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Description of the Cell =0 (4)
x 2
An electrochemical cell can be used in two different By considering the three-dimensional problem, one ob-
ways: first, to make chemical transformations (an tains the Laplace equation:1
electrolyzer in which electric power is supplied to the
cell); and second, to generate electric power (a generator 2 2 2
supplying power to the user). We will consider here an + + =0 (5)
electrolysis cell. x 2 y 2 z 2
At the laboratory scale, most electrochemical re-
search is done in a glass cell as pictured in Figure 1a. where each term of the sum can be different from zero.
Three different (most of the time metallic) electrodes are Given adequate boundary conditions (electrode po-
used: (i) the working electrode (WE), which is the elec- tentials), eq 5 can be solved by using the finite difference
trode under study; (ii) the counter electrode (CE), which method. To simplify the treatment, eq 5 is solved in two
is used to collect electrons, and (iii) the reference elec- dimensions (the term 2/z2 is not considered). In the
trode (REF), which is used to measure the potential dif- finite difference method (1), the region of interest (the
ference between the working electrode and the electro- interpolar volume R) is replaced by a horizontal grid
lytic solution. The working and counter electrodes are (Fig. 1b). The grid consists of equidistant straight lines
disposed in parallel in the electrolytic solution and are whose intersections are called mesh points. Then we use
connected to an external power supply device. a difference equation approximating the partial differ-
Let us consider the case of water electrolysis in aque- ential equation (5), by which we relate the unknown val-
ous sulfuric acid solution using platinum electrodes. The ues of at the mesh points to each other and to the given
electrode reactions are: boundary values.
anode: H2O 2 H+ + 12 O2 + 2e2
cathode: H + + 1e2 12 H2 2 x + 1,y + x 1,y 2 x,y
= (6)
If the aim of the study is the anodic reaction, then x 2 y x 2
the anode will be called the working electrode and the
cathode the counter electrode.
2 x, y+ 1 + x,y 1 2 x,y
Primary Current Distribution = (7)
y2 x y2
The fluxforce relation that applies to any electro-
chemical system is given by eq 1, where i is the current This yields a system of linear algebraic equations. By solv-
density, is the electric potential, and is the electric ing it, we obtain approximations to the unknown values
conductivity of the solution: of at the mesh points.
Figure 2 shows the solution of eq 5 when a potential
i = grad (1) difference of 2 V is applied between WE and CE.
Let us consider a one-dimension problem. Under
Secondary Current Distribution
steady state conditions, the current passing at a distance
x from the electrode surface is equal to the current pass- In the case of a primary current distribution as
ing at x + dx : 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
nF
i = i 0 exp n F exp (8)
RT RT
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.
Summary
Notes