rerrerereerMATHEMATICA S PROGRAM FOR COVOLUTIVE

MODELLIG. SIMULATIO WITH DIGISIM AD

DIGIELCH. CrEq MECHAISM I CV AT PLAAR
ELECTRODES
Manuel J. Barrera iebla, Margarita R. Garca Hernndez, Marcial J. Gonzlez Morn,
Luis C. Fernndez Mrida, Domingo M. Grandoso Medina, Mariano J. Prez Snchez
Department of Physical Chemistry. La Laguna University. Tenerife. Canary Islands
. Spain
mbarnie@ull.es
An important methodology of Semiintegral and Convolution Electrochemistry1 is th
e convolutive
modeling of electrochemical processes. It was developed by Oldham, Mahon and Myl
and using Extended
Semiintegrals and the Uuniversal Convolution Algorithm of Keith B. Oldham.
In this communication we report a program that runs inside Mathematica software
to make the
modeling of a CrEq mechanism in a CV experiment at planar electrodes, with the m
ethod based upon
g(t) . The equations (1) are the double integrals for gi (t) functions with i =
R,P .
{ }
( ) ( ) ( ) ( )
{ ( ) }
3/2
2 3/2
' ( ') 4 ' 1
( ) '
' 3 ' ' 2 ' R
k tExp k k t kt k
G t t Erf k k t
p k k p k k k k k k
- +  
= + +  -  +
+ + +  + 
;
3/2 4
( )
3 P
t
G t
p
= (1)
One of the main equations is the Semiintegral Butler-Volmer equation, namely
[ ( )] [ ( )]
( ) f R R b P P
R P
k M M t k M M t
I t
D D
- +
= - ; ; , b
i i i M = nFA D C i = R P (2)
together with the Universal Convolution Algorithm of Keith B. Oldham, it is to s
ay
( ) ( ) ( )
1
1 1 1
1
1
2

J
J i J i J j j j j i
j
M I G I G G G
- - +
=
 
=  + - + 
D  
 ; ( ) ( ) 1 1
2 , j j j j i i
G G G G i R P - + = - + = (3)
The combination of equations (2) and (3) leads to the following equation:
( ) ( )
( ) ( )
1 1
1 1
1 1
J J
f P R J j j b R P J j j
R P
j j
J
R P f P R b P
k D M I G k D M I G
I
D D k D G k G
- - = =
   
 D -  -  D + 
   
=
D + +
 
(4)
The equations (4) and (1) allow us to calculate the files I-E corresponding to t
he cyclic
voltammogram, in order to compare with those obtained by digital simulation with
DigiSim and
DigiElch. The agreement we found is excellent.
A very simple program written for Mathematica software is reported here to model
I-E curves in a
cyclic voltammetry experiment for a CrEq mechanism. The first lines of the progr
am collect the several
parameters of the electrochemical system as well as those of the instrumental te
chnique. Likewise, the
program calculates some other constants with the mentioned parameters. Next it i
s generated the potential
program and the files kf-E and kb-E for the heterogeneous electrochemical reacti
on. The following step is
the calculation of GR(t) and GP(t) functions for each one of the time values and
later they are
appropriately combined. Finally, the program calculates the files I-E, reporting
them as a table with the
TableForm Mathematica protocol and immediately with ListPlot protocol displays th
e modeled
voltammogram. The expressions (5), (6) and (7) show the last lines of the Mathem

atica program
reported in this communication for convolutive modeling for CrEq mechanism in a
cyclic voltammetry