Chemical Reactor Modeling - Lecture 1

Vinod M. Janardhanan
Department of Chemical Engineering
Indian Institute of Technology Hyderabad, Yeddumailaram 502 205
Introduction
Modeling of system is essentially the process of solving the mathematical equations that describes the system. The
information that we get by modeling a system depends on the amount of information contained in the system of math-
ematical equations, or the number of variables that are being solved. The equation system can be ODE, PDEs, DAEs,
or PDAEs. For a differential algebraic equation system, the difculty of the problem depends on the index of the
problem being solved and the stiffness of the equation systems.
The governing equations that describe a physical systems is derived by performing a control volume analysis.
Mass and energy balances can be performed over the control volume. The difculty oh the problem also depends on
whether the problem is solved in 3D, 2D, 1D or 0D.
Basic denitions
Molecules and gas mixture
A molecule is an ensemble of atoms. They are conveniently counted in terms of amount of substance or mole num-
bers. One mole of a compound corresponds to 6.02310
23
particles (atoms, molecules etc.), which is the Avogadro
number (Na = 6.02310
23
mol
1
). A molecule can be of monoatomic, linear or non-linear geometrical congura-
tions. Several properties of the substance such as reactivity, polarity, magnetism etc are determined by the geometry
of the molecules that make up the substance. A monoatomic molecule is composed of just one atom such as Ar, He
etc. All diatomic molecules are linear in which the bond angles are set at 180
o
C (eg.H
2
, CO, N
2
). In non-linear
molecules the bond angles are not set at 180
o
C (eg. H
2
O). Molecules can be polar or non-polar. Molecular polarity
depends on the electronegativity between the atoms in a compound and the molecular geometry. Solubility, melting
point and boiling point depends on the polarity. A bond is formed between two atoms, when the electrons are shared
by the atoms. However, one of the atoms can exert more attraction on the electron cloud than the other, leading to the
formation of an electric dipole (separation of +ve and -ve charges). Therefore, the bond formed between the atoms can
be completely polar or completely non-polar. Completely non-polar interaction occurs when the atoms are of equal
electronegativity. The atom with more electronegativity exerts higher pull on the electron cloud compared to the other.
In a polar molecule there is a net dipole as a result of opposing charges, eg. H
2
O. Due to the polar nature of water
molecule, polar molecules generally dissolve in water. Symmetrical arrangement of polar bonds in a molecule can
lead to non-polar molecules. Water is a polar molecule due to the assymetric arrangement of polar bonds. CH
4
is a
non-polar molecule, although C-H bond has polarity.
When it comes to reactor modeling, we need to evaluate the composition of chemical species that comes out of
the reactor or at various positions within the reactor. However, the count of molecules is not a convenient unit for
representing the concentration. The composition of a gas mixture is usually represented in terms of mass fraction,
mole fraction or concentration units.
Mole number
The mole number is the number of moles of a chemical species present in m units is dened as
n =
m
W
. (1)
Here W is the molecular weight of the species. Molar mass or molecular weight is the mass of one molecule. As an
example if 1 kg of a gas mixture is made up of 20%A, 30%B and 50%C, then the number of moles of each of the
species A, B, and C is dened as
n
A
=
20
W
A
n
B
=
30
W
B
n
C
=
50
W
C
. (2)
In the above denition the unit of W is in kg/mol.
1
Mole fraction
Mole fraction is x
i
is the ratio of mole number n
i
of the species to the total mole number n
i
. i.e
x
i
=
n
i
n
k
, k = 1, . . . , i, . . . K
g
(3)

x
k
= 1, k = 1. . . , i, . . . K
g
(4)
Mole fractions are very important in reactor modeling. Any systems that involves the ow of chemical species require
the inlet concentration, which normally is expressed in terms of mole fractions. If the volumetric ow rates are known,
the mole fraction of each specie is the ratio of volumetric ow of each species divided by the total volumetric ow rate.
Mass fraction
Mass fraction y
i
is the ratio of mass of species m
i
to the total mass i.e m
k
. i.e
y
i
=
m
i
m
k
, k = 1, . . . , i, . . . K
g
(5)

y
k
= 1, k = 1, . . . , i, . . . K
g
(6)
The mass ow rates are not generally known at the reactor inlet, since the mass ow controllers are set for the volu-
metric ow control. However, the mass ow rates can be calculated from known volumetric ow rates. Once the mass
ow rates are known, the mass fractions can be calculated by dividing the individual ow rates by the total ow rate.
Average molecular weight
The average molecular weight (kg/mol) of a gas mixture can be calculated from mole fraction according to
W =
K
g

k=1
x
k
W
k
(7)
The average molecular weight can also be calculated from mass fractions according to
1
W
=
K
g

k=1
y
k
/W
k
(8)
Conversion between mole and mass fractions
Mole fractions can be converted to mass fractions according to
y
i
=
x
i
W
i

K
g
k=1
x
k
W
k
=
x
i
W
i
W
(9)
Mass fractions can be converted to mole fractions according to
x
i
=
y
i
/W
i

K
g
k=1
y
k
/W
k
(10)
Partial pressure
Partial pressure is the pressure contributed by each species to the total pressure. Partial pressure of a chemical compo-
nent i is
p
i
= x
i
P. (11)
2
Here x
i
is the mole fraction and P is the total pressure dened as
P =
K
g

k=1
p
k
(12)
The concept of partial pressure originates from Daltons law for ideal gases. Ideal gas mixture is a mixture of pure
components. Each individual gas in a gas mixture behaves as if it alone occupies the volume of the mixture at mixture
temperature. In other words each individual component is under the pressure which it would exert if it occupies the
volume of the mixture. The pressure of each component is expressed as p
1
, p
2
, . . . p
n
. Which are nothing but the partial
pressures.
Selectivity
Selectivity towards a particular product is very important parameter for the choice of catalysts. For hydrocarbon
reforming, the major products are CO and H
2
. For this particular system the selectivities are dened as
S
H
2
=
X
H
2
X
H
2
+X
H
2
O
+yC
x
H
y
(13)
S
CO
=
X
CO
X
CO
+X
CO
2
+xC
x
H
y
(14)
S
H
2
O
=
X
H
2
O
X
H
2
+X
H
2
O
+yC
x
H
y
(15)
S
CO
2
=
X
CO
2
X
CO
+X
CO
2
+xC
x
H
y
(16)
Density and concentration
Density is an intensive property. i.e it does not depend on the size of the system. The mass density (kg/m
3
) of the
system is dened as
=
m
V
, (17)
where m is the total mass of the system and, V is the volume of the system. The concentration (mols/m
3
) also known
as molar density is dened as
C = [X] =
n
V
, (18)
The molar density (concentration) can be converted to mass density (density) by multiplying with the average molec-
ular weight of the gas-mixture
= [X]W (19)
Mean free path
Mean free path is the average distance traveled by a gas molecule before suffering a collision. This can be calculated
according to
l =
T
d
2
p
3.06710
29
(20)
When the mean free path is very small compared to the control volume size the continuum assumption is valid.
However, its important to calculate the Knudsen number before proceeding with any continuum models to assert that
the continuum assumption is valid. When Kn < 0.1 the continuum approximation is usually valid.
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Ideal gas equation
For gases and gas mixtures the ideal gas equation provides a relationship between temperature T, pressure p, volume
V. For many practical applications its satisfactory to use the ideal gas equation of state.
pV = nRT. (21)
Here R is the universal gas constant (8.314 J/mol-K), and n is the number of moles. The ideal gas equation may also
be written as
pW = RT (22)
Problems
1. A reactor operating at 800
o
C needs a S/C ratio of 2.5. If the ow rate of CH
4
at STP is 30 ml/min. Calculate
the ow rate of water required at STP.
2. Calculate the number of moles present in 0.5 g CH
4
3. A gas cylinder A of 10 liter contains 20% CH
4
and 80%N
2
. Another gas cylinder B of 5 liter contains 10%
CH
4
, 5%CO and the rest Ar. The contents of A and B are transferred to a 20 liter cylinder. Calculate the mole
fractions of each chemical species in cylinder C.
4. A gaseous mixture contains 9.5% CH
4
and the rest air by volume at 300 K and 1 bar. Calculate the following
(a) Average molecular weight of the mixture
(b) Density of the mixture
(c) Bulk concentration
(d) Concentration of individual species
(e) Mass fraction of CH
3
, O
2
, and N
2
5. In the above the problem the gaseous mixture is heated to 500 K isochorically. Calculate the partial pressure of
each component.
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