40 RESEARCH ANALYSIS AND EVALUATION

International Indexed & Refferred Research Journal, October 2012, ISSN 0975-3486, RNI- RAJBAL 2009/30097: VoL IV *ISSUE- 37
Research PaperMathematics
October,2012
1. Introduction
Recently, visco-elastic and channel electrodes have
been used in hydrodynamic voltammetry both for
electroanalytical and mechanistic investigations of
electrode process. Electrochemical techniques in which
visco-elastic electrodes have been used include linear
and voltammetry. In this paper the theory of linear
sweep voltammetry for the process in which reversible
change transfer is followed by reversible chemical
reaction is developed. The governing initial boundary
value problem in the form of coupled and time
dependent convective-diffusion equations with
interactive boundary conditions is transformed to a set
of integral equations which are solved numerically using
Wagners method.
2. Formulation of the problem
The reaction process in which a reversible electrode
charge transfer is followed by a reversible chemical
reaction is generalized as
O + ne- R1 (2.1)
R Z
1
k
f
k
b
(2.2)
wherr kf and kb are forward and backward chemical
reaction rate constants and n is the number of electrons
involved in charge transfer rections.
The mathematical model representing the above
process in which the reactants are flowing through a
tabular electrode, laminarly, is

,
_

+
r
C
r r
C
D
z
C
a
r
v
t
C
o o
o
o
a
o
1
1
2
2
2
2
(2.3)
z b R f
R R
R
R
a
R
C k C k
r
C
r r
C
D
Z
C
a
r
v
t
C
+

,
_

+
1
1
2
2
2
2
(2.4)
z b R f
z z
z
z
a
z
C k C k
r
C
r r
C
D
Z
C
a
r
v
t
C
+

,
_

+
1
1
2
2
2
2
(2.5)
subject to
t = 0, 0 < r < a, 0 < z < l; Co = Co, CR = CR (

0),
Cz = ) 0 (
*

R
KC
Mass Transport of Visco-Elastic Electrodes
* Hardeep Singh Teja
* Assot. Prof, Dept. of Mathematics, Govt. Mohindra College, Patiala (Punjab)
b
f
k
k
K
t > 0, 0 < r < a, z = 0; Co = Co, CR = CR (0), Cz =
t > 0, r = 0, 0 < z < 1; Co = Co, CR = CR (0), Cz =
t > 0, r = a, 0 < z < 1;
t > 0, r = a, 0 < z < 1; (2.6)
where
E = Ei t, and
Et = initial electrode potential.
The significance of various variables and parameters
is given in the nomenclature.
3. Solution :
The mathematical expressions given is eqs. (2.1) to
(2.6) are non-dimensionsalized and transformed as
0 ,
) (
0

r
C
D
nFA
i
r
C
D
r
C
D
Z
Z
R
R
o

) ( exp
0
E E
RT
nF
C
C
R
o
K
K
k k k k
f b f
) 1 ( +
+
Z R
C C +
) ( exp kt
K
C
C
Z
R

,
_

3 / 1
2

al
D v
a
Do = DR = DZ = D
P = (3.1)
k P /
D
r a k ) (

kt
2

The transformed model is
2
2
'

+
O
O
O
C
C
t
C
2
2
'
+
t
2
2
'
+
t
(3.2)
(3.3)
(3.4)
41 RESEARCH ANALYSIS AND EVALUATION
International Indexed & Refferred Research Journal, October 2012, ISSN 0975-3486, RNI- RAJBAL 2009/30097: VoL IV *ISSUE- 37
subject to
The above transformations are based on following
assumptions :
(i) The time taken for the rectants to diffuse across the
tubular electrode ( a2/D) is much greater than the
time taken for axial convection along the length of
electrode
0 ; 0 ,
2 / 1 2 / 1
< <

O
C D k a p
0 ; , 0 '
2 / 1 2 / 1


O
C D k a t
) ' (
) ' (
, 0 '
2 / 1 2 / 1
t f
D k nFA
t i C
t
O

>

) Ke (
K 1
1
C C
C
C C
, 0 ' t
' kt
*
O O
R
*
O O
+
+
+

+
>

' t
e

) E E (
RT
nF
exp
O
t
2
RTP
nF

( l/
a
) i.e.
a
a
2
/lD >> 1.
(3.5)
(3.6)
(3.7)
) ' (t f
) ' (t f exp ( ' t
2
);
(3.8)
(3.9)
=
(Say)
(3.10)
where
(ii) The diffusion layer is much smaller than the boundary
layer near the tubular electrode surface and the flow
profile is assumed linear instead of parabolic in the
diffusion layer. This approximation is known as the
Leveque approximation.
(iii)The smallness of the dimensions of tubular
electrode leads to the assumption of uniform
accessibility of the electrode surface. Thus the
concentration gradients of O, R, Z components along
the axial direction are approximated by their average
values over the whole length of the electrode. This
approximation is referred to as Singh and Dutt
approximation.
The use of the Laplace transformation of eqs. (3.2) to
(3.4) with respect of t reduces them to
With and s as the parameter of Laplace
transformation, these equations are of the form of Airys
equation. Since the region of interest under
investigation is near the electrode surface and not the
whole flow regime, the condition at the axis of the
tabular electrode can be safely taken as at infinity. Thus
the bounded solutions of eqs. are
O 2
O
2
C
d
C d

2
2
d
d
(3.11)
(3.12)

2
2
d
d
(3.13)
where L-1 is the inverse Laplace transform operator,
is the value of the variable at the surface of the electrode
and

) ( '
) (
) (
1
O
O
Ai
Ai
s F L C

) ( '
) (
) (
1
O
Ai
Ai
s F L

) ( '
) (
) (
2 1
O
Ai
Ai
s F L
(3.14)
(3.15)
(3.16)
)] ' ( [ ' ) ' ( ) (
'
0
t f L dt t f e s F
st

(3.17)
Where Ai( ) and Ai() are Airys function of the first
kind and its derivative, respectively.
The calculus of residuals technique is applied to get
the inverse Laplace transform of Ai() / Ai() as
Ai( ) / Ai'(
O
)
(3.18)
Where is the magnitude of the nth zero of Ai(). The
expressions for CO, and are obtained as
) ' ( exp
) (
) (
) ( '
) (
1
1
t
Ai
Ai
Ai
Ai
L
n
n n
n
n O

(3.19) d g f C C
O
O O
) , ( ) (
*

d g f
O
) , ( ) (

(3.20)

d ) , ( g e ) ( f
2
' t
0
(3.21)
The expression for concentrations CO, CR, CZ are
obtained using the transformation.

d ) , ( g ) ( f C C
' t
0
*
O O
(3.22)
42 RESEARCH ANALYSIS AND EVALUATION
International Indexed & Refferred Research Journal, October 2012, ISSN 0975-3486, RNI- RAJBAL 2009/30097: VoL IV *ISSUE- 37

+
+

d e K ( ) , ( g ) ( f
K 1
K
C
) ( 1
' t
o
R
2

d e 1 ( ) , ( g ) ( f
K 1
K
C
) (
' t
o
Z
2
dz ) z ( x ) z , y ( K
K 1
K
dz ) z ( x ) z , y ( K
K 1
1
2
y
O
1
y
O

+
+
+
dz ) z ( x ) z , y ( K e e
1
y
O
) u y ( ) u y (

Since we are interested to depict the variation of current

given by f(t) with change of potential function E(t),
the expression of CO and CR from eqs. are substituted
in the Nernst equation to get an integral equation :
(3.23)
(3.24)
(3.25)
(3.26)
1. R. G. Compton and G. R. Sealy, J. Electroanal Chem (1983).
2. C. Wogner. J. Marth. Phys (1954).
3. C. B. Ranger. Anol. Chem (1981).
4. B. A. Cales and R. G. Compton. J. Electroanal Chem. (1981).
5. J. Ruzicka and E. Hanson (1981).
6. T. Singh. J. Dutt J. Electroanal Chem (1991).
The integral equation is solved numerically using
Wagners method in which the range of integration is
subdivided in small subintervals and in each subinterval
the unknown function is replaced by a linear polynomial
satisfying at the nodal points.
Conclusion :
The study of effect of rotation and magnetic on
thermal instability in Walters Belastico-viscous fluid
in porous medium has been discussed. It is found that
rotation has only stabilizing effect. The medium
permeability and magnetic field have both stabilizing
and destabilizing effects depending upon on certain
conditions. The impact of rotation, medium permeability
and magnetic field has been obtained numerically.
R E F E R E N C E