Global Journal of Pure and Applied Mathematics.

ISSN 0973-1768 Volume 8, Number 2 (2012), pp. 101-111

© Research India Publications
http://www.ripublication.com/gjpam.htm

Approximate Analytical Solution of Non-Linear

Kinetic Equation in a Porous Pellet

V. Ananthaswamy and L. Rajendran*

Department of Mathematics, The Madura College,

Madurai-625011, Tamil Nadu, India.
*Corresponding Author E-mail: [email protected]

Abstract

A mathematical model for immobilized enzyme system in porous spherical particles

was developed. This model contains a non-linear term related to reversible Micahlies-
Menten kinetics. Analytical expression pertaining to the substrate concentration was
reported for all possible values of Thiele module φ , parameters cs and k . In this work,
we report the theoretically evaluated steady-state concentration for immobilized
enzyme systems in porous spherical particles for zero order, first order and second
order reaction meacnisms. Herein we employ “Homotopy perturbation method”
(HPM) to solve non-linear reaction /diffusion equation.

Keywords: Mathematical modelling, Non-linear equations, Homotopy perturbation

method, Reaction/diffusion equation, Porous media.

Introduction
Non linear problems frequently arise in engineering, but many texts are oriented
towards linear problems due to the difficulty of nonlinearity. In general, satisfactory
results can be reached by using the first few terms of the approximate, series, solution.
The Homotopy mehtod has been used to solve several mathematical problems in
science and engineering, but there has been no reported application in chemical
engineering to date.
The model for diffusion and reaction in fixed-bed reactor generates a typical
differentiation equation in chemical engineering. Thiele [1] obtained the analytical
solution for the first order reaction in 1939, and then Wheeler [2] and Aris [3], etc.
discussed this problem in details in their books. However, most of their conclusions
were based on the analytical solution for the irreversible reaction with the first
reaction order. Several researchers, such as Satterfild [4], have considered solutions
102 V. Ananthaswamy and L. Rajendran

for the nonlinear model with nth order reaction, but approximate solutions were not
derived. Finlayson [5] has applied many numerical methods to solve nonlinear models
of fluid flow, heat transfer and chemical reactor by using pre-programmed computer
packages. The difficulty in the solution of such problems occurs when there is a large
change in reaction rate, where the method does not always converge and convergence
may depend critically on the initial guess. A disadvantage of numeircal techniques is
that they cannot give analytical expressions as solution.
A steady state heterogeneous model of fixed-bed reactor is described by partial
differential equation (PDE) both for fluid and for catalyst pellet. The real difficulty in
a solution is the reason why this model, despite its quite good accuracy, is not
willingly used for modelling. The ordinary differential equation (ODE) based on
average concentration in the pellet is usually called “an approximate model “. Various
approximate models have been reported for diffusion and adsorption processes. They
differ from one another with respect to accuracy and validity range. One can find
more information e.g., in the papers by Goto and Hirose [6] (1993), and Zhang and
Ritter (1997) [7]. To make use of approximate models idea for diffusion and chemical
reaction processes other models should be developed. In a diffusion and reaction
process fields, only a small number of equations that approximate a mass balance in
the porous particle has been found (Kim, 1989 [8]; Goto & Hirose, 1993; Szukiewiez,
2000 [9]). Models reported so far in the literature concern only first-order reactions.
Recently, Miroslaw Szukiewicz and Roman Petrus [10] evaluated the
effectiveness factor corresponding to the non-steady-state concentration of component
observed at a porous pellet However, till date, to the best of our knowledge, there are
no general analytical expressions that describe the concentration of component for all
values of the Thiele modulus φ ⊂ [0,10] and the normalized parameters cs and k
have been reported. As a result, herein, we have deduced analytical expressions
corresponding to the concentrations of component immobilized in a porous pellet. The
purpose of this communication is to derive simple accurate polynomial expressions of
concentration generated at a porous spherical particle using Homotopy perturbation
method.

Mathematical formulation of the problem

The predict of diffusion and reaction rates in porous catalysts in an important problem
in chemical engineering, indeed when the reaction rate depends on concentration in a
nonlinear case. In this heterogeneous system, the system is constructed as simple
diffusion using an effective diffusion coefficient. Steady state diffusion and reaction
in a porous spherical particle can be described by [10]
⎛ ∂ 2 c 2 ∂c ⎞ 2
⎜⎜ 2 + ⎟ − φ R A (c ) = 0
x ∂x ⎟⎠
(1)
⎝ ∂x

where c is the concentration of component, φ is the Thiele module and R A (c) is the
reaction rate. The boundary conditions are as follows.
Approximate Analytical Solution of Non-Linear Kinetic Equation 103

c(x = 0) = extremum = k (2)

c( x = 1) = cs (3)

Analytical approximate solution with three cases

Most of engineering problems, especially some diffusion and reaction equations are
nonlinear, and in most cases it is difficult to solve them, especially analytically.
Perturbation method is one the well-known methods to solve nonlinear problems, it is
based on the existence of small/large parameters, the so-called perturbation quantity
[27, 30].

Linear case
Case (i): For zero order reaction, the reaction term RA (c ) = 1 . Analytical solution of
equation (1) with the boundary conditions equations (2) and (3) using Modified
Homotopy Perturbation method is
ϕ 2 x2 ϕ2x
c ( x) = k + − ( cs − k )( x log x − x ) −
2 2 (4)

Case (ii): The reaction term R A (c ) = c for the first order reactions. In this case,
solution of the equation (1) using Modified Homotopy perturbation method is
⎛c −k k ⎞ 2
c ( x ) = ( cs − k ) x + k − ϕ 2 x ⎜ s + ⎟ +ϕ
⎝ 6 2⎠
⎛ (cs − k ) x kx ⎞
3 2

⎜ + ⎟ + ( k − cs ) x log x
⎝ 6 2 ⎠
(5)

Non linear case

(iii): When the reaction term R A (c ) = c 2 (second order reactions) the analytical
solution of the equation (1) with the boundary conditions equations (2) and (3) using
Homotopy perturbation method ( Appendix-A) is
2 ⎛ cs kc k 2 ⎞
2
( cs − k ) x + k − ϕ ⎜ + s + ⎟ x + ( k − cs ) x log x +
⎝ 12 6 4 ⎠
c ( x) = ⎛ ( cs − k )2 x 4 k 2 x 2 kx 3 ( cs − k ) ⎞
⎜ + + ⎟
ϕ2 ⎜ 12 2 3 ⎟ (6)
⎜ ⎟
⎝ ⎠
104 V. Ananthaswamy and L. Rajendran

Case-(i).Figure-1
(a)

(b)

Figure 1: Influence of Thiele modulus φ on the concentration c obtained from the

equation

(4). The curve is plotted for some fixed values of k and c s (a) k = .1, cs = 10 ,
(b) k = .1, cs = 1
Approximate Analytical Solution of Non-Linear Kinetic Equation 105

Case-(ii). Figure-2
(a)

(b)

Figure 2: Influence of Thiele modulus φ on the concentration c obtained from the

equation

(5). The curve is plotted for some fixed values of k and c s . (a) k = .01, cs = 1
(b) k = .1, cs = 10
106 V. Ananthaswamy and L. Rajendran

Case-(iii).Figure-3
(a)

(b)

Figure 3: Influence of Thiele modulus φ on the concentration c obtained from the

equation

(6). The curve is plotted for some fixed values of k and c s . ( a) k = .01, cs = 1
(b) k = .1, cs = .5
Approximate Analytical Solution of Non-Linear Kinetic Equation 107

Figure: 4

From fig.4, it is clear that when k increases, the concentration c increases.

Discussion
The equations (4) to (6) represents the new analytical expressions of concentrations c
for zero, first and second order reactions. The kinetic response of a porous pellet
depends on the concentration of component A. The concentration of component
depends on the following three factors φ , c s , and k . Thiele modulus φ represents
the ratio of the characteristic time of the enzymatic reaction to that of component
diffusion. The variation in the Thiele modulus φ can be achieved by varying either
the thickness of the enzyme layer or the amount of enzyme immobilized in the porous
pellet. The Thiele modulus φ is indicative of the competition between the diffusion
and reaction in the enzyme layer. When φ is small, the kinetics dominate and the
uptake of component is kinetically controlled. Under these conditions, the
concentration of component profile across the porous pellet is essentially uniform.
The overall kinetics is governed by the total amount of active enzyme. Diffusion
limitations are the principal determining factor when Thiele modulus is large.
Fig. 1 to 3 represents the normalized steady state concentration c versus
dimensionless distance x for different values of the dimensionless parameter φ .
From the figure it is inferred that the value of the concentration c increases when the
value of φ decreases. Fig.4 represents the concentration versus the dimensionless
distance x for various values of k . From this figure it is observed that the
concentration increases when the constant k increases.
108 V. Ananthaswamy and L. Rajendran

Conclusions
The time independent linear and non-linear reaction/diffusion equation has been
formulated and solved analytically. An approximate analytical expression for the
concentrations in porous spherical particle under steady state conditions for various
reaction order are obtained by using the Homotopy perturbation method. The primary
result of this work is simple approximate calculation of concentration for all possible
values of sparameters. This method can be easily extended to find the solution of all
other non-linear reaction diffusion equations in porous cylindrical particle for various
complex boundary conditions.

References
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Approximate Analytical Solution of Non-Linear Kinetic Equation 109

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110 V. Ananthaswamy and L. Rajendran

Appendix A
We construct the Homotopy as follows
⎡ 2 ⎤ ⎡ 2 ⎤
(1 − p)⎢ d c2 ⎥ + p⎢ d c2 + 2 dc − φ 2 c 2 ⎥ = 0 (A1)
⎣ dx ⎦ ⎣ dx x dc ⎦

The approximate analytical solution of (4) is

c = c 0 + pc 1 + p 2 c 2 + .......... ....... (A2)

The initial approximations is as follows

c 0 (0 ) = k and c 0 , x (1) = c s (A3)
c i (0 ) = 0 and c i , x (1) = 0 , i = 1, 2

Substituting eqn. (6) into equation (5) we have

( )
⎡ d 2 c0 + pc1 + p 2 c2 + ...... ⎤
(1 − p ) ⎢ ⎥
⎢⎣ dx 2 ⎥⎦

⎡ d 2 ( c0 + pc1 + .....) 2 d ( c0 + pc1 + ....) ⎤

⎢ + ⎥
+p⎢ dx 2 x dx ⎥ = 0 (9)
⎣
2
(
⎢ −ϕ c0 + pc1 + p c2 + ......
2
)⎥
⎦ (A5)

Comparing the coefficients of like powers of p in equation (9) we get

d 2 c0
p0 : =0 (A5)
dx 2
d 2 c1 2 dc 0
+ −φ 2 c 0 =0
1 2
p : (A6)
2
dx x dx

Solving the equations (10) and (11), we can find the following results:
c0 ( x ) = (cs − k )x + k (A7)
⎛c kc k ⎞
2 2
c1 ( x ) = −ϕ 2 ⎜ s + s + ⎟ x + ( k − cs ) x log x
⎝ 12 6 4 ⎠

2 ( cs − k ) x k 2 x 2 kx ( cs − k ) ⎞
⎛ 2 4 3

+ϕ ⎜ + + ⎟
⎜ 12 2 3 ⎟
⎝ ⎠ (A8)

According to HPM, we can conclude that

c = lim c(x ) = c0 + c1 + ....
p→1
Approximate Analytical Solution of Non-Linear Kinetic Equation 111

2 ⎛ cs kcs k 2 ⎞
2
= (s )
c − k x + k − ϕ ⎜ + + ⎟ x + ( k − cs ) x log x + ϕ 2
⎝ 12 6 4 ⎠

⎛ ( cs − k )2 x 4 k 2 x 2 kx3 ( cs − k ) ⎞
⎜ + + ⎟ (A9)
⎜ 12 2 3 ⎟
⎝ ⎠

Notation
c Concentration of component A
cs Surface concentration of component A
RA Reaction rate
x Position in pellet
φ Thiele modulus
k Extremum value