Corrosion Engineering (Practical)

Name: Farwa Naeem Roll No: 16MME-S2-317

Semester: 6th Session: 2016-20

Date of Submission: 26/11/2019

Experiment No. 3 & 4

3. Understand the construction of the laboratory and field used reference electrodes and its
conversion as per ASTM G215.
4. Measuring the electrode potential in different aggressive medium with different reference
electrode and also construct the Galvanic series.
A. Nickle, copper, lead, steel, aluminum and zinc in simulated sea water with silver-silver
chloride reference electrode.
B. Nickle, copper, lead, steel, aluminum and zinc in soil with copper-copper sulphate
reference electrode.
C. Concrete with saturated copper-copper sulphate reference electrode.
D. Nickle, copper, lead, steel, aluminum and zinc in simulated sea water with silver-silver
chloride reference electrode.

Lab Instructor Signature: ________________

Grade/Marks: _______________
Figure 1: Single Electrode Potential (Reversible potential)

Figure 2: Irreversible Potential

Figure 3: Standard Hydrogen Electrode (SHE)

Experiment Title
Measuring the electrode potential in different aggressive medium with different reference
electrode and also construct the Galvanic series.
Objective
Aim of this experiment is to measure electrode potential of metals (Nickel, Copper, lead, Steel,
Aluminum and zinc) in different aggressive mediums with different reference electrodes and
construct galvanic series using data.
Principle
Electrode potential is measured by calculating the voltage difference between a metal in its
environment and an appropriate reference electrode by using a high impedance voltmeter.
Galvanic series is generated based on potential. Values of potential depend upon many factors
such as temperature, aeration, velocity of movement etc.
Background
Electrode Potentials
1. Reversible and Irreversible Potentials
The single electrode potential of a metal in an aqueous solution containing its own ions is
reversible potential. (as shown in Figure 1)
While single electrode potential of a metal in an aqueous solution containing insufficient
concentration of its own ions is irreversible potential as in Figure 2. (Corrosion Cell)

2. Standard Electrode Potentials

Construction
Standard Electrode Potential (SHE) is Pt rode in acidic environment. Hydrogen ions in
acidic solution (Electrolyte) have unit activity (aH+ = 1) at 25℃ and 1 atm pressure. (as
shown in Figure 3)

Principle
Equilibrium reaction is;
2H+ (aq)+ 2e- ↔ H2 (g) ↑ Eo = 0V vs SHE
Platinum itself act as catalyst.

Uses
SHE is used for standard potentials measurement. We can also measure single electrode
potentials experimentally in a wide variety of electrochemical fields.
Figure 4: Copper-copper sulphate electrode (CCSE)
Hydrogen gas released is flammable, therefore SHE is not practicable in laboratories.
Alternatively, four reference electrodes are used. They are potable. But fail at high temperature.
1. Copper-Copper Sulphate Electrode (CSE) or (CCSE)
2. Silver-Silver Chloride Electrode (SSCE)
3. Saturated Calomel Electrode (SCE)
4. Mercury-Mercury Sulphate Electrode

3. Reference Electrodes
A standard electrode having fixed value of potential is called Reference electrode or Half-cell
electrode. Used to calculate the value of potential of electrode under observation.
In Reference electrodes four factors are observed:
1. Electrode reaction
2. Electrode (which metal)
3. Electrolyte (Concentration)
4. Ionic conduction/ ionic plug/ frit/ salt bridge.
Types of Reference Electrodes
They are of two types.
1. Permanent Electrode.
2. Non-Permanent/ Potable Electrode (Copper-Copper Sulphate Electrode, Silver-Silver
Chloride Electrode, Saturated Calomel Electrode, Mercury-Mercury Sulphate Electrode)
Copper–Copper Sulphate reference Electrode (CCSRE)
Construction
The copper–copper sulfate reference electrode consists of metallic copper immersed in saturated
copper sulphate. The commercial reference electrode is a plastic tube holding the copper rod and
saturated solution of copper sulphate. A porous plug on one end is in contact with copper
sulphate electrolyte and ultimately with the earth is made. It is easily recharged when it becomes
contaminated. The copper rod protrudes out of the tube as shown in figure 4 The two standard
tips available are the Flat Tip and the Pointed Tip. Both the Flat and Pointed tips are made to
maximize the total surface area of the tip to ensure good contact area with the electrolyte. There
is no performance difference between the two types of tip. The Flat tip may be more versatile, as
a flat surface can be useful on a variety of electrolytes, such as soils, liquids and concrete.
A voltmeter negative lead is connected to the copper rod. The half-cell reaction is
Cu2+(aq) + 2e- → Cu(s) Eo red= 0.342V vs SHE
E Cu/Cu+2 = E Cu/Cu+2 + 0.059 log 10 aCu+2
Figure 5: Silver-silver chloride electrode (SSCE)

Figure 6: Saturated calomel electrode (SCE)

The equilibrium of half-cell reaction of Copper–Copper Sulphate reference Electrode is
influenced by temperature only. Therefore, other factors do not alter its potential i.e. have
constant half-cell potential.
Service to reference electrode is recommended based upon use. If the reference electrode is used
frequently, more than once per week, the instrument should be serviced on a bi-monthly basis.
With less frequent use, service to the half cell on a biannual basis might be more appropriate. If
the cell is used only once or twice per year, it is recommended that the cell be stored dry, with no
water.
Silver-Silver Chloride reference electrode (SSCRE)
The silver – silver chloride reference electrode, can be prepared by dipping a silver wire into
molten silver chloride, while in the laboratory electroplating of silver wire by silver chloride is
done. Ag is made cathode while AgCl is anode in an electrochemical cell. Saturated KCl solution
is used as an electrolyte in silver-silver chloride reference electrode. All these are contained in a
small vessel, typically made of glass tubing. The internal electrolyte and the external electrolyte
are in ionic contact through a separator. This separator is eventually a small porous ceramic plug
sealing the end of the glass tube as shown in figure 5.
The equilibrium electrode potential is a function of the chloride concentration of the internal
electrolyte. When the silver – silver chloride electrode is immersed in a chloride solution, the
following equilibrium is established:
AgCl(s) + e- →Ag + Cl- Eored = 0.222V vs SHE
EAg/AgCl = EoAg/AgCl – 0.059 log10 aCl-
Like the calomel electrode, the potential is more active the higher the KCl concentration.
Saturated calomel reference electrode:
Construction

The saturated calomel reference electrode is extensively used standard reference electrode, in the
laboratory. The word calomel is the combination of Mercury and Mercurius chloride i.e. Hg 2Cl2.
Is a liquid reference electrode because mercury is liquid at room temperature. It consists of a
small glass tube in which silver wire is placed. Wire is immersed in Hg over which black color
power of Hg2Cl2 is poured. One end of the glass tube is sealed by cotton plug. This whole
assembly is placed in another glass tube, which is sealed with the porous plug that is immersed in
a saturated KCl solution as shown in figure 6.

In the calomel half-cell the overall reaction is

Hg2Cl2 (s) + 2e- → 2Hg + 2Cl- Eo = 0.268V vs. SHE

Figure 7: Mercury-Mercury sulphate reference electrode

Figure 8: Cu-CuSO4 reference electrode

Mercury-Mercury sulphate reference electrode
Construction

The mercury-mercury sulphate electrode is used where a chloride free electrode is required. It is
especially used in experiments to do with lead–acid batteries. The electrode is usually
constructed from a platinum wire inserted into a mixture of Hg 2SO4 and liquid mercury, with an
electrolyte solution of H2SO4 / K2SO4 and porous ceramic frit acts as junction of electrode and
liquid as shown in figure 7. Half-cell reaction is

Hg2SO4 (s) + 2e- = 2Hg(s) + SO42-(aq.) E° = 0.660V vs. SHE

So the potential of electrode depends upon concentration of sulphate ions and temperature.

2.303 RT
E = E° - log [SO4-] 2
2F
The mercury-mercury sulphate electrode can operate on high temperatures of as much as 100
̊C.it is used in anodic protection and becomes inactive in only one use.

Standard for experiment

G 215 – 16, Standard guide for Electrode Potential Measurement

Experimental Procedure

A. Corrosion potential measurement of metals in soil with copper-copper sulphate

reference electrode and their galvanic series.
Reference Electrode Preparation
1. Remove either end of the electrode and fill with electrolyte i.e. Copper Sulfate.
2. Replace the end piece, making sure both ends are firmly screwed down for proper sealing. Do
not over tighten.
3. Shake electrode to obtain proper solution saturation.
Experimental work
 1. Copper/Copper Sulfate Reference Electrode was taken, vinyl protective cap from the
ceramic porous plug was removed and electrode is placed in the soil container containing
given metal samples to be tested as shown in figure 8.
2. Given samples (Nickle, copper, lead, steel, aluminum and zinc) already buried in
rectangular soil container are connected one by one with high impedance voltmeter to
measure their potential.
Observations
Electrolyte: Saturated Copper Sulfate Reference Electrode: Copper/copper
sulfate
Table 1: Electrode Potential of metal sample in soil

Sr. No. Metal sample Reduction Potential vs. CSE

Sat CuSO4
(mV)
1 Nickel -82
2 Lead -446
3 Zinc 940
4 Copper -167
5 Aluminum -658
6 Iron -484

Table 2: Galvanic Series

Galvanic series from anodic to cathodic
Aluminum
Iron
Lead
Copper
Nickel
Zinc
Figure 9: Corrosion potential measurement of metals in simulated sea water with silver-silver
chloride reference electrode (sea water)

3. The reference electrode connected with the black terminal of high impedance voltmeter
which act as anode and red terminal connect with metal sample which act as cathode.
4. Observe polarity and voltage.
5. Always replace the vinyl cover on the electrode after each usage to prevent moisture loss
in the ceramic plug.
Result
Al is most active (anodic) metal and Zn is most noble (cathodic) metal among given metals.
Discussion:
The galvanic series lists metals according to their electrical potential in an electrolyte. As
mentioned, metals that are anodic will corrode at a more rapid rate than passive or cathodic
metals. According to galvanic series from experimental readings, Al has the highest value of
negative reduction potential while Zn has less value of negative reduction potential as mention in
Table 2. But in reality, zinc is most active metal while copper is most noble metal so that Zn will
corrode more rapidly than other given metals according to the standard. To convert this potential
to a value on the scale in which the hydrogen electrode has a potential of zero, it is necessary to
add 0.318 volt to the potential that was measured, making it -0.641 volt vs. SHE. Human error
may be the cause.
B. Corrosion potential measurement of metals in simulated sea water with silver-silver
chloride reference electrode (sea water) and their galvanic series.

Experimental work
In this experiment Nickel, Lead, zinc, copper, aluminium and iron is immersed in simulated sea
water (3.5% NaCl). The Ag/AgCl reference electrode was kept at the corner of the simulated
seawater container, in which the black terminal was connected with the reference electrode and
red terminal was connected with the samples. Measured the electrode potential of all these
sample one by one using high impedance voltmeter. (Figure 9).
Result
Zn is most active (anodic) metal and copper is most noble (cathodic) metal among given metals.
Discussion
According to standard galvanic series trend from most active to most noble is Zn, Al, iron, Pb,
Ni and Cu. But galvanic series made from readings was different as mentioned in table 4, This
variation is due to human error and the voltmeter reading was not stable during performing the
experiment.

Observations
Electrolyte: sea water Reference Electrode: Silver-Silver Chloride
Table 3: Metals in sea water with reference to Silver-Silver Chloride

Sr. No. Metal sample Reduction Potential (mV) vs.

SSE seawater
1 Nickel -133
2 Lead -126
3 Zinc -140
4 Copper -136
5 Aluminum -144
6 Iron -120
Table 4: Galvanic Series
Galvanic series from anodic to cathodic
Aluminum
Zinc
Copper
Nickel
Lead
Iron
Figure 10: Corrosion potential measurement of concrete with saturated Cu-CuSO4 reference
electrode
Observations
Table 5: Potential of concrete vs CSE

Sr. no. Potential of concrete

1 -341
2 -358
3 -351
Potential of concrete = 350 mV vs. CSE
C. Corrosion potential measurement of concrete with saturated Cu-CuSO 4 reference
electrode.
Experimental work
A block of concrete containing iron rods was placed on table. A sponge was joined with
reference electrode (Cu-CuSO4). High impedance voltmeter was connected with reference
electrode and iron rod coming out of the block. Three readings were taken from different places
so get results with more accuracy. (Figure 10)

D. Corrosion potential measurement of metals in simulated sea water with silver-silver

chloride reference electrode (saturated KCl) and their galvanic series.
Experimental work
In this experiment Nickel, Lead, zinc, copper, aluminium and iron were placed by the side of
container containing sea water (3.5% NaCl). The Ag/AgCl reference electrode (Sat. KCL) was
immersed in sea water. The black terminal of high impedance voltmeter was connected with the
reference electrode and red terminal was connected with the samples. Measured the electrode
potential of all these sample one by one.
Discussion
The six different samples w.r.t. Ag/AgCl in saturated KCl were tested. The Table 7 show that,
the position of metals changed as compared to standard Galvanic series in simulated sea water.
According to standard, iron is more anodic as compared to lead. We can say this may happen
because of some error. Also nickel may be more passive than copper.

Observations
Electrolyte: sea water (external), Sat. KCL (internal)
Reference Electrode: Silver-Silver Chloride
Table 6: Metals in sea water with reference to Silver-Silver Chloride saturated KCl

Sr. No. Metal sample Reduction Potential vs. SSE

sat. KCl
(mV)
1 Nickel -182
2 Lead -362
3 Zinc -893
4 Copper -34
5 Aluminum -670
6 Iron -363

Table 7: Galvanic Series

Galvanic series from anodic to cathodic
Zinc
Aluminum
Iron
Lead
 Nickel
Copper

Table 8: Potential of Different metal w.r.t. different reference electrode

Sr. No. Metals E vs. CCSE in E vs. SSCE in E vs. SSCE in
soil sea water KCl
(mV) (mV) (mV)
1 Nickel -82 -133 -182
2 Lead -446 -126 -362
3 Zinc 940 -140 -893
4 Copper -167 -136 -34
5 Aluminum -658 -144 -670
6 Iron -484 -120 -363

Table 9: Standard galvanic series showing reduction half-cell potential by decreasing order of
potential

Half-cell reaction Eo red (V)

Cu+2 + 2e- → Cu 0.3402
Pb+2 + 2e- → Pb -0.1263
Ni+2 + 2e- → Ni -0.23
Fe+2 + 2e- → Fe -0.409
Zn+2 + 2e- → Zn -0.7628
Al+3 + 3e- → Al -1.706

References
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