Noakhali Science and Technology University

Department of Applied Chemistry & Chemical Engineering

Assignment Title: Exchange Current Density, Tafel Equation

Course Code & Name: ACCE - 3107; Applied Electrochemistry

Submitted to:

Khodeja Afrin
Lecturer
Department of Applied Chemistry & Chemical Engineering

Submitted by:

MD. Rayhan Imam Shaidi

ID No.: MUH2104048M

Date of Submission: 17/09/2024

 Index
S.I. No. Contents Page No.
1 Exchange Current 2
2 Exchange Current Density 3
3 Tafel Equation 4-5
4 Derivation of Exchange Current 6-9
Density from Tafel Equation

1
 Exchange Current
Exchange current refers to the rate that charges, either positive or negative, enter or leave a
metal’s surface when an electrode reaches dynamic equilibrium in an electrolyte. It is the
current at equilibrium, or the rate that oxidized and reduced species transfer electrons with
the electrode.

For example, when a metal is immersed in an electrolyte, a dynamic equilibrium is

established across the interface with a potential difference between the metal and the
electrolyte. The metal atoms are ionized and electrons are produced as follows:

M —> Mn+ + ne-

where M represents metal atoms. The metal is left with a negative charge and its positively
charged metal ions (Mn+) in the electrolyte are attracted back toward the metal surface. Since
the rate of ionization on the metal surface becomes equal to the rate of discharge across the
contact layer, a potential difference and dynamic equilibrium between the metal and the
solution is established1.

Factors that affect the exchange current include

Forward reaction
The atoms that are at energetically unfavorable positions, such as at grain boundaries,
dislocations and half planes, are able to detach themselves and participate in the reaction.

Electrode composition
The exchange current depends on the composition of the electrode. The exchange current is
different for different electrodes.

Surface roughness
Larger surface areas provide a high exchange current.

Impurities
The presence of trace impurities causes current fluctuations.

1
corrosionpedia.com

2
 Exchange Current Density
Exchange current density can be defined as the current density that flows equally in
equilibrium and in both directions. The larger the exchange current density, the faster the
reaction, and vice versa.2

When describing the corrosion of a specific reaction, the exchange current is the current from
each of the two directions of the reversible reaction. These currents are denoted as "Ia" for
anodic current and "Ic" for cathodic current. The reactions can be described as:

Fe(s) = Fe2+(aq) + 2e-

The resultant current of the above reaction is zero since the net current at equilibrium is zero.
Exchange current can only be determined experimentally. In electrochemical
characterization, the current value is normalized by the electrode surface area and the current
density expressed as (i).

The main variables that help express the exchange current density include

Metal composition
Exchange current density is very dependent on the composition of the metal or alloy and on
the solution. It depends on the metal that supports the redox reaction at equilibrium.

Roughness of the metal surface

It is expressed as a geometrical surface area known to depend on the surface roughness of the
metal. The higher the exchange current density, the larger the surface area.

Concentration of soluble species

Exchange current density is also dependent on the concentration of the soluble species in that
it is a complex function of both the reactants' and the products' concentrations.

Impurities
These are impurities that dissolve on the surface of metals that tend to reduce the exchange
current density. These include arsenic, sulfur and antimony.

2
corrosionpedia.com

3
 Tafel Equation
The Tafel Equation is a mathematical expression that describes the relationship between the
electrochemical reaction rate and the overpotential of an electrode.3

η = ± A log10 (i/i₀)

where

η is the overpotential in V,

A is the Tafel slope in V,

i is the current density in A/m² ,

and i₀ is the exchange current density in A/m².

The +/- sign depicted in the equation relates to whether the analysis refers to an anodic (+) or
cathodic (-) process.

Assumptions of the Tafel Equation

The Tafel equation is a simplified equation based on empirical data to describe the
relationship between reaction rates and overpotentials at an electrode surface. As such, this
equation was developed with certain assumptions listed below:

● The reaction at the electrode is a reaction consisting of a single electron transfer.

● The reaction at the electrode is irreversible, thus, the reverse reaction is either
inexistent or negligible.
● The reaction is controlled only by an anodic or a cathodic process, but not both.
● The overpotential applied is small, so that the reaction rate follows a linear trend with
the overpotential.
● The exchange current density is constant over the potential range of interest.

3
meciassensors.com/ GerardMacias/ February 17, 2023/ Knowledge Base

4
Applications of the Tafel Equation
Corrosion studies
The Tafel equation is perhaps most known for its application in the study of corrosion. With
it, it is possible to evaluate the effectiveness of corrosion inhibitors, which are significant in a
wide variety of industries like consumer electronics and construction.

Studying electrode reaction kinetics

The Tafel equation allows electrochemists to quantify the kinetics of electrochemical
reactions. By looking at the slope of the Tafel equation it is possible to determine what type
of reaction is occurring:

Activation-controlled reaction
In this case the limiting step is the transfer of electrons to the electrode surface. This type of
reaction has a small Tafel slope between 30 and 120 mV/decade. An example of an activation
control would be the oxidation of iron in acidic media.

Diffusion-controlled reaction
In this case the limiting step is the transport of chemical species from or to the electrode
surface. This type of reaction has large tafel slopes, typically between 120 and 240
mV/decade. An example of a diffusion controlled reaction is the reduction of oxygen to
water.

Mixed-controlled reaction
In this case we have a combination of activation and diffusion processes. This type of
reaction has an intermediate Tafel slope between 60 and 120 mV/decade. An example would
be the oxidation of a metal in an electrolyte with a low concentration of oxygen dissolved in
it. In this case, the metal oxidation is an activation controlled reaction that is also limited by
the amount of oxygen available in the electrolyte.

5
Derivation of Exchange Current Density
from Tafel Equation

To calculate the exchange current density (i₀) from a Tafel plot, one typically follow these
steps:

1. Plot Construction
A Tafel plot is obtained by plotting the logarithm of the current density (log|i|) versus the
applied potential (η).

2. Identification of Tafel Region

It needs to be ensured that the plot covers a region where the relationship between log|i| and η
is linear. This linear region typically occurs at low overpotentials (small deviations from
equilibrium potential).

3. Determination of Tafel Slope (A)

The slope of the Tafel plot (A) is related to the exchange current density (i₀) by the Tafel
equation:

A = (2.303RT)/(αF)

where:

R is the gas constant (8.314 J/mol K),

T is the temperature in Kelvin,

α is the charge transfer coefficient,

F is the Faraday constant (96,485 C/mol).

Therefore, the exchange current density (i₀) can be calculated using the slope A as:

i₀ = (10A)/k

where k is a proportionality constant depending on the units used for i₀

6
4. Calculation of i₀
Slope A is substituted into the equation to find i₀ . It is ensured that the units of i₀ correspond
to the units of current density used in the experiment (often mA /cm² or A / m² ).

5. Verification and Interpretation

After calculating i₀ , its consistency is verified and the physical significance is interpreted
within the context of the electrochemical system.

Example Data

Assume we have the following data from an electrochemical experiment:

Overpotential (η) vs. Logarithm of Current Density (log|i|):

η (V) | log|i| (A/cm²)

0.05 | -4.0

10.10 | -3.5

10.15 | -3.0

0.20 | -2.5

0.25 | -2.0

Step-by-Step Calculation

1. Plot the Data

A plot with η on the x-axis and log|i| on the y-axis is created.

Fig: η vs log|i| graph for the given value.

2. Identification of Tafel Region

The linear region of the plot is identified. In this case, the entire range appears to be linear.

3. Determination of Tafel Slope (A)

7
The slope (A) of the linear region is calculated by taking two points from the table and using
the slope formula:

A = Δη/Δ(log|i|)

Using points (0.05, -4.0) and (0.25, -2.0):

A = 0.25-0.05 / -2.0-(-4.0) = 0.20 2.0 = 0.10

4. Calculation of Exchange Current Density ( i₀ )

The Tafel equation relates the overpotential to the current density as follows:

η = A log(i/i₀)
At η = 0 ,log|i| = log i₀.

Using A = 0.10 V/decade:

We can write the Tafel equation as:

η = A log(i/i₀)

Solving for i₀:

At η = 0:

0 = A log(i/i₀)
This simplifies to:

log(i) =log i₀
When η = 0.1V, log|i| = - 3.5:

0.1 = 0.1 log(i/i₀)

Substituting log|i| = -3.5:

0.1 =0.1( log|i| - logi₀ )

1= log|i| - logi₀
log i₀ = log|i| - 1
Substituting log i = -3.5:

log i₀ = -3.5 - 1 = -4.5

Therefore:

i₀ = 10-4.5 A/cm2 = 3.16 × 10-5 A/cm²

8
Conclusion
The exchange current density o calculated from the Tafel plot is 3.16 × 10-5 A/cm².