Chemical Engineering Science 62 (2007) 27502764

www.elsevier.com/locate/ces
Optimumreference temperature for reparameterization of the Arrhenius
equation. Part 1: Problems involving one kinetic constant
Marcio Schwaab, Jos Carlos Pinto

Programa de Engenharia Qumica/COPPE, Universidade Federal do Rio de Janeiro, Cidade Universitria-CP: 68502, Rio de Janeiro, RJ 21941-972, Brazil
Received 7 December 2006; received in revised form 3 February 2007; accepted 13 February 2007
Available online 24 February 2007
Abstract
The Arrhenius equation is one of the most well-known equations in the chemical eld and is widely used to describe the temperature
dependence of kinetic constants. This equation contains two parameters, the frequency factor and the activation energy, which are usually
estimated from experimental data. However, the correlation between the two parameter estimates is usually very high and in many cases is
practically equal to one. This makes the precise identication of the parameter values very difcult. The high parameter correlation can be
diminished through reparameterization of the Arrhenius equation and denition of a reference temperature. For problems involving a single
kinetic constant, it is shown here both analytically and through numerical examples that the proper denition of the reference temperature
allows for estimation of the parameters of the Arrhenius equation without correlation and with minimum relative error, leading to improvement
of the parameter estimation procedure.
2007 Elsevier Ltd. All rights reserved.
Keywords: Arrhenius equation; Reparameterization; Parameter estimation; Correlation; Kinetics; Modeling
1. Introduction
In the end of the 19th century, several equations were devel-
oped to describe the temperature dependence of reaction rates
(Logan, 1982). One of the most important and well-known
equations in the chemical eld came from this period: the
Arrhenius equation:
k =k
0
exp
_

E
RT
_
, (1)
where k is the rate constant (or the specic reaction rate), T is
the absolute temperature, R is the ideal gas constant, k
0
is the
frequency (or pre-exponential) factor and E is the activation
energy. Both k
0
and E are the parameters of the Arrhenius
equation, usually estimated from experimental data.
Arrhenius and other researchers also attempted to give phys-
ical signicance to the parameters of Eq. (1). By assuming that

Corresponding author. Tel.: +55 21 25628337; fax: +55 21 25628300.

E-mail address: pinto@peq.coppe.ufrj.br (J.C. Pinto).
0009-2509/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2007.02.020
the rate constant represents a transformation between two states
(the reaction) that is controlled by an intermediate high-energy
excited state, it can be said that the parameter E represents the
energy difference between the initial state and the intermediate
state (activated species). In this case, the parameter k
0
repre-
sents the frequency of collisions between the reactants.
According to the Collision Theory, the rate constant k should
be proportional to [T
1/2
exp(E/RT )]. On the other hand, the
Transition State Theory asserts that k should be proportional
to [T exp(E/RT )]. Both theories can be summarized in the
following equation (Levenspiel, 1999):
k =k
0
T
m
exp
_

E
RT
_
, (2)
where m is an additional parameter, also estimated from avail-
able experimental data. m is frequently in the range 0 <m<1,
but in some cases it may be greater than 1 (Levenspiel, 1999).
However, it is important to notice that the inuence of T
m
on
k in Eq. (2) is very small when compared to the inuence of
the exponential term [exp(E/RT )]. Besides, extremely pre-
cise data is required to detect the effect of T
m
on k in Eq.
(2) (Froment and Bischoff, 1990). In practice, the Arrhenius
M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764 2751
equation can provide very good ts for most reactions and the
exceptions are relatively few, as in high temperature combustion
reactions (Bendtsen et al., 1998).
The most frequent difculty associated with the application
of the Arrhenius equation is the proper estimation of its two pa-
rameters from experimental data. The mathematical structure
of the Arrhenius equation, involving the exponentiation of the
reciprocal of the absolute temperature, introduces a high cor-
relation between the two parameter estimates and makes pa-
rameter estimation very difcult, particularly during numerical
minimization of the objective function that weighs the squared
difference between measured and calculated data.
The usual way to overcome this difculty is to represent the
Arrhenius equation in the linear form (Hill, 1977). This proce-
dure consists in estimating k values at some different temper-
atures and then computing the best linear t for ln(k) in the
form:
y =ln(k) =ln(k
0
)
E
R
1
T
=a +bx. (3)
This way, the parameter estimates are obtained as the slope
(E/R) and the intercept [ln(k
0
)] of the linear t. As the lin-
ear least squares problem has analytical solution, the difcul-
ties associated with numerical minimization of the objective
function are avoided.
The use of the so-called linear form of the Arrhenius equa-
tion is very controversial and has been the subject of an in-
volving debate (Chen and Aris, 1992; Curl, 1993; Brauner and
Shacham, 1997; Kli cka and Kub cek, 1997; Sundberg, 1998).
In our opinion, the linear representation of the Arrhenius
equation should be avoided. First of all, the parameter estima-
tion procedure must preserve statistical meaning (for instance,
by using the maximum likelihood method, Bard, 1974). In
this case, the error structure of the experimental observations
should be known and should be preserved during the estimation
of the model parameters. As k is not measured experimentally,
its error structure is normally unknown. For simple linear rate
models, the error structure of k can be obtained from the error
structure of available experimental data. However, for nonlinear
models the error structure of the kinetic constant can be very
complex. Schwaab et al. (2007) studied the condence regions
of kinetic constants in nonlinear models and observed that the
condence regions can be nonconvex, open and constituted by
disconnected regions. For this reason, it is recommended that
the Arrhenius equation be inserted into the kinetic rate expres-
sions and that all parameters be estimated simultaneously using
the complete set of available experimental data. Although the
simultaneous estimation of many model parameters may be
difcult sometimes, the use of heuristic algorithms, such as the
genetic algorithm (Goldberg, 1989; Park and Froment, 1998),
the simulated annealing (Kirkpatrick et al., 1983; Eftaxias
et al., 2002) and the particle swam optimization (Kennedy and
Eberhart, 1995; Kennedy and Eberhart, 2001), can efciently
provide both the parameter estimates and a rigorous statistical
evaluation of condence regions (Schwaab et al., 2007).
In order to minimize the high correlation between the
parameters of the Arrhenius equation, one may perform
the reparameterization of the Arrhenius equation in one of the
following suggested forms (Box, 1960; Himmelblau, 1970;
Kittrell, 1970; Pritchard and Bacon, 1975; Agarwal and Brisk,
1985):
k =k
T
ref
exp
_

E
R
_
1
T

1
T
ref
__
, (4a)
k =exp
_
A
E
R
_
1
T

1
T
ref
__
, (4b)
k =k
T
ref
exp
_
B
_
T T
ref
T
__
, (4c)
k =exp
_
A +B
_
T T
ref
T
__
, (4d)
where the parameters of the reparameterized equations can be
related to the parameters of the traditional Arrhenius equation
in the form:
k
T
ref
=k
0
exp
_

E
RT
ref
_
, (5a)
A =ln(k
T
ref
) =ln(k
0
)
E
RT
ref
, (5b)
B =
E
RT
ref
. (5c)
One should observe that k
T
ref
is the specic reaction rate at
the reference temperature T
ref
. Besides, if the reference temper-
ature is innite, Eq. (4a)(4d) becomes equal to Eq. (1). There-
fore, the frequency factor k
0
of the original Arrhenius equation
can be understood as the specic reaction rate at innite tem-
perature. One should also observe that the parameters k
T
ref
, A
and B depend on the denition of the reference temperature.
Besides allowing for reduction of the parameter correlation,
reparameterization of the Arrhenius equation can also dimin-
ish the computational effort required for minimization of the
objective function (Espie and Macchietto, 1988) and improve
the elliptic representation of the parameter condence regions
(Watts, 1994) during estimation of model parameters.
One must observe that all proposed reparameterized forms
of the Arrhenius equation depend on a new parameter T
ref
,
which is the reference temperature. Little attention has been
given in the literature to the value of the reference temperature,
which is commonly dened as the average temperature of the
analyzed experimental range. It is shown here both analytically
and through numerical examples that the proper selection of
the reference temperature in Eq. (4) can allow for estimation of
uncorrelated parameters and for simultaneous improvement of
the precision of the parameter estimates in problems involving
a single kinetic constant.
2752 M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764
2. Parameter estimation
The parameter estimation procedure involves the minimiza-
tion of some objective function through manipulation of the
model parameters. Assuming that independent variables x are
free of errors, that experiments are performed independently
and that dependent variables y are subject to experimental uc-
tuations that follow the normal distribution with known covari-
ance matrix, the maximum likelihood estimation consists in
minimizing the following equation:
S() =
NE

i=1
[y
e
i
y
m
i
(x
i
, )]
T
V
1
i
[y
e
i
y
m
i
(x
i
, )], (6)
where S() is the objective function to be minimized with re-
spect to the parameter vector , y
e
i
and y
m
i
are the vector of
experimental observations and model predictions of the depen-
dent variables at experimental condition i and NE is the total
number of experiments. V
i
is the covariance matrix of experi-
mental observations at experimental condition i. The objective
function should be minimized with the help of appropriate nu-
merical procedures, such as the traditional Newton methods
(Edgar and Himmelblau, 1988; Nocedal and Wright, 1999) or
the recent heuristic optimization methods (Park and Froment,
1998; Eftaxias et al., 2002; Schwaab et al., 2007).
The signicance of the parameter estimates may be charac-
terized through the covariance matrix dened as (Bard, 1974):
V

=
_
NE

i=1
B
T
i
V
1
i
B
i
_
1
, (7)
which assumes that the model equations may be linearized at
the optimum parameter estimates. B
i
is the sensitivity matrix
of model responses with respect to the parameters at the exper-
imental condition i and is dened as
B
i
=

jy
1,i
j
1

jy
NP,i
j
1
.
.
.
.
.
.
.
.
.
jy
NY,i
j
1

jy
NY,i
j
NP

, (8)
where NP is the number of parameters and NY is the number
of model responses.
The main diagonal of the covariance matrix contains the vari-
ances of the parameter estimates, while the off-diagonal ele-
ments characterize the covariance between pairs of parameters,
which is a measure of the dependence between the parameter
estimates. In order to normalize the importance of this depen-
dence, the correlation matrix of parameter estimates should be
calculated from the covariance matrix of parameter estimates as

ij
=
v
ij

v
ii
v
jj
, (9)
where v
ij
is the element ij of the covariance matrix of param-
eter estimates. The values of all
ij
are in the range [1, 1].
As the absolute values of
ij
get closer to 1, the parameters
become more correlated and the parameter estimation becomes
poorer. The high correlation between parameter estimates can
be originated from different reasons, such as an inappropri-
ate model representation, a bad experimental design and/or the
model nonlinearities. This is exactly the case of the Arrhenius
equation, as the exponentiation of the reciprocal of the absolute
temperature inserts a high correlation between the frequency
factor and the activation energy.
Based on the covariance matrix of parameter estimates, a
condence region of parameter estimates can be dened as a
hyper-ellipsoid in the parameter space. When parameters are
not correlated, the axes of the hyper-ellipsoid are parallel to
the parameter axes; however, for highly-correlated parameters,
the axes of the hyper-ellipsoid are not parallel to the param-
eter axes. It must be noticed that the elliptical approximation
of the condence region of parameter estimates is exact for
linear models only. Depending on the degree of nonlinearity
of the model, the condence region can present very complex
shapes (Donaldson and Schnabel, 1987; Schwaab et al., 2007).
When the Arrhenius equation is used without reparameteriza-
tion, the condence regions are curved and the elliptical ap-
proximation may be worthless. The use of a proper reference
temperature and the reparameterization of the Arrhenius equa-
tion can improve the elliptical representation of the condence
regions (Watts, 1994).
3. The optimum reference temperature
Let us assume that the following mass balance equation rep-
resents a rst order irreversible reaction:
dC
A
dt
=kC
A
, C
A
(t =0) =C
A0
, (10)
which has an analytical solution when k is constant (that is,
when experiments are performed at isothermal conditions):
C
A
=C
A0
exp(kt ). (11)
If Eq. (4a) is inserted into Eq. (11), then:
C
A,i
=C
A0,i
exp
_
t
i
k
T
ref
exp
_

E
R
_
1
T
i

1
T
ref
___
, (12)
where i denotes the analyzed ith experimental condition. As-
suming that the variances of experimental uctuations are the
same for all experimental conditions, the objective function of
Eq. (6) can be written as
S() =
NE

i=1
[C
e
A,i
C
m
A,i
(x
i
, )]
2
. (13)
In this case, the covariance matrix of parameter estimates
can be written as
V

=s
2
(B
T
B)
1
, (14)
M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764 2753
where s
2
is the constant variance of the experimental uctua-
tions. If the model is perfect, then the residuals can be used to
determine s
2
(Draper and Smith, 1998):
s
2
=S(

)/(NE NP), (15)

where S(

) is the minimum value of the least squares function

(Eq. (13)) calculated with optimum parameter estimates , NE
is the number of experiments and NP is the number of param-
eters. For single response models containing only one kinetic
constant, the sensitivity matrix of model responses with respect
to the parameters can be written as
B =

jy
1
jk
T
ref
jy
1
jE
.
.
.
.
.
.
jy
NE
jk
T
ref
jy
NE
jE

(16)
so that the covariance matrix of parameter estimates can be
written as
V

=s
2

NE

i=1
_
jC
A,i
jk
T
ref
_
2
NE

i=1
_
jC
A,i
jE
__
jC
A,i
jk
T
ref
_
NE

i=1
_
jC
A,i
jk
T
ref
__
jC
A,i
jE
_
NE

i=1
_
jC
A,i
jE
_
2

1
.
(17)
After inversion of the term between brackets, Eq. (17) becomes
V

=
s
2
det(B
T
B)

NE

i=1
_
jC
A,i
jE
_
2
NE

i=1

_
jC
A,i
jE
__
jC
A,i
jk
T
ref
_
NE

i=1

_
jC
A,i
jk
T
ref
__
jC
A,i
jE
_
NE

i=1
_
jC
A,i
jk
T
ref
_
2

.
(18)
The main objective here is determining the best value of T
ref
that leads to =0; that is, that makes the correlation between
parameters k
T
ref
and E equal to zero and allows for independent
estimation of the model parameters. As the parameter correla-
tion is proportional to the parameter covariance (element v
12
of
matrix V

), elimination of the parameter correlation is equiv-

alent to nding the value of T
ref
that satises the following
equation:

NE

i=1

jC
A,i
jk
T
ref
jC
A,i
jE
=0. (19)
As the derivatives of model responses in respect to the model
parameters are
jC
A,i
jk
T
ref
=
C
A,i
ln(C
A,i
/C
A0,i
)
k
T
ref
, (20)
jC
A,i
jE
=
_
1
T
i

1
T
ref
_
C
A,i
ln(C
A,i
/C
A0,i
)
R
. (21)
Eq. (19) becomes
NE

i=1
1
k
T
ref
R
_
1
T
i

1
T
ref
_
[C
A,i
ln(C
A,i
/C
A0,i
)]
2
=0. (22)
The solution of Eq. (22) leads to:
1
T
ref
=

NE
i=1
[C
A,i
ln(C
A,i
/C
A0,i
)]
2
T
i

NE
i=1
[C
A,i
ln(C
A,i
/C
A0,i
)]
2
(23)
or
T
ref
=

NE
i=1
[C
A,i
ln(C
A,i
/C
A0,i
)]
2

NE
i=1
[C
A,i
ln(C
A,i
/C
A0,i
)]
2
T
i
. (24)
Eq. (23) shows that 1/T
ref
is a weighted average of the 1/T
i
values used to perform the experiments and that the weights
depend on the concentration values and on the initial concen-
tration. It must be emphasized that the reference temperature is
normally dened as the midpoint T value in the analyzed range
of temperatures, while Eq. (23) clearly shows that the optimum
reference temperature is the reciprocal of the weighted average
of the 1/T
i
. Eq. (24) denes the reference temperature that al-
lows for estimation of uncorrelated parameters. The values of
C
A,i
used in Eq. (24) are the ones calculated from the model
with the optimum parameters. As these values are unknown a
priori, the values of C
A,i
in Eq. (24) can be made equal to the
experimental values and the reference temperature can be cal-
culated exactly afterwards.
It is important to notice that all proposed reparameteriza-
tions presented in Eqs. (4a)(4d) lead to the same solution for
T
ref
. Therefore, independently of the particular reparameteri-
zation considered, the reference temperature that leads to un-
correlated model parameters is the same (see the Appendix).
For this reason, the analysis performed here is concentrated
on Eq. (4a). The other reparameterization forms are analyzed
here only when they lead to distinct numerical performances,
as discussed below.
At this point one should observe that the parameter corre-
lation is indeed a function of the experimental data, of the
parameter estimates and of the reference temperature. There-
fore, the calculation of the optimum reference temperature can
be dened implicitly as
(x
e
, y
e
,

, T
ref
) =0. (25)
Eq. (25) can be solved numerically, so that Eq. (24) can be
seen as a particular analytical solution of Eq. (25), obtained for a
particular kinetic problem. In order to illustrate this point, let us
assume that the reaction temperature is allowed to vary linearly
from an initial value T
0
with a heating rate of , as performed
in typical temperature programmed experiments (Hedrick and
Chuang, 1998; Bhering et al., 2002; Kanervo et al., 2006):
T =T
0
+t . (26)
2754 M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764
Inserting Eq. (26) into Eq. (10), one gets:
dC
A
dt
=k
T
ref
exp
_

E
R
_
1
T
0
+t

1
T
ref
__
C
A
,
C
A
(t =0) =C
A0
. (27a)
As dT/dt = , Eq. (27a) can be rewritten as
dC
A
dT
=
k
T
ref

exp
_

E
R
_
1
T

1
T
ref
__
C
A
,
C
A
(T =T
0
) =C
A0
. (27b)
Eq. (27b) is used more often than Eq. (27a) for interpretation
of real experiments, as temperature can be related more easily
to catalyst characteristics than time. Anyway, the integration
of Eq. (27a) or (27b) must be performed numerically. As a
consequence, an analytical solution for a T
ref
value that leads to
uncorrelated model parameters is not possible. However, given
a set of experimental data (C
A0
, , T
0
, t and C
A
) and of model
parameters (k
T
ref
and E), can be computed for any value
of T
ref
. Therefore, one may devise the following numerical
procedure:
1. an initial guess for T
ref
is provided (for instance, the mid-
point T value in the analyzed range of temperatures);
2. model parameters (which are probably correlated) are esti-
mated with the available set of experimental data and the
value provided for T
ref
;
3. Eq. (25) is solved for T
ref
, using the available experimen-
tal data and the set of estimated model parameters (for in-
stance, using a direct search method or a NewtonRaphson
procedure).
In practice, Eq. (25) is a function of the reference temperature
only. First, for a given set of experimental data, the values of x
e
and y
e
are xed. Second, for a xed set of experimental data,
the kinetic parameter k is the one that minimizes the objective
function, regardless of the proposed reparameterization. For
instance, let us assume that two distinct values T
ref 0
and T
ref 1
are compared. As
k =k
T ref 0
exp
_

E
0
R
_
1
T

1
T
ref 0
__
=k
T ref 1
exp
_

E
1
R
_
1
T

1
T
ref 1
__
(28)
then it can be concluded that
E
1
=E
0
, (29a)
k
T ref 1
=k
T ref 0
exp
_

E
0
R
_
1
T
ref 1

1
T
ref 0
__
. (29b)
In other words, if the parameter estimates (k
T ref 0
, E
0
) are
known for a certain reparameterization variable (T
ref 0
), then
they can be readily updated (k
T ref 1
, E
1
) when the values of
the reparameterization variables change (to T
ref 1
) without af-
fecting the model performance. Therefore, once the parameters
are estimated with a specic reference temperature (T
ref 0
) and
a specic reparameterization form, the parameters of an alter-
native reparameterization form become functions of the new
Initial guess for T
ref
0
Set k = 0
Estimate the model
parameters
Calculate the
covariance matrix of
parameter estimates
Calculate the
parameter correlation
Is the
parameter
correlation
null?
END
Update the T
Tref
k
Recalculate the
parameters
k
Tref
k
and E
k
YES
NO

T
ref
k
, k
Tref
k
, E
k
k = k + 1
Fig. 1. A schematic representation of the procedure for optimum reference
temperature determining.
T
ref
only. For this reason, the steps 13 of the proposed algo-
rithm must be performed only once, as the parameter estimation
(step 2) does not have to be repeated after modication of T
ref
(step 3). This procedure is illustrated in Fig. 1. It is important
to emphasize that after the parameter estimation (step 2), the
values of parameters k
T ref 0
and E
0
for a reference tempera-
ture T
ref 0
become available. Starting from these values, one
can readily calculate the parameter values for any other T
ref
values and reparameterization forms. Then, the covariance ma-
trix of parameter estimates can be recalculated (Eq. (8)) and
the parameter correlation can be updated (Eq. (9)). A suitable
numerical procedure can be used for searching the value of T
ref
that leads to uncorrelated model parameters. Alternatively, one
can allow T
ref
to vary and, after recalculation of the covari-
ance matrix of parameter estimates, observe how the parameter
correlation and parameter errors are affected by the changing
valuebreak of T
ref
.
As a matter of fact, reparameterization does affect step 2 of
the proposed algorithm because parameter correlation affects
M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764 2755
the performance of the minimization procedure (Agarwal and
Brisk, 1985, 1986; Rimensberger and Rippin, 1986; Espie and
Macchietto, 1988). If the parameter correlation is too high, it
may be difcult to nd the minimum of Eq. (6), which means
that steps 2 and 3 should be performed iteratively until conver-
gence in order to guarantee attainment of optimum parameter
estimates without correlation. This procedure is indicated in
Fig. 1 by a dashed line, where the parameter estimation step is
included in the iterative procedure.
When there are N >1 independent kinetic constants, then
the number of reference temperatures that must be dened by
the user is equal to N, while the number of independent pa-
rameter correlations is equal to N(2N 1), which may be
much larger than N. Therefore, it cannot be guaranteed that the
proposed reparameterization scheme can allow for the simul-
taneous removal of all parameter correlations. However, the
minimization of parameter correlation effects can be performed
with the proposed numerical scheme (Fig. 1) if a proper norm
of the parameter correlation matrix is provided by the user
(for instance, the sum of the squares of all correlations terms).
An analysis of this multi-dimensional problem is beyond the
scope of this text and will be the subject of future communica-
tions in this series. In the following examples, it is shown that
the proposed numerical scheme can handle one-dimensional
problems satisfactorily and that one is encouraged to propose
similar schemes to handle more involving multi-dimensional
problems.
4. Examples
In the two following examples, the parameter estimation
procedure was performed through combination of the parti-
cle swarm optimization (Kennedy and Eberhart, 1995) and tra-
ditional Newton procedures (Noronha et al., 1993). The rst
method is characterized by a global minimization character that
avoids local minima. The method can also be used for construc-
tion of the likelihood condence regions, providing a more rig-
orous statistical evaluation of the parameter estimates (Schwaab
et al., 2007). Other methods have been proposed in the literature
to allow for construction of the likelihood condence regions
(Lobry et al., 1991; Klepper and Hendrix, 1994), but the use
of particle swarm optimization should be preferred due its ca-
pability for solving high-dimensional and multi-minima prob-
lems. Proling t-plots (Bates and Watts, 1988) can be used for
construction of the likelihood condence intervals for parame-
ter estimates, but the condence regions can only be obtained
through interpolation. Besides, when particle swarm optimiza-
tion is used, the likelihood condence regions of parameter
estimates are obtained with the objective function evaluations
performed during the previous optimization steps. This means
that PSO does not require any additional calculation for com-
putation of condence regions, so that one has only to select
the previously evaluated points that satisfy the likelihood cri-
teria (Schwaab et al., 2007).
The second method is a GaussNewton-based proce-
dure that uses the best point provided by the particle
swarm optimization method as the initial guess, assuring
Table 1
Experimental data used in Example 1
t (min) T (K) y t (min) T (K) y
120.0 600 0.900 60.0 620 0.802
60.0 600 0.949 60.0 620 0.802
60.0 612 0.886 60.0 620 0.804
120.0 612 0.785 60.0 620 0.794
120.0 612 0.791 60.0 620 0.804
60.0 612 0.890 60.0 620 0.799
60.0 620 0.787 30.0 631 0.764
30.0 620 0.877 45.1 631 0.688
15.0 620 0.938 30.0 631 0.717
60.0 620 0.782 30.0 631 0.802
45.1 620 0.827 45.0 631 0.695
90.0 620 0.696 15.0 639 0.808
150.0 620 0.582 30.0 639 0.655
60.0 620 0.795 90.0 639 0.309
60.0 620 0.800 25.0 639 0.689
60.0 620 0.790 60.1 639 0.437
30.0 620 0.883 60.0 639 0.425
90.0 620 0.712 30.0 639 0.638
150.0 620 0.576 30.0 639 0.659
90.4 620 0.715 60.0 639 0.449
120.0 620 0.673
the precision of the point estimate and giving the nal
covariance matrix of parameter estimates, used for con-
struction of the elliptical condence regions. The deriva-
tives used for minimization of the objective function and
for calculation of the covariance matrix of parameter esti-
mates were evaluated numerically through central difference
approximations.
Finally, parameter correlation and the relative error of
parameter estimates were obtained as illustrated in Fig. 1.
After initial parameter estimation with a guess for T
ref 0
, the
reference temperature was allowed to vary and the covariance
matrix of parameter estimates was recalculated for every new
T
ref
value, allowing us to show how the parameter correlation
and the relative errors of parameter estimates depend on T
ref
.
This way, one can obtain very good approximations of the
T
ref
values that lead to uncorrelated model parameters or to
minimum relative parameter errors. As discussed, alternative
numerical procedures could be used for searching the optimum
value of T
ref
. In this case, some concern should be given to
the initial guess of the reference temperature, as it may exert
a signicant inuence on the convergence of the numerical
procedure.
4.1. Example 1analytical solution
In order to illustrate the application of the solution obtained
for the rst order kinetics, the thermal isomerization of the
bicycle[2.1.1]hexane is considered (Srinivasan and Levi, 1963).
The available data are the remaining fraction of reactant y (that
is, C
A
/C
A0
) for different times t and temperatures T, as reported
by Englezos and Kalogerakis (2001) and shown in Table 1.
2756 M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Predicted Values
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
O
b
s
e
r
v
e
d

V
a
l
u
e
s
Fig. 2. Observed values versus model prediction in Example 1.
560 580 600 620 640 660 680 700
T
ref
[K]
-1.00
-0.75
-0.50
-0.25
0.00
0.25
0.50
0.75
1.00
C
o
r
r
e
l
a
t
i
o
n
Fig. 3. Correlation behavior as a function of the reference temperature in
Example 1.
Therefore, the rst order kinetic model is written as
y
i
=exp
_
t
i
k
T
ref
exp
_

E
R
_
1
T
i

1
T
ref
___
, (30)
where the reparameterization formdened in Eq. (4a) was used.
The optimum reference temperature is
T
ref
=

NE
i=1
[y
i
ln(y
i
)]
2

NE
i=1
[y
i
ln(y
i
)]
2
T
i
. (31)
The least squares objective function (Eq. (13)) was used for
estimation of the model parameters and its minimum value was
equal to 1.028 10
3
. It is important to emphasize that the
model responses and, consequently, the model performance are
not sensitive to reparameterization, so that Fig. 2 illustrates the
model behavior independently of the used reparameterization.
In order to observe the effect of the reference temperature on
the parameter correlation and on the parameter relative errors
(dened in the Appendix, Eqs. (A.6) and (A.7)), the reference
temperature was allowed to vary, as shown in Figs. 3 and 4.
Fig. 3 shows that uncorrelated model parameters can indeed be
achieved. Parameter correlation is close to 1.0 for low refer-
ence temperatures and increases continuously as T
ref
increases,
approaching the value of +1.0 for high values of T
ref
.
400 500 600 700 800 900 1000 1100 1200 1300
T
ref
[K]
0.0
20.0
40.0
60.0
80.0
100.0
R
e
l
a
t
i
v
e

E
r
r
o
r

[
%
]
Fig. 4. Relative error behavior of parameters k
T
ref
(line) and E (dashed line)
as functions of the reference temperature in Example 1.
Fig. 4 shows how the relative errors of parameters k
T
ref
and E
change, as functions of the reference temperature. The relative
error of parameter E is independent of the reference tempera-
ture and is equal 3.37%. However, for parameter k
T
ref
the rela-
tive error attains its minimum value of 2.29% at the reference
temperature value that also leads to null parameter correlation.
(This can be proved analytically, as shown in the Appendix.)
This point can be determined by Eq. (31), and this optimum ref-
erence temperature is equal to 628.45 K, where the parameters
k
T
ref
and E are equal to 6.808 10
3
min
1
and 229.8 kJ/mol.
Using Eqs. (29a)(29b) one can calculate these parameters
for any other reference temperature and reparameterization
form.
As discussed previously, when the reference temperature
tends to innity, the reparameterized form of the Arrhenius
equation becomes equal to the traditional form. One should ob-
serve in Fig. 3 that the parameter correlation approaches the
value +1.0 for the traditional form of the Arrhenius equation.
Fig. 4 also shows that the relative error increases for the tra-
ditional form of the Arrhenius equation, showing again that it
may be advantageous to use Eq. (4). In fact, if the traditional
form of the Arrhenius equation is used in this case, the parame-
ter correlation becomes equal to 0.999881 and the relative error
of parameter k
T
ref
becomes equal to 148.4%.
For calculation of the reference temperature in Eq. (31),
model outputs should be used, leading to the value of 628.45 K.
If model outputs are replaced by the experimental measure-
ments, then the value of the reference temperature obtained
with Eq. (31) becomes equal to 628.54 K, which leads to pa-
rameter correlation of 0.01 and relative error of parameter k
T
ref
of 2.29%. These values are very close to the best ones, indicat-
ing that experimental data can be indeed used to provide very
good initial guesses for T
ref
. In this particular case, the good
agreement between model predictions and available experimen-
tal data, shown in Fig. 2, supports the use of the experimental
data for calculation of T
ref
.
If the reference temperature of 620 K is used (the midpoint
temperature value within the analyzed experimental range), the
parameter correlation becomes equal to 0.66 and the relative
error of parameter k
T
ref
becomes equal to 3.06%. These values
M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764 2757
-1.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0
k
Tref
[10
+17
min
-1
]
215
220
225
230
235
240
245
E

[
k
J
/
m
o
l
]
Fig. 5. Elliptical and likelihood condence regions of parameters k
T
ref
and
E with an innite reference temperature (traditional Arrhenius equation) in
Example 1.
-0.5 0.0 0.5 1.0 1.5 2.0 2.5
k
Tref
[10
-13
min
-1
]
215
220
225
230
235
240
245
E

[
k
J
/
m
o
l
]
Fig. 6. Elliptical and likelihood condence regions of parameters k
T
ref
and
E with a reference temperature of 400 K in Example 1.
are certainly worse than the ones obtained with the optimum
reference temperature.
It is interesting to observe that the reparameterization of the
Arrhenius equation also improves the elliptical approximation
of the condence region. For the traditional form of the Arrhe-
nius equation, the elliptical approximation of the condence
region is very inadequate and leads to the conclusion that pa-
rameter k
T
ref
is not signicant (the condence interval crosses
the zero), as shown in Fig. 5. It can also be seen in Fig. 5 that
the likelihood condence region is narrow and curved, char-
acterizing the poor approximation of the elliptical condence
region. Similar results are obtained when a low reference tem-
perature is used, as shown in Fig. 6.
When the reparameterized Arrhenius equation is used with
the adequate reference temperature, the elliptical approxima-
tion is improved very signicantly and becomes very close
to the likelihood condence region. This can be observed in
Figs. 7 and 8, where the reference temperatures are equal to
620 and 628.45 K. In both gures, the elliptical approximation
of the condence region is very close to the likelihood con-
dence region, showing that the statistical characterization of
the parameter estimates is much easier after reparameterization.
3.5 3.6 3.7 3.8 3.9 4.0
k
Tref
[10
3
min
-1
]
215
220
225
230
235
240
245
E

[
k
J
/
m
o
l
]
Fig. 7. Elliptical and likelihood condence regions of parameters k
T
ref
and
E with a reference temperature of 620 K in Example 1.
6.5 6.6 6.7 6.8 6.9 7.0 7.1
k
Tref
[10
-3
min
-1
]
215
220
225
230
235
240
245
E

[
k
J
/
m
o
l
]
Fig. 8. Elliptical and likelihood condence regions of parameters k
T
ref
and
E with the optimum reference temperature of 628.45 K in Example 1.
Fig. 8 shows, however, that the axes of the ellipses are parallel
to the parameter axes, due to removal of parameter correlation.
If Eq. (4b) is for reparameterization, the rst order kinetic
model can be written as
y
i
=exp
_
t
i
exp
_
A
E
R
_
1
T
i

1
T
ref
___
. (32)
As expected, the model performance is not affected by the
reparameterization. Similarly, the parameter correlation and the
relative error of parameter E respond equally to perturbations
of T
ref
. However, the behavior of the relative error of parame-
ter A presents some different aspects, as shown in Fig. 9. The
relative error of parameter A presents a minimum at a T
ref
value that is similar (although, not the same) to the T
ref
value
that leads to uncorrelated parameters. As T
ref
increases, the
relative error also increases and goes to innity. An additional
increase of T
ref
causes the asymptotic decrease of the relative
error. This means that, although the different reparameteriza-
tion forms lead to similar reference temperatures when one is
interested in nullifying the parameter correlations, the perfor-
mances may be different when one is also interested in min-
imizing the relative error content of the pre-exponential term.
By comparing Figs. 4 and 9, one may conclude that inclusion of
k
T
ref
into the exponential term may be benecial for improving
2758 M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764
400 500 600 700 800 900 1000 1100 1200 1300
T
ref
[K]
0.0
3.0
6.0
9.0
12.0
15.0
R
e
l
a
t
i
v
e

E
r
r
o
r

[
%
]
Fig. 9. Relative error behavior of parameters A (line) and E (dashed line) as
functions of the reference temperature in Example 1.
the performance of numerical procedures but may be deleteri-
ous for nal statistical interpretation of parameter estimates.
The relative error of parameter A (Eq. (A.6)) is a function
of the reference temperature and, as shown in the Appendix,
presents three critical points; that is, three points where the
derivatives of the relative error with respect to T
ref
are null,
which are
T
ref
=
[E/ ln(k
0
)R]

N
i=1
[y
i
ln(y
i
)]
2
T
i

N
i=1
[y
i
ln(y
i
)]
2
[E/ ln(k
0
)R]

N
i=1
[y
i
ln(y
i
)]
2
T
2
i

N
i=1
[y
i
ln(y
i
)]
2
T
i
,
(33a)
T
ref
=
E
ln(k
0
)R
, (33b)
T
ref
=, (33c)
where the value of ln(k
0
) can be computed with the help of
Eq. (5b) and the values of the parameters A and E are valid for
one specic reference temperature.
Eq. (33a) denes the condition of minimum relative error
(T
ref
= 627.13 K), which leads to parameter correlation of
0.14. In this case, the point where the relative error attains the
minimum is slightly smaller than the value that leads to uncor-
related parameters (T
ref
=628.45 K). Eq. (33b) represents the
point where parameter A becomes equal to zero, causing the
relative error to become innite. Eq. (33c) is the result obtained
when the effect of the reference temperature is eliminated. The
relative error of parameter A decreases asymptotically as the
reference temperature goes to innity, where the relative error
of parameter A becomes equal to 3.81% and the parameter cor-
relation becomes equal to 0.999881, the same values found for
the rst reparameterization form.
When T
ref
is equal to innity for the rst analyzed param-
eterization, the relative error of parameter k
T
ref
is equal to
148.4%, which is much larger than the relative error of param-
eter A for this second form. Besides, Fig. 5 shows that the el-
liptic approximation of the condence region is inadequate in
the rst case. When the second reparameterization form of the
37 38 39 40 41
A
215
220
225
230
235
240
245
E

[
k
J
/
m
o
l
]
Fig. 10. Elliptical and likelihood condence regions of parameters A and E
with an innite reference temperature in Example 1.
-31.5 -31.0 -30.5 -30.0 -29.5 -29.0 -28.5
A
215
220
225
230
235
240
245
E

[
k
J
/
m
o
l
]
Fig. 11. Elliptical and likelihood condence regions of parameters A and E
with a reference temperature of 400 K in Example 1.
Arrhenius equation is used (Eq. (4b)), the elliptic condence
region becomes very close to the likelihood condence region,
as shown in Fig. 10. The same behavior is observed in Fig. 11
for a low reference temperature. These results seem to indicate
that inclusion of k
T
ref
into the exponential term may be bene-
cial for improving the performance of numerical procedures
and for nal statistical interpretation of parameter estimates si-
multaneously, contradicting expectations raised from Fig. 9.
As observed by Watts (1994) and in the rst part of this
example, the denition of a reference temperature improves
the reliability of the elliptical approximation of the condence
regions. When Eq. (4b) is used, even without denition of a
reference temperature (the reference temperature is equal to in-
nity), the elliptical approximation of the condence regions
becomes very similar to the likelihood condence regions. Un-
fortunately, the high correlation between the parameters is still
present and can only be eliminated after the proper denition
of the reference temperature, as shown in Fig. 12 and discussed
here for the rst time.
4.2. Example 2numerical solution
In order to illustrate the case where an analytical solution
for the optimum reference temperature is not available, a
M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764 2759
-5.04 -5.02 -5.00 -4.98 -4.96 -4.94
A
215
220
225
230
235
240
245
E

[
k
J
/
m
o
l
]
Fig. 12. Elliptical and likelihood condence regions of parameters A and E
with the optimum reference temperature of 628.45 K in Example 1.
temperature programmed experiment is considered. Temper-
ature programmed experiments are widely used for catalysts
characterization (Bhering et al., 2002), study of transient kinet-
ics (Kanervo et al., 2006) and for characterization of polymeric
materials (Hedrick and Chuang, 1998). The proper mathemat-
ical interpretation of these experiments can encourage the de-
velopment of new applications and improve the understanding
of the kinetic mechanisms of the studied phenomena.
For a temperature programmed reduction (TPR), the cata-
lyst (generally, a metal oxide supported onto an inert support)
is exposed to a reducible atmosphere (like a mixture of 5% H
2
in N
2
). As the temperature increases, the metal oxide is con-
verted into the metal state, which is believed to be active for
a particular reaction. This procedure is used for catalyst acti-
vation. Assuming the perfect control of the temperature, the
model equations that describe this type of experiments can be
written as
r =k
T
ref
exp
_

E
R
_
1
T
0
+t

1
T
ref
__
C
S
C
H
2
, (34)
dC
S
dt
=r, (35)
C
in
H
2
C
H
2
(V/q)r =0, (36)
where Eq. (4a) was used as a reparameterization form of the
Arrhenius equation, r is the reaction rate, C
S
is the concentra-
tion of reducible catalyst specie, C
H
2
is the hydrogen concen-
tration in the gas phase and C
in
H
2
is the hydrogen concentration
in the feed. V is the catalyst volume, q is the volumetric ow
rate, T
0
is the initial temperature and is the heating rate. The
model equation for the gas phase (Eq. (36)) assumes quasi-
steady state, since the dynamics of the gas phase is negligible
when compared to the dynamics of the solid phase transforma-
tions. The independent measured variables are the time t and
the temperature T, assumed to be precisely measured. The hy-
drogen concentration at the reactor outlet C
H
2
is the dependent
variable, whose error measurement is assumed to be constant.
The experimental data used here were generated from the
model equations described in Eqs. (34)(36). Parameters k
T
ref
and E were set equal to 10 m
3
/mol/s and 100 kJ/mol, with T
ref
400 450 500 550 600 650 700 750 800
T [K]
0.06
0.07
0.08
0.09
0.10
C
H
2

[
1
0
-
3

m
o
l
/
m
3
]
Fig. 13. Simulated experimental data (points) and obtained model predictions
(line) in Example 2.
400 450 500 550 600 650 700 750 800 850 900
T
ref
[K]
-1.00
-0.75
-0.50
-0.25
0.00
0.25
0.50
0.75
1.00
C
o
r
r
e
l
a
t
i
o
n
Fig. 14. Correlation behavior as a function of the reference temperature in
Example 2.
equal to 573.15 K. was equal to 0.167 K/s (10 K/min), T
0
was equal to 373.15 K, V/q was equal to 1 s and C
in
H
2
equal
to 10
4
mol/m
3
. Random errors with normal distribution and
standard deviation equal to 10
6
mol/m
3
were added to the
simulated hydrogen concentration values in order to simulate
the experimental deviation. These values are in accordance with
published material (Bhering et al., 2002).
Model tting consisted in estimating the parameters k
T
ref
and E that minimize the least squares function of the hydro-
gen concentrations measured along the time. The simulated ex-
perimental data and the obtained tted model are presented in
Fig. 13. The initial value of T
ref
was the same one used for
data generation (T
ref 0
= 573.15 K). With this reference tem-
perature, the estimated values of parameters k
T
ref
and E were
equal to 9.55 m
3
/mol/s and 9.66 kJ/mol, while the parameter
correlation was equal to 0.773 and the relative errors of pa-
rameters k
T
ref
and E were equal to 1.25% and 0.787%. Then,
the procedure presented in Fig. 1 was used both to determine
the optimum reference temperature and to observe how the pa-
rameter correlation and parameter relative errors were affected
by T
ref
.
Figs. 14 and 15 show the parameter correlation and the rel-
ative error of model parameters as functions of the reference
2760 M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764
400 500 600 700 800 900
T
ref
[K]
0.0
3.0
6.0
9.0
12.0
15.0
R
e
l
a
t
i
v
e

E
r
r
o
r

[
%
]
Fig. 15. Relative error behavior of parameters k
T
ref
(line) and E (dashed line)
as functions of the reference temperature in Example 2.
0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7
k
Tref
[10
+10
m
3
/mol/s]
97
98
99
100
101
102
E

[
k
J
/
m
o
l
]
Fig. 16. Elliptical and likelihood condence regions of parameters k
T
ref
and
E with an innite reference temperature (traditional Arrhenius equation) in
Example 2.
temperature. In both cases, obtained results are similar to the
ones obtained in Example 1. The parameter correlation is close
to 1.0 for small values of T
ref
, increasing asymptotically to
+1.0 as T
ref
increases. Uncorrelated parameters can be clearly
obtained for an intermediate value of T
ref
. The relative error
of parameter E is the same for all T
ref
values, while param-
eter k
T
ref
presents a minimum amount of error for the same
T
ref
value where the parameter correlation becomes null. The
optimum reference temperature for this problem is equal to
608.88 K, where the parameter correlation is null, the relative
error of parameter k
T
ref
is equal to 1.56% and the relative error
of parameter E is equal to 1.55%. If the traditional form of the
Arrhenius equation is used, obtained parameter correlation is
equal to 0.9987, with a relative error of parameter k
T
ref
equal
to 30.5%.
The condence regions presented in Figs. 16 and 17 clearly
show the effect of the adequate determination of the reference
temperature. Although in this example the likelihood and the
elliptic condence regions are similar in all analyzed cases,
when the optimum reference temperature is used (Fig. 17)
the agreement is higher than when the traditional form of the
Arrhenius equations is used (Fig. 16).
31.5 32.0 32.5 33.0 33.5
k
Tref
[m
3
/mol/s]
97
98
99
100
101
102
E

[
k
J
/
m
o
l
]
Fig. 17. Elliptical and likelihood condence regions of parameters k
T
ref
and
E with the optimum reference temperature of 608.88 K in Example 2.
400 500 600 700 800 900
T
ref
[K]
0.0
3.0
6.0
9.0
12.0
15.0
R
e
l
a
t
i
v
e

E
r
r
o
r

[
%
]
Fig. 18. Relative error behavior of parameters A (line) and E (dashed line)
as functions of the reference temperature in Example 2.
When Eq. (4b) is used for the reparameterization of the Ar-
rhenius equation, Eq. (34) can be rewritten as
r =exp
_
A
E
R
_
1
T
0
+t

1
T
ref
__
C
S
C
H
2
. (37)
As in the rst example, the change of the reparameteriza-
tion form affects neither the parameter correlation nor the rela-
tive error of parameter E, but the relative error of parameter A
(Fig. 18) presents a more complex behavior.
Fig. 18 shows the asymptotic behavior of the relative error of
parameter A at very low and very high reference temperatures
and the singular value when A is equal to 0 (T
ref
=517.29 K).
When T
ref
is equal to 618.00 K, the relative error of parameter
A attains the minimum value of 0.430% and the parameter cor-
relation becomes equal to 0.277. Uncorrelated parameters are
obtained when the reference temperature is equal to 608.88 K.
At this point, the relative error of parameter A is equal 0.448%.
The relative error of parameter A when T
ref
is innite is equal
to 1.31%.
Fig. 19 shows the elliptical and the likelihood condence re-
gions for an innite T
ref
value. The good agreement between
the condence regions, in accordance with the result obtained
M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764 2761
22.7 22.8 22.9 23.0 23.1 23.2 23.3 23.4 23.5 23.6
A
97
98
99
100
101
102
E

[
k
J
/
m
o
l
]
Fig. 19. Elliptical and likelihood condence regions of parameters A and E
with an innite reference temperature in Example 2.
3.45 3.46 3.47 3.48 3.49 3.50 3.51
A
97
98
99
100
101
102
E

[
k
J
/
m
o
l
]
Fig. 20. Elliptical and likelihood condence regions of parameters A and E
with the optimum reference temperature of 608.88 K in Example 2.
in Example 1 (Fig. 10), supports the conclusion that the use of
Eq. (4b) can improve the reliability of the elliptical approxi-
mation for the condence regions, even when innite reference
temperatures are used. Despite that, very high parameter cor-
relation can still be present if the reference temperature is not
selected appropriately. Using the optimum reference tempera-
ture of 608.88 K, the parameter correlation becomes null, as
shown in Fig. 20.
5. Conclusions
The reparameterization of the Arrhenius equation through
denition of a reference temperature allows for minimization
of parameter correlation and makes parameter estimation and
interpretation much easier. As shown in this work both ana-
lytically and numerically, the proper choice of the reference
temperature allows for estimation of uncorrelated parameters
with minimum relative error. For dynamic models where an
analytical solution is not available, a closed analytical solution
cannot be derived and a numerical procedure can be used to
determine the optimum reference value. The numerical proce-
dure comprises two steps. In the rst one, parameter estimates
are obtained after denition of an initial guess of the reference
value. In the second step, the reference temperature is updated
in order to make the parameter correlation equal to zero. The
procedure can be repeated iteratively to lead to uncorrelated
parameters with minimum error content.
Acknowledgment
The authors thank CNPqConselho Nacional de Desen-
volvimento Cientco e Tecnolgiafor providing scholar-
ships and for supporting this work.
Appendix
The covariance matrix of parameter estimates V

is dened
in Eq. (6). If the covariance matrix of experimental deviation is
diagonal (errors are independent) and the variance is the same
in all observations (diagonal elements are equal), the covariance
matrix of parameter estimates can be written as
V

=s
2
(B
T
B)
1
. (A.1)
For single response models containing only one kinetic con-
stant, as described in Examples 1 and 2 of this manuscript, the
sensitivity matrix of model responses with respect to the pa-
rameters can be written as
B =

jy
1
j
1
jy
1
j
2
.
.
.
.
.
.
jy
NE
j
1
jy
NE
j
2

, (A.2)
where
1
stands for the parameters k
T
ref
or A and
2
stands for
the parameters E or B, depending on the considered reparame-
terization form. The covariance matrix of parameter estimates
can be written as
V

=s
2

NE

i=1
_
jy
i
j
1
_
2
NE

i=1
_
jy
i
j
2
__
jy
i
j
1
_
NE

i=1
_
jy
i
j
1
__
jy
i
j
2
_
NE

i=1
_
jy
i
j
2
_
2

1
.
(A.3)
After inversion of the term between brackets, one gets:
V

=
s
2
det(B
T
B)

NE

i=1
_
jy
i
j
2
_
2

NE

i=1
_
jy
i
j
2
__
jy
i
j
1
_

NE

i=1
_
jy
i
j
1
__
jy
i
j
2
_
NE

i=1
_
jy
i
j
1
_
2

,
(A.4)
where det(B
T
B) is the determinant dened as
det(B
T
B) =
NE

i=1
_
jy
i
j
1
_
2
NE

i=1
_
jy
i
j
2
_
2

_
NE

i=1
_
jy
i
j
1
_
NE

i=1
_
jy
i
j
2
_
_
2
. (A.5)
Therefore, one can use Eqs. (A.3) or (A.4) to obtain the
covariance matrix of parameter estimates. For simple models, as
2762 M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764
used in Example 1, the derivatives can be obtained analytically.
For more complex models, as the one presented in Example
2, the derivatives must be calculated numerically or through
integration of the sensitivity equations (Bard, 1974).
The elements of the covariance matrix of parameter estimates
give the variances of model parameters (v
11
and v
22
). Assuming
a normal distribution for the parameters estimates, the relative
errors of each parameter can be dened as (Himmelblau, 1970):
e

1
=
t
(1+)/2
NENP

v
11
=
t
(1+)/2
NENP

_
s
2
det(B
T
B)
NE

i=1
_
jy
i
j
2
_
2
,
(A.6)
e

2
=
t
(1+)/2
NENP

v
22
=
t
(1+)/2
NENP

_
s
2
det(B
T
B)
NE

i=1
_
jy
i
j
1
_
2
,
(A.7)
where t
(1+)/2
NENP
is the t-Student distribution value with a con-
dence level equal to (always equal to 0.95 in this work) and
with NE NP degrees of freedom.
In Example 1, it is possible to develop an analytical solu-
tion for the optimum value of T
ref
that leads to uncorrelated
model parameters, as shown in Section 3 and described in
Eq. (24). This optimum value is the same for all the reparam-
eterization forms of the Arrhenius equation, because the opti-
mum value does not depend on the model parameters, but only
on the model outputs. However, when one considers the rel-
ative errors of parameter estimates, distinct solutions can be
obtained, depending on the particular form of the reparameter-
ization. Initially, the reparameterization of Arrhenius equation
(dened in Eq. (4a)) is considered:
k
i
=k
T
ref
exp
_

E
R
_
1
T
i

1
T
ref
__
. (A.8)
In Example 1:
y
i
=exp(t
i
k
i
). (A.9)
The derivatives of the model response with respect to the
model parameters are
jy
i
jk
T
ref
=
y
i
ln(y
i
)
k
T
ref
, (A.10)
jy
i
jE
=
_
1
T
i

1
T
ref
_
y
i
ln(y
i
)
R
(A.11)
so that the determinant dened in Eq. (A.5) becomes
det(B
T
B) =
N

i=1
[y
i
ln(y
i
)]
2
k
2
T
ref
N

i=1
_
1
T
i

1
T
ref
_
2
[y
i
ln(y
i
)]
R
2
2

_
N

i=1
_
1
T
i

1
T
ref
_
[y
i
ln(y
i
)]
2
Rk
T
ref
_
2
. (A.12)
Expanding and simplifying Eq. (A.12), one nds the follow-
ing equation:
det(B
T
B) =
1
(Rk
T
ref
)
2

i=1
[y
i
ln(y
i
)]
2
i
N

i=1
[y
i
ln(y
i
)]
2
T
2
i

_
N

i=1
[y
i
ln(y
i
)]
2
T
i
_
2

, (A.13)
where the term inside the braces does not depend on the ref-
erence temperature. Inserting Eqs. (A.11) and (A.13) into Eq.
(A.6), one obtains:
e
k
T
ref
=C

_
NE

i=1
_
1
T
i

1
T
ref
_
2
[y
i
ln(y
i
)]
2
, (A.14)
where
C =
s t
(1+)/2
NENP

N
i=1
[y
i
ln(y
i
)]
2
i

N
i=1
[y
i
ln(y
i
)]
2
T
2
i

N
i=1
[y
i
ln(y
i
)]
2
T
i
_
2
(A.15)
is constant with respect to the reference temperature. The
reference temperature that leads to the minimum relative error
of parameter k
T
ref
is the value that minimizes the square of
the relative error of parameter k
T
ref
(that is, the square of Eq.
(A.14)):
e
2
kT
ref
=C
2
NE

i=1
_
1
T
i

1
T
ref
_
2
[y
i
ln(y
i
)]
2
. (A.16)
Differentiation of Eq. (A.16) with respect to T
ref
gives
je
2
kT
ref
jT
ref
=2C
2
NE

i=1
_
1
T
i

1
T
ref
_
[y
i
ln(y
i
)]
2
T
2
ref
. (A.17)
In order to obtain the value of T
ref
that minimizes the relative
error of parameter k
T
ref
, the following equation must be solved:
NE

i=1
_
1
T
i

1
T
ref
_
[y
i
ln(y
i
)]
2
T
2
ref
=0 (A.18)
leading to:
T
ref
=

NE
i=1
[y
i
ln(y
i
)]
2

NE
i=1
[y
i
ln(y
i
)]
2
T
i
(A.19)
One can observe that Eq. (A.19) is equal to Eq. (31), which
means that the reference temperature that eliminates the param-
eter correlation also leads to minimum relative error content of
k
T
ref
.
M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764 2763
The relative error of parameter E can be derived with the
help of Eqs. (A.7), (A.10) and (A.13):
e
E
=
s t
(1+)/2
NENP
E/R

NE
i=1
[y
i
ln(y
i
)]
2

N
i=1
[y
i
ln(y
i
)]
2
i

N
i=1
[y
i
ln(y
i
)]
2
T
2
i

N
i=1
[y
i
ln(y
i
)]
2
T
i
_
2

. (A.20)
One should observe that the relative error of the parameter E
does not depend on the T
ref
value, as shown in the Examples.
Considering now the second reparameterization form (Eq.
(4b))
k
i
=exp
_
A
E
R
_
1
T
i

1
T
ref
__
. (A.21)
In Example 1, the derivatives of the model response with
respect to the parameters are
jy
i
jA
=y
i
ln(y
i
), (A.22)
jy
i
jE
=
_
1
T
i

1
T
ref
_
y
i
ln(y
i
)
R
(A.23)
so that the determinant dened in Eq. (A.5) becomes
det(B
T
B) =
N

i=1
[y
i
ln(y
i
)]
2
N

i=1
_
1
T
i

1
T
ref
_
2
[y
i
ln(y
i
)]
2
R
2

_
N

i=1
_
1
T
i

1
T
ref
_
[y
i
ln(y
i
)]
2
R
_
2
. (A.24)
Expanding and simplifying Eq. (A.24), one nds the follow-
ing equation:
det(B
T
B) =
1
R
2

i=1
[y
i
ln(y
i
)]
2
i
N

i=1
[y
i
ln(y
i
)]
2
T
2
i

_
N

i=1
[y
i
ln(y
i
)]
2
T
i
_
2

(A.25)
that does not depend on the reference temperature.
Inserting Eqs. (A.11) and (A.25) into Eq. (A.6) one obtains:
e
A
=
C
A

_
NE

i=1
_
1
T
i

1
T
ref
_
2
[y
i
ln(y
i
)]
2
, (A.26)
where C is the constant dened in Eq. (A.15). The minimum of
the relative error of parameter A is found through minimization
of the square of Eq. (A.26):
e
2
kT
ref
=
C
A
2
2
NE

i=1
_
1
T
i

1
T
ref
_
2
[y
i
ln(y
i
)]
2
. (A.27)
One should observe that parameter A is an implicit func-
tion of the reference temperature (Eq. (5b)) and should be
written as
A =ln(k
0
)
E
RT
ref
, (A.28)
where k
0
is the specic reaction rate at innite temperature.
Inserting Eq. (A.28) into Eq. (A.27) and differentiating with
respect to T
ref
gives
je
2
A
jT
ref
=2C
2
A

NE
i=1
_
1
T
i

1
T
ref
_
[y
i
ln(y
i
)]
2
T
2
ref

E
R

NE
i=1
_
1
T
i

1
T
ref
_
2
[y
i
ln(y
i
)]
2
T
2
ref
A
3
. (A.29)
In order to obtain the value of T
ref
that minimizes the relative
error of parameter A, the numerator of Eq. (A.29) must be equal
to zero. Therefore,
A
NE

i=1
_
1
T
i

1
T
ref
_
[y
i
ln(y
i
)]
2
T
2
ref

E
R
NE

i=1
_
1
T
i

1
T
ref
_
2
[y
i
ln(y
i
)]
2
T
2
ref
=0. (A.30)
Eq. (A.30) has three solutions, as discussed previously:
T
ref
=
[E/ ln(k
0
)R]

N
i=1
[y
i
ln(y
i
)]
2
T
i

N
i=1
[y
i
ln(y
i
)]
2
[E/ ln(k
0
)R]

N
i=1
[y
i
ln(y
i
)]
2
T
2
i

N
i=1
[y
i
ln(y
i
)]
2
T
i
,
(A.31a)
T
ref
=
E
ln(k
0
)R
, (A.31b)
T
ref
=. (A.31c)
The minimum relative error of parameter A is obtained with
the rst solution, given by Eq. (A.31a). However, this solution
is different from the one obtained for estimation of uncorre-
lated parameters, which means that the minimum error content
of parameter A and uncorrelated parameters are not obtained
simultaneously for the same value of T
ref
, when k
T
ref
is inserted
into the exponential term.
The relative error of parameter E can be derived with the
help of Eqs. (A.7), (A.10) and (A.25). The result obtained is the
2764 M. Schwaab, J.C. Pinto / Chemical Engineering Science 62 (2007) 27502764
similar to the one obtained previously for the rst reparameter-
ization (Eq. (A.20)), showing that the relative error of E does
not depend on the T
ref
value and for both reparameterizations.
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