A SIMPLE METHOD OF SOLVING ILKOVIC'S DIFFERENTIAL

EQUATION FOR THE TRANSFER OF DEPOLARIZER TO THE

DROPPING MERCURY ELECTRODE

R. S. SUBRAHMXNYA
Tlzc Departn~entof I n o ~ g a n i ca?zd Physical Cheti~istry,Indian Institute of Science, Bangalore-12, Soutlt India
Received M a y 18, 1961

ABSTRACT
The nlethod developed by 1ll:ovic for solving the differential equation
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which governs the diffusion of the depolarizer t o the surface of the dropping mercury electrode
is very difficult. In the present work a simple method is presented. T h e above equation is
transformed into d C / d T = d2C/as2by introducing the two new variables s = xt213/2..\/((3/7)D)
and T = (1/4)t7I3.T h e boundary conditions for the transformed differential equation are formu-
lated and the equation is solved by the Laplace transform method.

NOTATIONS
C ( x , t ) : concentration of the depolarizer a t a distance ' x ' from the electrode surface
a t time ' t ' .
C ( 0 , t ) : concentration of the depolarizer a t the electrode surface a t time 't' (OC)
* C : bulk concentration of the depolarizer
D : diffusion coefficient of the depolarizer in cm2 sec-I
A : area of the electrode
p : variable in Laplace transformation
L ( C ) : Laplace transforin of C
L-lzt: inverse transfornl of 'LL'
s = xtU3/2.\/((3/7)D) : new variable
T = ( 1 / 4 ) t 7 I 3 : new variable
INTRODUCTION
Several authors have treated the problem of diffusion of depolarizer to the dropping
inercury electrode. A critical review of the various nlethods has been given by Markowitz
and Elving ( I ) . The methods employed fall into two classes. T o the first class belong the
differential methods wherein a differential equation is formulated and the equation
solved using the appropriate boundary conditions. T o the second class belong the integral
nlethods where the problem is formulated as an integral equation. Ilkovic ( 2 ) treated the
problem by assunling t h a t the depolarizer reaches the surface of the dropping mercury
electrode by linear diffusion. Since the thickness of the diffusion layer is much smaller
than the radius of the mercury drop the curvature of the diffusion layer does not signifi-
cantly differ from t h a t of the inercury drop. In the formulation of the differential
equation he also added an additional term to include the effect of the growing drop on
the thickness of the diffusion layer. The following differential equation was formulated
by him:

Canadian Journal of Chemistry. Volume 40 (1962)

296
 SUBRAHMAXYA: SOLUTION O F ILKOVIC EQUATION 397

This differential equation was solved by him by en~ployi~lgthe Fourier integral method after
introducing a new variable zi = xt2l3.MacGillavary and Rideal ( 3 ) treated the problem
as three dimensional spherical diffusion, and formulated the following differential equation :
d2c 7 dC --.-
dC D 7+r.--
--
dt - ( d r - r dr) i':f7
where 'r' is the distance from the center of the mercury drop. Due to the simplifications
introduced in the subsequent mathematical operations they obtained the same final
equation as Illtovic for the current. The following equation for the average diffusion
current was obtained :
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a, = fjo7nDll"cm2/3t'/G.
Ilkovic had noticed that the differential thicltness of the diffusion layer in the case of
linear diffusion to a stationary electrode was d(rrDt) and in the case of linear diffusion
to a growing drop d ( ( 3 / 7 ) r r D t ) .Lingane and Loveridge (4) argued that even in the
case of spherical diffusion an equation for the diffusion current can be obtained provided
a correction is applied to the gradient obtained in the problem of diffusion to a stationary
spherical electrode. The gradient is written

The following expression was obtained for the diffusion current:

The value of 'K' was 39.

Strehlow and Stackelberg (5) re-examined the derivation of MacGillavary and Rideal
and modified the intermediate inathematical steps and obtained the same equation as
above but in which 'K' has the value 17. Karnbara and Tachi ( 6 ) applied Ilkovic's
technique of the formulation of the differential equation to the case of spherical diffusion
to a growing drop. They obtained the same differential equation a s MacGillavary and
Rideal. After introducing a new dependent variable p (= rC) and transferring the co-
ordinates from the center to the surface of the drop they obtained the following differential
equ at'Ion:

The above differential equation is of the same form as that obtained by Ilkovic in the
case of linear diffusion (eq. [ I ] ) . The procedure employed for solving this differential
equation is not clear. However, they get the same equation for the diffusion current as
Lingane and Loveridge.
The above is only a short account of the differential methods used in solving the
problem of diffusioil of the depolarizer to the dropping nlercury electrode. I t is clear that
in these problems one ineets differential equations of the form of equation [ I ] . The
published procedures for the solution of such equations are either very difficult or not
clearly given. Hence work was undertaken in this laboratory to exainine the possibilities
of solving such equations by suitable mathematical techniques, i.e. conversion of these
partial differential equations into standard forms by the technique of change of variables
and then solution by the Laplace transform method. In the present paper the method
of solving the Ilkovic differential equation is given.
 298 CANADIAN JOURNAL O F CHEMISTRY. VOL. 40, 1902

THEORETICAL
( i ) Transformation of Ilkovic's Dzfferential Equation
In the differential equation

'x' and 't' are the independent variables. Let us now express the above differential equa-
tion in terms of the new independent variables 's' and ' T ' . Employing the chain rule the
following transformations can be written:
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. 2- .x- .a-c = 2- .x- . t?/3

ac - -.-.-
a s ac
-- 3 t ax 3 t 2 4 ( ( 3 / 7 ) ~ ) ' K 3- t a s '
a2c -.-=-
-- a ac a
(c) ax' - ax ax ax
Since

On substituting for aC/at, Da2C/ax2,and 2 / 3 ( x / t )(aC/ax) in terms of the new variables

's' and ' T ' , in equation [I] one gets
ac - --a2c
-
aT - as'
( i i ) Boundary Conditions for the Equation aC/aT = a2C/as2
The boundary conditions for equation [I] can be written as follows:
C(xlO) = *C; C(0,t) = OC; C(x,t) = *C as 'x' + a.
Ilkovic transformed equation [I.] into a c / a t = D(a2C/au2)t4/3
by introducing the new
variable u = xt2I3and has given the following boundary conditions:
C(u,O) = *C and C(0,t) = OC.
 SUBRAHMAKYA: SOLUTlON O F lLKOVlC EQUATION 299

For equation [2] obtained in the present work the following boundary conditions can be
given :
C(s,O) = *C, C(0,T) = OC, and C(s,T) = *C as 's' + a.
I t is interesting to exanline the significance of the boundary conditions t h a t have
been given above for equation [ 2 ] .The variable 'x' represents the distance of any point
from the surface of the electrode and Ilkovic has restricted the range of 'x' such t h a t
' A x ' is always a constant. The significance of this becomes clear if we consider the differ-
ence in volume between concentric spheres of radius rl+x and rl:
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= 4 ~ ( 3 m / 4 ~ d ) ~ l ~=t "Ax
~ x (when 'x' is small as coinpared to 'r,').
I t is interesting t o find out the error that is introduced in neglecting 3rlx and x2 in
comparison with 3r12. Let us take the case of a depolarizer with diffusion coefficient
10-j cm2sec-l diffusing to the surface of a dropping mercury electrode with the following
capillary characteristics: m = 1.5 nlg per sec; t = 5 sec. At the maximuin size of the drop
the error introduced when the value of 'x' is equal to 4 ( ( 3 / 7 ) n D t J (thickness of the diffu-
sion layer in the case of the dropping mercury electrode) is about 16%. When the value
of 'x' is about one eighth the thickness of the diffusion layer, 'Ax' is constant within
about 2%. For smaller values of 'x' the error introduced becomes much smaller. I t is
therefore obvious that the condition put by Ilkovic that 'Ax' be a constant highly
restricts the range of 'x'. Similar results are also obtained in calculations made a t different
times during the life time of a mercury drop.
Introduction of the variable 's', xt2I3/2d((3/7)D),suggests t h a t we are considering the
value of C a t different concentric spheres from the surface of the electrode. Regarding
'T' it can be said t h a t changes in 't' are similar t o changes in 'T'.
(iii) Solution of the Equation aC/aT = a2C/as2
The boundary conditions are given by C(s,O) = *C, C(0,T) = OC, and C(s,T) = "C
as 's' 4 a. a c / a T = a2C/as?s a partial differential equation with constant coefficients.
Hence the Laplace transform method can be used for solving this equation.
We define the Laplace transform of C(s,T) (abbreviated as L C(s,T)) a s

The equation aC/aT = azC/as2is transformed into

since *C is the value of the function C(s,T) when T = 0.

The solution of [3] is

Since the concentration of the depolarizer does not increase indefinitely with an increase
in 's', A l = 0. C(0,T) = OC = constant. A Laplace transforination of a constant is the
constant itself.
 300 CANADIAN JOURNAL O F CIIEMISTRY. VOL. 40, 1962

Therefore
0
L C ( 0 , T ) = u ( 0 , p ) = constant = C
A2 = -(*c-OC)
2L = *c- (*c- OC)~-'/(")."
C ( s , T ) = L-'z~(s,p) = L-'*c-L-~ (*C-OC)~-"(~)'~
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S
= OC+ (*c-OC) erf -- -
2dT '
I n terms of the old co-ordinate systenl we have
X
C(x,t) = OC+ (*C- OC) erf
2 d ((3/7)Dt) '
The value of (dC/dx),,o can be obtained by differentiating with respect to 'x' under the
integral sign either from [4] or [5]:

The current at any time 't' is given by

ACI<NOWLEDGMENTS
The author wishes to express his thanks to Professor M. R. A. Rao for helpful discus-
sions. His thanks are also due to Dr. S. K. Lakshmana Rao, Assistant Professor of
Mathematics, Regional Engineering College, Warrangal, for his scrutiny of the mathe-
matical aspects of this paper.

REFERENCES
1. J. M. MARKOWITZ and P. J. ELVING. Chem. Rev. 58, 1047 (1958).
2. D. ILKOVIC. J. chim. phys. 35, 129 (1938).
3. D. MACGILLAVARY and E. I<. RIDEAL. Rec. trav. chim. 56, 1013 (1937).
4. J. J. LINGANEand B. A. LOVERIDGE. J. Am. Chern. Soc. 72, 438 (1950).
5. H. STREHLOWand M. VON STACICELBERG.Z. Elektrochem. 54, 51 (1950).
6. A I. TACHI.Proceedings of the First International Polarographic Congress, P r a g ~ ~ e .
T. I ~ M B A Rand
Vol. 1. 1951. p. 126.