Experiment-1

Aim of the Experiment

Galvanic series
To calculate the electrode potential of different materials and to
study different aspects of the galvanic series

Theory:
An electrochemical cell is based on an oxidation-reduction (redox)
reaction and consists of two half-cells: an anode half-cell and a
cathode half-cell. Oxidation occurs at the anode; reduction occurs
at the cathode.
An electrochemical cell can produce an electric current, which is
driven by an electrical potential difference between the two halfcells. In this experiment we will use a voltmeter to measure and
compare
the electrical potential differences
of several
electrochemical cells, some of which will have different
concentrations of metal ions.
Electrochemical Cell
If two half-cells are connected by placing a wire between the pieces
of metal and by adding a salt bridge between the two solutions, a
direct electric current can flow through the circuit. The electric
current is generated because metal atoms in the more reducing
metal convert to ions and leave one electrode to enter the solution
and ions of the less reducing metal accept electrons and plate
out on the other electrode. The electrons left behind when positive
ions are formed at one electrode pass through the external circuit
and into the other electrode. There the electrons combine with ions
from the solution to form metal atoms. By measuring the direction
of current flow, and the voltage generated in the cell, we can
determine which is the more reducing metal (stronger reducing
agent), and by how much.
Salt Bridge
1

In order for current to flow, there must be a complete electric

circuit. The wire is part of the circuit and the salt bridge completes
the circuit. In this experiment, the salt bridge is a porous cylinder
soaked with aqueous potassium chloride and agar-agar gel. The
solutions of salts, such as potassium chloride, are electrolytes
they conduct electrical current by movement of positive and
negative ions in the solution. Thus the porous cylinder provides a
path for conduction of electricity, just as the wire does, completing
the electrical circuit. Because diffusion of the solutions through the
porous cylinder is slow, there will be no mixing of the solution of
one half-cell with the solution of another on the time scale of the
experiment. Thus the half-cells are connected electrically, but not
chemically, by the salt bridge. Without a salt bridge a cell will not
produce an electric current and we will not be able to measure the
electrical potential difference between the two electrodes.
Anode and Cathode
The half-cell in which oxidation occurs is called the anode. This is
the half-cell in which metal atoms lose electrons (are oxidized) to
form positively charged ions (which go into solution). The electrons
flow into the external circuit from the anode.
The half-cell in which reduction occurs is called the cathode. This is
the half-cell in which metal ions from the solution gain electrons
(are reduced) and plate out onto the electrode as uncharged atoms.
The electrons flow out of the external circuit into the cathode.

Apparatus :1. Reference Electrode-Saturated Calomel Electrode(SCE)

2. Salt bridge
3. Potentiostat
4. Lead strip
5. Zinc strip
6. Copper strip
7. Aluminium strip
8. Stainless steel strip
9.Graphite rod
10.Multimeter

Procedure:1. The sample is immersed in a beaker containing tap water.

2. The sample is connected to the positive end of the multimeter
and the reference electrode is connected to the negative end of the
multimeter.
3. The potential of the sample is measured.
4. Another sample strip is placed and the potential of it is measured
following the above procedure.

Observations:-

Remarks:1. Care is taken to ensure that the electrodes do not touch the
glass-walls as it might lead to erroneous results.
2. Care is taken to avoid any parallax error.
****
3

Experiment-2
Aim of the Experiment

Cyclic Voltammetry
To study the Cyclic Voltagram of Pt in 1 mole KOH and 0.2M
glucose solution

Theory:
Cyclic Voltammetry (CV) is an electrochemical technique which
measures the current that develops in an electrochemical cell
under conditions where voltage is in excess of that predicted by the
Nernst equation. CV is performed by cycling the potential of a
working electrode, and measuring the resulting current. It is a
potentiodynamic
electrochemical
measurement.
Cyclic
voltammetry is generally used to study the electrochemical
properties of an analyte in solution.
The potential of the working electrode is measured against a
reference electrode which maintains a constant potential, and the
resulting applied potential produces an excitation signal such as
that of figure 1.
In the forward scan of figure 1, the potential first scans negatively,
starting from a greater potential (a) and ending at a lower potential
(d). The potential extrema (d) is call the switching potential, and is
the point where the voltage is sufficient enough to have caused an
oxidation or reduction of an analyte. The reverse scan occurs from
(d) to (g), and is where the potential scans positively. Figure 1
shows a typical reduction occurring from (a) to (d) and an oxidation
occurring from (d) to (g). It is important to note that some analytes
undergo oxidation first, in which case the potential would first scan
positively. This cycle can be repeated, and the scan rate can be
varied. The slope of the excitation signal gives the scan rate used.

Figure 1: CV Excitation Signal

A cyclic voltammogram is obtained by measuring the current at the

working electrode during the potential scans. Figure 2 shows a
cyclic voltammogram resulting from a single electron reduction and
oxidation.

Figure 2: Voltammogram of a Single electron oxidation-reduction

In Figure 2, the reduction process occurs from (a) the initial

potential to (d) the switching potential. In this region the potential
is scanned negatively to cause a reduction. The resulting current is
5

called cathodic current (ipc). The corresponding peak potential

occurs at (c), and is called the cathodic peak potential (E pc). The
Epc is reached when all of the substrate at the surface of the
electrode has been reduced. After the switching potential has been
reached (d), the potential scans positively from (d) to (g). This
results in anodic current (Ipa) and oxidation to occur. The peak
potential at (f) is called the anodic peak potential (E pa), and is
reached when all of the substrate at the surface of the electrode
has been oxidized.

Experimental setup:A CV system consists of an electrolysis cell, a potentiostat, a

current-to-voltage converter, and a data acquisition system. A
standard CV experiment uses a reference electrode (RE), a
working electrode (WE), and a counter electrode (CE). This
combination is sometimes referred to as a three-electrode setup.
An electrolyte is usually added to the sample solution to ensure
sufficient conductivity. The solvent, electrolyte, and material
composition of the working electrode will determine the potential
range that can be accessed during the experiment.
The counter electrode (also known as auxiliary electrode), is
an electrode which is used to close the current circuit in the
electrochemical cell it does not participate in the electrochemical
reaction. Because the current is flowing between the WE and the
CE, the total surface area of the CE (source/sink of electrons) must
be higher than the area of the WE so that it will not be a limiting
factor in the kinetics of the electrochemical process under
investigation.
The reference electrode is an electrode which has a stable and
well-known electrode potential and it is used as a point of reference
in the electrochemical cell for the potential control and
measurement. Here saturated calomel electrode is used. The
high stability of the reference electrode potential is usually reached
by employing a redox system with constant (buffered or saturated)
concentrations of each participants of the redox reaction. Moreover,
the current flow through the reference electrode is kept close to
zero (ideally, zero) which is achieved by using the CE to close the
current circuit in the cell together with a very high input impedance
on the electrometer (> 100 GOhm).
6

The working electrode is the electrode in an electrochemical

system on which the reaction of interest is occurring.

Three-electrode system
In this case, the current flows between the CE and the WE. The
potential difference is controlled between the WE and the CE and
measured between the RE (kept at close proximity of the WE) and
S. Because the WE is connected with S and WE is kept at pseudoground (fixed, stable potential), by controlling the polarization of
the CE, the potential difference between RE and WE is controlled all
the time. The potential between the WE and CE usually is not
measured. This is the voltage applied by the control amplifier and it
is limited by the compliance voltage of the instrument. It is
adjusted so that the potential difference between the WE and RE
will be equal to the potential difference specified by the user. This
configuration allows the potential across the electrochemical
interface at the WE to be controlled with respect to the RE.
The working electrodes potential is varied linearly with time, while
the reference electrode maintains a constant potential. The counter
electrode conducts electricity from the signal source to the working
electrode. The purpose of the electrolytic solution is to provide ions
to the electrodes during oxidation and reduction.
A potentiostat is an electronic device which uses a d.c. power
source to produce a potential which can be maintained and
accurately determined, while allowing small currents to be drawn
into the system without changing the voltage. The current-tovoltage converter measures the resulting current, and the data
acquisition system produces the resulting voltammogram.
Common materials for the working electrode include glassy carbon,
platinum, and gold.

The counter electrode (here graphite) can be any material. To

maintain the observed current the counter electrode will often
oxidize or reduce the solvent or bulk electron.

Observation:-

Fig.3 Cyclic voltagram

Conclusion:The peaks show wide separation and the maximum values in the
positive cycles is not very large, indicating slow electron transfer
kinetics, hence given sample is not a viable electrolyte for
commercial purposes

Applications:8

Cyclic voltammetry (CV) has become an important and widely used

electro-analytical technique in many areas of chemistry. It is often
used to study a variety of redox processes, to determine the
stability of reaction products, the presence of intermediates in
redox reactions, reaction and electron transfer kinetics and the
reversibility of a reaction. CV can also be used to determine the
electron stoichiometry of a system, the diffusion coefficient of an
analyte, and the formal reduction potential of an analyte, which can
be used as an identification tool. In addition, because concentration
is proportional to current in a reversible,\ Nernstian system, the
concentration of an unknown solution can be determined by
generating a calibration curve of current vs. concentration. This
latter application is gaining interest in the field of cellular biology
where it is used to measure the concentrations of various chemicals
in the cells of organisms, including living ones.
****

Experiment-3
Aim of the Experiment:-

Reversible electrochemical cell :

To determine the thermodynamic properties of a reversible
electrochemical cell. (G)

Theory:
In the Daniell cell, which is made up of a zinc electrode in zinc
sulfate solution and a copper electrode in copper sulfate solution,
viz., Zn | ZnSO4 || CuSO4 | Cu, the two solutions are separated by
means of a porous partition, neither metal is attacked until the
electrodes are connected and a current is allowed to flow. The
extent of the chemical reaction occurring in such a cell is
proportional to the quantity of electricity passing, in accordance
with the requirements of Faraday's laws. Many, although not
necessarily all, cells in this second category are, however,
thermodynamically reversible cells, and the test of reversibility is
as follows. If the cell under consideration is connected to an
external source of E.M.P. which is adjusted so as exactly to balance
the E.M.F. of the cell, i.e. so that no current flows, there should be
no chemical change in the cell. If the external E.M.F. is decreased
by an infinitesimally small amount, current will flow from the cell
and a chemical change, proportional in extent to the quantity of
electricity passing, should take place. On the other hand, if the
external E.M.F. is increased by a small amount, the current should
pass in the opposite direction and the cell reaction should be
exactly reversed. The Daniel cell, mentioned above, satisfies these
requirements and it is consequently a reversible cell. It should be
noted that voltaic cells can only be expected to behave reversibly
when the currents passing are infinitesimally small and the system
is always virtually in equilibrium. If large currents flow,
concentration gradients arise on account of diffusion being
relatively slow, and the cell can no longer be regarded as being in a
state of equilibrium.
Reactions in Reversible Cells
10

It is of importance in many respects to know what is the reaction

occurring in a reversible cell.
The Daniel cell, for example, is
Zn | ZnS04 (aq.) || CuSO4 (aq.) | Cu
Taking the left-hand electrode as the electron source, i.e., the E.M.F.
as stated is positive, the reaction here is
Zn = Zn++ + 2eWhile at the right-hand electrode the electrons are removed by the
process
Cu++ + 2e- = Cu
The complete reaction is thus
Zn + Cu++ = Zn++ + Cu
Free Energy and Heat Changes in Reversible Cells
Since the quantitative consequences of the second law of
thermodynamics are mainly applicable to reversible processes, the
study of reversible cells is of particular importance because it is
possible to apply thermodynamic methods to the results. If the
E.M.F. of a voltaic cell is E volts, and the process taking place in it is
accompanied by the passage of n faradays, i.e., nF coulombs,
where F represents 96,500 coulombs, the work done by the system
in the cell is nFE volt-coulombs or joules. If the cell is a reversible
one, this work represents maximum work and since electrical work
does not involve mechanical work resulting from a volume change,
it may be taken as equal to the change of free energy
accompanying the cell reaction. The increase of free energy of a
process is equal to the reversible net work, i.e., excluding
mechanical work, done on the system, and hence it follows that
G = - nFE
where G is the increase of free energy for the process taking
place in the cell under consideration.

11

Procedure:1. An electrochemical cell i.e. a Daniel cell is prepared with Zn

electrodes and Cu-electrodes with their respective solutions ZnSO 4
and CuSO4 is made.
2. Zn electrodes are dipped in ZnSO 4 solution and Cu-electrodes are
dipped in CuSO4 solution, the two half-cells are connected by a salt
bridge, which consists of KCl ions and agar-agar gel. The reference
electrode used here is saturated calomel electrode.
3. The electrodes are connected by wires to a voltmeter and an
ammeter which measures the external voltage and the current
through the circuit respectively. The external voltage is supplied by
the potentiostat.
4. At first when current is zero at the ammeter, we note the E ext by
the voltmeter reading.
5. Then we calculate the E0 of the overall cell, and by the Nernst
equation we calculate the ratio of activity co-efficients of Zn and Cu
(aZn and aCu).
6. By the formula of G = nFEext we calculate the thermodynamic
property G where F= 96500 coulombs.
7. Then the current is increased by an interval of 0.01 mV which is
a very small value results in increase in E ext and chemical change
takes place.
8. We increase the current 5 times by an amount of 0.01 mV and by
each increase we note the values of Eext, E=0, (aZn/aCu) and G.
9. We decrease the current from 0.05mV to 0.00mV.
10. Again we decrease the amount of current by 0.01mV 5 times
and note down the values of Eext, E=0, (aZn/aCu) and G.

12

Observations:I (mA)

E0 (mV)

Eext
(mV)

aZn / aCu

G (kJ)

0.00
0.01
0.02
0.03
0.04
0.05
-0.01
-0.02
-0.03
-0.04
-0.05

1100
1100
1100
1100
1100
1100
1100
1100
1100
1100
1100

1068
1083
1098
1112
1127
1143
1054
1039
1024
1009
994

12.15
3.76
1.17
0.21
0.12
0.03
36.25
116.89
376.94
1215.47
3919.41

-206.0
-208.6
-211.5
-214.2
-217.1
-220.1
-203.0
-200.1
-197.2
-194.3
-191.4

Calculations:
Cathodic half cell: Zn = Zn++ + 2eEocathode= -0.76V
Anodic half cell: Cu++ + 2e- = Cu Eoanode=+0.34V
Overall reaction:
Zn + Cu++ = Zn++ + Cu
Eo overall= Eocathode - Eoanode = 0.34-(-0.76) = 1.1V = 1100mV
Nernst Equation:
Eext= Eo overall (2.303RT/nF) log(aZn/aCu)
where R= 8.314 J/ mol-k , T= 298K , n=2 , F=96500 coulomb
Free Energy (G):
13

G= nFEext

Conclusion:
As we increase the current from 0.00A to 0.05A we see that G
becomes more negative which indicates the chemical change,
proportional in extent to the quantity of electricity passing, should
take place.
As we decrease the current (applying the current in opposite
direction) from 0.00A to -0.05A we see that G becomes less
negative which indicates that the chemical change gets reversed in
direction therefore the cell behaves as a reversible electrochemical
cell.

Precautions:
1. Care is taken to ensure that the electrodes do not touch the
glass-walls as it might lead to erroneous results.
2. Care is taken to avoid any parallax.
****

14

Experiment-4
Aim of the experiment:-

Effect of Organic Chemicals

Corrosion of Mild Steel

on

To get potential vs current Graph by adding various chemicals

Apparatus:Beaker, glass rod, voltmeter, ammeter, salt bridge, saturated

calomel electrode.

Chemicals:3.5% NaCl Solution, p-Anisidine, Dimethyl Digol

Theory:The use of corrosion inhibitor is one of the most effective measures

for protecting metal surfaces against corrosion in acid
environments. The corrosion of iron and mild steel (MS) is a
fundamental academic and industrial concern that has received a
considerable amount of attention. A study of the mechanism of the
action of corrosion inhibitors has relevance both from the point of
view of the search for new inhibitors and also for their effective use.
Acid solutions are very commonly used for removal of undesired
scales and rust in many industries. To control corrosion of metals,
organic inhibitors are used since many years. In recent times,
organic inhibitors are generally used to protect the metal from
corrosion by forming a barrier film on the metal surface. Their
effectiveness is related to the chemical composition, their
molecular structure, and their affinities to get adsorbed on the
metal surface. The addition of corrosion inhibitors effectively
secures the metal against an acid attack. Inhibitors are used in
these processes to control metal dissolution and, during past
15

decade many organic inhibitors have been studied in different

media.
The mechanism of their action can be different, depending on the
metal, the medium and the structure of the inhibitor. One possible
mechanism is the adsorption of the inhibitor, which blocks the
metal surface and thus does not permit the corrosion process to
take place. Organic compounds containing electronegative
functional groups and -electrons in conjugated double or triple
bonds generally exhibit good inhibitive properties by supplying
electrons via -orbitals. Specific interaction between functional
groups and the metal surface and heteroatoms like N, O and S
plays an important role in inhibition due to the free electron pairs
they possess. When both these features combine, increased
inhibition can be observed.

Procedure:At first we add 3.5% NaCl solution and stirred it and note the
current and potential.
Then we add p-Anisidine and Dimethyl Digol respectively and note
the corresponding current and potential in both the cases.

Results:Current (I) (mA)

E(mV)

-900
-880
-860
-840
-820
-800
-780
-760
-740
-720
-700
-680

Adding 3.5%
solution
-12.3
-9.86
-7.23
-4.08
-2.98
-0.87
1.09
3.2
4.6
6.4
8.3
10

Nacl Adding
p-Anisidine
-10.8
-8.36
-8.5
-5.9
-3.76
-2.18
-0.13
1.3
2.7
5.1
6.5
8.2

Adding
Dimethyl digol
-19.4
-16.48
-13.46
-10.44
-7.95
-5.45
-2.72
-1.39
1.22
2.16
3.75
4.22
16

From the above data the following graph we get

****

17

Experiment-5
Aim of the Experiment:-

Conductometric Titration
To determine the equivalence point of HCl with N/10 NaOH

Theory:
Conductometric titration is a type of titration in which the
electrolytic conductivity of the reaction mixture is continuously
monitored as one reactant is added. The equivalence point is the
point at which the conductivity undergoes a sudden change.
Marked increases or decrease in conductance are associated with
the changing concentrations of the two most highly conducting ions
the hydrogen and hydroxyl ions.
As the titration progresses, the protons are neutralized to form
water by the addition of NaOH. For each amount of NaOH added
equivalent amount of hydrogen ions is removed. Effectively, the
mobile H+ cation is replaced by the less-mobile Na+ ion, and the
conductivity of the titrated solution as well as the measured
conductance of the cell fall. This continues until the equivalence
point is reached, at which one obtains a solution of sodium chloride,
NaCl. If more base is added, an increase in conductivity or
conductance is observed, since more ions Na+ and OH- are being
added and the neutralization reaction no longer removes an
appreciable amount of H+. Consequently, in the titration of a
strong acid with a strong base, the conductance has a minimum at
the equivalence point.
The conductometric titration curve is a plot of the measured
conductance or conductivity values as a function of the volume of
the NaOH solution added. The titration curve can be used to
graphically determine the equivalence point.
The equation for the reaction in this experiment is:
NaOH (aq) + HCl (aq) = NaCl (l) + H2O (l)
18

The net ionic equation is:

Na+ (aq) + OH- (aq) + H+ (aq) + Cl- (aq) = NaCl (l) + H2O (l)

Procedure:1. The conductivity meter is calibrated.

2. 25 ml of given HCl is pipetted out in a clean beaker and then it is
make up to 100 ml by adding 50 ml distilled water.
3. Now, the conductivity cell is immersed in the beaker and and the
initial conductance of the solution is taken by stirring the solution
and keeping it constant.
4. Then, 2 ml portions of NaOH is added from the burette and
stirred well. The conductance of the solution for each addition is to
be noted.
5. The conductance of the solution decreases till the equivalence
point of strong acid is observed.
6. After the equivalence point, on continuing the addition of NaOH
there will be a small raise in conductance values till the end point
of the acid is reached.
7. After that, the conductivity values increases suddenly due to the
conductance of OH ions.
8. A graph is plotted with respect to the volume of NaOH consumed
versus corrected conductance. From the intersection point on the
graph we obtain the equivalence point of the acid-base
combination.
9. From known solution, we can calculate the strength of HCl.

19

Observations:Strength of NaOHN/10
Volume of HCl=25ml
Volume of NaOH added(ml)
0
2
4
6
8
10
12
14
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
38
40
42
44

Conductance (S)

30
25
22
19
17
14
13
12
10
9
9
8
8
7
6
5
5
4
4
3
3
4
5
5
6
6
7
7
8
8
9
9
10
20

46
48
50

12
13
15

Calculations:
At equivalence point,
V1S1 = V2S2
=> S1 = V2S2/V1
where,
V1= Volume of HCl =25 ml
V2=Volume of NaOH at equivalence point
S2= Strength of NaOH = 0.1 N
S1=Strength of HCl
21

Results:
1. Strength of NaOH solution = 0.1 N
2. Strength of acid HCl = 0.11 N

Precautions:
1. Care is taken to ensure that the electrodes do not touch the
glass-walls as it might lead to erroneous results.
2. Care is taken to avoid any parallax error whilst recording the
readings from the conductance meter.
****

22

Experiment-6
Aim of the Experiment:-

Pourbaix Diagram
To plot the e-pH diagram of stainless steel

Theory:
Pourbaix diagram, also known as a potential/pH diagram, EHpH diagram or a pE/pH diagram, maps out possible stable
(equilibrium) phases of an aqueous electrochemical system.
Predominant ion boundaries are represented by lines. As such a
Pourbaix diagram can be read much like a standard phase
diagram with a different set of axes. Similarly to phase diagrams,
they do not allow for reaction rate or kinetic effects.
Under certain conditions, when a metal or alloy is exposed to an
aqueous solution with a concentration of inorganic/organic mixture,
corrosion phenomena occur at a corresponding degree. During
corrosion, some metallic phases dissolve, the metal or alloy surface
gets damaged and some secondary solid phases form at the solidliquid interfaces (such as oxides, hydroxides, silicates, sulphides,
sulphates, carbonates, nitrates, phosphates, borates, or halides).
Such corrosive chemical or electrochemical reactions can be
studied by means of the so-called Pourbaix diagrams if the
reactions reach their equllibrium states. The speciation and
partition in the aqueous solution and the interacting phases depend
not only on pH and Eh, but also on other factors such as the bulk
composition, temperature and pressure in the system. The
interacting phases may be gas mixtures, stoichiometric solids or
solid solutions. A Pourbaix diagram is divided in regions of
immunity, corrosion and passivity. These regions provide
information about the stability of a particular metal or alloy in a
specific aqueous electrochemical environment under certain pH, E H,
pressure and temperature conditions.

23

Fig. 1 .E-pH diagram of stainless steel

Apparatus
pH meter,beaker,saturated calomel electrode,multimeter .

Chemicals Used
NaOH solution,HCl solution

Procedure:1.The metal surface in contact with the working solution of sodium

hydroxide is polished.
2.The pH is noted for each step wise addition of sodium hydroxide
by using ph meter.Here graphite is used as counter electrode and
standard calomel electrode as reference electrode.
3.At each step the corresponding voltage is noted from the
multimeter.

24

Observations:pH
1.5
1.6
1.7
1.8
2
2.1
2.2
2.7
3.5
3.9
4.2
4.7
5.7
6
6
6
6.3
6.3
6.8
7
7.3
7.3
7.9
8.1
8.5
8.7
8.9
9.1
9.5
9.8
10.2
10.3
10.4
10.7
10.8
10.9

E
-606
-604
-603
-614
-628
-628
-623
-620
-619
-615
-612
-605
-606
-610
-608
-605
-603
-599
-596
-584
-555
-577
-608
-609
-615
-607
-605
-604
-604
-604
-602
-600
-594
-593
-593
-591

Results:25

Based on the readings obtained from the multimeter,we plot the EpH diagram.

Precautions:
1.Mutlimeter readings should be taken using an approximate mean
of the readings since fluctuations occur often.
2. When testing for acidic region of the pH scale,fresh solution
should be used and acid added.
****

26

Experiment-7
Aim of the Experiment:

Pit Density
To find pit density along the given area of stainless steel sample .

Theory:
Pitting corrosion, or pitting, is a form of localized corrosion that
leads to the creation of small holes in the metal. The driving power
for pitting corrosion is the depassivation of a small area of the
specimen, which becomes anodic while an unknown but potentially
vast area becomes cathodic, leading to very localized galvanic
corrosion. The corrosion penetrates the mass of the metal, with
limited diffusion of ions. The mechanism of pitting corrosion is
probably the same as crevice corrosion.
Mechanism
Pitting can be separated into two different regions, namely pit
initiation and pit growth. The growth mechanism is reasonably well
understood, while initiation mechanism is not very clear.
Pit Initiation
Pit initiation is not well understood. Pit initiation time can vary from
very short, days, to very long times, many years. Small changes in
conditions can make the difference in whether pits occur or not.
There are many mechanisms of pit initiation. The initiation
mechanism could be metal specific and history dependent in some
cases. In other situations a general type of pit initiation mechanism
may be invoked. Most mechanisms involve a breakdown of the
passive layer on a metal. The passive layer is thought to be a
complicated layer on the surface of a metal. It is a layer which is 30
to 100 Angstroms thick. As an atom is only about 2 Angstroms in
diameter, then a passive layer is only about 15 to 50 atoms thick.
Experimentally this is very difficult to examine, especially in pitting
27

investigations when the experimentalist does not know which site is

going to pit.
The passive layer is thought to be a two phase type of structure
with the side nearest the metal a crystalline phase while the layer
nearest the solution side is thought to be an amorphous mixture of
metal ions and hydroxyl ions.
Initiation Mechanisms
1. Defect Theory
Early investigators suspected that defects in the film broke down.
The film defects were related to metal defects such as grain
boundaries or slip steps due to dislocations emerging form the
surfaces. These sites would be local anodes and initiate breakdown
as the film probably was not fully formed over these local
anomalies. Unfortunately, although some materials show a
relationship between pits and defects, it is not a general rule.
2. Chloride Ion Dissolution
Many metal chlorides are soluble in water. One theory used this fact
to suggest that at the solution/passive layer interface the chloride
ion replaced the hydroxyl ion to form a metal chloride that
dissolved. Another chloride ion at the same location then dissolved
some more of the passive layer until the bare metal was exposed.
Further chloride ion dissolution would then form a pit into the
metal. This mechanism predicts that once a pit forms it will
continue to grow. Unfortunately, some pits cease to grow.
Pit Growth
From a mechanistic point of view, the growth of a pit can be
regarded as similar to the corrosion process in a crevice, covered in
the previous section. The exposed surface outside the growing pit is
cathodically protected by supporting the reduction of oxygen to
hydroxyl ion reaction:O2 + 2H2O + 4e- = 4(OH-)
As this cathodically protects the region outside the pit, the metal
dissolution region cannot spread laterally across the surface. In
28

addition the large cathodic surface can maintain this reaction and
form a large cathode to small anode ratio which will accelerate the
anodic reaction.
Within the pit, which is regarded as a small hemisphere at this
stage, the metal dissolution reaction is taking place. This is the
general anodic reaction of:M = Mz+ + zeHowever, it is the only reaction within the pit and results in an
electrical imbalance again which attracts negatively charge ions,
usually chloride ions.
The autocatalytic reaction to form hydrochloric acid in the pit is
initiated and continues:Mn+ + Cl- + zH2O = M(OH)z + z(H+Cl-)
Pitting, like crevice corrosion, is an autocatalytic reaction once it is
started and the pH decreases while chloride ion concentration
increases inside the pit.

Procedure:1. A stainless steel sample is taken and the surface of the

sample is thoroughly polished.

2. It is dipped in a solution containing 1 N H2SO4 and 0.3 N NaCl

for a designated time.

3. The surface is observed under the optical microscope and the

total number of pits on the surface are calculated.

4. The procedure is repeated with a similar sample for a different

time interval

Observations:Length of the sample- 2.4 cm.

29

Width of the sample- 0.3 cm.

Area= 0.75 cm2.
Time interval=5 seconds
Total number of pits=122
Pit density = 163 pits/cm2
Time interval = 15 seconds
Total number of pits- 187.
Pit Density= 250 pits/cm2.
Time interval= 20 seconds
Total number of pits= 225
Pit density=300 pits/cm2
Time interval = 30 seconds
Total number of pits = 240
Pit density=320 pits/cm

Precautions:
1. Care is taken to ensure that the electrodes do not touch the
glass-walls as it might lead to erroneous results.
2. Care is taken to avoid any parallax error.
3. The pit density doesnt increase after a specific time interval as
new pits stop forming and the initiated pits grow in depth.
****

30

Experiment-8
Aim of the Experiment:-

Pitting corrosion
Measurement of the pitting potential, passivity breakdown
potential through potentiodynamic polarization technique

Theory:
Pitting Corrosion:- Pitting corrosion is a localized form of
corrosion by which cavities or "holes" are produced in the material.
Pitting is considered to be more dangerous than uniform corrosion
damage because it is more difficult to detect, predict and design
against. Corrosion products often cover the pits. A small, narrow pit
with minimal overall metal loss can lead to the failure of an entire
engineering system. Pitting corrosion, which, for example, is almost
a common denominator of all types of localized corrosion attack,
may assume different shapes. Pitting corrosion can produce pits
with their mouth open (uncovered) or covered with a semipermeable membrane of corrosion products. Pits can be either
hemispherical or cup-shaped.
Pitting is initiated by:
a. Localized chemical or mechanical damage to the protective
oxide film; water chemistry factors which can cause
breakdown of a passive film are acidity, low dissolved oxygen
concentrations (which tend to render a protective oxide film
less stable) and high concentrations of chloride (as in
seawater).

b. Localized damage to, or poor application of, a protective

coating. c. The presence of non-uniformities in the metal
structure of the component, e.g. nonmetallic inclusions.
31

Theoretically, a local cell that leads to the initiation of a pit can be

caused by an abnormal anodic site surrounded by normal surface
which acts as a cathode, or by the presence of an abnormal
cathodic site surrounded by a normal surface in which a pit will
have disappeared due to corrosion.
In the second case, post-examination should reveal the local
cathode, since it will remain impervious to the corrosion attack as
in the picture of an aluminium specimen shown on the right. Most
cases of pitting are believed to be caused by local cathodic sites in
an otherwise normal surface.
Apart from the localized loss of thickness, corrosion pits can also be
harmful by acting as stress risers. Fatigue and stress corrosion
cracking may initiate at the base of corrosion pits. One pit in a large
system can be enough to produce the catastrophic failure of that
system

Procedure:1. The specimen is ground and polished to remove any surface

indulations and to obtain a smooth surface.
2. A part of the specimen surface is wrapped in Teflon and the
sample is then immersed in the solution.
3. The corrosion process is initiated from the Gamry instrument and
the graph is plotted in the software.

Observations:-

32

Precautions:
1. Care is taken to ensure that the electrodes do not touch the
glass-walls as it might lead to erroneous results.
2. Care is taken to avoid any parallax error.
3. The surface should be polished smooth without any surface
undulations or pits prior to experiment.
****

33

Experiment-9
Aim of the Experiment:Tafel Extrapolation Method :
Polarisation measurement of corrosion rate by galvano-static
process

Theory:
Tafel Extrapolation Method
This technique uses data obtained from cathodic and anodic
polarization measurements. Cathodic data are preferred, since
these are easier to measure experimentally.The total anodic and
cathodic polarization curves corresponding to hydrogen evolution
and metal dissolution and are superimposed as dotted lines. At
relatively high-applied current densities the applied current density
and that corresponding to hydrogen evolution have become
virtually identical. To determine the corrosion rate from such
polarization measurements, the Tafel region is extrapolated to the
corrosion potential.
At the corrosion potential, the rate of hydrogen evolution is equal to
the rate of metal dissolution, and this point corresponds to the
corrosion rate of the system expressed in terms of current density.
Tafel constants must be calculated from both the anodic and
cathodic portions of the Tafel Plot. These measurements may be
complicated by two interfering phenomena: concentration
polarization and resistance drop effects.
Concentration polarization occurs when the reaction rate is so high
that the electro active species cannot reach the electrode surface
at a sufficient rapid rate and the reaction rate becomes diffusion
controlled.
Resistance drops across the solution can also cause nonlinear Tafel
behavior at high currents:

Procedure:34

1. The specimen is ground and polished to remove any surface

indulations and to obtain a smooth surface.
2. A part of the specimen surface is wrapped in Teflon and the
sample is then immersed in the solution.
3. The corrosion process is initiated by changing the current across
the potentiostat.
4. The corresponding potential to the current is recorded.
5. A curve was plotted with the current density along X-axis and
potential along Y-axis.
6. Tangents were drawn to the cathodic and anodic curve through
the 2nd observation point and the point of intersection is
extrapolated to both the axes.

Observations:-

Precautions:
1. Care is taken to ensure that the electrodes do not touch the
glass-walls as it might lead to erroneous results.
2. Care is taken to avoid any parallax error.
35

3. The tangent to the polarization curve is taken from the 2nd point
of both the cathodic and anodic curve because it is the best fit
data.
****

36

Experiment-10
Aim of the Experiment
Organic inhibitor:
Effect of organic inhibitor thiourea on mild steel in 1N HCl acid
solution

Theory:
Inhibitor is a chemical substance when added in small
concentration in a corrosive environmentretards the anodic or
cathodic or both the electrochemical reactions, accordingly it is
called anodic or cathodic or mixed inhibitor.
Types of inhibitorsi) passivators
ii) hydrogen poisons
iii)scavengers
iv)organic inhibitorsa) adsorption type inhibitors
b) vapour phase inhibitor
c) pickling inhibitor
Thio-urea is an organic compound which acts as pickling inhibitors.
Pickling is a process in which metal is dipped in acid bath to remove
scale oxide or clean rust.
Here thio-urea acts as a good inhibitor in pickling bath; they adsorb
on metal surface and increase hydrogen overvoltage and therefore
stops metal dissolution reactions preventing further corrosion.
Pickling inhibitors get adsorbed on the clean surface & increase the
hydrogen overvoltage so that the cathodic reactions are very much
retarded and some inhibitors also inhibit the anodic reactions as
well. Thus pickling inhibitors are cathodic or mixed inhibitors.

37

Mechanism
When charge on metal is zero, metal always gets adsorbed by a
layer of charge when metal is in an electrolyte.
-Inhibitors have to remove other ions that has already adsorbed on
the metal surface.
-Inhibitors are adsorbed on the metal surface as charge decreases,
so that the action of inhibitor gets easier.
The inhibitor forms a diffusion barrier layer over the surface of the
metal by adsorption, there by trying to separate the metallic
surface from the corrosive environment. Then they block either
anodic sites or cathodic sites or both. In this way they retard the
corrosion rate.

Observations:-

38

Results:
By studying graph, we see that for 1(N) HCl solution the corrosion
rate is higher than when thio-urea inhibitor is added.

Precautions:
1. Care is taken to ensure that the electrodes do not touch the
glass-walls as it might lead to erroneous results.
2. Care is taken to avoid any parallax error.
3. The surface of the specimen should be polished smooth without
any surface undulations or pits prior to experiment.
****

39

Experiment 11
Aim of the experiment:Cathodic
anode

protection

using

sacrificial

To cathodically protect a sample of steel using zinc as sacrificial

anode and approximate the average service life of the steel sample

Theory:
Cathodic protection prevents corrosion by converting all of the
anodic sites on the metal surface to cathodic sites of an
electrochemical cell by supplying electrical current from an
alternate source. This practise is also referred to as sacrificial
system, since the galvanic anodes sacrifice themselves to protect
the structural steel from corrosion. Cathodic protection addresses
protection in two ways. The first is passively by connecting a
sacrificial metal to the metal to be protected. This sacrificial anode
takes the corrosion on behalf of the structure (cathode), and is
therefore replaced as it oxidises and is depleted. The structure does
not corrode, only the desired sacrificial anode. Polarization of the
target structure is caused by the electron flow from the anode to
the cathode, so the two metals must have a good electrically
conductive contact. The driving force for the cathodic protection
current is the difference in electrode potential between the anode
and the cathode. There must be two other conditions existing
besides the anode and the cathode for the sacrificial anode method
to work. There must be a return current path for the electrons to
flow from the anode to the material it is protecting and an
electrolyte to convey the electrons. The second method of cathodic
protection utilizes impressed current to actively alter the electrical
properties of the metal to be protected from corrosion.
Sacrificial anodes are highly active metals that are created from a
metal alloy with a more negative electrochemical potential than the
metal it will be used to protect. Sacrificial anodes generally come in
three metals: magnesium, aluminium, and zinc. Magnesium has the
40

most negative electron potential of the three and is suitable for onshore pipelines where the electrolyte resistivity is higher.
Magnesium anodes are not suitable in sea-water, because low
solution resistivities allow rapid consumption of the anodes. Zinc
and aluminium are generally used in sea-water where the resistivity
is generally lower. Typical uses are for the hulls of ships and boats,
offshore pipelines and production platforms, in salt-water-cooled
marine engines, on small boat propellers and rudders, and for the
internal surface of storage tanks.

Experimental Set-up:
1. The experiment of sacrificial cathodic protection was
performed on a steel sample using zinc as sacrificial anode.
The steel sample can be considered as a hull of a ship.
2. In a small glass tumbler containing an electrolyte having
composition of sea-water(3.5% NaCl) is taken.

3. Both steel and zinc plate are partially dipped in the

electrolyte. A Cu/CuSO4 reference electrode is used to measure
the potential across half-cell formed by steel.

4. 4. A saturated calomel electrode is used in a similar way

across zinc.

5. Two multimeters are connected across the reference

electrodes and half-cells to record the potential across them.
Another multimeter is connected across the electrochemical
cell formed by zinc and steel which measures the amount of
current flow from cathode to anode.

6. The current flow and the potential across anode and cathode
are recorded at intervals until they reach a steady value.
41

Observations:Impressed
current(I)

Esteel

Ezinc

0
-12.1
-10
-8.9
-8.5
-8.2
-7.9
-7.7
-7.6
-7.4
-7.3
-7.2
-7
-6.9
-6.8
-6.7
-6.7
-6.5
-6.4
-6.3
-6.1
-6
-5.9
-5.9
-5.8
-5.7
-5.7
-5.7
-5.6
-5.6
-5.6

-697
-980
-997
-1002
-1005
-1009
-1010
-1012
-1013
-1015
-1016
-1017
-1018
-1019
-1021
-1021
-1022
-1024
-1025
-1026
-1028
-1029
-1030
-1031
-1032
-1032
-1033
-1033
-1034
-1034
-1035

1106
973
983
990
995
998
1001
1003
1005
1007
1008
1010
1011
1012
1014
1015
1017
1018
1020
1020
1024
1025
1026
1027
1028
1029
1030
1033
1030
1031
1032
42

-5.5
-5.5
-5.4
-5.4
-5.4
-5.4

-1035
-1036
-1036
-1036
-1036
-1036

1033
1033
1034
1035
1036
1036

Zinc(Zn)

Steel

Calculations :Resistivity of sea-water()= 45 ohm-cm

Submerged portions :
Zinc :
Length(L)=2.1
Width(W)=2.1cm
Thickness(T)=0.3cm
Steel :
Length=20.3cm
Width=1.7cm
Thickness=0.5cm
Area of steel submerged = 70.72 cm2
Area of zinc submerged = 10.08 cm2
Current density of steel in sea water= 0.05 mA cm -2
Overall current demand = (70.72*0.05) = 3.536 mA

cm

Now,
43

Resistance of the sacrificial anode = 15/(L+0.8W+0.8T)

= 167.9
Iohm=|( Esteel Ezinc)|/R = 10.54 mA
Since Iohm is bigger than the current demand, hence the zinc plate
can act as the sacrificial anode.
Assuming that the submerged zinc is completely used to protect
the steel,
Volume of sacrificial anode = (2.1*2.1*0.3) cc = 1.323 cc
Density = 71 gm/cc
Hence, Mass of sacrificial anode necessary = (71*1.323) = 93.93
gm
SINCE THE DIMENSIONS OF THE SACP ARE FIXED THE EFFICIENCY
BE MULTIPLIED TO THIS AND NOT DIVIDED
Efficiency of zinc() =90%
Amount of zinc present within that 93.93 = 93.93*.9=84.537 gm
Let the service life of the steel specimen be x hours
Now,
1000 gm of zinc can produce 810 A-hr
Thus, 84.537 gm of zinc can produce 68.475 A-hr
But, Current supplied over the entire service life = (3.536*10 -3*x) Ahr
Thus equating, we get, x= 2.21 years
So, the probable service life of the steel specimen would be 2.21
years

Results:Thus,the purpose of the experiment is served and the service life of

the sample is about 2.21 years.
Conductivity of the used sample solution=45 moh-cm

Precautions:1.The multimeter terminals should be connected properly so as to

observe steady values of current and voltages.
44

2.Proper circuit should be made in accordance with the experiment.

****

45

Experiment-12
Aim of the Experiment:-

Crevice Corrosion
To find the crevice corrosion rate & generate the polarisation
curves showing the nature of crevice corrosion.

Theory:
Crevice corrosion is a form of localized attack that occurs frequently
on metals exposed to stagnant solutions within shielded areas such
as holes, gaskets, lap joints and crevices under bolts. This form of
corrosion is usually very difficult to detect, predict and design
against due to the size and locations of the corroding crevice. It can
also be thought of as a galvanic process that occurs between
different areas of an identical metal galvanic couple immersed in
an electrolyte. This form of corrosion starts close to the crevice
mouth and becomes more widespread, progressively moving to the
interior of the material throughout the period of exposure to the
aggressive solution. Materials with high corrosion resistance are
usually the most vulnerable to this form of corrosion. Well known
examples of susceptible metals are stainless steel alloys, nickel,
titanium and aluminium.
Crevice corrosion is encountered particularly in metals and alloys
which owe their resistance to the stability of a passive film, since
these films are unstable in the presence of high concentrations of
Cl-and H+ ions.
Mechanism
The general conditions for crevice corrosion include a stagnant
solution and a gap between two surfaces, one of which is metal, of
the order of 1/100th of an inch. Initially, the usual anodic and
cathodic reactions occur over the surface of the metal.
The general anodic reaction is:M = Mz+ + ze46

The general cathodic reaction is :O2- + 2H2O + 4e- = 4(OH-)

These initially occur over the whole surface. However a restriction
occurs in the crevice region such that the dissolved oxygen in the
crevice cannot easily be replaced. The region inside the crevice
cannot then support a cathodic reaction. It can still support an
anodic reaction of the type shown above. Outside the crevice
region the cathodic reaction proceeds but anodic reaction ceases as
it is concentrated in the crevice.
An electrical charge imbalance exists between the high positive
charge within the crevice from metal ions and the negative charge
outside the crevice. As a result, negative ions are attracted into the
crevice. The limit is the small size of the crevice. Chloride ions are
the favored ions to be attracted into the crevice. Associated with
the negative chloride ion is the very small positive hydrogen ion.
Both the chloride ion concentration and the hydrogen ion
concentration increase within the crevice. That is the pH in the
crevice decreases from values of 6 to 2 - 3. The effect of this
acidification is that the corrosion rate inside the crevice increases.
The chloride ion repeatedly reacts as shown below where the
chloride ion associates with the metal ion and the metal chloride
reacts with water to form metal hydroxide and hydrochloric acid.
The dissociated chloride ion can react again with the metal ion and
the series of reactions repeat. This is termed autocatalytic
behaviour. With the increase in anodic rate the cathodic reaction
of oxygen outside the crevice increases, further protecting the
region outside the crevice.
Reactions inside the crevice include:M+ + Cl- = M+ ClMz++ zCl- + zH2O =M(OH)z + z(H+Cl-)
H+Cl- = H+ + ClThis results in acidification within the crevice. Note that only the
region inside the crevice will be corroded. This is also important as
the anodic area is localized and small in comparison to the cathodic
area. The area effect then also comes into play with a small anode
carrying the same current as the cathode, leading to an increased
current detnsity and corrosion rate. So several factors are involved
47

in crevice corrosion, electrical charge imbalance, leading to a lower

pH and chloride ion concentration increase, and a very unfavorable
anode to cathode area ration all if which lead to an enhanced
anodic rate.

Procedure:1. A stainless steel sample is taken and the surface of the

sample is thoroughly polished.

2. It is dipped in a beaker containing tap water.

3. The corrosion process is initiated by the instrument and the

software plots the polarisation curve (Linear Sweep
Voltammetry)

Observations:-

48

Results:
Crevice corrosion starts suddenly as a critical value of current is
reached
****

49