Short Reference

on
Kinetic Modeling of Catalytic Reactions

Tarek Moustafa, Ph.D.

2002
 T. M. Moustafa

Contents

1. Introduction
1.1 Rate of Reaction: Basic Definition
1.2 Measurement of Rate of Reaction: Why?
1.3 Steps in Catalytic Reactions
2. Kinetics in Relation to Thermodynamics and Transport Phenomena
2.1Kinetics and Thermodynamics/Equilibrium
2.2 Kinetics and Transport Phenomena
3. Lab Reactors Used for Measuring Kinetics
3.1 Types of Reactors
3.1.1 Integral Reactors
3.1.2 Differential Reactors
3.1.3 Stirred Contained Solids Reactors (SCSR)
3.1.4 Straight-through Transport Reactors (STR)
3.2 Criteria for Choosing a Lab Reactor
3.3 Precautions in Kinetic Experiments
3.3.1 Radial Concentration and Temperature Gradients
3.3.2 Axial Concentration, Temperature and Pressure Gradients
3.3.3 Interfacial Concentration and Temperature Gradients
3.3.4 Intraparticle Concentration and Temperature Gradients
4. Kinetic Modeling
4.1 Pre-Experimental Phase
4.2 Calculation of Experimental Reaction Rates
4.3 Fitting of Kinetic Parameters
4.3.1 Non Linear Optimization Methods
4.3.2 Discrimination of Kinetic Models
4.4 Future Trends in Kinetic Modeling
5. Comprehensive Examples

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Summary
This manual is a short reference dealing with the kinetic modeling of catalytic
reactions. It highlights the most important issues concerning kinetic studies and
kinetic modeling from a process development prospective. It is driven by the
necessity to express quantitatively the chemical reactions in terms of process
variables for the sake of reactor design and process optimization. Although each
reaction system is unique in its components, mechanism, catalytic species etc.,
yet the overall approach to handle the kinetic modeling task had some
similarities. The objective of this short reference is to unveil the main steps
involved in this task. Software is also attached containing complete solution of a
comprehensive example for a typical kinetic modeling problem.

1. Introduction
In this section, the basic definition of the rate of reaction and the need for having a
rate law is introduced. A brief description of transport, adsorption and reaction
steps taking place in catalytic systems is also given. The approach taken in this
reference is to start with the basic element of kinetics and chemical reaction
engineering and to highlight on the important aspects in kinetic modeling for
process development purpose.

1.1 Rate of Reaction: Basic Definition

The extensive rate of reaction with respect to a species A, rA is the observed rate of

formation of A referred to a specified normalizing quantity such as volume of

reacting system or volume/mass of catalyst:

moles A formed
rA =
(unit time)(unit volume)

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The rate of reaction is defined for a species involved in a reacting system either as
a reactant or as a product. This rate is positive if A is produced and negative if A is
consumed.

1.2 Measurement of Rate of Reaction: Why?

The primary use of chemical kinetics in reaction engineering is the development of
a rate law (for a simple system) or a set of rate laws (for a kinetic scheme in a
complex system). This requires experimental measurement of rate of reaction and
its dependence on concentration, temperature, etc. The development of such rate
law (which is often referred to as “kinetic modeling’) is the first step to design a
reactor for a certain process or to optimize an existing one.
Having a rate law, one is able to quantify the effect of various process variables
on the reactor performance and consequently on the overall process.

1.3 Steps in Catalytic Reactions

The overall process by which heterogeneous catalytic reactions proceed can be
broken down into a sequence of individual steps. These are shown in Table 1. The
overall rate of reaction is equal to the rate of the slowest step in the mechanism.
When the diffusion steps (1, 2, 6 and 7) are very fast compared with the adsorption
and reaction steps (3, 4 and 5), the concentrations in the immediate vicinity of the
catalyst active sites are the same as the bulk fluid. In this situation, the transport or
diffusion steps do not affect the overall rate of reaction. In other situations, if the
reaction steps are very fast compared with the diffusion steps, mass transport does
affect the reaction rate.
As for the surface reaction step, when a reactant (or more) has been adsorbed onto
the catalyst active site, it is capable of reacting in different ways. By way of
example, this surface reaction may be a single-site mechanism in which only the
site where the reactant is adsorbed is involved. The surface reaction may be a
dual-site mechanism in which the adsorbed reactant, A·S, interacts with another

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vacant site, S, or with a different adsorbed species, B·S to form products C·S.
Another example is the reaction of two species on different types of sites, S and
S’. These types of reactions are referred to as following Langmuir-Hinshelwood
kinetics, and are schematically represented in Fig 1.
Another mechanism may involve the reaction between an adsorbed molecule and a
molecule in the gas phase, which we refer to as an Eley-Rideal mechanism and is
depicted in Fig 2.

Table 1. Steps in a Catalytic Reaction

No Step
1 Mass transfer (diffusion) of the reactant(s) (e.g. species A) from the bulk fluid to the external
surface of the catalyst pellet
2 Diffusion of the reactant from the pore mouth through the catalyst pores to the immediate vicinity
of the internal catalytic surface
3 Adsorption of reactant A onto the catalytic surface
4 Reaction on the surface of the catalyst (e.g. A = B)
5 Desorption of the product(s) from the surface
6 Diffusion of the product(s) from the interior of the pellet to the pore mouth at the external surface
7 Mass transfer of the products from the external pellet surface to the bulk fluid

2. Kinetics in Relation to Thermodynamics and Transport Phenomena

To understand a chemical reaction system, it is important to be aware of
thermodynamics/equilibrium and/or the transport phenomena involved.
Thermodynamics can answer a question such as: what is the maximum conversion
for a certain reaction system. Diffusion and mass transfer of reactants in a liquid
solvent or solid catalyst may also affect (and sometimes controlling) the overall
performance of the system. Heat transfer is also important as chemical reactions
are usually accompanied by heat consumption or production. A typical example is
oxidation reactions of hydrocarbons.

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A B A B

Single Site Mechanism: Dual Site Mechanism:

A·S ? B·S A·S + S ? B·S + S

A B C D A B C D

Dual Site Mechanism: Dual Site Mechanism:

A·S + B·S ? C·S + D·S A·S’ + B·S ? C·S’ + D·S

Fig 1. Langmuir-Hinshelwood kinetics

B D
A C

A·S + B(g) ? C·S + D(g)

Fig 2. Eley-Rideal mechanism

2.1Kinetics and Thermodynamics/Equilibrium

Kinetics and thermodynamics address different kinds of questions about a reacting
system. Differences between chemical kinetics and chemical thermodynamics can
explain the domain of each as follows:
(a) Time is a variable in kinetics but not in thermodynamics, e.g. equilibrium is
a time-independent state

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(b) One is able to get information about mechanism of chemical reaction from
kinetic study but not from thermodynamics. Kinetics is concerned with the
path of chemical change while thermodynamics is concerned with the
“state” and the “change of state” of a system.
(c) The Gibbs energy ( G) of reaction, which is a thermodynamic property, is
a measure of the tendency for reaction to occur, but it tells nothing about
how fast this reaction is.
(d) Chemical kinetics is concerned with the rate of reaction and factors
affecting rate, while chemical thermodynamics is concerned with the
position of equilibrium and factors affecting equilibrium.
Nevertheless, equilibrium can be important aspect of kinetics, because it imposes
limits on the extent of chemical change (conversion).

2.2 Kinetics and Transport Phenomena

Mass and heat transfer may take place in chemical reaction systems. In solid
catalytic reaction system, there is an external mass transfer between the bulk gas
and the catalyst pellet. There is a difference between the rate by which a chemical
component reacts at the surface of the catalyst, ( rA ), and the rate by which it is
S

diffused from the bulk gas to this catalyst surface, ( rA ). If it happens that rA >
D S

rAD , we call the situation in this case: “An external mass transfer controlled”, as

the rate of diffusion is a slower step. If the situation is the opposite, it is a surface
reaction controlled case.
This mass transport may be also internal in the pores of the catalyst pellets. In
some cases, the rate of diffusion inside the pellet becomes controlling when it is
slower than the rate of surface reaction, i.e. The rate by which the reactant
transfers from the gas phase to the inner part of the catalyst pellet is slower than
the rate by which it reacts. Typical industrial examples for this case are methane
steam reforming and dehydrogenation of ethylbenzene to styrene.

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Heat transport is due to the difference in temperature between the bulk gas and the
catalyst pellets or within the pellet itself. This temperature difference is due to heat
of reaction, which is generated or consumed at the catalyst surface. Again, it is
important to consider this in some cases where heat of reaction is considerably
high and/or if the thermal conductivity of the catalyst pellet is low.
A clear illustration is given in Fig 3, showing the possible profiles of concentration
and temperature in the bulk gas and the catalyst pellet for transport limited cases.

Gas film

Catalyst particle
surface (s)
Bulk gas
R
Catalyst particle
interior

Exothermic
reaction

Ts Tg

CAg
CAs Endothermic
reaction
CA T

Fig 3. Concentration (CA) and temperature (T) gradients in a porous catalyst pellet

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3. Lab Reactors Used for Measuring Kinetics

3.1 Types of Reactors
There are a lot of options while choosing a reactor for kinetic study. Criteria like
ease of construction, sampling, analysis of data, isothermality, cost etc. may lead
to the superiority of one reactor configuration over the other. For continuous
systems, there are mainly four types of reactors used to perform a kinetic study for
a given catalyst, and these are given below.

3.1.1 Integral Reactors

This is a typical fixed bed reactor type. A schematic is given in Fig 4. It is easy to
construct and to operate near the targeted plant conditions. Care should be taken
while designing this type of lab reactor to avoid possibilities of transport
limitations during the reaction. The possibility of operating such reactor at high
conversions makes it attractive option for studying the effect of product inhibition
on reaction rates. Having said that, this reactor configuration may have poor
performance for certain catalytic systems. By way of example, achieving
isothermality may be a problem in this reactor along the bed length.

3.1.2 Differential Reactors

This reactor consists of a tube containing a very small amount of catalyst. A
typical schematic is given in Fig 5. Because of this small amount of catalyst the
conversion of the reactants is extremely small and consequently the change in the
concentration of the reactants through the bed. As a result the concentration of the
reactants are assumed to be constant and the reaction rate is considered constant
through the bed. This makes the data analysis simple if compared to the integral
reactor case.
Owing to low conversion, this reactor can operate essentially in an isothermal
manner but care should be taken to avoid channeling or bypass of reactants.
Ensuring sampling accuracy may be also difficult for multicomponent systems due

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to low conversion. The effect of product inhibition is not also felt in the reaction
rate, as the products’ concentration is always very low due to low conversion. This
drawback can be overcome by introducing products in the feed stream.

Inert material

CAo CA
CAo CA

Catalyst Catalyst

Fig 4. Integral Reactor Fig 5. Differential Reactor

3.1.3 Stirred Contained Solids Reactors (SCSR)

A typical design for this reactor is shown in Fig 6. Catalyst particles are contained
in paddles that rotate at sufficiently high speed to minimize external mass transfer
effects and to keep the fluid contents well mixed as well. Isothermal condition can
be maintained and data can be analyzed based on outlet concentrations measured.
If the catalyst particle size is small, difficulties could be encountered containing
the particles in the paddle screens.

3.1.4 Straight-through Transport Reactors (STR)

This type of reactor configuration is used to study kinetics when there is a
considerable decay in the catalyst activity with time. One example of this catalyst
deactivation is coke formation as in zeolite catalysts. A schematic of this
configuration is given in Fig 7.

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CA

CA

Catalyst Catalyst Feed

CA

CA
Fig 6. Stirred Contained Solids Reactor Fig 7. Straight-Through Reactor

3.2 Criteria for Choosing a Lab Reactor

The ratings of various reactors discussed above are summarized in Table 2.
Depending on the catalyst and the reaction system, one can determine the
appropriate configuration. In some cases more than one reactor type can be used.

Table 2 Summary of Reactor Ratings a

Sampling & Fluid-Solid Decaying Ease of
Reactor Type Isothermality
Analysis Contact Catalyst Construction
Integral G P-F F P G
Differential P-F F-G F P G
SCSR G G F-G P F-G
STR F-G P-F F-G G F-G
a
G, good; F, fair; P, poor.

3.3 Precautions in Kinetic Experiments

In the design and/or selection of lab scale reactor to study kinetics, it is important
to avoid transport resistances. Since the most frequently used in our labs in SABIC

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are tubular reactors (either differential or integral) it is important to highlight the

precautions that should be taken to perform kinetic studies using these reactors and
to satisfy the criteria for each precaution. Some of these precautions are also valid
for other reactor types. Further, it is important to check these criteria (clarified in
the following sections) in the given order, as they are physically dependent.

3.3.1 Radial Concentration and Temperature Gradients

To avoid radial concentration gradient (wall effects), the ratio of the effective
reactor tube diameter (accounting for the thermocouple if it is present inside the
tube) to the pellet diameter should satisfy the following criterion.
(dt dTC )
f 10
2d p

Once this is satisfied, radial temperature gradient is avoided if the following

criterion is satisfied:
0.4 RTmax 4 er Tmax
f1
d p rmax H r d t2
E (1 + 8Bi w ) B

dt

3.3.2 Axial Concentration, Temperature and Pressure Gradients

To avoid axial concentration gradient, the following relations should be satisfied
for each reacting component:
rmax B dp
Peai ff
u sCimax

Further, if the following L/dp ratio is satisfied, there will be no axial temperature
gradient.
L
f1
30d p

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The Ergun equation is used to calculate the pressure drop along the reactor and the
P
percentage drop should be minimum (preferably less than 3%) to avoid
P

variation of total pressure:

aG (1 ) 2 µL bG 2 (1 ) L
P= +
g d p2 3
gdp
3

where a and b are constants and depend on the shape of the catalyst pellets.

3.3.3 Interfacial Concentration and Temperature Gradients

The interfacial concentration gradient over the external film (between the catalyst
and the bulk gas) should be examined. The J-factor correlation can be used to
estimate the mass transport coefficient. The partial pressure gradient and
consequently the percentage pressure drop along the external gas film for each
component should be calculated. The later should be minimum. The equations are
given as follows:
For Reynolds number = dpG/µ > 350
2/3 0.41
k g i MP µ d pG
JD = = 0.99
G g Di µ

For Reynolds number = dpG/µ < 350

2/3 0.51
k g i MP µ d pG
JD = = 1.82
G g Di µ

and the pressure difference will be:

rmax
pi =
k g i am

For interfacial temperature gradient there is an analogous correlations. For

external heat transfer calculation and for Re > 350:

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2/3
hf C pg µ d pG
0.41

JH = = 0.99
C pg G g µ

And for Re < 350,

2/3
hf Cpg µ d pG
0.51

JH = = 1.82
Cpg G g µ

and the temperature difference will be:

rmax H r
T =
h f am

3.3.4 Intraparticle Concentration and Temperature Gradients

The Weisz-Proter correlation should be used to examine the existence of
intraparticle mass transfer limitations. To ensure that the measured kinetics is truly
intrinsic and free from internal mass transfer limitations, the following parameter
should be less than 1.0:
rmax RTmax p d p2
CWP =
4 Deff i pi s

To ensure that there is no significant temperature gradient inside the pellet, the
criterion given by Parter for the temperature difference within a catalyst pellet
(between the center and the surface) should be minimum:
De pi s H r
Tparticle =
RTmax s

Note: Temperature gradient is less likely to occur for unsupported metal and metal
oxide catalysts due to high thermal conductivity.

4. Kinetic Modeling
4.1 Pre-Experimental Phase
To perform kinetic modeling for a catalytic reaction, it is very important to start by
(1) the deep understanding of the underlying chemistry. This is an initial and

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important step. (2) Writing proper mechanism(s) based on detailed elementary

steps taking place in the catalytic system should be the following step in the
kinetic modeling task. The exact mechanism taking place on the catalyst surface is
not usually known. This is due to the complexity of the catalytic reactions and the
fact that it is very hard (or even impossible) to trace out the adsorbed intermediates
and/or activated complexes formed during the reaction. Also the nature and type
of active sites are not really known particularly for complex catalysts’ systems
composed of different species. This is why one usually has more than one possible
mechanism and consequently more than one rate law. It is then the task to
discriminate between these mechanisms as will be described in the coming
sections.
The following step is (3) the design of experiment. This includes (a) the choice of
reactor type suitable for the reaction system to be investigated. It also includes (b)
the determination of the range of variables to be studied e.g. partial pressures,
temperature, and finally (c) the number of experiments needed to be performed
including repetitions. It is advisable that the variation of variables should be
around the typical industrial conditions. Also, the number of experiments should
be large enough to ensure the statistical significance of the estimated kinetic
parameters on a later stage.
It is worth noting that simplified power law can fit the kinetic data in a certain
range, yet they don’t reflect the real physical situation of the chemical system.
Further, power law forms can fail in case of reaction rates having non-monotonic
behavior, which may result form different reasons one of which is product
inhibition. Examples reported in the literature for non-monotonic rate behavior are
in aromatics hydrogenation, steam reforming, ethylene partial oxidation to
ethylene oxide, etc.

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4.2 Calculation of Experimental Reaction Rates

The value of reaction rates can be computed based on the lab reactor configuration
used to perform kinetic study. The experimental rate of formation of a certain
product in a differential reactor is calculated by dividing the outlet flow rate of this
product by the catalyst weight in the reactor bed. The same approach for rate
calculation is applied in case of SCSR. Both types usually called “one point
reactor” as the rate is not changing with the reactor dimension.
In case of integral reactor, the rate cannot be directly evaluated since it is changing
with the reactor length. The material balance (ODE, ordinary differential equation)
should be written for the component(s) and hence the rate could be calculated by
integration either analytically or numerically depending on the form of the rate
law. The same approach is applied for the STR, but the material balance in this
case should account for the slip between the gas and the solid catalyst (due to
difference in flow velocity of gas and solid).

4.3 Fitting of Kinetic Parameters

According to the reactor used for kinetic study, the algorithm for estimating the
rate parameters may change. In all cases, one should start the fitting task by
formulating the objective function. The value of this function needs to be
minimized and physically it reflects the difference between the experimental and
the calculated rates. For n experiments, the objective function (also called sum of
residuals) can be written as:
n
(ri rˆi )(ri rˆi )
S= 2
i =1 i

where i is the measurement error (standard deviation) of the ith data point,
presumed to be known. If the measurements errors are not known, they may all be
set to the constant value i = 1. As explained in the previous section, if the source
of kinetic data was a differential reactor or SCSR, then the values of rate (i.e. ri)

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are known and the algorithm for finding the kinetic parameters is as shown in Fig
8. If the data source was from integral reactor or STR, then the algorithm should
include in integration step and instead of comparing the rates, the modified
objective function will compare the outlet composition of certain component(s) or
reaction conversion (xi) etc. The algorithm for this case is shown in Fig 9. The
objective function will be written as:
n
( xi xˆi )( xi xˆi )
S= 2
i =1 i

4.3.1 Non Linear Optimization Methods

Rate laws of catalytic reactions are usually non linear. In rare cases (like when
power law forms are used), it is possible to linearize these rate forms and linear
regression method (often called least square method) can be used. In most cases
linearization is not possible and efficient non-linear optimization method should
be used to estimate the kinetic parameters. The non-linear optimization methods
can be categorized into two main branches, namely the gradient and the non-
gradient methods.
As appearing from the name, the gradient methods involve the calculation of the
partial derivatives of the objective function with respect to the parameters. This is
usually done numerically at a certain set of values for these parameters and the
result is called the gradient matrix. The matrix of the second derivative with
respect to the parameters is called the Hessian matrix, H.
S (k p )
k1
.
Gradient = , p=1,m
.
S (k p )
km

and

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2 2
S (k p ) S (k p )
2
...
k 1 k1 km
H = ... ... ... , p=1,m
2 2
S (k p ) S (k p )
...
km k1 km2

The most famous gradient method used is the Marquardt-Levenberg. This elegant
method is based on a combination of the so-called inverse-Hessian method and the
steepest descent method. Mathematically, formulae of this method to estimate m
parameters is given as follows:
m
S
lp kp = , l=1,m
p =1 kl

and
2
S
ll = 2
(1 + )
kl
2
S
lp = for (l p)
kl k p

The non-gradient methods (often called search methods) involve less numerical
calculations and less preparation of the problem. On the other hand, they are in
general converging much slower to the optimum value (minimum) compared with
gradient methods. One famous method is Rosenbrock, which is based on iterative
procedure. The objective function is calculated every time after changing the value
of each parameter. The direction of changing the parameter value is accordingly
based on weather the objective function is decreasing (success) or increasing
(failure).
Both gradient and non-gradient methods are sensitive to initial estimates for the
parameters especially for high dimensional problems.

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4.3.2 Discrimination of Kinetic Models

As discussed in the previous sections, fitting of experimental data to various
available rate laws (obtained from the possible mechanisms) is generally
performed using a non-linear optimization routine to minimize the residuals
(objective function). There is a possibility after finishing this step that more than
one rate law can give close values for the objective function, and in a sense these
can all be regarded as “good fitting models”. There are other important criteria that
should be satisfied before accepting certain model and not only the value of
residuals’ sum. These criteria are thus used to discriminate between models in case
there is more than one model well fitting the data.
The first criterion is that the kinetic parameters estimated by data fitting should be
all positive. Further they should be thermodynamically consistent (e.g. Arrhenius
and Van’t Hoff relations should be satisfied) and their values should not violate
the basics of the reaction chemistry. That is why it is sometimes advisable to
perform a constraint minimization so that to ensure that this criterion is satisfied.
The second criterion is the statistical significance of the estimated kinetic
parameters. This is critical because usually the amount of uncertainty in the
parameters for the hyperbolic models (rate laws having Langmuir-Hinshelwood
forms) is typically high. Quantitative measure of the precision of parameter
estimates is thus important. F-test and t-test should typically lie within the 95%
confidence interval for the estimated parameters.

4.4 Future Trends in Kinetic Modeling

Recently, more interest has been given to the quantitative estimates of kinetic
parameters using Transition State Theory (TST) and Statistical Mechanics. The
TST, which is sometimes referred to as Activated Complex Theory focuses on
thermodynamics/statistical considerations and use this to predict how many
combinations of reactants are in transition state configuration under reaction

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conditions. By way of example, let’s consider three atomic species A, B and C

and reaction represented by:
AB + C A + BC
The TST considers the reaction to take place in the manner:
AB + C ABC‡ A + BC
According to TST, the intermediate is treated as unstable species in equilibrium
with the reactants. Using statistical theories leads to the formulation of the reaction
kinetic parameter as follows:
k BT
k = K c‡
h
Kc‡ can be calculated using statistical mechanics as a function of the so called the
partition function (Q‡) which is related to the modes of energy storage of the
molecules and the activated complexes (e.g. transitional, rotational and
vibrational). Present day quantum chemical packages (e.g. ab initio versions), lead
to values for the energy level of the transition state which are in good agreement
with the available experimental data.

5. Comprehensive Examples
5.1 The following data were obtained for a catalytic dehydrogenation reaction in a
SCSR reactor at 260ºC. Partial pressures are determined at the outlet of the
reactor.
(i) Show that the rate law having the following form is fitting the data.
pB pH 2
k ( pA )
rA = K , with K(260ºC) =2.150
(1 + K A p A + K B pB ) 2

(ii) Estimate the parameters, specify their standard deviation and show their
statistical significance.
(iii) Plot the data on a parity plot.

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Exp. pA pB PH2 rA
1 3.487 0.603 0.603 0.770
2 4.255 0.652 0.652 0.863
3 4.302 0.721 0.601 0.721
4 4.315 0.792 0.502 0.715
5 5.214 0.686 0.686 0.910
6 5.205 0.742 0.618 0.775
7 5.185 0.782 0.537 0.796
8 5.026 0.963 0.412 0.526
9 5.042 1.128 0.385 0.533
10 6.205 0.759 0.759 0.823
11 60184 0.952 0.621 0.695
12 6.315 1.328 0.537 0.415
13 6.420 1.528 0.621 0.408
14 6.587 2.050 0.324 0.241
15 7.208 0.956 0.956 0.736
16 7.186 1.385 0.648 0.435
17 7.333 1.489 0.544 0.440
18 7.287 1.662 0.502 0.330

Solution:
Description of the “Main Sheet” of the Excel file, Example 1:
(a) The given data is tabulated in columns A to F.
(b) Column G contains the calculated value for the rate law (Ybar) based on the
estimated parameters k, KA and KB in column K.
(c) The residuals are calculated in column H, and the sum is given in cell H21.
The regression sum of squares is given in cell I21.
(d) Keq, number of parameters and number of data points are given in column
L, together with the calculated mean of the experimental reaction rates.
(e) The square root of the variance of the error in the estimated parameters (T)
is calculated in Cell M24.
(f) The gradient matrix of the partial derivatives is placed in columns P,Q and
R. The differentiation of the predicted rate is calculated numerically in a
separate work sheet called “Differentiation”.

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(g) The covariance matrix, which is the inverse of the (XTX) is calculated in
columns U,V and W. The diagonal elements of this matrix (Cjj) are
variances of the estimated parameters.
Description of the “Differentiation” of the Excel file, Example 1:
(a) Partial differentiation of "Ybar"function with respect to the parameters, k,
KA and KB was calculated numerically in columns M, N and O. Second
derivatives are in columns P, Q and R Central formula was used for
calculation:
dy y1 y 1
=
dx 2h
d y y1 2 yo + y
2
= 1

dx 2 h2
(b) Columns from W to AE contain the basic calculation for the Inverse
Hessain method while columns AG to AK contain the Marquardt-
Levenberg method. Both are for demonstration and are not used to estimate
the parameters.
(c) Small values for “delta bj“ in both methods are indicative of how close the
parameter values to the minimum.
Description of the “Parity Plot & Results’ Summary” of the Excel file, Example 1:
(a) The parity plot for the experimental and calculated rates is presented in the
former worksheet. The dashed lines represent the 10% deviation lines.
Almost all points are lying between these lines.
(b) The Results’ Summary worksheet contains the estimates of the parameters
with the upper and lower confidence limits. The t test is also given the
same table showing acceptable significance for the estimates. The F-test
was also acceptable as given in the second table, and the last table gives the
degrees of freedom for regression and residuals respectively.

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Nomenclature

am External surface are of catalyst per unit mass (m2/kg cat)

dp Catalyst particle diameter (m)
dt Reactor tube diameter (m)
dTC Thermocouple diameter (m)
De Average diffusivity of the mixture (m2/s)

Deff i Effective diffusivity of component i (m2/s)

Di Mean diffusivity of component i (m2/s)

E Activation energy of the reaction (J/kmol)
G Mass velocity (kg/m2 s)
h Planks’ constant (-)
hf Interfacial heat transfer coefficient from gas to pellet (J/s K m2)
Hr Heat of reaction (J/kmol)
kB Boltzmann constant (-)
Kc‡ Equilibrium constant for activated complex formation
kgi Interfacial mass transfer coefficient of component i (kmol/s Pa m2)
kp Kinetic parameter
9kp Change in kinetic parameter value
L Catalyst bed length (m)
M Average molecular weight (kg/kgmol)
P Total pressure (bar)
Peai Peclet number of component i in the axial direction (uiL/Dei) (-)
pi s Partial pressure of component I on the catalyst surface (bar)
R Universal gas constant (J/kmol K)
P Pressure drop across the bed (bar)
pi Pressure difference for component i between bulk gas and external (bar)
catalyst surface
ri Experimental reaction rate
r̂i Calculated reactions rate
rmax Maximum expected rate in the reactor (kmol/kg cat s)
T Reaction temperature (K)
Tmax Maximum temperature inside the reactor (K)
Tparticle Maximum temperature across the catalyst pellet (K)

Greek letters

µ Gas viscosity (kg/m s)

Porosity of the catalyst bed (-)
Shape factor for catalyst pellet (-)
B
Bulk density of the catalyst (kg/m3)

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 T. M. Moustafa

s
Particle density of the catalyst (kg/m3)
er
Effective radial thermal conductivity of the bed (J/m s K)
g
Gas thermal conductivity (J/m s K)
s
Catalyst pellet thermal conductivity (J/m s K)
Parameter for Marquardt-Levenberg method (-)

References
X Fogler, S. (1992) Elements of Chemical Reaction Engineering, 2nd ed., Prentice
Hall, New Jersy.
X Froment, G. and Bischoff, K. (1990) Chemical Reactor Analysis and Design, 2nd
ed., Wiley, New York.
X Himmelblau, D.M., (1972) Applied Nonlinear Programming, Mc Graw Hill.
X Kitrrel, J.R. (1970) Mathematical modeling of chemical reactions in Advances
in Chemical Engineering, Vol 8.
X Levenspiel, O. (1999) Chemical Reaction Engineering, 3rd ed., Wiley, New
York.
X Missen, R.W., Mims, C.A. and Saville, B.A. (1999) Chemical Reaction
Engineering and Kinetics, 1st ed., Wiley, New York.
X Moustafa, T.M. (1997) Ph.D. Thesis, Faculty of Engineering, Cairo University.
X Perry, R.H. and Green, D. (1984) Perry’s Chemical Engineers Handbook, 6th
ed., Mc Graw Hill.
X Elnashaie, S. and Elshishini, S. (1993) Modelling, Simulation and Optimization
of Industrial Fixed Bed Catalytic Reactors, 1st ed., Gordon and Breach.
X Press, W., Teukolsky, S., Vetterling, W. and Flannery, B. (1992) Numerical
Recipes, 2nd ed., Cambridge University Press.

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