Dept of Chemistry, CMR Institute of Technology BCHES102/202

MODULE 3: Corrosion and Electrode System

Corrosion Chemistry: Introduction, electrochemical theory of corrosion, types of

corrosion-differential metal and differential aeration. Corrosion control -galvanization, anodization and
sacrificial anode method. Corrosion Penetration Rate (CPR) –Introduction and numerical problem.

Electrode System: Introduction, types of electrodes. Ion selective electrode –definition, construction,
working and applications of glass electrode. Determination of pH using glass electrode. Reference
electrode -Introduction, calomel electrode –construction, working and applications of calomel electrode.
Concentration cell–Definition, construction and Numerical problems.

Analytical Techniques: Introduction, principle and instrumentation of Conductometry; its application in

the estimation of weak acid. Potentiometry; its application in the estimation of iron.

1
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

CORROSION:
Corrosion is defined as the destruction and consequent loss of metals through chemical or electrochemical
attack by the environment
Example: Rusting of iron

Corrosion classified as
• Dry corrosion (Chemical corrosion)
Corrosion of metal occurs by direct attack of atmospheric gases such as oxygen in the absence of
moisture to form a metal oxide layer.
• Wet corrosion (Electrochemical corrosion)
Wet corrosion occurs in the presence of an aqueous solution of electrolyte and atmospheric oxygen by
setting up tiny galvanic cells on the metal surfaces.
Electrochemical theory of corrosion

• According to electrochemical theory, the metal’s corrosion occurs due to the formation of anodic and
cathodic regions on the same metal surface in the presence of a conducting medium.
• At the anodic region oxidation reaction takes place and the metal gets corroded into ions liberating the
electrons. Consequently, metals undergo corrosion at the anodic region.
• At the cathodic region reduction reaction takes place. Metal ions in the cathodic region are unaffected
by the cathodic reaction.
• The electrons liberated at the anodic region migrate towards the cathodic region constituting corrosion
current.
• The metal ions liberated at the anode form a corrosion product somewhere between the anode and the
cathode.
• Corrosion of metal continues as long as both the anodic and cathodic reactions take place
simultaneously.

Anodic Reaction (Oxidation process):

At the anodic area metal undergoes oxidation with the release of electrons
Fe → Fe2+ + 2 e-

2
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Cathodic reaction (Reduction process)

The reaction at cathode (reduction reaction) depends on the nature of the environment: If the medium is
acidic,
(a) Liberation of Hydrogen: It takes place in the absence of oxygen
(i) In acidic medium
2 H+ + 2e-→ H2↑
(ii) Neutral / alkaline medium
2 H2O → 2 H+ + 2OH-
2 H+ + 2e- → H2
(b) Absorption of oxygen: It takes place in the presence of oxygen
(i) Acidic medium
O2 + 4 H+ + 4e- → 2 H2O
(ii) Alkaline medium

O2 + 2 H2O + 4e- → 4 OH-

Fe2+ ions combine with OH- ions near the cathodic area, forming insoluble ferrous hydroxide.
2 Fe2+ + 4 OH- → 2 Fe(OH)2
Ferrous hydroxide further combines with oxygen and water resulting hydrated ferric oxide.
4 Fe(OH)2 + O2 + 2H2O→ 2 [Fe2O3.3H2O] Yellow rust
In the presence of oxygen ferrous hydroxide is converted into magnetic oxide, known as black rust.
3 Fe(OH)2 + ½ O2 → Fe3O4.3H2O Black rust

Types of Corrosion:
A. Differential metal corrosion

• When two dissimilar metals are in contact with each other, the metal with lower reduction potential
undergoes oxidation whereas the metal with higher reduction potential undergoes reduction.
• The potential difference between the two metals is the cause for corrosion, higher the difference faster
is the rate of corrosion. The anodic metal undergoes corrosion and the cathodic metal is unaffected.
Let us consider a bimetallic sample of iron and copper as shown below.

3
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Case 1: The standard electrode potential of Fe is – 0.44 V which is less than that of Cu whose standard
electrode potential is 0.34 V. Hence in this case iron acts as anode and undergoes corrosion whereas copper
acts as cathode and remains unaffected.
Cell reactions:
During differential metal corrosion when Fe is in contact with Cu
At anode: Fe → Fe2+ + 2e-
At cathode: either hydrogen evolution or oxygen absorption
2 H+ + 2e- → H2↑
O2 + 2 H2O + 4e- → 4 OH-
B. Differential aeration corrosion

• It occurs when a metal surface is exposed to differential air (or) oxygen concentration.
• Part of the metal exposed to lower concentration of oxygen will have lower potential and therefore acts
as anode. This part undergoes corrosion.
• The other part of the metal exposed to higher concentration of oxygen acts as cathode and remains
unaffected.
• The difference in oxygen concentration produces a potential difference and causes corrosion current to
flow from cathode to anode.

B1. Water line corrosion

• This take place due to the formation of different oxygen concentration.

• The part of metal exposed to lower concentration of oxygen (dissolved oxygen) acts as anodic area
and undergoes corrosion.
• The part of the metal above the water level is exposed to higher concentration of oxygen acts as
cathodic are and remains unaffected.
• A distinct brown line is formed just below the water line due to the deposition of rust.
• Water line corrosion is observed usually in steel water tanks and ships floating in sea water for a long
time.

4
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Cell Reaction:
At the anode (less O2 concentration): Fe → Fe2+ + 2e-
At the cathode (more O2 concentration): O2 + 2 H2O + 4e- → 4 OH-
Fe2+ + 2OH- → Fe (OH)2
2Fe(OH)2+1/2O2+H2O → [Fe2O3. 3H2O] (rust)

B2. Pitting line corrosion

• It arises when a small portion of the metallic surface is covered by dust or scale or oil drops.
• The metal below the dust which is exposed to lower concentration of oxygen acts as anodic area.
• In the presence of suitable corrosive environment metal is lost at that place a pit is formed.
• The whole remaining part of the metal which is exposed to higher concentration of oxygen acts as
cathodic area and remains unaffected.
• Once a pit is formed corrosion occurs rapidly because of small anodic area (pit) and large cathodic
area.

Cell Reaction:
At the anode (less O2 concentration): Fe → Fe2+ + 2e-
At the cathode (more O2 concentration): O2 + 2 H2O + 4e- → 4 OH-
Fe2+ + 2OH- → Fe (OH)2

2Fe(OH)2+1/2O2+H2O → [Fe2O3. 3H2O] (rust)

5
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Corrosion control
A. Metal coating: Galvanization
Galvanization is a process of coating a base metal surface with Zinc metal.
Galvanization consists of hot dipping method which involves the following steps.
• The metal surface is washed with organic solvents to remove organic impurities such as oil and grease
present on it.
• Then metal surface is washed with dilute sulphuric acid (pickling) to remove rust and other inorganic
deposits.
• Then it is washed well with water and air dried.
• The metal is treated with mixture of aqueous solution ZnCl2 and NH4Cl which acts as flux and dried.
• The metal is then dipped in molten zinc maintained at 450°C.
• Excess zinc is released by passing the metal through rollers (or) by wiping.

B. Anodization
Anodizing is the process of oxidation of outer layer of metal to its metal oxide by electrolysis. Metal
oxide layer formed over the metal itself acts as protective layer.
In anodization of aluminium, clean and polished aluminium is taken as anode and immersed in an
electrolytic cell containing chromic acid. Inert electrode like lead is generally used as cathode. The anodic
oxide film formed on Al in bath as aluminium oxide, which is porous. The pores are finally sealed by dipping
in hot water to produce Al2O3 .H2O, which acts as a non-porous protective layer preventing corrosion.
Anode reaction: 2Al + 3H2O → Al2O3 + 6H+ +6e-
Cathode reaction: 6H+ + 6e- → 3H2
Advantages:
1. Anodized Al2O3 .H2O act as a protective layer, increasing the corrosion resistivity of the surface as it
prevents further oxidation.

6
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

2. They have harder and durability than normal aluminium.

3. The anodized surface shows good adhesion to paint and gives a colored appearance.

Applications:
• Anodization is used for aluminium pressure cookers and cooking pots.
• Aluminium window frames are anodized.
C. Cathodic protection
Cathodic protection is a method of protecting a metal or alloy from corrosion by converting it
completely into cathodic and no part of it is allowed to act as anode. Example:
Sacrificial anodic protection:

• The base metal is usually iron, copper or brass.

• The metal to be protected from corrosion is converted into cathode by connecting to a metal which is
anodic to it.
• Metals like Mg, Al and Zn are more active and hence are used as anodes.
• Since the anodic metals are sacrificed to protect the metal structure, the method is known as sacrificial
anode method.
• These metals being more active acts as anode undergo corrosion and supply electrons to the target
metal.
• In this way the protected metals acts as cathode.

Advantages:
• The method is simple.
• Low installation cost.
• Minimum maintenance cost.
• Does not require power supply.
Applications:
a) A magnesium block connected to a buried oil storage tank.
b) Mg bars are fixed to the sides of ocean going ships to act as sacrificial anodes.
c) Mg blocks are connected to buried pipe lines.

7
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Corrosion Penetration Rate (CPR)

The speed at which any metal in a specific environment deteriorates due to a chemical reaction in the
metal when it is exposed to a corrosive environment.

The CPR is calculated as follows:

CPR = (K x W) / (D x A x T)
Where, K = a constant (constant depends on unit used. when K = 534, the mpy will be used. when K = 87.6,
mm/yr will be used.
W = total weight lost (mo – m) [m = weight after corroded mo = weight before corroded]
T = time taken for the loss of metal
A = the surface area of the exposed metal

D = the metal density in g/cm³

Numerical problems

1) A thick steel sheet of area 400 cm2 is exposed to air near the ocean. After 1 year it was found to experience
a weight loss 375 g due to corrosion. If the density of the brass is 7.9 g/cm3

2) A piece of corroded plate was found in the submerged ocean vessel. It was estimated that the original area
of the plate was 6.4 inch2 and that approximately 2.2 kg had corroded away during the submersion for a period
of 10 years. Calculate CPR in terms of mpy and mm/y. Given density of iron = 7.9 g/cm 3, K (mpy)= 534,
K(mm/y)= 87.6.

Note:
Unit of CPR is mils per year (mpy) if W is in mg, A in Inch2, D in g/cm3, T in hrs and k value will be 534.
Unit of CPR is mm/yr if W is in mg, A in cm2, D in g/cm3, t in hrs and K value will be 87.6.
Conversion factor: 1 inch2 = 6.45 cm2

8
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

ELECTRODE SYSTEM:
Electrode: An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit.
Anode: Anode is an electrode where oxidation occurs.
Cathode: Cathode is an electrode where reduction process occurs.
Electrode potential: In electrochemistry, electrode potential is the electromotive force of a galvanic cell built
from a standard reference electrode and another electrode to be characterized.
The electrode potential of an electrochemical cell is represented by
Ecell = Ecathode- Eanode
Nernst equation:
𝟐.𝟑𝟎𝟑𝑹𝑻
Ecell = E° + log [M+n]
𝒏𝑭

Substitute the value of R = 8.134 J K-1mol-1, T = 298 K and F= 96500 C/mol

𝟎.𝟎𝟓𝟗𝟏
Ecell = E° + log [M+n]
𝒏

Different types of electrodes

1. Metal-Metal ion electrode: An electrode of this type consists of a metal dipped in a solution containing its
ions.
Example: Zn/Zn²+, Cu/Cu²+ etc
2. Metal-Metal salt ion electrode: These electrodes consist of a metal which is in contact with a sparingly
soluble salt of the same metal dipped in a solution containing an anion of the salt.
Example: Calomel (Hg/Hg₂Cl₂|CI-), Silver-Silver salt electrode (Ag/ AgCI / CI-)
3. Gas electrode: Gas electrode consists of a gas bubbling about an inert metal wire, immersed in a solution
containing ions to which the gas is reversible.
Example: Hydrogen electrode: Pt/H2(g) 1 atm /H+ (1M)
4. Oxidation-Reduction electrode: An oxidation-reduction electrode is a one in which the electrode potential
arises from the presence of oxidized and reduced forms of the same substance in solution. The potential
developed is picked up by an inert electrode like platinum.
Example: Pt|Fe²+, Fe³+ and Pt/Sn2+, Sn3+
5. Ion selective electrode: In ion selective electrode, a membrane is in contact with a solution, with which it
can exchange ions.
Example: Glass electrode.

9
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Ion selective electrode:

The ion-selective electrode generally consists of a membrane that selectively responds to a specific
ion in a mixture of ions in solutions that ignore all other ions and develop a potential.
Example: Glass electrode.
Working principle of Glass electrode
Cell construction

• The glass electrode consists of a glass tube made up of a special type of glass with high electrical
conductivity.
• The glass tube contain a solution of concentration C1 (0.1M HCl)
• An Ag-AgCl electrode is placed inside the solution which acts as internal reference electrode and also
serves for the external electrical contact.
• The glass electrode is dipped in unknown solution of concentration C2.
Cell representation
Ag / AgCl /HCl (0.1M) / unknown solution / Glass
Diagram

Working

• The potential developed across the membrane by the exchange of ions is known as boundary potential
Eb = E2– E1. Where E2 and E1 are the potential developed at outer and inner membrane respectively.
• Even when C1= C2 , E ≠ 0 a small potential is developed across the membrane, it is called as
asymmetric potential (Easy).
Therefore the boundary potential
Eb = E2 - E1
0.0591 0.0591
= (E° + 𝑛
log C2) - (E° + 𝑛
log C1)
0.0591 0.0591
= 𝑛
log C2 - 𝑛
log C1
0.0591 0.0591 1
= log C2 + log
𝑛 𝑛 𝐶1
10
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

0.0591 0.0591 1
= log C2 + L Where L = log
𝑛 𝑛 𝐶1

Here n=1, [C2] = [H+] ions in outer membrane, Then 𝐸𝑏 = L + 0.0591 log [H+]
Eb = L - 0.0591 pH Where pH= - log [H+]
The Glass electrode potential is given by EGlass = Eb + Easy+ EAg/AgCl
Substitute the value of Eb
𝐸𝐺 = L - 0.0591 pH + Easy+ EAg/AgCl
Consider L1 = L + Easy+ EAg/AgCl,
Therefore, EG = L1− 0.0591 pH
Determination of pH using glass electrode
The potential of a glass electrode depends on the concentration of H+ ions. Hence, pH of a solution can be
determined by using glass electrode and calomel electrode assembly.
The cell assembly is represented as:
Hg/Hg2Cl2/Cl- // solution of unknown pH / glass /0.1 M HCl / AgCl / Ag

Ecell is the difference between glass electrode potential EG and the calomel electrode potential Ecal.
Ecell = ECathode - EAnode
= EG - ECal
= L1− 0.0591 pH - ECal
𝐊−𝐄𝐜𝐞𝐥𝐥
pH = Where K is electrode assembly constant, K = L1-Ecal
𝟎.𝟎𝟓𝟗𝟏

11
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Reference Electrode:
A reference electrode is an electrode that has a stable and well-known electrode potential. This electrode is
used to determine the electrode potential of other electrodes.
Three are two types of reference electrodes
1. Primary reference electrode
Example: Standard hydrogen electrode
2. Secondary reference electrode
Example: Calomel electrode

Calomel electrode
Construction

• The calomel electrode consists of two glass tube.

• At the inside glass tube, there is a paste (calomel) of mercury and mercurous chloride (Hg2Cl2) at the
bottom of a narrow glass tube.
• Pure mercury is filled below the paste and connected with platinum wire for external electrical contact
• This narrow tube placed inside an outer glass tube filled with a saturated KCl solution.
Cell representation
The calomel electrode is represented as, Hg/ Hg2Cl2 / KCl

Diagram

Working
Calomel electrode behaves as anode or cathode depending upon the
nature of another electrode.
When it acts as anode, oxidation takes place. Thus, the half-cell reaction
is
2𝐻𝑔 + 2𝐶𝑙− → 𝐻𝑔2𝐶𝑙2 + 2𝑒−
When it acts as Cathode, reduction takes place. Thus, the half-cell reaction is
𝐻𝑔2𝐶𝑙2 + 2𝑒− →2𝐻𝑔 + 2𝐶𝑙−
The net cell reaction is, 𝐻𝑔2𝐶𝑙2 + 2𝑒− ↔ 2𝐻𝑔 + 2𝐶𝑙−
The electrode potential for calomel electrode is
0.0591 1
E = E° + log [Cl−]2
2

E = E° - 0.0591 log [Cl-] at 298K

• The calomel electrode potential is depending on the concentration of chloride ions in KCl.
12
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

• If the Concentration of chloride ions increases, the potential decreases and vice versa. (The potential
of calomel is inversely proportional to the concentration of chloride ions)

Applications of calomel electrode

1. It is used as a secondary reference electrode to measure single electrode potentials.
2. It is used in potentiometric analysis.
Concentration cell
Definition
The concentration cells consist of identical electrodes immersed in the solutions of the same
electrolytes but with varying concentrations. Potential difference arises due to difference in electrolyte
concentration.
Construction
There are three components
• Electrodes: The two electrodes are called the cathode (right
side) and the anode (left side). The anode loses electrons
through oxidation reaction. The cathode gains electrons
through reduction reaction.
• Salt Bridge: A salt bridge is a device used in an
electrochemical cell for connecting its oxidation and reduction
half cells. The main function of a salt bridge is to maintain the
electrical neutrality within the internal circuit. It consists of a
saturated solution of a salt such as KCl or NH4NO3.
• Voltmeter: The voltmeter is used to measure the cell potential of the cell.

Cell representation: Concentration cell is represented as,

Cu/Cu+2 (C1= 0.01M) || (C2= 0.1M) Cu+2/Cu
Working
Anode: Cu Cu+2 (C1) +2e-
Cathode: Cu+2 (C2) +2e- Cu
Net cell reaction: Cu+2 (C2) Cu+2 (C1)
The electrode potential for concentration cell is represented by
Ecell = ECathode - EAnode
0.0591 0.0591
=(E⁰Cathode - log C2) - (E⁰Anode - log C1)
𝑛 𝑛
13
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

In concentration cell, both electrodes are same, hence

0.0591 C2
Ecell = log C1 at 298K
𝑛

Now, Ecell will be positive only if C2 > C1.

Numerical problems
Q1. A concentration cell is constructed by dipping copper rods in 0.001M and 0.1 M copper sulphate
solutions. Calculate the EMF of cell at 298K.
Cell representation:
Cu/Cu+2 (C1= 0.001M) || (C2= 0.1M) Cu+2/Cu
Cell reactions:
Anode: Cu Cu+2 (C1) +2e-
Cathode: Cu+2 (C2) +2e- Cu
Net cell reaction: Cu+2 (C2 = 0.1M) Cu+2 (C1 = 0.001M)
0.0591 C2
Now, Ecell = log C1 at 298K
𝑛

0.0591 0.001
= log
2 0.1

= 0.0591 V
Q2. EMF of the cell Cu/CuSO4 // CuSO4/Cu is 0.0595V at 25°C. C1= 0.001M, C2 = X and n= 2. Find X
value?

Cell representation:
Cu/Cu+2 (C1= 0.001M) || (C2= x M) Cu+2/Cu
Cell reactions:
Anode: Cu Cu+2 (C1) +2e-
Cathode: Cu+2 (C2) +2e- Cu
Net cell reaction: Cu+2 (C2 = x M) Cu+2 (C1 = 0.001M)
0.0591 C2
Now, Ecell = log C1 at 298K
𝑛

0.0591 x
0.0595 = log 0.001
𝑛

x = 0.103 M
Q3. EMF of the cell Ag/AgNO3 // AgNO3/Ag is 0.8V at 25°C. C2= 0.2M, Find C1 =?
Cell representation:
Ag/Ag+ (C1= x M) || (C2= 0.2) Ag+/Ag
14
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Cell reactions:
Anode: Ag Ag+ (C1) +e-
Cathode: Ag+ (C2) +e- Ag
Net cell reaction: Ag+1 (C2 = 0.2M) Ag+ (C1 = x M)
0.0591 C2
Now, Ecell = log C1 at 298K
𝑛

0.0591 0.2
0.8 = log
1 C1

0.2 0.8
log = 0.0591
C1

0.2
log = 13.536
C1

0.2
= Antilog (13.536) = 3.4355 x 1013
C1

C1 = 5.83 x 10-15 M
Analytical Techniques:
Potentiometry; its application in the estimation of iron

Aim: Determination of the weight of ferrous ammonium sulphate and ferrous iron in the given solution by
potentiometric titration method.
Theory: In this titration the amount of substance in the solution is determined by measuring the emf between
two electrodes that are dipped into the solution. When the metal M is immersed in the solution containing its
own ions Mn+ ions, the electrode potential is given by Nernst equation,
𝟎.𝟎𝟓𝟗𝟏
Ecell = E° + log [M+n]
𝒏

From this equation the potential of the electrode is directly proportional to the concentration of the ionic
species present in the solution.
Instrumentation:
A potentiometer consists of an indicator electrode (e.g.: Platinum) and a saturated reference electrode (E.g.:
Calomel electrode), stirrer & potentiometer to measure the potential values.
EMF of the solution can be measured by combining the reference electrode with an indicator electrode. The
electrode which responds to the change in the concentration of the ion in the solution is called indicator
electrode & reference electrode is one whose potential is constant. A known volume of the analyte is taken in
beaker and its potential is measured. The titrant is added in increments of 0.5 ml and potential is measured
each time. Near the equivalence point there is a sharp increase in the potential. The end point is determined by
plotting change in potential against volume of the titrant.

15
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

Applications
1. Estimation of the concentration of the ionic species present in the given solution.
2. Coloured solution can also be titrated
3. Acid-base titration can also be done in this method.
4. In this method Oxidation-reduction titrations can also be carried out.
5. Precipitation reactions can also be carried out potentiometrically.
For example:
Procedure: Pipette out 25 cm3 of FAS solution into a 50 cm3 beaker. Add one test tube full of dil H2SO4.
Immerse Platinum. & calomel electrodes into the solution, & connect the electrodes to a potentiometer. Fill
the burette with K2Cr2O7 solution. Add K2Cr2O7 solution from the burette with increment of 0.5 cm3, stir well
and measure the potential after each addition. Continue the titration till the potential indicates a rapid jump
with a drop of titrant. Plot the graph of ΔE/ ΔV v/s vol. of K2Cr2O7.
Conductometry; its application in the estimation of weak acid

Theory

Electrolyte solution conducts current by the migration of ions under the influence of an electric field. This
experiment is based on Ohm’s law which states that the current’ I ‘ flow through conductor is directly
proportional to the applied potential, E and inversely to the resistance R of conductor.
E= I R
Specific conductance of an electrolyte solution is the conductance of the solution present between two parallel
electrodes of 1cm3 area of cross-section and 1cm apart.
Instrumentation
1. It consists of a platinum electrode each of unit area of cross-section placed unit distance a part.
2. The electrodes are dipped in the electrolyte solution taken in a beaker.
3. It is connected to a conductivity meter.
4. The titrant (NaOH) is added from a burette and solution is stirred.

16
 Dept of Chemistry, CMR Institute of Technology BCHES102/202

5. The conductance is measured after the addition of the titrant at intervals of 1.0 ml.

Application: Weak acid v/s Strong base (CH3COOH v/s NaOH)

Consider the titration of acetic acid against NaOH. The conductance of the acid will be initially low since
acetic acid is a weak electrolyte. When NaOH is added to the acid, the salt formed is highly ionized and the
conductance increases. On complete neutralization of the acid, further addition of base leads to an increase in
the number of mobile OH- ions.
Hence the conductance increases sharply.
CH3COOH+NaOH→CH3COONa+H2O
A plot of conductance against the volume of base added is shown in the figure. The point of intersection of
two curves gives the neutralization point.

17