3-1)
and
5^ . . ko e-E/RT A
(3.2)
dt
for a reaction carried under a constant heating rate:

13-
(3.3)
dt
combining (3.2) and (3.3)

^ = - O e-E/RT dT
A
/9
(3.4)
integrating from:
T = To
A = Ao
T = T
A = A
gives:
10
11
Lni- -- ^ f ^ e-E/RT dT
Ao
^ JTO
The
right hand
analytical
side
solution.
To
(3.5)
of
equation
integrate
(3.5) has no
it, the
following
closed
form
change
of
variable is required.
Let
(3.6)
X -
RT
so
dx -'
dT
(3.7)
and
-E dx
dT
(3.7a)
R x2
replacing (3.6) and (3.7a) in (3.5)
Lni_ = 0 r ldx
Ao
/9R Jxo x2
(3.8)
integration by parts yields:

-X
\L1
dx =
x2
Jx2
(3.9)
X3
another integration by parts gives

4
.e-x ^ 2e-x ^ r6x-^
x2
x3
(3.10)
J x*^
thus, further integration gives the series

dx
\T2
-e-X
1 -l + il
2
substituting (3.11) into (3.8):
(-l)"(n+l)!
rT
(3.11)
12
A
koE e-^
AO
;9R x2
(-l)"(n+l)!
1 - 2'
11 + 3'
l
X
x^2
(3.12)
rT\
and substituting x-E/RT

2IRT ^ 3 ! R 2 T 2
e-E/RT
I^QRT^
(3.13)
Ê
AO
Coats and Redfern approximate the above equation as follows:

Ln
'2
.^koRT^
fiE
RT
AoJ
(3.14)
now defining:
(3.15)
- 1-x
AO
substitution of the last equation in (3.14) gives;
Ln
Ln(l-x)
Ln 'koR
L )9E J
(3.16)
RT
This last equation is of the form:
y - ax + b
(3.17)
where:
Ln(l-x)
y - Ln
(3.18)
X - 1/T
(3.19)
a - -E/R
(3.20)
Ln
k_oR_
Ê J
(3.21)
13
As
shown above, Coats and Redfern approximates
equation
since
(3.11) by neglecting
it may
temperature
be
shown
of
except the first one,
for most values
of
and for the
range over which reactions generally occur the expression
[1-2!RT/E+3!RT/E-...]
calculate
that
all the terms
the series
is
the parameters
essentially
constant
(equal
to
using this method, a plot of
1). To
the weight
fraction left versus the inverse of temperature yields a straight line

with
slope equal
calculated
and
to -E/R
the
from which
frequency factor
the activation
can be
energy can be
calculated
from the
intercept.
3.2 Numerical Determination of Kinetc Pararaeters

Using the CR Technique
Equation (3.4) can be integrated with great accuracy using Gear's
method.
The procedure is the following: a set of selected parameters
(frequency
factor and heating
rate combined as
one, and
activation
energy) are given to perform the numerical integration this last gives
as
output
values
of 1-x
(dependent variable) and T
(independent
variable), these values are used with equations (3.18), (3.19), (3.20)
and
(3.21) to produce a plot which gives a straight line with slope E
and
ko/^
predicted.
The results
are given in Tables
1, 2 and
in
Figure 1.
Table
1 shows the results
of the integration of
equation (3.4)
and then used in the Coats and Redfern method, as defined in equations
(3.18) and (3.19).
This data is plotted in Figure 1, from
can be seen that a straight line is found.
which
it
14
Table 1
Results from Integration of Equation (3.4) Used
in the Coats And Redfem Method to Calculate
Kinetic Parameters
Parameters
20,000
ko/)9 = 1 E 5
Temp
Ln[-Ln(l-x)/T2]
X
1000./T
510
520
530
540
550
0.99356
0.99030
0.98560
0.97891
0.96956
-17.5291
-17.1519
-16.7890
-16.4395
-16.1028
1.9608
1.9231
1.8868
1.8519
1.8182
560
570
580
590
600
0.95667
0.93920
0.91590
0.88542
0.84629
-15.7780
-15.4647
-15.1622
-14.8699
-14.5874
1.7857
1.7544
1.7241
1.6949
1.6667
610
620
630
640
650
0.79719
0.73714
0.66583
0.58402
0.49390
-14.3141
-14.0496
-13.7936
-13.5455
-13.3051
1.6393
1.6129
1.5873
1.5625
1.5385
660
670
680
690
700
0.39927
0.30542
0.21842
0.14398
0.08605
-13.0719
-12.8457
-12.6262
-12.4131
-12.2060
1,5152
1 4925
1 4707
1 4493
1 4286
710
720
0.04574
0.02115
-12.0047
-11.8091
1 4085
1 3889
15
Coats and Redfcrn plot

-14.5
-15 -15.5 (N
-16 16.5 17 -17.5 -18 -18.5

0.00165
0.00175
0.00185
0.00195
1/T
Figure 1.
Coats and Redfern plot for the data in Table 1
0.002'
16
Table
using
2 shows a linear regression in the form of equation (3.17)
the least squares method, and the desired parameters calculated
from equations (3.20) and (3.21).
17
Table 2
Linear Regression Results Obtained by Using the

Coats and Redfern Technique on the Data
Given in Table 1
Parameters : E
= 20,000
ko/)8 = 1 E 5
Intercept = b
2.06
Slope - a
-9991.97
R-square
0.9999
ko/^ * E 5
0.79137
E * E-3
19.856
CHAPTER IV
THE BEHAVIOR OF FIRST ORDER GAUSSIAN
DISTRIBUTED KINETICS
4.1 Introduction
It has been pointed out earlier that the use of a single reaction
model
is not adequate for many reactions.
In 1975 Anthony and Howard
proposed a decomposition mechanism of coal pyrolysis based on multiple

first order reactions that lead to a Gaussian distributed raodel.
The Gaussian distribution function is used to take
into
account
the range of activation energies expected with such a reaction systera.

The
assumptions
simultaneously,
rate,
and
Gaussian
made
are
that
the
and each reaction can
that only
multiple
be described by a
the activation energies
distribution
function.
reactions
The
occur
first order
vary according to
frequency
factors,
on
the
the
contrary, can be assumed to be identical.

Efforts
have been made to integrate this reaction raodel, such as
Suuberg (1983), and Nutall, et al. (1983), but they are

and
not
accurate
have not shown the behavior of this reacting systera for different
experimental conditions.
4.2 Derivation of Gaussian Distributed Model

Consider
a material which
is assumed to
large number of independent chemical reactions:
18
decompose following
19
Ai
A
>
Bi
(4.1)
first order kinetic expression for this single reaction can be
expressed as:
dA
(-E /RT)
_
dt
- -k e
"
(4.2)
If the reaction is carried under a constant heating rate, fi

dT/dt, equation (4.2) transforms to:
dA.
k^
-E./RT
t - - J: e ^
A^
dT
The integration of this equation will produce
(4.3)
conversion versus
temperature data for this particular system, such as:
k^
A^
Ln
^
A^
Since
J: e ^
fi
To
lo
-E^/RT
this equation is
dT
(4.4)
for only a differential element of the
reacting material, it can be extended to the whole material by:
Lim
S A.
(4.5a)
- A
Lim
n-
now defining:
S A^
lO
= A
(4.5b)
20
A
(4.6)
1 -X
equation (4.4) transforms to
-E/RT
T Y
Lim
1 -X
n-+o
dt
2
i=l
A.
e " o '^
lO
(4.7)
and in the limit
î -E/RT dT
^
^
d
lo
(4.8)
The fraction of original pyrolyzable material which at

has
an
activation energy
corresponding
probability
between
E and
distribution
E + dE
function,
is
and
time
t=0
equal to its
it can
be
expressed as:
A.
(4.9)
d _12 = f(E)dE
Because
it
can be seen
that
the raass lost
frora any single
reaction, is siraply a differential element of the totalraasslost from

the sample upon complete pyrolysis.
In
addition, if f(E)
is assuraed to be a Gaussian
distribution
with mean activation energy EQ and standard deviation a thus:
2a2
f(E)
y27r
(4.10)
^^
and:
E [0,oo]
Replacing
(4.11)
(4.9) and
(4.10) in
(4.8), and
assuming a
constant
value for k, the resulting equation is:
k
- -
00
1 - X
-E/RT^^
e ^ dT
f(E)dE
(4.12)
-00
The extension of the lower limit adds nothing to the value of the
integral.
4.3 Niomerical Approximation for the Gaussian Model

Equation
numerical
(4.12) does not have an analytical solution and needs a
solution.
Its inner
integral, or the
right hand side
of
equation (4.4) can be approximated by using one of several techniques,

such
as
(1963),
Gorbachev
those of
Coats
and
Freeraan and Carroll

Redfern
(1964),
(1958), Horowitz and

McCallum
and
Tanner
Metzger
(1970),
(1975), Reich and Stivala (1980) and modifications thereof.
Of these techniques, the one developed by Coats and Redfern
(CR)
is
the one used in this paper because it is the simplest to use and gives
good
agreement with predicted data.
this
correlation and improved the
CR.
The original CR equation was:
Fischer, et al. (1987)
accuracy of the data
studied
predicted by
22
2
Ln(l-x) -
Fischer,
selected
et
al. ,
values of
integrated
e"^/^"^
equation
activation energy
(4.13)
(4.2)
and k/^
nuraerically
ratio,
for
With
these
values, they produced conversion versus temperature data that was used
in
obtaining
kinetic
parameters
using
equation
(4.13).
It
was
demonstrated that there was a consistent difference between the values

of
the kinetic
produce
them
parameters predicted
(See
Table 3) ; but
by CR
there
and the
was a
values used
to
very good agreement
between the values of conversion produced by the numerical integration

and the ones generated using equation (4.15) with the values predicted
by
CR in
modified
nuraerical
Table 3.
A correlation
values from
the original
integration.
was proposed
to
obtain
kinetic pararaeters
Several regression
used
models were used
the
CR
in
the
for the
data in Table 3, and the following were selected because of their good
accuracy and simplicity:
Ln(k/)9)cR - Cii + C21 Ln(E) + 031 Ln(k/)3) + C4i[Ln(k/)3) ] ^(4.14a)
2
Ln(E)cR = C21 + C22 Ln(E) + C32 Ln(k/)9) + C42[Ln(k/y3) ]
The
values
1%
values
for the
coefficients are given
in Table 4.
These
will allow equation (4.13) to reproduce conversion data within
accuracy for the kinetic
data range shown in
Table 3.
shows a comparison between the method proposed here and

CR
. (4.14b)
technique.
Substitution
of the
correlations in equation (4.13) gives:
CR equation
and
the
Figure
original
the raentioned
23
Table 3
Comparison Between the Selected Set of Parameters

Used in the Integration of Equation (4.3), and
the Predicted Values Obtained With a Linear
Regression With Equation (4.20)
Used in Nijimerical Simulation

E X 10-3
ko/)9
Predicted by CR
E X 10-3
ko/fi
10
1
1
1
1
1
1
X
X
X
X
X
X
102
103
lO^
105
lO^
107
9.84
9.88
9.91
9.93
9.94
9.96
.7056
.7416
.7723
.7953
.8192
.8324
X
X
X
X
X
X
lO^
103
lO^
105
lO^
107
20
1
1
1
1
1
1
X
X
X
X
X
X
102
103
lO^
105
lO^
lO^
19.70
19.78
19.84
19.87
19.90
19.92
.7133
.7519
.7786
.8031
.8218
.8343
X
X
X
X
X
X
102
103
lO^
105
lO^
lO^
30
1
1
1
1
1
1
X
X
X
X
X
X
102
103
lO^
105
lO^
lO^
29.58
29.69
29.77
29.82
29.85
29.88
.7222
.7568
.7842
.8046
.8241
.8371
X
X
X
X
X
X
102
103
lO^
105
106
107
40
1
1
1
1
1
1
X
X
X
X
X
X
102
103
lO^
105
lO^
lO^
39.46
39.61
39.70
39.76
39.81
39.84
.7270
.7606
.7861
.8072
.8245
.8397
X
X
X
X
X
X
102
103
lO^
105
lO^
lO^
50
1
1
1
1
1
1
X
X
X
X
X
X
102
103
lO^
105
lO^
lO^
49.35
49.52
49.63
49.71
49.76
49.81
.7307
.7640
.7883
.8091
.8258
.8409
X
X
X
X
X
X
102
103
lO^
lO^
lO^
lO^
60
1
1
1
1
1
1
X
X
X
X
X
X
102
103
lO^
105
lO^
lO^
59.24
59.44
59.57
59.66
59.72
59.77
.7338
.7651
.7916
.8109
.8278
.8413
X
X
X
X
X
X
102
103
lO^
lO^
lO^
lO^
24
Table 4
Coefficients for Equations (14a) and (14b)
Cij
i/j
-0.56784
0.013176
0.03234
1.000922
1.0265
-0.002244
-0.000687
-0.000067503
25
n
u
Io
[i
t:
o
<
_ NUMERICAL SOLUTION
Figure 2.
THIS V.ORK
COATS-REDFERM
Comparison between the values of conversion versus

temperature predicted using Coats and Redfem, the
method proposed and numerical integration of the
Arrhenius expression
26
^CR/^T
RT
00
1 -X
e ^CR
f(E)dE
CR
(4.15)
00
Gauss-Hermite
equation
Hermite
and
quadrature
is based
will be
on the orthogonality
polynomials on the interval
weighting
used
function e-^2
[-,
^ Gaussian
to
integrate
this
property of the Gauss-
<]
with respect
quadrature can be
to the
stated as
follows:
00
g(x) e"^
m
S w
j-1
dx
-00
g(x.)
(4.16)
where
X = Roots of Gauss-Hermite Poljmomial
Wi
Using
= Weight factor of Gauss-Hermite Pol^momial
this
approach,
equation
(4.15)
needs
a variable
transformation as follows:
E -E
(4.17)
72 a
Substituting
this
change
into
equation
distributed model can be represented as follows:
(4.16)
the Gaussian
27
2
, s
-y dy
g(y) e -^ -^
- x - ^
(4.18)
-00
where
2
RT
k
^CR
'^CR
g(y) - e
The
hCR
the
(i.e., activation energy,

standard
combined
deviation).
as a ratio,
In
frequency factor, heating
this
the activation energy and
values
of
equation,
the frequency factor
only three parameters need to be varied.

for
(4.19)
solution of equation (4.18) requires the knowledge of four
parameters
and
^CR/^T
two of
them are
and the heating
ramp, so
The range of values selected
this ratio is given
standard deviation were selected as
activation
ramp
in Table 3.
The
a percentage of the
energy. Values of 0, 5, 10, 15, and 20% were selected for
this study.
For
this data ranges,
were studied.
The
orthogonal
values of
were studied
but the
the weight factors
accuracy
found
equation
in Stroud
(4.18)
conversion
versus
selected.
To
and
produces
Secrest
teraperature for
analyze
(1966).
simulated
this data
the
order
The
integration of
set of kinetic
CR
for this
polynomials
thermograviraetric
each
gain was
and the roots
polynomial are given in Table 5, values for higher

can be
polynomial
The results presented here are all based in a 5th order
pol^momial, higher orders

minimal.
several orders of
data of
pararaeters
method is widely used in
practice, where it is given as (refer to equation 4.13):
28
Table 5
Roots of the Hermite Polynomial of Order 5,

and Weight Factors for the Gauss-Hermite
Quadrature
Roots
(Xi)
Weight Factors
(w^)
+ 2.02018
28705
0.01995
32421
+ 0.95857
24646
0.39361
93232
00000
0.94530
87205
0.0000
29
Ln
^"^^-^^
Ln
T^
Where,
shows
and from
slope the
produce
similar results and need
values
but
at
10,000) as
the activation
the frequency
of the behavior
20,000;
(4.20)
RT
value of
the intercept
typical example
-
-L
;8E
from the
calculated
!!!
viewed using
energy
factor.
of a reacting
CR.
All
not be shown.
Figure
system (E =
other sets
As
is
of data
expected, at low
of activation energy the lines tend to follow a straight line,
some curvature is observed.

values of a
appears
between 10 to 20% of E, where the line is broken and
to have
interpreted
The most interesting behavior occurs
two values
as some sort of
for activation
energy.
This
parallel or serial competitive
mechanism, if Gaussian kinetics is not suspected; but as

Gokalgandhi
dominant
(1984), for
could
this type
reaction is observed.
of reaction
reaction
reported
mechanisras only
At higher values of a
be
by
the
the plot does
not behave like a line and no conclusions can be obtained.

Another
of
with
slope
important
between 10 to
the
value
observation
20% of E, the
of k/y9.
is
that
for
the
change in slope varies
values
slightly
This implies a change in the value of the
for different heating rates.
As can be seen frora Figure 4, for
a standard deviation equal to zero (that is Arrhenius
type
kinetics)
and different values of heating ramp, the data produces straight lines
with the same slope indicating constant activation energy,
Figure
illustrates the behavior of the reaction for a selected value of

20,000 and a - 10% for different values for k//9.
5
=
30
-10
-11 -
X
I
5
I
.
0.001
0.0014
0.0016
r
0.0018
1A
Figure 3.
Coats and Redfern plot of concentration versus teraperature

profiles obtained with Gaussian distributed kinetics for
E-20,000, ko/)9-10,000 and different values of standard
deviation
31
CM
*
0.0013
0.0017
0019
0.0021
1/T
Figure 4,
Coats and Redfern plot of concentration versus temperature

profiles obtained with Arrhenius type expressions for
E-20,000 and different values of ko/;9 (different heating
ramps)
32
1 o
X
A
X
A
X
A
-13.5
+
-14
A
O
+
+
-15
"^
-14.5 -
CM
X
o
"
0
O
-15.5 -
-16
O
A
-16.5
-17 0.0008
D
Figure 5
0.001
1E4
5E4
0.0014
0.0012
o
1/T
1E5
5E5
1E6
Coats and Redfem p l o t of concentration versus temperature

p r o f i l e s obtained with Gaussian d i s t r i b u t e d k i n e t i c s for
E-20,000, a-10% and different values of ko/;3 ( d i f f e r e n t
heating ramps)
33
As
can be seen, none of the data sets represent a straight line,
and the difference in slope is more evident at lower heating rates.

For constant temperature kinetics the solution for
the
equation
is similar to equation (4.18), where:
- _
-E/RT^
'
( X
g(y) = e
where t represents the reaction time in the system.
(4.21)
CHAPTER V
COMPARISON AMONG TECHNIQUES TO RETRIEVE KINETIC
PARAMETERS FROM THERMOGRAVIMETRY DATA
5.1 Introduction
Using theoretical TGA data for a first order simple reaction, six
kinetic
models will be compared
difference
following
in
the prediction
methods:
and try to establish

of kinetic
parameters
Coats and Redfern, Modified CR
if there is a
between the
(I), Modified
CR(II), Chen-Nuttal, Reich and Stivala and Horrowitz and Metzger.

It
is inevitable that error arises during any experimental data.
Therefore,
it is important to study the effect of the error contained
in experimental data for any of the above techniques.
5.2 Perturbed Data

To
study the behavior of
the above
methods in real systems,
simulated experimental values will be used.

values
of
integration
conversion versus
temperature
of equation (3.4) with
To obtain these data, the

obtained
by
numerical
the selected pararaeters shown in
Table 6, will be perturbed using:

(I-X)PERTURBED " [ 0-95 + 0.10 * RND *
(5.1)
(I-X)NUM]
Equation (5.1) will introduce a 10% random error in the values of

fractional
experiraental
conversion,
simulating
experimental error
for
a given
run. RND is a random variable that varies between 0 and
34
35
Table 6
Selected Values of E and V.Q/P to be Used for

the Integration of Equation (3.4).
E
ko/)3
20,000
1E5
30,000
1E6
60,000
1E3
10,000
1E7
36
1, and is obtained using the Knuth (1978) algorithm.
produces
This
algorithm
a set of random numbers for a given initial pararaeter called
the seed,
Different sets of random numbers can then be obtained using
different
seeds, and when
"simulated"
used in equation
experimental runs, the values
(5.1) they will
produce
used for the seeds
are in
Table 7.
The six approaches proposed above are described as follows.
5.3 Coats and Redfern Technique

Perturbated data of 1-x and a linear regression
equations
technique,
with
(3.18), (3.19), (3.20) and (3.21) will be performed to find
the predicted pararaeters E and ko/y3.
5.4 Modified Coats and Redfern Technique I

This
approach
technique;
right
however,
hand side of
is basically
the 1-2RT/E
the sarae as
term will not
equation (3.13). Equation
the Coats and
Redfern
be neglected in
the
(3.16) is arranged
to
obtain the following equation:
Ln
Ln(l-x)'
- Lnri-2RT/El - L n M - L
\-
-'
(5.2)
y9E RT
The linear regression approach will be used again with the form:
v = ax + b
with
(5.3)
37
Table 7
Values of Seed to be Used With the Random Number Generator
123456
4.75
122
562566
87
1010
53.26
354141
53421
3222
38
"-Ln(l - X ) '
-n
T2
1/T
(5.5)
-E/R
(5.6)
b - Ln "koR '
First
(5.7)
. )9E .
and
(5.4)
- Ln 1 - 2 R T / E J
an estimate of E is used in equation
Redfern equation and the
(5.4) from the Coats
frequency factor will be
obtained from
the intercept of the regression line.

This
original
method
takes
more computer
Coats and Redfern
time
to
method and requires
converge
than
a good guess
the
at the
activation energy but it is expected to give better predictions of the

kinetic parameters.
5.5 Modfied Coats and Redfern Technque II

Fischer
Redfern
et al. (1987) proposed
a modification of the
Coats and
equation that according to his work is very accurate and does
not need an iterative technique.
The equations are the following:
Ln(k//9)cR = Cii + C21 Ln(E) + C31 Ln(k/^)

+ C4i[Ln(k/;3)]2 .
(4.14a)
Ln(E)cR = C21 + C22 Ln(E) + C32 Ln(k/^)

+ C42[Ln(k/^)]2 .
Refer
to
chapter
(4.14b)
IV
for
derivation of these equations.
more
detailed
description
and
39
5.6 Chen-Nuttal Equation
Chen-Nuttal developed an approximation which gives
Ln
E+2RT r
T2
Ln koR
Ln(l-x)
1]
(5.8)
. fi i
RT
equation (5.8) is of the form:

y - ax + b
(5.9)
with
E+2RT
Ln
-Ln(l
-]
(5.10)
1/T
(5.11)
-E/R
(5.12)
Ln
koR
(5.13)
L P
An
iterative analysis will
intercept of equation (5.8).

E,
with which it computes y.
allow calculation of
the slope
and
This iteration first needs a guess value

Next, the slope and intercept are found
using regression analysis; the new value for E from equation (5.10) is
then
used to reiterate
the regression until
a desired tolerance
is
achieved.
5.7 Reich and Stivala Equation

Equation
(2.7)
first order reaction:
can
be written
in
the
following forra
for
40
Ln
Ti+i 21
Ln(l-Xi)
.Ln(l-Xi+i)
Ti
(5.14)
R Ji
Ti+lJ
values of E/R can be calculated from equation (5.14) for a
given set
of 1-x and T data. Then with the value of E obtained, V.Q/P
can be
found with the following equation.

k
Ln(l-x) E g-E/RT
These
are:
(5.15)
investigators claim that
that it is
some advantages of
relatively simple to use; it allows
this method
the
user to
readly discern whether the data are homogeneous, and if not, at what
conversions the data deviate.
5.8 Horowitz and Metzger Equation

Equation
(3.5) can be reduced by making use of the definition of
Ts:
(5.16)
Tg - T -
and when T-Tg, ^ = 0, w/w^ - 1/e so for a first order reaction:
l^-Ln(l-x)]
Ln -Ln(l
Ytd
(5.17)
RT.
thus, a plot of ln[-ln(l-x)] against 9
should give a
whose
evaluated with the
slope
is E/RTg.
ko/)3
can be
straight
line
following
equation;
.E/RTs
ko_
RT<
where Te is the temperature at conversion - 1/e = 0.368.
(5.18)
41
This equation gives good agreement between values
of
activation
energy reported in literature for some polymers and hydrated salts.

For
ease
of discussion,
the
following abbreviations
will be
used.
CR
denotes the Coats and Redfern technique in equation (3.16).
MCRI denotes the modified Coats and Redfern technique in equation

(5.2).
MCRII
denotes
the modified
Coats
and Redfern
technique
in
equations (4.14a) and (4.14b).

CN
denotes the Chen-Nuttal technique in equation (5.8).
RS
denotes the Reich and Stivala technique in equation (5.14)
HM
denotes
the Horowitz
and Metzger
technique
in equations
(5.17) and (5.18).

Comparisons
perturbation
there
of
the
results
of
these
six
models without
are presented in Table 8, from which it can be seen that
is a good agreement on the prediction of the kinetic parameters
between all the methods, except from the Horowitz and Metzger.
The
results
of the mentioned
perturbations for
the different
methods are shown in Tables 9, 10, 11 and 12. Figure 6, the

1-x
of
plot of
versus temperature shows the perturbated data of a particular set

conditions, and
Figure 7 represents the perturbed data plotted
using the Coats and Redfern equation.

The
following
data in Tables
test from the
analysis of variance.
9, 10, 11 and 12 will be treated with

Statistic Analysis Software
(SAS);
the
one-way
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^
-^
V,
47
E = 20000
K0/B=1E5
SEED=4.75
g
U)
>
2
O
O
560
580
600
620
640
660
TEMPERATURE
Figure 6.
Perturbation of theoretical dt using random number

generator
48
CR TECHNIQUE
E=20000
KO/B=1E5
SEED = 4.75
-12.5 -13 (N
-13.5 -
I-
J.
-14 -14.5 -15 15.5 -
0.0014
Figure 7.
Coats and Redfern plot for the data in Figure 6
49
5.9 One-Wav Analysis of Variance
A one way AOV is used when we wish to test the equality
population means.
of some
The assumptions made are that each of the groups of
observation is a random sample from a normal distribution and that the

population variance a^ is constant among the groups.
There are two ways to estimate the population variance:
estimates, and calculation of the variance of group means
grand mean.
the
population
variance,
the
These estimators will lead to a test of the

means.
The
pooled
estimator
S^^ is an unbiased estimator for a^
population means /i^
of
pooled
around the
equality of
the population
regardless of whether
are equal or not and it
is given by the
following equation:
S 2 . J e _ , MSe
J(I-l)
(5-19)
where:
SSg - Error sum of squares

J(I-l) - Degrees of freedom
MSe - Error mean square
To calculate the sample variance of the group means around the

grand mean, Sy^, the following equation is used:
S 2.!!b.MSb
J-1
where:
(5.20)
50
SS^ - Between groups sum of squares
J-1 - Degrees of freedom
MS^j - Mean square between groups
The
group
estimator Sy^ is an unbiased estimator of a^
population means are equal.
only when the
If the population means
not all equal then the estimator Sy^ overestimates a^.

I^
are
if the means
are all equal then Sp^ and Sy^ are independent so that the random
variable
, , S^2 ^ SS,/(J-1) _ M S b
Sp2
SSe/J(I-l)
^3 21)
MSe
Has an F-distribution with J-1 and J(I--l) degrees of freedom.

under the null hypothesis Ho: Ml"*;^^"- /'n
So
^^ expected value of
F is to be close to 1 and if Ho is not true then the value of Sy2 will

tend to be larger than Sp2 forcing F to be greater than I.
the
is
Based
on
data, the hypothesis Ho would be rejected if the computed F value

too large.
greater
J(I-I)
than
So to
the
reject Ho the calculated
value of F has
value of an F distribution with ui
degrees of freedom and
I-a
to be
- J-I, i/^
confidence level [Bethea
et al.
(1985)].
Tables 13, 14, 15 and 16 are the results from the procedure ANOVA
from
SAS, and from them it can be seen that the calculated F value is
all
cases
the
F distribution.
rejected
is
greater than 2.83 the value from F found in a table of

So the hypothesis Ho: /i^
- /i^
Mn
^^
at the 95X confidence level. So from this hypothesis it can
be stated that a least one method gives significantly different values

of predicted E.
51
c r^.
r: QO
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3 i.)
O O
crt X
55
To
identify
comparison
which
of the
among means was
methods
is
different,
performed(Scheffe test option
multiple
in ANOVA).
The results are given in Tables 17, 18, 19 and 20.

From
Tables 17, 18, 19 and 20 it can be seen from the confidence
interval comparison between the different methods that the

Stivala
equation gives significantly different
the other equations.
Reich
and
predicted values than
AIl the other method comparison contains zero in
their confidence interval so the hypothesis that their means are equal
is accepted as probably true.
However,
from
Table
8 it
can
be
seen that
Metzger
equation gives predicted values of E and VQ/^
greater
(statistically significant) than
the Horowitz and

that are much
the selected values
of the
parameters mentioned.
So,
here
experiment,
determination
it
is
this can be
recommended
to
seen from the
of the kinetic
perf orm
more
than
variation that arises
parameters between the
because it is the
statistically
gives
simplest to use of
very good
agreement
and
in the
Redfern
all the other methods
and
between the
and
selected
predicted parameters for a dynamic TGA with random noise of

order reaction system.
TGA
different runs.
Also the method recommended to use is the modified Coats

II,
one
first-
56
Table 17
Scheffe^s Test for the Data in Table 13

Scheffe's Test for Variable: Eact
Parameters Used: E-20,000 ko/j9-lE5
Alpha-0.05 Confidence-0.95 DF-54 MSE-19.7511
Critical Value of F-2.3860
Minimum Significant Difference-6.865
Comparisons Significant at the 0.05 Level are Indicated by '***'
Method
Comparison
Simultaneous
Lower
Confidence
Limit
Difference
Between
Means
Simultaneous
Upper
Confidence
Limit
RS
RS
RS
RS
RS
-HM
-MCRI
-CN
-MCRII
-CR
5.709
11.223
11.258
11.268
11.399
12.574
18.088
18.123
18.133
18.264
19.493
24.953
24.988
24.998
25.129
HM
HM
HM
HM
HM
RS
MCRI
CN
MCRII
CR
19.439
-1.351
-1.315
-1.305
-1.174
12.574
5.514
5.550
5.559
5.691
-5.709
12.379
12.415
12.424
12.555
***
MCRI
MCRI
MCRI
MCRI
MCRI
RS
HM
CN
MCRII
CR
24.953
12.379
6.830
6.820
6.689
18.088
-5.514
0.035
0.045
0.176
11.223
1.351
6.900
6.910
7.041
***
***
***
***
***
CN
CN
CN
CN
CN
-RS
-HM
-MCRI
-MCRII
-CR
24.988
12.415
6.900
6.855
6.724
18.123
-5.550
-0.035
0.010
0.141
11.258
1.315
6.830
6.875
7.006
***
MCRII
MCRII
MCRII
MCRII
MCRII
-RS
-HM
-MCRI
-CN
-CR
24.988
12.424
6.910
6.875
6.734
18.133
-5.559
-0.045
-0.010
0.131
11.268
1.035
6.820
6.855
6.996
***
CR
CR
CR
CR
CR
-RS
-HM
-MCRI
-CN
-MCRII
25.129
12.555
-7.041
-7.006
-6.996
-18.264
-5.691
-0.176
-0.141
-0.131
-11.399
1.174
6.698
6.724
6.734
***
57
Table 18

Parameters Used: E-30,000 ko/^-lE6
Minimum Significant Difference-17.085
Method
Comparison
Simultaneous
Lower
Confidence
Limit
Difference
Between
Means
Simultaneous
Upper
Confidence
Limit
RS
RS
RS
RS
RS
-HM
-MCRI
-CN
-MCRII
-CR
8.369
16.250
16.289
16.301
16.445
25.454
33.335
33.374
33.387
33.530
42.540
50.421
50.460
50.472
50.616
***
***
***
***
***
HM
HM
HM
HM
HM
-RS
-MCRI
-CN
-MCRII
-CR
-42.540
-9.204
-9.165
-9.153
-9.009
-25.454
7.881
7.920
7.933
8.076
-8.369
24.967
25.006
25.018
25.161
***
MCRI
MCRI
MCRI
MCRI
MCRI
-RS
-HM
-CN
-MCRII
-CR
-50.421
-24.967
-17.046
-17.034
-16.891
-33.335
-7.881
0.039
0.051
0.195
16.250
9.204
17.124
17.137
17.280
***
CN
CN
CN
CN
CN
-RS
-HM
-MCRI
-MCRII
-CR
-50.460
-25.006
-17.124
-17.073
-16.930
-33.374
-7.920
-0.039
0.012
0.156
-16.289
9.165
17.046
17.098
17.241
***
-RS
-HM
-MCRI
-CN
-CR
-50.472
-25.018
-17.137
-17.098
-16.942
-33.387
-7.933
-0.051
-0.012
0.143
-16.301
9.153
17.034
17.073
17.229
***
MCRII
MCRII
MCRII
MCRII
MCRII
"RS
HM
MCRI
CN
MCRII
-50.616
-25.161
-17.280
-17.241
-17.229
-33.530
-8.076
-0.195
-0.156
-0.143
-16.445
9.009
16.891
16.930
16.942
***
CR
CR
CR
CR
CR
58
Table 19

Parameters Used: E-60,000 ko/j8-lE3
Minimiam Significant Difference-22.565
Method
Comparison
S imultaneous
Lower
Confidence
Limit
Difference
Between
Means
Simultaneous
Upper
Confidence
Limit
RS
RS
RS
RS
RS
-HM
-MCRI
-CN
-MCRII
-CR
13.669
32.441
32.675
32.697
33.309
36.234
55.006
55.240
55.262
55.874
59.799
77.571
77.805
77.827
78.439
***
HM
HM
HM
HM
HM
-RS
-MCRI
-CN
-MCRII
-CR
58.799
-3.793
-3.559
-3.537
-2.925
36.234
18.771
19.006
19.028
19.640
13.699
41.336
41.571
41.593
42.204
***
MCRI
MCRI
MCRI
MCRI
MCRI
-RS
-HM
-CN
-MCRII
-CR
77.571
41.336
22.330
22.308
21.697
55.006
18.771
0.235
0.257
0.868
32.441
3.793
22.799
22.821
23.433
***
CN
CN
CN
CN
CN
-RS
-HM
-MCRI
-MCRII
-CR
77.805
41.571
22.799
22.543
21.931
55.240
19.006
-0.235
0.022
0.633
32.675
3.559
22.330
22.587
23.198
***
MCRII
MCRII
MCRII
MCRII
MCRII
-RS
-HM
-MCRI
-CN
-CR
77.827
41.593
22.821
22.587
21.953
55.262
19.028
-0.257
-0.022
0.612
32.697
3.537
22.308
22.543
23.176
***
-RS
-HM
-MCRI
-CN
-MCRII
78.439
42.204
23.433
23.198
23.176
55.874
19.640
-0.868
-0.633
-0.612
33.309
2.925
21.697
21.931
21.953
***
CR
CR
CR
CR
CR
***
***
***
***
59
Table 20

Parameters Used: E-10,000 ko/)3-lE7
Minimum Significant Difference-3 .6469
Method
Comparison
Simultaneous
Lower
Confidence
Limit
Difference
Between
Means
Simultaneous
Upper
Confidence
Limit
6.890
9.025
9.031
9.034
9.084
10.537
12.671
12.678
12.681
12.731
***
***
***
***
***
-10.537
-1.512
-1.505
-1.502
-1.452
-6.890
2.135
2.142
2.145
2.194
-3.243
5.782
5.788
5.792
5.841
***
-RS
-HM
-MCRII
-CN
-CR
-12.671
-5.782
-3.640
-3.637
-3.587
-9.025
-2.135
0.007
0.010
0.060
-5.378
1.512
3.654
3.657
3.707
***
MCRII
MCRII
MCRII
MCRII
MCRII
-RS
-HM
-MCRI
-CN
-CR
-12.678
-5.788
-3.654
-3.644
-3.594
-9.031
-2.142
-0.007
0.003
0.053
-5.384
1.505
3.640
3.650
3.700
***
CN
CN
CN
CN
CN
-RS
-HM
-MCRI
-MCRII
-CR
-12.681
-5.792
-3.657
-3.650
-3.597
-9.034
-2.145
-O.OIO
-0.003
0.050
-5.388
1.502
3.637
3.644
3.697
***
CR
CR
CR
CR
CR
-RS
-HM
-MCRI
-MCRII
-CN
-12.731
-5.841
-3.707
-3.700
-3.697
-9.084
-2.194
-0.060
-0.053
-0.050
-5.437
1.452
3.587
3.594
3.597
***
RS
RS
RS
RS
RS
-HM
-MCRI
-MCRII
-CN
-CR
HM
HM
HM
HM
HM
-RS
-MCRI
-MCRII
-CN
-CR
MCRI
MCRI
MCRI
MCRI
MCRI
3.243
5.378
5.384
5.388
5.437
CHAPTER VI
TEMPERATURE DEPENDENT RATE CONSTANTS IN
NON-ISOTHERMAL FIRST ORDER REACTIONS
6.1 Introduction
The
certain
easiest interpretation of a
fraction
sufficiently
distributed
of
molecules
of
high energy to react.

between the different
first order reaction is

the
reactant
species
Depending on how this

vibration modes of
that a
have
energy is
this activated
molecules, vibrations can be produced causing its decomposition.

The theory of reaction rates gives approximations of the type:
k - koTê-E/RT
for
(6.1)
rate constants.
In thermal
a n a l y s i s the most common
expression
used for the r a t e c o n s t a n t k i s :

k - koe-E/RT
(6.2)
Application of equation (6.2) seems to be the most
suitable
way
of describing the overall kinetics of most reaction systems. However,

the theory of unimolecular reactions leads to the approximation:
k-koTe-E/RT
(6.3)
While in the case of a bimolecular type reaction the expression:

k - koTV2e-E/RT
seems
to be more
(6.4)
correct than equation
60
(6.2) [Varhegyi (1978)],
in
61
this
equation
the
factor
TV^
connected
with the
number
of
molecules colliding with the reaction surface in unit time.

In thermoanalytical calculations. the case where b-0 is
kinetic
calculations.
treatment
of
the
However,
non-isothermal
if b
used
in
is
regarded
as a variable,
kinetic
equation
is
not
more
complicated than in the special case of b-0.

Here,
constants
least
the behavior of non-isothermal

has
been studied.
squares
technique
temperature dependent rate
The Coats and
Redfern equation and
are used to try to fit the data produced by
numerical integration of equations of the type:

jTbe-E/RTdT
where
(6 5)
b-0,I/2, and
1.
Different
values of
activation
energy
and
frequency factors are studied.
6.2 Theorv
For
the
decomposition
reaction of
B(g)
component
to a
gaseous
component B,
A(s)
(6.6)
The mathematical description of the weight loss for a first order

reaction
during heating can be represented by using an Arrhenius-type
reaction equation.
f - -kA
dt
(6.7)
62
If
this
pyrolyzed
(3.3).
reaction
with a
i s carried
constant heating
in
TGA, the
ramp, ^,
sample
defined
as
will
be
equation
By use of t h i s parameter in equation (6.7) to remove the time
dependency for t h i s equation

^ - - - A
dT
(6.8)
then the integral will be:

TA
dA _
jAo A
k dT
jTo ^
TT
(.^)
then using the d e f i n i t i o n in equation (3.15).
Ln(l-x) - P - d T
jTo ^
(6.10)
and equation (6.1) is substituted for k

Ln(l-x)
-X) -- rr .20Tbe-E/RTdT
3
<6.11)
JTO /
where b can be 0, 1/2, and 1.
The
right hand side of equation (6.11) will be
approximated by
the Coats and Redfern equation.

The decomposition rate based on the unconverted fraction
can be
written as:
1 - ^ 0 Tbe-E/RT(l-x)
dT
^
^^-^'^
with the initial conditions,
(6.13)
X - 0
T-To
63
Numerical
integration
Gear's method (1971).

(6.12)
can be
performed with
The values used for the integration of equation
values of temperature and fraction unconverted obtained frora
numerical
equation
factor.
in
equation
are reported in Table 21.
The
the
of this
to evaluate the
It
be used with
the Coats and
activation energy and
Redfern
the pre-exponential
The results of this are in Tables 22, 23 and 24
Figure
values.
integration will
and
plotted
for a particular set of conditions and all cases for b
Similar plots can be obtained for all the other conditions.

can be
seen from
Figure 8
that for
the three
cases of b
studied
a straight line was found.
And comparison between Tables 22,
23
24
cases of b-1/2
and
indicate
significant
specially
Redfern
that for the
difference
in the case
equation
can
between
the selected
when b-1, so
not
be
and
and I there
predicted values,
this means that
used,
bringing
no
is a
the
more
Coats
and
practical
advantages to the kinetics of the reaction.

However,
Redfern
proposed
close inspection
of the
equation in chapter III

here to
reduce the
derivation of
the Coats
and
of this work, two raodifications are
differences between
the
selected
and
predicted parameters.
For
the
case
when b-1
equation
(3.18)
is modified
in the
following way:
,
Ln
Ln(l-x)
(6.14)
64
Table 21
Selected Parameters Used in the Integration

of Equation (6.11)
E
VQ/P
20,000
20,000
30,000
30,000
20,000
60,000
1E5
1E6
1E5
1E6
1E7
1E5
65
T a b l e 22
R e s u l t s From t h e I n t e g r a t i o n of E q u a t i o n ( 6 . 1 1 )
Case When b - 0
Selected
Predicted
20,000
1E5
19,857
.792E5
ko/)9
20,000
1E6
19,883
.809E6
E
Ô/
30,000
1E5
29,793
.795E5
E
lco/)8
30,000
1E6
29,829
.81IE6
E
ko//3
20,000
IE7
19,899
.82IE7
E
ko/i8
60,000
59.610
.800E5
ô/fi
E
E5
66
Table 23

Case When b-1
Selected
Predicted
E
k0/)9
20,000
1E5
21,053
2.028E5
E
ko/;3
20,000
1E6
20,943
2.057E6
30,000
1E5
31,555
2.025E5
E
ko//9
30,000
1E6
31,391
2.067E6
E
ko//9
20,000
1E7
20,849
2.099E7
E
ko/)3
60,000
1E5
63,027
2.061E5
ô/P
67
Table 24

Case When b-1/2
Selected
Predict
ô/P
20,000
1E5
20,455
1.267E5
E
ko/i8
20,000
IE6
20,413
I.290E6
E
k0//9
30,000
1E5
30,673
1.268E5
30,000
1E6
30,610
1.295E6
20,000
IE7
20,373
1.311E7
60,000
1E5
61,296
1.276E5
ko/3
E
ko/)9
E
ô/P
68
CR PLOT
E=30000
12.5
-16.5
0.00096
D
Figure 8.
0.001
NORMAL
0.00104.
4-
K0/B=1F.5
0.00108
T DEP
0.00112
o
0.001 16
0.0012
T**.5 DE:
Coats and Redfem plot for the three cases of b studied
69
This
last equation
is used
(3.21) to calculate E and ko/)9.
with equations
(3.19), (3.20)
and
The results of this modification are
presented in table 25.

Now for the case when b-1/2, equation (3.18) is modified
in
the
following way:
y - Ln
-Ln(l-x)"
(6.15)
T5/2
Again this equation is used in conjunction with equations (3.18),

(3.19)
and (3.21) to calculate
the desired kinetic parameters,
the
results of this last are given in Table 26.

It can be seen from the comparison between Tables 22, 25
that
there
is a
very good agreement
kinetic parameters.
of
in the selected
and
26
and predicted
So, if there is a prior knowledge that a reaction
the types discussed in this chapter is likely to occur, instead of
using directly the Coats and Redfern equation to calculate the desired
kinetic
parameters, it is
modifications
to
exponential factor.
retrieve
recommended here the

the
activation
use of the
energy
and
proposed
the
pre-
70
Table 25

Using a Modified Coats and Redfern Equation
Case When b-1
Selected
Predict
ô/fi
20,000
1E5
19,876
.767E5
E
ko//3
20,000
IE6
19,894
.783E6
E
k0/)9
30,000
1E5
29,819
.769E5
E
ko/)9
30,000
1E6
29,848
.786E6
E
ko/i9
20,000
IE7
19,906
.794E7
E
ko/)9
60,000
1E5
59,681
.782E5
71
Table 26

Using a Modified Coats and Redfern Equation
Case When b-1/2
Selected
Predicted
E
ko/)9
20,000
1E5
19,867
.778E5
E
ko/)9
20,000
1E6
19,888
.793E6
E
ko/)9
30,000
1E5
29,813
.784E5
30,000
1E6
29,839
.798E6
E
ko/^
20,000
1E7
19,904
.807E7
E
ko//9
60,000
1E5
59,649
.790E5
ô/fi
CHAPTER VII
CONCLUSIONS
When
multiple
slopes
are
observed
using
Coats
and
Redfern
technique one has to suspect Gaussian distributed kinetics.

There
has been demonstrated that
the kinetic methods tested
in
this work give statistically the same results except for the RS and HM
methods
so one
should not
use this
last two
if error
in data
is
suspected.
From
knowledge
the
of
last
the
part of
this work,
if there
is a
before hand
type of the reaction, here it is recomended to use
the proposed modifications to retrieve the kinetic parameters.
7.1 Recommendations
The use of another type of distrubution to represent the range of
activation
energies.
Another interesting
study is to
let the pre-
exponential factor to vary in the Gausian distributed model.
72
LITERATURE CITED
Anthony, D. B. , Howard, J. B. , AIChE Jonrn;,!
1976, 22, p265.
Campbell, J. H. , Gallegos, G. , and Gregg, M. , Fiiel, 1980, 59, 727.

Coats, A. W., Redfern, J. P. , Nature (London) , 1964, 201, 68.
Fischer, P. E. , Ind. Eng. Chem. Reg
1987, 26, 5.
Freeman, E. S., Carroll, B. J., Phvs. Cheni. , 1958, 62, 394.

Gear, C. W., "Numerical Initial Value Problems in Ordinary
Differential Equations," Prentice-Hall, New Jersey, 1971, p. 158-166.
Gokalgandhi, S. S., "Optimal Search of Kinetic Parameters," M.S.
Thesis, Texas Tech University, 1984.
Gorbachev, V. M. , J. Therm. Anal. . 1975, 8, 349.
Horowitz, H. H., Metzger, G. , Anal. Chem. . 1961, 38, p. 571.
House, J. R. , Thermochim Acta. 1981, vol. 47, p. 379.
Lewellen, P. C , Peters, W. A. , and Howard, J. B. , I6th Symp. (int) on
Comb., The Combustion Institute, 1977, pl471.
McCallum, J. R. , Tanner, J. Nature (London) , 1970, 225, 1127.
Nuttal, H. E., Guo, T. M., Schrader, S., Thakur, D. S., ACS Symp.
Series, 1983, 230, 269.
Pitt, G. J., Fuel, 1962, 41, p. 267.
Reich, L. , Stivala, S. S., Thermochim. Acta. 1980, 36, 103.
Stroud, A. H. , Secrest, D., Gaussian Quadrature Formulas. Prentice
Hall, New Jersey, 1966.
Suuberg, E. M. , Comb. and Flame. 1983, 50, 243.
Varhegyi, G., Thermochim. Acta. 1978, vol. 25, p. 201.
73
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STUDY OF THE BEHAVIOR OF NON-ARRHENIUS

FIRST ORDER KINETIC EXPRESSIONS

I would like to express my gratitude to my advisor Dr. E. Fischer

help and suggestions

to express my gratitude to Dr. R. R. Rhinehart for his suggestions and

Dominguez and E. Lozano, and to my

brother, R. J. Flores, for their constant support and inspiration.

took the time to listen and make suggestions.

thankful to E. D. de Larralde for her help and encouragement.

COATS AND REDFERN TECHNIQUE

Derivation of the CR Technique

N\americal Determination of Kinetic Parameters

THE BEHAVIOR OF FIRST ORDER GAUSSIAN DISTRIBUTED

Derivation of Gaussian Distributed Model

Numerical Approximation for the Gaussian

PARAMETERS FROM THERMOGRAVIMETRY DATA

Coats and Redfern Technique

5.4 Modified Coats and Redfern Technique I

Modified Coats and Redfern Technique II

Reich and Stivala Equation

Horowitz and Metzger Equation

One-Way Analysis of Variance

TEMPERATURE DEPENDENT RATE CONSTANTS IN

Results from Integration of Equation (3.4) Used in the

Linear Regression Results Obtained by Using the Coats

Comparison Between the Selected Set of Parameters Used

Coefficients for Equations (14a) and (14b)

Roots of the Hermite Pol^momial of Order 5, and Weight

Selected Values of E and \Q/P to be Used for the

Values of Seed to be Used With the Random Number

Comparison of Results by Different Methods Using

Comparisons of the Results of Different Methods for

Comparisons of the Results of Different Methods for

Comparisons of the Results of Different Methods for

Comparisons of the Results of Different Methods for

One Way Analysis of Variance for Perturbed Data of

One Way Analysis of Variance for Perturbed Data of

One Way Analysis of Variance for Perturbed Data of

One Way Analysis of Variance for Perturbed Data of

Scheffe's Test for the Data in Table 13

Scheffe's Test for the Data in Table 14

Scheffe's Test for the Data in Table 15

Scheffe's Test for the Data in Table 16

Results From the Integration of Equation (6.11)

Results From the Integration of Equation (6.11)

Results From the Integration of Equation(6.11)

Results From the Integration of Equation (6.11) Using a

Results From the Integration of Equation (6.11) Using a

Coats and Redfern plot for the data in Table 1

Comparison between the values of conversion versus

Coats and Redfern plot of concentration versus

Coats and Redfern plot of concentration versus

Coats and Redfern plot of concentration versus

Perturbation of theoretical data using random number

Coats and Redfern plot for the data in Figure 6

Coats and Redfern plot for the three cases of b

reactant concentration, concentration units

product concentration, concentration units

parameters defined in Equations (14a) and (14b)

activation energy, kcal/gmol

mean value of activation energies

Arrhenius frequency factor

Gauss-Hermite polynomial order

ideal gas constant, 1.9872 kcal/gmol K