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In the Classroom

Electric Potential Distribution in an Electrochemical Cell

Pierre Millet Laboratoire des Composés Non Stoechiométriques, Université de Paris Sud, Bâtiment 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:

H _{2} O

cathode:

2 H ^{+} + ^{1} _{2} O _{2} + 2e ^{}

H ^{+} + 1e ^{}

^{1} _{2} H _{2}

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 flux–force 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 :

i

x + dx

= i

x

(2)

Combination of eqs 1 and 2 gives eq 3:

When dx

∂

– ∂

∂x

∂x

x + dx

0, we can write:

2

∂x 2 = 0

∂

= 0

x

(3)

(4)

By considering the three-dimensional problem, one ob- tains the Laplace equation: ^{1}

2

∂x ^{2} ^{+} ∂

∂

∂y ^{2} ^{+} ∂ ∂z ^{2} ^{=} ^{0}

2

2

(5)

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} /∂z ^{2} 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.

y

x

=

=

x + 1,y

+

x – 1,y x ^{2}

– 2

x,y

x, y+ 1

+

x,y– 1

– 2

x,y

y ^{2}

(6)

(7)

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

956 Journal of Chemical Education • Vol. 73 No. 10 October 1996

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 metal–so- 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 cm ^{–}^{2} 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 Butler–Volmer relation (2–4):

i = i _{0}

exp

n F

RT

– exp

n F

–

RT

(8)

where i _{0} 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 mol ^{–}^{1} ), R is the gas constant (8.32 Pa m ^{3} mol ^{–}^{1} K ^{–}^{1} ), and T is the temperature (K). In most cases, especially when the cell is rated at el- evated current densities, the reverse term of the reaction

can be neglected. This results in the simplification of eq 8,

in which one of the two exponentials can be neglected. Coupling of eqs 5 and 8 at the electrode–electrolyte

interface results in a nonlinear relation that can be solved numerically using a Newton–Raphson 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 be altered by any modification of the geometry of the sys- 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-

rect relation with the disposition of the electrodes.

Figure 1. (a) Schematic diagram of an electrochemical cell. WE = working electrode; CE = counter electrode; REF = reference elec- trode; G = gas (to de-aerate the cell). (b) 2-D grid. The electric po- tential is computed at each mesh point.

Figure 2. 2-D electric potential distribution in an electrochemical cell. Solution to the Laplace equation.

Figure 3. 2-D electric potential distribution in an electrochemical cell. Secondary current distribution. _{c}_{a}_{t}_{h}_{o}_{d}_{e} = 17.5 ln i + 7.4; _{a}_{n}_{o}_{d}_{e} = 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 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 (1749–1827), 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- ability theory. Napoleon Bonaparte was his student for a year.

Literature Cited

1. Kreyszig, E., Advanced Engineering Mathematics, 5th ed.; John Wiley & Sons:

New York, 1983.

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.

(a)

(b)

Figure 4. 2-D electric potential distribution in an electrochemical cell. Effect of the electrode size. (a) Same size. (b) Factor 2 dif- ference in size.

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

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