CHAPTER 5:

OVERPOTENTIALS AT POLARIZED ELECTRODES

1. The Overpotential and its components

2. The activation overpotential
3. The concentration overpotential
4. The ohmic overpotential
5. Polarization curves under mixed overpotential
control

5-1
CHAPTER 5

OVERPOTENTIALS AT POLARIZED ELECTRODES

1. The Overpotential And Its Components

Processes taking place at an appreciable rate, i.e. all practical processes where current
is flowing, deviate from thermodynamic equilibrium. This deviation from reversibility
is associated with an overpotential, η, i.e., a potential in excess of the equilibrium
potential E, required to drive the reaction at the specified rate. Hence, the potential
difference, ΔV, applied across the electrodes in a current carrying electrochemical cell
is given by:

ΔV = E + η
Of the two components on the right, η is by far the more intriguing one since it
provides the driving force for the current flow and is intimately linked to the current
distribution. A current carrying electrode is said to be “polarized” or to exhibit
overpotential. The overpotential can be regarded as the penalty we pay in order to
drive the reaction away from equilibrium. The higher the current density, the larger
the overpotential required. The overpotential is consumed in the electrochemical cell
by various dissipative processes associated with different resistive mechanisms for
current passage. Although numerous dissipative processes can be identified, it is
convenient, particularly for engineering purposes to consider the overpotential in
terms of three components: activation, concentration, and ohmic, each acting in dif-
ferent regions of the cell.

a. Ohmic (i-r) overpotential:. Associated with ohmic losses mainly in the bulk of the
electrolyte phase, but occasionally also significant in the electrodes and leads. After i-r
drops in bulk phases and leads taken into account, some i-r drop may persist -
associated with electrode surfaces. Most commonly caused by some type of oxide
film, which is poor conducting.

b. Activation overpotential: caused by limiting rate at which some steps in electrode

reactions can proceed. Energy barrier and hence activation energy are involved.

c. Concentration overpotential: arises from decrease in concentration of reactants and

increase for products relative to bulk phase, because of mass transport limitations.

These resistive mechanisms or overvoltages depend on the current density (often non-
linearly), and different mechanisms are dominant at different regions of the
electrochemical cell. The current is adjusted along the electrodes such that at any local
point the overall voltage balance is maintained,

Note that ηa is limited to the surface and does not extend beyond the double layer, i.e., ~
100 A. The concentration overpotential ηC, is at the surface and typically extends to few
mm or less depending on the convective flow. In stagnant electrolyte ηC changes with
time and will eventually extend between the electrodes

5-2
Since the expressions for the overpotentials involve the current implicitly, the resulting
expression relating the local current to the applied voltage is not simple. Rather than
solving it rigorously, the concept of controlling overpotential is conveniently introduced.
Accordingly, the current distribution is specified mostly by only one dominant
overpotential model referred to as the controlling overpotential.

Notice: Overpotentials are losses, therefore, a close circuited battery will operate at a
voltage lower than its open circuit EMF. Similarly, an electrolysis or plating cell will
require voltage higher than what is indicated from thermodynamic analysis.

Sign Convention:

Overpotentials are dissipative – always working against us.

+ Anodic overpotentials and current densities: Positive
- Cathodic overpotentials and current densities: Negative

5-3
5-4
 Polarization Curves

 C F
 RTA F  a a 
i  i0 e e RT

 
o
i0 (‘exchange current density’): 100 – 10-16 A/cm2
o Transfer Coefficients: αA + αC~n

Alternate form:
 RTn F a  RTn F a 
i  i0 e e 
 
α+ β ~1

5-5
 THE BUTLER-VOLMER EQUATION
 C F
 RTA F a a  Transfer Coefficients:
i  i0 e e RT
 αA + αC~n
 
i

‘Tafel’
V

‘Tafel’ ‘Linear’

Approximations:
(1) Tafel (High Field): |ηa| >> RT/F ~ 0.12 V or i >> i0

RT i RT RT
a  ln   ln i0  ln i
 F i0 F F
a  a  b ln i
b=2.3 RT/αF - ‘Tafel Slope’
(2) Linear (Low Field): |ηa| << RT/F ~ 0.02 V or i << i0

RT i RT
a   i  b' i
n F i0 n F i0

(3) Linear Extrapolation:

a” = ηa0 – 0.343 b
ηa = a” + b” i
b” = 0.343 b /i0
5-6
5-7
5-8
 The Exchange Current Density – i0
The electrode-electrolyte interface involves a dynamic current balance:

i+
Equilibrium i+ = | i- | = i0
i-

Anodic i+ - i- = i (anodic, positive)

Current

Cathodic i- = i+ = i (cathodic, negative)

Current

i0 varies across a very broad range: 103 – 10-16

Nickel: i0 ~ 10-6 A/cm2 i ~ 10-1 – 10-2 A/cm2

Zinc: i0 ~ 10-1 A/cm2 i ~ 10-1 – 10-2 A/cm2
Li : i0 ~ 1 -10 A/cm2 i ~ 10-2 – 10-3 A/cm2

i0 = f (Ce, T, electrolyte composition, substrate [only in redox

reactions])

CONCENTRATION EFFECT:
i0 ~ [Ce, reactant]  ~½ for most di-valent ions

i0, (Ce) = i0, (Creference) [Ce/Creference] 

5-9
The Transfer Coefficients – A, C
 A & C represent the fraction of the overpotential that is spent in accelerating or
decelerating the anodic and cathodic processes, respectively.
In deposition: A decelerates the anodic process
C accelerates the cathodic process.
Typically,
αA + αC~n
Temperature dependence:

Theoretically - None or weak

Practically - α ~ T (Since: αF/RT is temperature independent)

5-10
5-11
SIGNIFICANCE OF THE ACTIVATION OVERPOTENTIAL
 Low overpotential sought for primary cell reaction to minimize
energy loss
 High activation overpotential for suppressing competing
reactions
 Corrosion protection is often based on arranging high
overpotential for hydrogen evolution
M Mn+ + ne
+
nH + ne n/2 H2

M + nH+ Mn+ + n/2 H2

 In plating, high activation overpotential is desired for attaining
level deposits
 Low i0 minimizes roughness and dendritic growth
 Low αC corresponds to a high Tafel slope, indicating a
large increase of the overpotential with the current density.
This produces uniform thickness deposits (high ’throwing
power’, or high Wa number)
 In batteries, fuel-cells and industrial electrolysis it is essential to
have low activation overpotential (high surface area electrodes
are often employed)
 Alloy deposition is often based and controlled by activation
overpotential
 The activation overpotential may extend the range of aqueous
electrochemistry by suppressing hydrogen and oxygen evolution

MEANS OF CONTROLLING AND MODIFYING THE

ACTIVATION OVERPOTENTIAL
 Catalytic electrodes (only in redox reactions)
 Elevated temperature lowers ηa
 ηa can be enhanced by raising the interfacial concentration
 Additives and contaminants typically increase ηa

5-12
 THE CONCENTRATION OVERPOTENTIAL

ηC

CB, B
RT C E
C  n
nF C B
CE, E

CE i nFD (C B  C E )
i
1  (1  t r ) N
CB iL
nFDCB
iL  
RT  i  (1  t r ) N
C  n 1  
nF  i L 
Anodic: i, ηC are positive
RT  | i | 
Cathodic: i, ηC are negative C  n 1  
nF  iL 
i

iL
5-13
 SIGNIFICANCE OF THE CONCENTRATION
OVERPOTENTIAL
 Maximum reaction rate
 Energy dissipation when i iL
 Minimal below iL
 Need for forced convection
 Source for roughness in plating and electroforming
 Porous structures
 A problem in dilute, stagnant electrolytes

MEANS OF MINIMIZING THE CONCENTRATION

OVERPOTENTIAL
 High bulk reactant concentration
 Effective agitation
 Reduce (eliminate) supporting electrolyte

THE OHMIC OVERPOTENTIAL

L
  i

 Linear with the current density
 Inversely proportional to the conductivity
 Strongly affected by the supporting electrolyte
 L – the current path is not known a-priory, except in trivial
geometries

5-14
Transport effects on the kinetically controlled current

5-15
5-16
Voltage Balance in Electrochemical Cells

We are quite interested in the potential distribution in electrochemical cells, since, it is the 
parameter which determines the current distribution. The potential applied externally between 
the electrodes includes, as we have seen, a thermodynamic component (standard potential, E0) 
and an overpotential which is dissipated 
 
throughout the cell in terms of mainly three dissipative mechanisms. We can formally write: 

AV = E + a + C +  [6-23]

As we have discussed, both E and a are present only at the electrode/electrolyte 
interface, within the extremely narrow, 0[Å], double layer. The concentration 
overpotential, C, in systems involving free or forced convection persists across a 
relatively thin, 0(m), mass transport (diffusion) boundary layer near the electrodes. The 
ohmic overpotential , on the other hand, is dissipated throughout the electrolyte in the 
interelectrode gap. Consequently, we can rewrite more explicitly Equation [6‐‐23], 
associating various overpotentials with the corresponding electrodes: 

  V  VA  VC   E A  aA  CA   AC   EC  aC  CC  [6-24] 

 
We Recall that the cathodic overpotentials are negative, hence the absolute values of all the 
overpotentials contribute to the voltage across the cell: 
 
V  V A  V C   E A  E C   aA  CA  AC  aC  CC [6-24’] 

 
Here, the standard potentials and the overpotentials associated with each electrode were lumped 
together. The ohmic overpotential which cannot be linked to any specific electrode stands alone. 
It should be remembered that the overpotentials are all functions of the current density, and of 
position in the cell. We can therefore rewrite Equation [6‐24]: 

V  V A  V C   E A  E C   aA (i, x, z )  CA (i, x, z )  AC (i, x, y , z )  aC (i, x, z )  CC (i, x, z )

Here the activation and concentration overpotentials were considered as essentially two 
dimensional thin layers on the electrodes and the ohmic overpotential was considered to vary 
throughout the entire cell.
 
Recall that overpotential are losses and always work against us. In a plating cell or during 
charging of a battery we must put in excess voltage, in a battery discharge we obtain less than the 
standard potential. The higher the current density, the larger are the losses. In order to decrease 
losses we want to lower the current density. This is achieved by either lowering the current or 
increasing the electrode area. The penalty is a larger capital equipment investment. 
 

5-17
Synthesis of overall polarization curve from its components: 
 
 
 
  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Overpotential components and their synthesis (From J. Newman, ‘Electrochemical Systems’, John 
Wiley, 1968). 
 
Note: We can synthesize a curve by picking a current density and adding the overpotential 
components, i.e., I  V. The reverse procedure (V  i) is much more complex. We can do this 
also numerically, 
 
Calculate, e.g., in Excel sheet, for a number of given currents, i1, i2, i3, …: 
 
Anode          Ohmic          Cathode 
 
EA AC
EC
l
RT i .1  i1 1
RT i
  A
 ln A1                 aC,1  ln C1    
a ,1
 AF i 0 C F i 0
RT i RT i
A 
C ,1
ln(1  A1 ) C 
C ,1
ln(1  C1 )
nF i L nF i L
 
Adding the components at i1, i2, i3, etc. 
 
V  V1 A  V1C   E A  E C   aA,1  CA,1  A,1C  aC,1  CC,1  
 
 

5-18
 Analysis of an operating cell: 
 
Effect of operating conditions (controlling mechanism)  
 
 

i i

V V

i i

V V

How can you tell experimentally where you are located?

Ohmic control: Vary cell gap, add supporting electrolyte, look for linear
dependence on current, insensitive to flow. Not very sensitive to T.

Activation control: Very sensitive to T. Insensitive to cell geometry or gap.

Sensitive to additives

Mass transport control: Sensitive to agitation, reactant conc. Insensitive supporting

electrolyte.

5-19
Operating Curves for a Process: Cu  Cu++ + 2e
I
Copper electrorefining:
V

‐+  Cu ++

Cu
+ 2e  Cu

 Cu++ + 2e
C
E = 0.34

EA=0.34 0.34 V V
  E = 0.34 – 0.34 = 0 V

Cu++ + 2e  Cu

Copper electrowinning:

‐+  2Cu++ + 4e 2Cu

2H2O  O2 + 4H++ 4e
EC= 0.34

EA=1.23

E = 1.23 – 0.34 = 0.89 V

I V

1.23 V

0.34 V V

5-20
Water Electrolyzer:

‐+  4H+ + 4e 2H2

2H2O  O2 + 4H++ 4e
EC= 0

EA=1.23

E = 1.23 – 0 = 1.23 V

2H2 4H+ + 4e
I
V
1.23 V

0V
V

4H+ + 4e 2H2

H2- O2 Fuel Cell :

+  2H2  4H+ + 4e EC= 0

‐ O2 + 4H++ 4e  2H2O EA=1.23

E = 0 – 1.23 = - 1.23 V

2H2 4H+ + 4e
I

V
1.23 V

0V
V

4H+ + 4e 2H2
O2 + 4H++ 4e H2O

5-21