To evaluate the polarization by Tafel Scan using Potentiostate

technique
Theory
Potentiostate
A potentiostate is an analytical instrument designed to control the working electrode's
potential in a multiple electrode electrochemical cell. The potentiostat contains many internal
circuits that allow it to function in this capacity. The circuits generate and measure potentials and
currents. External wires in a cell cable connect the potentiostat circuit to the electrodes in the
electrochemical cell. In a conventional three-electrode cell, the cell cable connects to the working,
counter (auxiliary), and reference electrodes on one end and the potentiostat cell cable connector
on the other end. The internal circuitry of the potentiostat controls the applied signal. In the case
of potential controlled methods, for example, the working electrode's potential is held with respect
to the reference electrode. At the same time, current flows between working and counter
electrodes. The potentiostat circuit design prevents all but a tiny current from flowing between
the working and the high impedance reference electrode.

Polarization Scans
In a potentiodynamic experiment, the driving force (i.e., the potential) for anodic or
cathodic reactions (depending on the nature of the scan) is controlled, and the net change in the
reaction rate (i.e., current) is observed. The potentiostat measures the current which must be
applied to the system in order to achieve the desired increase in driving force, known as the applied
current. As a result, at the open circuit potential (potential at which the total anodic current is
equivalent to the total cathodic current) the measured or applied current will be zero.
The Anodic Scan
A schematic anodic polarization curve is illustrated in Figure 2.1. As can be seen in the
figure, the scan starts from point 1 and progresses in the positive (potential) direction until
termination at point 2. There are a number of notable features on the curve. The open circuit or
rest potential is located at point A. At this potential the sum of the anodic and cathodic reaction
rates on the electrode surface is zero. As a result, the measured current will be close to zero. This
is due to the fact that the potentiostat only measures the current which it must apply to achieve the
desired level of polarization. As the potential increases, we move into region B, which is the active
region. In this region, metal oxidation is the dominant reaction taking place. Point C is known as
the passivation potential, and as the applied potential increases above this value the current density
is seen to decrease with increasing potential (region D) until a low, passive current density is

achieved (Passive region - Region E). Once the potential reached a sufficiently positive value
(Point F, sometimes termed the breakaway potential) the applied current rapidly increases (region
G).
The Cathodic Scan
A schematic cathodic polarization scan is illustrated in Figure 2.2. In a cathodic potentiodynamic
scan, the potential is varied from point 1 in the negative direction to point 2. The open circuit
potential is located at point A. As with the anodic scan, the open circuit potential represents the
potential at which the sum of the anodic and cathodic reactions occurring on the electrode surface
is zero. Depending on the pH and dissolved oxygen concentration in the solution, region B may
represent the oxygen reduction reaction. Since this reaction is limited by how fast oxygen may
diffuse in solution (mass transport controlled) there will be an upper limit on the rate of this
reaction, known as the limiting current density (as discussed above in Section 2.3).
Further decreases in the applied potential result in no change in the reaction rate, and hence the
measured current (Region C). Eventually, the applied potential becomes sufficiently negative for
another cathodic reaction to become operative (i.e., there is a sufficient thermodynamic driving
force for an additional cathodic reaction to begin taking place), such as illustrated at Point D. As
the potential, and hence driving force, becomes increasingly large, this reaction may become
dominant, as illustrated in Region E. This additional reaction is typically the reduction of other
species in the environment (such as the hydrogen evolution reaction, also known as the water
reduction reaction). An increase in current may also be observed if sufficient driving force exists
to reduce the oxide present on the electrode surface.

Experimental work
Appratus
 Working electrode
 Reference electrode
 Lugging capillary
 Auxiliary electrode
 Electrolyte
 Electrolyte beaker
 Connecting cables
 Potentiostat
Software
 Data acquisition
 Data analyst
Procedure
I. Clean the surface contaminations from the sample surface using sand blast, griding with
amery papers upto 600 grit size and rinse this with deionized water.
II. To produce the working electrode, sample was connected with copper wire using soldering
and spot welding processes. The surface to be studied connected with wire was kept bare
and other sides were embeded using epoxy resin.
III. Measure exposed area of the sample, density and its equivalent weight. Prepare the
electrolyte sollution.
 IV. Assemble electrochemical sell as given in figgure. Place the working electrode, refference
electrode and counter electrode into the electrolyte container and connect them with
potentiostate using connecting cables.

V. Start the experiment by clicking framework experiment and then selecting tafel from
expanded list.
VI. The graphical output of the experiment is a plot of log current vs potential. Analysis of the
curve revealed the following information,
 Corrosion potential
 Corrosion current and corrosion rate
 Kinetic information for anodic and cathodic reactions

VII. Following are the main controlling parameters in tafel scan,

Observations
Open-circuit potential
Open-circuit potential, Ecorr changes were measured against a standard saturated calomel electrode
placed in the same compartment. The stainless steel samples (as a working electrode) were
immersed in the electrolyte solution exposing an area of about 1 cm2.
 3.0E-01
Open Circuit Potential (OCP)
2.0E-01

1.0E-01

0.0E+00

-1.0E-01

-2.0E-01

-3.0E-01
0 100 200 300 400 500 600
Time (Second)
SS 316L SS 316L – E SS 316L – E + 1% (P)
SS 316L – E + 1% (I) SS 316L – E + 4% (P) SS 316L – E + 4% (I)

Cyclic potential
A cyclic voltammogram is obtained by measuring the current at the working electrode during the
potential scans. A cyclic voltammogram resulting from a single electron reduction and oxidation.
(libertexts, 2020)

Cyclic Potential
4.00E-01

3.00E-01

2.00E-01

1.00E-01

0.00E+00
1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00
-1.00E-01

-2.00E-01

-3.00E-01

-4.00E-01
Potential E

Results and Discussion

Results of open-circuit corrosion potential, Eoc were measured against a standard saturated calomel
electrode in the solution. In solution, no significant changes occurred in OCP. The cyclic potential is
obtained by measuring the current at the working electrode during potential scans.
References
 corrosion. (2019, september 4). polarization-electrochemistry. Retrieved from
corrosionpedia: https://www.corrosionpedia.com/definition/896/polarization-
electrochemistry
 libertexts. (2020, august 16). Cyclic_Voltammetry. Retrieved from chem.libretext:
 https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Supplemental_Modules_(
Anal ytical_Chemistry)/Instrumental_Analysis/Cyclic_Voltammetry