CHAPTER FIVE

ELECTRODE POTENTIAL VS. REACTION RATE

 Electrode potential
2

 When a metal dissolves in an aqueous solution by

releasing cations it becomes negatively charged.

 As more and more ions are released the metal surface

becomes increasingly negatively charged. This process
continues until equilibrium is reached.

 If the potential is altered by superimposing an external

electomotive force, the electrode is polarized and hence
there is a deviation from equilibrium conduction.
 Polarization
3

Polarization (Over potential):

 The change of potential from stabilized state as a result of
passing current.

 Also referred to over-voltage or over-potential

Over potential (ηA) = E applied – E Reversible (1)

 The main types of polarization are the concentration

polarization and the activation (or chemical) polarization.
 Concentration polarization
4

A) Concentration Polarization:
concentration polarization is the polarization of an
electrolytic cell resulting from changes in the
electrolyte concentration due to the passage of
current through the electrode/solution interface.
 Concentration polarization
5

 To illustrate what is meant by concentration polarization

(overpotential), consider the deposition of a metal (e.g.
copper) from its electrolytic solution (e.g. CuSO4) of
concentration Cb.

Cu+2 + 2e- → Cu
 The equilibrium potential needed to deposit the metal at the
cathode is given by the reversible value which is calculated
from Nernst equation:
E1= E°-(RT/nF) ln Cb (2)
 Concentration polarization
6

 After deposition, the metal ion concentration drops from Cb

in the bulk of solution to Ci at the electrode surface.
 Accordingly, the new potential which is needed to deposit
the metal is given by:
E2 = E°-(RT/nF) ln Ci (3)
 The difference between E2 and El is known as the
"concentration polarization or overpotential" and is given by:
ήc= E2 -E1 = (RT/nF) ln (Cb/Ci) (4)
 This is illustrated in Figure (1) in which the current "I" is
plotted against the voltage or potential “E”.
 Concentration polarization
7

•Concentration polarization arises

from slowness (delay) of the rate
of mass transfer of the electroactive
ion from the bulk of solution to the
electrode surface.

•If the rate of mass transfer of the

electroactive ion is fast enough to
compensate for the decrease in
metal ion concentration at the
electrode surface, there should be
concentration overpotential.

Figure (1): I versus E plot

 Concentration polarization
8

Experimental Determination of Concentration

Polarization (ήc) and Limiting Current (IL):
 The concentration polarization is experimentally

measured at a specified current density by measuring

the potential difference between the cathode and a
reference electrode placed in the cup of the Luggin
tube which is filled with the same solution as that in
the cell (Figure 2).
 The tip of the Luggin tube is placed close to the

cathode surface.
 Concentration polarization
9

Figure (2): Luggin tube

 Concentration polarization
10

 The potential difference between the cathode and the

reference electrode is measured by a potentiometer
according to the compensation method. The same
apparatus shown in Figure (3)is also used in the
experimental determination of the limiting current.
 A current-potential curve is constructed by increasing
the cell current stepwise and measuring the
corresponding cathode potential.
 The limiting current is obtained from “I” versus “E”
curve (Figure 4).
 Concentration polarization
11

Figure (2): Cell apparatus for concentration polarization measurement

 Concentration polarization
12

•A current-potential curve is
constructed by increasing the
cell current stepwise and
measuring the corresponding
cathode potential.

•The limiting current is

obtained at the plateau
shown in the indicated “I”
versus “e” curve
Figure (4) : Limiting current in the “I” versus “e” curve
 Activation Polarization
13

B. Activation Polarization:
 This is the extra voltage which should be added to the

theoretical potential in order to start the

electrochemical reaction or the change in potential that
is required just to make the reaction go faster.

 This type of polarization arises due to the slowness in

the charge transfer step, that is, the charge transfer step
needs more energy than the theoretical value (ΔG) to
take place.
 Activation Polarization
14

 Activation polarization is exhibited with the

discharge of gases, e.g. H2, O2 and Cl2.

 Most metals deposit with a negligible activation

overpotential except Co, Ni and Fe.
 Tafel equation
15

 The relation between activation polarization and the

rate of reaction is given by Tafel equation.

 Tafel equation

Eq. (1)

Eq. (2)
 Tafel equation
16

 where η is over-potential. A plot of over polarization

(η ) vs log(i) is linear for both anodic and cathodic
polarization fig (5)

 βC and βA are called the Tafel slopes and i◦ is the

exchange current density
 Tafel equation
17

 When
Eq.
(3)

Eq. (4)
 Tafel equation
18

Figure (5) : Tafel graph

 Tafel equation
19

 From equ. (3) anode plot

Eq. (3)

Eq. (5)

Eq. (6)

Eq. (7)
 Tafel equation
20

Eq. (8)

Eq. (9)

Eq. (10)
 Tafel equation
21

Eq. (10)

Eq. (11) Anode plot

equation
 Tafel equation
22

 From equ. (4) Cathode plot

Eq. (4)

Eq. (12)

Eq. (13)
 Tafel equation
23

Eq. (14)

Eq. (15) Cathode plot

equation
 Tafel equation
24

 Example : plot polaraization diagram of a giving

metal if:
i◦ =10-3 β =0.5 Z=2

ia = ic as follows
ia = ic
10-4
10-3
10-2
10-1
 Tafel equation
25

 Solution
 Tafel equation
26
 Tafel equation
27

Example
 The Rxn M→M+2+2e- is taking place on electrode

surface at 25°C, determine the cathodic current

density.
ηC = - 0.155 V
i◦ (M/ M+2) = 5*10-7 A/cm2
Z=2
Β=0.5
 Tafel equation
28

Solution
by using equ. (4)
 Activation Polarization
29

Experimental Determination of
Activation Polarization :

 Is measured by the same method

used for measuring concentration
polarization except for the fact that
the cell should be fitted with a
stirrer.
 The function of the stirrer is to
eliminate concentration
polarization which may be present.
 Summary
30

 Any electrochemical reaction involves two steps:

1. Mass transfer of the electroactive ion from the bulk of the solution
to the electrode surface.
2. Charge transfer from the electrode surface to the electroactive ion:
Mn+ + ne-→ M
 Slowness in any of the two steps results in overpotential at the
electrode surface.
 If the first step (mass transfer) is slow, concentration polarization
will be produced. If the second step (charge transfer) is slow,
activation polarization will be produced.
 Summary
31

 If the two steps are slow, both concentration and

activation polarizations will be produced:
ή = ήc+ ήa

 Concentration polarization decreases with stirring,

whereas activation polarization and IR drop are not
affected significantly with stirring.