In the Classroom
Electric Potential Distribution in an Electrochemical Cell
Pierre Millet
Laboratoire des Composs Non Stoechiomtriques, Universit de Paris Sud, Btiment 415, 91405 Orsay Cedex, France
Many students learning electrochemistry do not un-
derstand how current flows from one electrode to the other
in an electrochemical cell. This is generally because in-
terfacial phenomena and ionic conductivity in the elec-
trolytic solution tend to be treated separately by chemis-
try teachers. An easy way to improve students under-
standing of how it works is to compute the two-dimen-
sion electric potential distribution in the cell and to make
a gravitational analogy. Current flows from one electrode
to the other just as a ball would do in a gravitational field.
Description of the Cell
An electrochemical cell can be used in two different
ways: first, to make chemical transformations (an
electrolyzer in which electric power is supplied to the
cell); and second, to generate electric power (a generator
supplying power to the user). We will consider here an
electrolysis cell.
At the laboratory scale, most electrochemical re-
search is done in a glass cell as pictured in Figure 1a.
Three different (most of the time metallic) electrodes are
used: (i) the working electrode (WE), which is the elec-
trode under study; (ii) the counter electrode (CE), which
is used to collect electrons, and (iii) the reference elec-
trode (REF), which is used to measure the potential dif-
ference between the working electrode and the electro-
lytic solution. The working and counter electrodes are
disposed in parallel in the electrolytic solution and are
connected to an external power supply device.
Let us consider the case of water electrolysis in aque-
ous sulfuric acid solution using platinum electrodes. The
electrode reactions are:
anode: H2O 2 H+ + 12 O2 + 2e2
cathode: H + + 1e2 12 H2
If the aim of the study is the anodic reaction, then
the anode will be called the working electrode and the
cathode the counter electrode.
Primary Current Distribution
The fluxforce relation that applies to any electro-
chemical system is given by eq 1, where i is the current
density, is the electric potential, and is the electric
conductivity of the solution:
i = grad (1)
Let us consider a one-dimension problem. Under
steady state conditions, the current passing at a distance
x from the electrode surface is equal to the current pass-
ing at x + dx :
956 Journal of Chemical Education Vol. 73 No. 10 October 1996
i =i (2)
x + dx x
Combination of eqs 1 and 2 gives eq 3:
x =0 (3)
x + dx x x
When dx 0, we can write:
2
=0 (4)
x 2
By considering the three-dimensional problem, one ob-
tains the Laplace equation:1
2 2 2
+ + =0 (5)
x 2 y 2 z 2
where each term of the sum can be different from zero.
Given adequate boundary conditions (electrode po-
tentials), eq 5 can be solved by using the finite difference
method. To simplify the treatment, eq 5 is solved in two
dimensions (the term 2/z2 is not considered). In the
finite difference method (1), the region of interest (the
interpolar volume R) is replaced by a horizontal grid
(Fig. 1b). The grid consists of equidistant straight lines
whose intersections are called mesh points. Then we use
a difference equation approximating the partial differ-
ential equation (5), by which we relate the unknown val-
ues of at the mesh points to each other and to the given
boundary values.
2 x + 1,y + x 1,y 2 x,y
= (6)
x 2 y x 2
2 x, y+ 1 + x,y 1 2 x,y
= (7)
y2 x y2
This yields a system of linear algebraic equations. By solv-
ing it, we obtain approximations to the unknown values
of at the mesh points.
Figure 2 shows the solution of eq 5 when a potential
difference of 2 V is applied between WE and CE.
Secondary Current Distribution
In the case of a primary current distribution as
treated above, the rate at which electrons are transferred
from (or to) the electrode is not considered. A more real-
istic picture of the potential distribution in the cell is
 In the Classroom

obtained when the rate of electron transfer is taken into

consideration. In electrochemical applications, high cur-
rent densities are sought in order to improve the cell ef-
ficiency. This departure from equilibrium has a cost: the
overvoltage. The overvoltage at any given metalso-
lution interface where electrons are transferred is de-
fined as the potential difference between the equilibrium
potential and the rating potential. The product ( i) is
homogeneous to the J cm2 scale and corresponds to a
loss in the cell efficiency: heat is generated and exchanged
with the surroundings. The relation between overvolt-
age and current density is given by the ButlerVolmer
relation (24):

nF
i = i 0 exp n F exp (8)
RT RT

where i0 is the exchange current density, and are the

symmetry factors (related to the activation energy of the
charge transfer process), n is the number of electrons
exchanged in the process, F is the Faraday constant
(96,487 C mol1 ), R is the gas constant (8.32 Pa m3 mol 1
K1 ), and T is the temperature (K).
In most cases, especially when the cell is rated at el- Figure 1. (a) Schematic diagram of an electrochemical cell. WE =
evated current densities, the reverse term of the reaction working electrode; CE = counter electrode; REF = reference elec-
can be neglected. This results in the simplification of eq 8, trode; G = gas (to de-aerate the cell). (b) 2-D grid. The electric po-
in which one of the two exponentials can be neglected. tential is computed at each mesh point.
Coupling of eqs 5 and 8 at the electrodeelectrolyte
interface results in a nonlinear relation that can be solved
numerically using a NewtonRaphson method (5, 6). Re-
sults obtained in the case of water electrolysis are shown
in Figure 3. The cathodic process is fast (a low overvolt-
age has to be applied to obtain a substantial current den-
sity), whereas the anodic one is slow. As a consequence,
it can be seen in Figure 3 that the distribution of electric
potential in the vicinity of the cathode is similar to that
obtained in Figure 2 in the case of a primary current
distribution. On the contrary, a very strong potential drop
is observed between the anode and the electrolyte be-
cause the anodic process is slow.

Effect of Size and Position of Electrodes on the

Potential Distribution

The distribution of electric potential in the cell will Figure 2. 2-D electric potential distribution in an electrochemical cell.
be altered by any modification of the geometry of the sys- Solution to the Laplace equation.
tem. We shall consider the size of the electrodes and their
position in the cell.
Size of the Electrodes
Figure 4 shows the distribution of electric potential
in two different cases. In Figure 4a, the two electrodes
have the same area. In Figure 4b, one of the electrodes is
twice the area of the other.
It can be seen from Figure 4b that the distribution of
electric potential is more regular in the vicinity of the
smallest electrode. This is why the counter electrode is
generally larger than the working electrode.
Position of the Electrodes
The distribution of electric potential in an electro-
chemical cell is directly related to the position of the elec-
trodes in the cell. Figure 5 shows the result when we con-
sider two square electrodes perpendicular one to another.
A strong distortion of the electric field is observed, in di- Figure 3. 2-D electric potential distribution in an electrochemical cell.
rect relation with the disposition of the electrodes. Secondary current distribution. cathode = 17.5 ln i + 7.4;
anode = 17.4 ln i 6.9.

Vol. 73 No. 10 October 1996 Journal of Chemical Education 957

 In the Classroom

Summary

The way current flows from one electrode to the other

in an electrochemical cell is easier to understand by pre-
senting the calculated 2-D electric potential distribution
in the cell. The curves obtained can be compared to gravi-
tational fields, and the electrons (or ions) are analogous
to small balls jumping out of the anode and falling down-
hill to the cathode. It appears clearly from the figures that
the current can go from the back of the anode to the back
of the cathode, even though it flows most directly through
the interpolar region. The current lines flow close to the
boundary of the cell and the entire solution is affected.
From these figures, it is easy to understand that the (a)
position of the reference electrode in the cell must be
chosen carefully in order to measure the interfacial ov-
ervoltage precisely. This is especially the case for fast
electrochemical reactions where the overvoltage is small
in comparison with the electric conductivity of the solu-
tion. The size and the position of the electrodes in the
solution is also of importance and determines the distri-
bution of electric potential.

Notes

1. Pierre Simon, marquis de Laplace (17491827), French

mathematician, was a professor in Paris. He developed the founda-
tion of potential theory and made important contributions to celes-
tial mechanics, astronomy in general, special functions, and prob-
(b)
ability theory. Napoleon Bonaparte was his student for a year.

Literature Cited Figure 4. 2-D electric potential distribution in an electrochemical

cell. Effect of the electrode size. (a) Same size. (b) Factor 2 dif-
1. Kreyszig, E., Advanced Engineering Mathematics, 5th ed.; John Wiley & Sons:
New York, 1983.
ference in size.
2. Tafel, J. Z. Physik. Chem. 1905, 50, 641.
3. Butler, J. Trans. Faraday Soc. 1924, 19, 729.
4. Erdey-Gruz, T.; Volmer, M. Z. Physik. Chem. 1930, 150, 203.
5. Ortega, J.; Rheinboldt, W. Iterative Solution of Nonlinear Equations in Several
Variables; Academic: New York, 1970.
6. Press, W. H.; Flannery, B. P.; Teukolsky S. A.; Vetterling, W. T. Numerical Reci-
pes; Cambridge University: Cambridge, 1986.

Figure 5. 2-D electric potential distribution in an electrochemical cell.

Effect of the position of the electrodes: the two electrodes are per-
pendicular.

958 Journal of Chemical Education Vol. 73 No. 10 October 1996