Module 3: Corrosion and Electrode System

1. CORROSION or METAL CORROSION is defined as “the destruction or

deterioration of metals or alloys by the surrounding environment through
chemical or electrochemical reactions”.

Corrosion may occur either in dry environment or in aqueous medium.

Dry corrosion (Chemical corrosion): It occurs by direct attack of atmospheric gases

such as oxygen, hydrogen sulphide, halogens and sulphur dioxide on the metal
forming oxide layer (chemical reaction).

Wet corrosion (Electrochemical corrosion): Wet corrosion occurs in presence of

an aqueous solution of electrolyte and atmospheric oxygen by setting up of tiny
galvanic cells on the metal surface.

2. Electrochemical Theory of Corrosion

According to this theory, when a metal such as iron, is exposed to atmospheric air,
the following electrochemical changes occur gradually.

Air

Water film or moisture

(neutral)

anodic area Cathodic area

2+ - - -
Fe Fe + 2e O 2 + 2H2O + 4e 4OH
Iron rod

Fig. Rusting of iron

➢ Formation of galvanic cells: Anodic and cathodic areas are formed resulting in
minute galvanic cells.
➢ Anodic reactions: At the anodic area, oxidation takes place resulting in the
corrosion of iron.
2+ -
Fe Fe + 2e
➢ Cathodic reactions: The electrons flow from anodic to cathodic areas and cause
reduction. There are three possible ways in which the reduction can take place.
1) If the solution is aerated and almost neutral, oxygen is reduced in presence of
water to form OH- ions according to the equation.
- -
O2 + 2H2O + 4e 4 OH

2) If the solution is deaerated and almost neutral, water is reduced to H2 and OH.
3) If the solution is deaerated and almost acidic, the H+ ions are reduced to
H2 .

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 + -
2H2O 2 H + 2 OH
+ -
2 H + 2e H2
- -
2H2O + 2e H2 + 2 OH

The metal ions (formed at the anode) combine with the OH- ions to form the
metal hydroxide and finally the hydrated metal oxide (rust).
2+ -
2 Fe + 4 OH 2 Fe(OH) 2

4 Fe(OH) 2 + O2 + 2H 2O 2 (Fe 2O 3 .3H 2O)

Rust

4) If the solution is deaerated and almost acidic, the H+ ions are reduced to
H2

Ill effects of corrosion

Eventually, corrosives can cause damage to not only metal but the human digestive
tract, respiratory tract, eyes, and skin. The effects of corrosion can threaten our lives
largely.

3. Types of Electrochemical corrosion:

There are mainly two types of corrosion:

i) Differential metal corrosion ii) Differential aeration corrosion

i) Differential metal corrosion (Galvanic corrosion):- This arises when two

dissimilar metals are in contact with each other. Ex: zinc coated on mild steel. Under
this condition, a potential difference is set up resulting in a galvanic current. The
metal placed higher in the electrochemical series is anodic to one below it. For
example, the iron is anodic to copper, nickel and tin but cathodic to zinc and
magnesium. Therefore, iron corrodes in contact with copper whereas zinc and
magnesium corrode in presence of iron. The rate of differential metal corrosion
depends upon the amount of current passing from the anode to the cathode, that is,
on the difference in the potentials; higher the difference faster is the rate of corrosion.

Consider the galvanic cell in which iron and copper are in contact with an aerated
solution of NaCl as shown in the figure. Current flows from iron to copper indicating
that iron is the anode and copper is the cathode. The reactions that take place in the
cell are Fe
2+ -
Fe + 2e (anode)
- -
O2 + 2H2O + 4e 4 OH (cathode)

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Hence iron corrodes in preference to copper.
2+ -
2 Fe + 4 OH 2 Fe(OH) 2

4 Fe(OH) 2 + O2 + 2H 2O 2 (Fe 2O 3 .3H 2O)

Rust

The differential metal corrosion occurring in a simple cell can be extended to

a bimetallic couple.

e- e-
Fe Cu Fe Zn
- 2+
2+ - 2OH Zn
Fe 2OH

Anodic site Cathodic site Cathodic site Anodic site

(a) (b)

If a piece of iron combined with copper metal is exposed to corrosive

atmosphere a galvanic current flows. Iron acts as anode in the presence of
copper. In such a bimetallic couple, iron undergoes corrosion and copper is
unaffected (Figure a). On the other hand, in a bimetallic couple of iron and
zinc (Figure b) zinc gets corroded and iron is unaffected because zinc is more
anodic.

To generalize “When two metals are in contact with each other, a galvanic cell is set
up and a current flows. The metal acting as anode undergoes corrosion and the metal
acting as cathode is unaffected”. So, bolts and nuts are always made of similar metal.

ii) Differential aeration corrosion – This occurs due to difference in

concentration of air over the surface of a metal.

Consider a strip of pure iron partially immersed in a solution as shown

in the figure. The concentration of oxygen is high at the surface than that

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inside the solution. Since the cathodic reaction involves the use of oxygen, the
cathodic area tends to concentrate near the water–line as shown in the figure.
Therefore, the bottom portion (less oxygenated) of the iron strip acts as anode
where the corrosion process begins.

Electrons pass from the bottom of the strip to the top of the strip. The
corrosion product (rust) is formed between the anodic and cathodic areas and
not on the active electrode surface. The anodic and cathodic reactions are

2+ -
Fe Fe + 2e ( at the bottom-anode)
- -
O2 + 2H2O + 4e 4 OH (Near the water line-cathode)

Typical examples of differential aeration corrosion are the water line corrosion
and pitting corrosion.

a) Water line corrosion: This type of corrosion commonly observed in steel

water tanks. The part of the metal below the water line is exposed only to the
dissolved oxygen while the part above the water is exposed to higher oxygen
concentration of the atmosphere. Thus part of the metal below the water acts
as the anode (less oxygenated) and undergoes corrosion and the part above
the water line acts as the cathode (more oxygenated) and is unaffected. The
anodic area moves gradually upwards and entire tank corrodes with an
intense corrosion (creep) just below the waterline. The size of the creep
determines the rate of corrosion.

Ex: This type of corrosion is commonly observed in ships floating in sea water
for long period of time.

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4. Corrosion control:

Corrosion can be controlled by preventing the formation of galvanic cells.

The methods commonly used to control corrosion of metals are the
following.

i. Metal coatings:

Covering the metal (substrate or base metal) with a layer of another metal in
order to control the corrosion of the base metal by the environment is called
as a metal coating.

Anodic metal coating:-Anodic coatings are produced by coating a base metal

with more active metals which are anodic to the base metal.

In anodic metal coating, a base metal Fe is coated with more anodic metal
in the galvanic series to protect the base metal Fe from corrosion, so that more
anodic metals like Mg, Zn, Al & Cd undergo corrosion protecting the base
metal (Fe). A characteristic feature of anodic coating is that the base metal on
which the coating is done will not get corroded even if coating peels off. This
is due to the formation of large anodic and small cathodic areas. Hot dipping
or galvanizing is an example of anodic metal coating.

Hot dipping or galvanizing:

Coating of Zn on Fe is commonly called as galvanization. It is an anodic metal

coating process, this is done using hot dipping method which involves several
steps.

➢ The iron sheet is subjected to pretreatment by degreasing with organic

solvents.
➢ The sheet is passed through dilute sulphuric acid (pickling) and rinsed
with water.
➢ The sheet is treated with a mixture of aqueous solution of zinc chloride
and ammonium chloride and dried.
➢ The treated sheet is dried and dipped in molten zinc at 4300 -4700C.
➢ Excess Zinc is removed by rolling, wiping or passing blast of air.

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Applications:

1. To galvanized sheet metal.

2.To galvanized house-hold items such as buckets, tubs and other containers.

3.To galvanized machine parts, tools, ships, tanks and wires.

4. Metal pipes and wires are most popular galvanized items which find
application in industrial use as well as in articles made for domestic use.

ii. Anodizing:-When metals like aluminium, titanium, chromium, vanadium

and zirconium etc are made as anode in presence of chromic acid and
sulphuric acid, a thin layer of oxide is formed, which acts as a protective layer.
This phenomenon is known as anodizing.

Anodizing of aluminium:

Degreased and polished aluminium metal object is made as anode and

electrolyzed in H2SO4 or chromic acid or oxalic acid at 350C. A plate of Copper
or steel or lead is made the cathode. When current of moderate density is
passed, at the anode form oxide which takes the form of thick film, i.e Al2O3
deposits on the surface of the object.

Thickness of the deposit is controlled by adjusting the current and the

bath solution.

The coating is slightly porous and it is sealed by dipping in hot water. Al2O3
gets hydrated to Al2O3.H2O which occupies more volume and hence protects
the metal from corrosion.

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Applications: Widely used in industrial, commercial and domestic materials
like air craft, window frames, utensils, roof ceilings, computer hardware,
scientific instruments etc.

iii. Cathodic protection: Cathodic protection is a method of protecting a

metal or alloy from corrosion by converting it completely into cathode and no
part of it is allowed to act as anode.

The corrosion of the metal takes place at the anodic region whereas at the
cathodic region, the metal is unaffected. Therefore, corrosion can be prevented
by eliminating the anodic sites and converting the entire metal into cathodic
area.

Cathodic protection can be achieved by the following method.

a) Sacrificial anode method: In this method the metal to be protected is

connected by a wire to more anodic metal. More anodic metal undergoes
corrosion supplying electrons to the base metal thereby making the
base metal as cathode and protecting the base metal. The more anodic
metals get corroded and hence are called sacrificial anodes. So, this is
called as sacrificial anode method. After continuous use these sacrificial
anodes have to be replaced.

Base metals: - Fe, Cu and alloys like brass.

Anodic metals: - Mg, Zn and Al.

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Applications:

Sacrificial anode method is used to protect buried pipe lines, ship hull,
industrial water tanks and steel rods in R.C.C by connecting to a more anodic
metal using a wire.

5. Corrosion Penetration Rate:

The corrosion penetration rate (CPR) is defined in three ways:

• 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 amount of weight loss per year in the thickness of the metal or
alloy.

The speed or rate of deterioration depends on the environmental conditions

and, the type and condition of the metal under study.

Corrosion penetration rate may also be known as corrosion rate.

The CPR is calculated as follows:

CPR = (k x W) / (ρ x A x T)

Where
k = is a constant
W = total weight lost
T = time taken for the loss of metal
A = the surface area of the exposed metal
ρ = the metal density in g/cm³

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Numerical problems on Corrosion Penetration Rate

Questions:

1) Define corrosion. Explain the electrochemical theory of corrosion taking iron as an

example.
2) What is differential aeration corrosion? Write a note on water line and pitting corrosion.
3) Give reasons--Nuts and bolts are made up of same metal.
4) Explain the type of corrosion- Ship sailing in the sea.
5) Write a note on the following a) Anodizing b) Galvanizing
6) What is cathodic protection? Explain anodizing of aluminium.
7) What is anodizing? Explain anodizing of aluminium.
8) Explain types of corrosion in following cases.
9) Write a note on Sacrificial anode method

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 6. Electrode System:
Electrode
A substance or a piece of metal which conduct electric current is called as electrode.
Example: Cu, Zn, Fe, Pt, Ag etc…
Types of Electrodes
Some important types of single electrodes are
(1) Metal ion-metal electrode: where a metal is in contact with its ionic solution.
Example: Cu 2+ / Cu, Zn2+/Zn, Ag+/Ag.
(2) Gas electrode: where a gas is in contact with an inert metal dipped in an ionic
solution of the gas molecules.
Example: Standard Hydrogen electrode (SHE)
(3) Metal insoluble salt electrode: where a metal is in contact with a solution containing
the anion of the salt.
Example: Calomel electrode Hg/Hg2Cl2, KCl (salt), Ag/AgCl electrode.
(4) Ion selective electrodes: The electrode in which a membrane is in contact with an
ionic solution.
Example: Glass electrode, solid state electrode and liquid membrane electrode.

i. Ion selective electrodes: Ion selective electrodes are the electrodes that respond to certain
specific ions present in solution containing mixture of ions and they develop potential due to
the presence of these specific ions by ignoring the presence of other ions in the solution.

Example: Glass membrane electrode.

Glass electrode: It is an electrode, which shows sensitivity to specific ions ignoring

other ions. In this electrode, a glass membrane is in contact with a solution, with which it can
exchange ions. It is also called an ion selective electrode.
Construction of Glass electrode:
The glass electrode consists of a long glass tube with a thin walled bulb at one end of
the glass electrode as shown fig. The composition of the glass used in glass electrode is Na2O
22%, CaO 6% & SiO2 72%. It has low melting point, high electrical conductance and can sense
hydrogen ions up to pH 9. The bulb contains 0.1M HCl. An Ag/AgCl electrode (internal
reference electrode) is placed in the solution and connected by a platinum wire for electrical
contact.

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 The electrode is represented as
𝐴𝑔/𝐴𝑔𝐶𝑙. 𝐾𝐶𝑙(𝑎𝑞) /𝐻𝐶𝑙(0.1𝑀) /𝐺𝑙𝑎𝑠𝑠

Figure 1.5 Construction of glass electrode

Working of Glass Electrode

When the glass electrode is dipped in the test solution, the Na+ ions of the glass
membrane are exchanged for H+ ions of the test solution.
+ + - + + -
H + Na Gl Na + H Gl
solution glass solution glass membrane
membrane

The boundary potential established due to the above reaction is mainly responsible for
the glass electrode potential EG. The potential of the glass electrode is given by

𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙

When two solutions are of the same concentration then C1=C2, Eb=0. However it has
observed that even when C1=C2 a small potential is developed this is called asymmetric
potential (Easy). Hence above equation can be written as
𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝑎𝑠𝑦

𝐸𝐺 = 𝐿 − 0.0591𝑃𝐻 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝑎𝑠𝑦

𝐸𝐺 = 𝐿1 − 0.0591𝑃𝐻
( 𝑤ℎ𝑒𝑟𝑒 𝐿1 𝑖𝑠 𝑎 𝑎𝑛𝑜𝑡ℎ𝑒𝑟 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑤ℎ𝑖𝑐ℎ 𝑖𝑠 𝑒𝑞𝑢𝑎𝑙 𝑡𝑜 𝐿 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 )

Application of Glass electrode

pH measurement by glass electrodes is used in many chemical and industrial analyses.

The main applications are
➢ Analysis of foods and cosmetics
➢ Control of industrial processes

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 ➢ Microelectrode measurements
➢ Environmental analysis
➢ Clinical analysis
➢ Measurement of soil pH level by glass electrode is an important
process to observe soil acidity.

Application of Glass Electrode for the Determination of pH

The glass electrode is immersed in the solution whose pH is to be determined. It is

combined with a reference electrode such as a calomel electrode through salt bridge.

The cell assembly is represented as

H
Hg HgCl2 KCl(aq) solution of unknown P glass HCl AgCl /Ag
(0.1M)

𝐻𝑔/𝐻𝑔2 𝐶𝑙2 /𝐾𝐶𝑙(𝑎𝑞) //𝑇𝑒𝑠𝑡 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛/𝐺𝑙𝑎𝑠𝑠/𝐻𝐶𝑙(0.1𝑀)/𝐴𝑔𝐶𝑙/𝐴𝑔

The emf of a given cell is measured using an electronic voltmeter.

Emf of the cell is given by

𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐺 − 𝐸𝑆𝐶𝐸

𝐸𝑐𝑒𝑙𝑙 = 𝐿1 − 0.0591𝑃𝐻 − 𝐸𝑆𝐶𝐸

𝐿1 − 𝐸𝑆𝐶𝐸 − 𝐸𝑐𝑒𝑙𝑙
𝑃𝐻 =
0.0591
𝐾 − 𝐸𝑐𝑒𝑙𝑙
𝑃𝐻 = … … … … . . (1)
0.0591

Where K is another constant is equal to L1-ESCE called glass electrode assembly constant.

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ii. Reference electrodes:
These are the electrodes whose potentials are known and are used for the
determination of potentials of other electrodes.
Types of reference electrodes
Reference electrodes are of two types
(a) Primary reference electrodes (b) Secondary reference electrodes

(a) Primary reference electrodes: These are the electrodes whose potential is
arbitrarily taken as zero and used to measure the potential of another electrode.
Example: Standard hydrogen electrode (SHE)

(b) Secondary reference electrodes: whose potential with respect to SHE are known
and are commonly used for determination of the electrode potentials of the other
electrodes.
Example: Calomel electrode and Ag/AgCl electrode

Construction and working of Calomel electrode

Fig.1.3 Calomel electrode

The calomel electrode consists of solid mercurous chloride (Hg2Cl2) in contact with
mercury. A small amount of mercury is placed at the bottom of the vessel. It is covered with
paste of solid calomel, mercury and KCl solution. A saturated solution of KCl and Hg2Cl2 is
placed over the solid mixture. Electrical connection is made through a platinum wire dipped in

13
the mercury at the bottom of the vessel. This constitutes one half cell. It is connected to the
other half cell through a salt bridge.

The calomel electrode is represented as Hg Hg2Cl 2 . KCl(aq)

The calomel electrode can act as anode or cathode depending on the nature of the other
electrode of the cell.

When it acts as anode the electrode reaction is

2𝐻𝑔 → 𝐻𝑔22+ + 2𝑒 −
𝐻𝑔22+ + 2𝐶𝑙 − → 𝐻𝑔2 𝐶𝑙2

2𝐻𝑔 + 2𝐶𝑙 − → 𝐻𝑔2 𝐶𝑙2 + 2𝑒 −

When it acts as cathode the electrode reaction is

𝐻𝑔22+ + 2𝑒 − → 2𝐻𝑔
𝐻𝑔2 𝐶𝑙2 → 𝐻𝑔22+ + 2𝐶𝑙 −

𝐻𝑔2 𝐶𝑙2 + 2𝑒 − → 2𝐻𝑔 + 2𝐶𝑙 −

The electrode potential is given by

0.0591
𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸 0 − log[𝐶𝑙 − ]2
𝑛
0.0591
𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸 0 − 2 log[Cl− ]
2

𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸 0 − 0.0591 log[Cl− ]

The potential of the calomel electrode depends on the concentration of the KCl solution.

Concentration of KCl E0 Calomel

0.1M 0.33 V
1M 0.281 V
Saturated 0.242 V
Applications:

➢ Used in pH measurement
➢ In voltammetric techniques
➢ General aqueous electrochemistry
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➢ Used in the determination of potential of unknown electrode

15
Numerical Problems on concentration cells

7. Analytical Techniques

There are two types of chemical analysis:

1) Qualitative analysis: It is the determination of the chemical composition of a sample.

2) Quantitative analysis: It deals with the determination of the amount or percentage of

one or more constituents of a sample.

a. Potentiometry:

Introduction:
Potentiometry is a technique used to measure the concentration of an analyte present
in the given solution by measuring the change in the potential by a suitable indicator
electrode, as a function of volume of titrant.

Theory
The measurement EMF to determine the concentration of ionic species in solution is referred
to as potentiometry. The relation between electrode potential and metal ion concentration is
given by the Nernst equation.

0.0591
𝐸 = 𝐸𝑜 + log [𝑀𝑛+ ]
𝑛
it can be seen from the equation that the potential of an a electrode E depends upon the
concentration of the ion Mn+ to which it is reversible.

Application of Potentiometry in the estimation of iron in ferrous ammonium sulphate

Potentiometer consists of a reference (Calomel) electrode, an indicator (Platinum)

electrode and a device for measuring the potential. The indicator electrode responds rapidly to
the changes in the potential due to the concentration changes of the analyte. A known volume
of the analyte (FAS) is taken in a beaker and its potential is determined by connecting the

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assembly to a potentiometer. The titrant (K2Cr2O7) is added in the increments of 0.5ml and
the potential is measured each time. Near to the equivalence point, there is a sharp increase in
the potential. The end point is determined by plotting change in potential against the volume
of titrant. From this can find out the amount of iron present in the FAS solution.

Other Applications of Potentiometric titration:

• Clinical chemistry – analysis of metals.

• Pollutants in water such as metal ions, cyanide, fluorides, ammonia.
• Agriculture - Determination of various elements in soil, fertilizers etc.
• Food processing industries
• Detergent manufacturing industries.
• Other industries such as cosmetic, textile, paper, paint, explosive, energy etc.

b. Conductometry:

Theory:

Electrolyte solution conducts current by the migration of ions under the influence of an
electric field. Like metallic conductor, they obey Ohm's law,

𝐸 = 𝐼𝑅
Ohm's law states that the current “I” flowing through a conductor is directly
proportional to the applied potential E, and inversely proportional to the resistance R of the
conductor.

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 The reciprocal of the resistance is called the conductance. The resistance of a
homogeneous material of uniform cross section with an area of “a” sq. cm. and length “𝑙” cm
is given by

𝑙
𝑅=𝜌
𝑎
Where, 𝜌 is the specific resistance. The reciprocal of the specific resistance is termed the
specific conductance (K).
𝑎
𝐶=𝑘
𝑙
Specific conductance of an electrolyte solution is the conductance of the solution
present between two parallel electrodes of 1 cm2 area of cross section and 1 cm apart.

𝑘=𝐶

The specific conductance of an electrolyte solution at a given temperature is

related to the number of ions present, size of the ions and mobility of the ions.

On dilution of an electrolyte solution, its specific conductance decreases as the

number of ions per mL decreases.

Conductance measurements are used to determine the equivalence point in acid-base

titrations, there is a sudden change in conductance of the solution after the equivalence point.
The equivalence point is determined graphically by plotting conductance against the titre
values.

Instrumentation:

It consists of two platinum electrodes each of unit area of cross section placed unit distance
apart. The electrodes are dipped in the electrolyte solution taken in a beaker. It is connected

18
to a conductance measuring device. The titrant is added from the burette and the solution is
stirred. The conductance is measured after the addition of the titrant at intervals of 0.5 ml.

Conductometric Estimation of weak acid

Weak acid with strong base (CH3COOH v/s NaOH)

Consider the titration of Acetic acid with a strong base NaOH.

𝑁𝑎𝑂𝐻 + 𝐶𝐻3 𝐶𝑂𝑂𝐻 → 𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎 + 𝐻2 𝑂

On addition of NaOH, the conductance of the weak acid solution increases until the acid is
completely neutralized. A plot of conductance against the volume of NaOH is shown in the
figure. The point of intersection of the two lines is the neutralization point.
The conductance increases, because the partially dissociated, weekly
conducting weak acid gradually becomes fully dissociating conducting salt (Sodium Acetate).
Addition of base beyond the neutralization point leads to increase in the number of highly
mobile OH- ions. Hence the conductance increases sharply.

Plot the graph of conductance against the volume of alkali added. The point of intersection of
two lines gives the volume of alkali required for neutralization. Form this can calculate the
Amount of CH3COOH present in the given solution

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NOTE:

Acid mixture with a strong base (HCl & CH3COOH v/s NaOH)

Consider the titration of acid mixture (HCl & CH3COOH) & with strong base (NaOH).

On addition of NaOH, the conductance of the acid mixture solution decreases steeply. the
conductance decreases steeply, because the small and highly mobile H+ ions in the strong
acid is gradually replaced by heavier and less mobile in Na+ ions.

HCl + NaOH →NaCl+ H2O

Addition of base beyond the first neutralization point leads to moderate increase in
conductance. The conductance increases moderately, because the poorly conducting weak
acid (acetic acid) is gradually converted to highly conducting salt (sodium acetate) until the
second neutralization.

𝐶𝐻3𝐶𝑂𝑂𝐻+𝑁𝑎𝑂𝐻 →𝐶𝐻3𝐶𝑂𝑂𝑁𝑎 + 𝐻2𝑂

Further addition of NaOH, increases number of highly mobile OH- ions. Hence conductance
increases steeply.

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