Engineering Chemistry: Corrosion

Dr Rangarajan B
Assistant Professor
Dept of Chemistry,
BMS College of Engineering,
Bangalore
 Syllabus
Unit 1- Electrochemistry : Electrode Systems and Corrosion
Electrodes and Cells –

• Introduction- Classification of cells - primary, secondary and concentration cells;

• Reference electrodes - Calomel electrode;

• Ion-selective electrodes - Glass electrode. Determination of pH using glass electrode,

• Numerical on concentration cells.

Corrosion –

• Definition, Electrochemical theory of corrosion, Types of corrosion - differential metal, differential aeration and stress corrosion;

• Factors affecting the rate of corrosion;

• Corrosion Penetration Rate (CPR) , Numerical.

• Corrosion control: Cathodic protection – Sacrificial anode, Impressed current method.

• Metal finishing - Introduction, technological importance;

• Electroless plating: Introduction, Electroless plating of copper (PCB).

• Inorganic coatings – anodizing and phosphating.

Corrosion :
Corrosion is defined as the “destruction or deterioration of a metal or its alloy and consequent
loss of metal, caused due to direct chemical action or electrochemical reactions with its
environment”
The process of corrosion of metals depends on the environment to which the metals
are exposed.

The corrosion of metals can be either

(1) Dry corrosion
or
(2) Wet corrosion.
Dry Corrosion: Dry corrosion occurs in the absence of moisture or conducting electrolyte medium, due to direct
attack of metals by dry gases mainly through chemical reactions. Ex: the attack of dry gases such as O2, Halogen,
H2S, SO2, NOX etc., on a metal to form an oxide layer over the surface.

It is generally due to :
1. Oxidation corrosion : It is brought about by the direct action of oxygen on the metal surface at high or low
temperature. At low temperature, alkali and alkaline earth metals are oxidized and at high temperatures
except Ag, Au and Pt, all other metals are oxidized.

2. Corrosion by other gases : In this, dry gases like H2, Cl2, F2, SO2 and CO2 directly attack the
metal surface. Rate of corrosion depends upon the chemical affinity between the metal and
gas and also on the nature of the film formed

3. Liquid metal corrosion : It occurs when an anhydrous liquid attacks the metal surface. When a liquid metal
flows over a solid metal at high temperature it weakens the solid metal
Wet Corrosion:

Wet corrosion involves reactions in aqueous medium. The conducting surface of the metal
undergoes an electrochemical reaction with the moisture & oxygen present in the atmosphere.
Ex: Rusting of Iron.

Wet corrosion can be better explained on the basis of Electrochemical theory

Electrochemical Theory of Corrosion:
According to electrochemical theory, When a metal is exposed to a corrosive environment,
corrosion sets in by the formation of anodic and cathodic areas within the metal, forming a
large number of minute galvanic cells.

The reactions taking place at the anode and cathode are as follows :
Anodic reactions : Oxidation occurs at the anode. The metal loses electrons and passes them
into the solution. Thus, the metal at anode is destroyed by dissolving or by changing into
metal ions. Hence, corrosion always occurs at the anodic areas

Cathodic reactions : The electrons released at the anodic areas are consumed in the reactions
at the cathode. Depending on the nature of the environment, the cathodic reactions are of
two types
1. Evolution of Hydrogen : This mechanism occurs when oxygen is absent and the
environment is acidic. Eg: Rusting of Iron in Acids
2. Absorption of oxygen : This mechanism occurs when oxygen is present and the
environment is neutral or alkaline Eg:
1. Evolution of Hydrogen :

The Fe2+ reacts with the anion of the acid to form the corrosion product Ex: FeCl2, FeSO4

2. Absorption of Oxygen:

The Fe2+ formed at the anode and OH– formed at the cathode diffuse towards each other to
form Fe(OH)2 if the oxygen concentration is high then the Fe(OH)2 further reacts with O2 and
H2O to form Fe(OH)3 a sort of brown /red rust which is deposited on the surface (Fe2O3.nH2O)
Types of corrosion –
1. Differential metal corrosion : It occurs when two dissimilar metals (for example, Zn and Cu)
are electrically connected and exposed to an electrolyte and then the metal higher in the
electrochemical series undergoes corrosion. This is also called as galvanic corrosion

For example, if Zn and Cu are connected, Zn acts as anode and undergoes corrosion, whereas Cu
acts as cathode.

Mechanism in a Zn-Cu couple

(At Anode) Zn → Zn2+ + 2e–

(At Cathode) The reaction at the cathode depends upon the environment.

Acidic environment : 2H+ + 2e– → H2 ↑(evolution of hydrogen)

1
Alkaline or neutral environment : O2 + H2O + 2e– → 2OH– (absorption of oxygen)
2
Zn2+ and 2OH– ions interact to form Zn(OH)2. Hence, Zn dissolves and Cu is protected
2. Differential Aeration corrosion :
It occurs when one part of the metal is exposed to a different air concentration than the other
(different concentrations of Oxygen) . There will be a difference of potential between
differently aerated areas.
• Poorly oxygenated areas become anodic and
• Highly oxygenated areas become cathodic.

(At Anode) Zn → Zn2+ + 2e–

(At Cathode) The reaction at the cathode depends upon the environment.

Acidic environment : 2H+ + 2e– → H2 ↑(evolution of hydrogen)

1
Alkaline or neutral environment : O2 + H2O + 2e– → 2OH– (absorption of oxygen)
2
Zn2+ and 2OH– ions interact to form Zn(OH)2. Hence, Zn dissolves and Cu is protected
Differential Aeration corrosion : b) Rusting along a line just beneath the level of water stored in an iron
tank is also called waterline corrosion and is because of differential
aeration.
I. Waterline Corrosion
During water line corrosion, the part of the Metal below the waterline is
exposed to less Oxygen concentration and acts as anode which
undergoes corrosion. The other part which is more exposed to
atmospheric oxygen, acts as the cathode

a) If a Zn metal is partially immersed in a neutral solution (say

NaCl) and the solution is not stirred, the parts above and close to
the waterline are well aerated and act as cathode. Areas deep
inside the solution are anodic, as the concentration of oxygen is
less. Thus, a potential develops that causes a flow of current
between two areas of the same metal. Zn dissolves at the anodic
area
II. Pitting Corrosion

• Pitting corrosion occurs when tiny particles, like dust, mud, etc, get deposited on a
metal surface.
• The portion of metal covered by dust or other particles is less aerated and acts as an
anode.
• The other portion of the metal exposed to more atmospheric oxygen acts as the
cathodic region.
• Corrosion takes place at the portion below dust, and a small pit is formed.
• The rate of corrosion increases due to small anodic area and large cathodic area.
Stress Corrosion

Metals under tensile stress due to bending, welding, riveting, and hammering
are prone to stress corrosion.
When any portion of a metal is under stress, highly ‘localized’ corrosion takes
place in a specific corrosive environment.

In a corrosive environment, the stressed portion of the metal acts as anodic area
with respect to the unstressed (cathodic) area and undergoes corrosion
Caustic Embrittlement : A type of stress corrosion known as Caustic Embrittlement occurs at the stress areas
such as crevices or rivets, joints and bent portion of steam boilers and/or heat transfer equipment at high pressure
in which alkaline water attacks the mild steel

Na2CO3 added to water/boiler (To soften hard water) gets converted to NaOH
𝑁𝑎2𝐶𝑂3 + 𝐻2𝑂 → 2𝑁𝑎𝑂𝐻 + 𝐶𝑂2 ↑
Water containing NaOH flows through the stressed areas like cracks, joints and sharp corners and attacks the Iron
to form Na2Fe2O2
𝐹𝑒 + 2𝑁𝑎𝑂𝐻 → 𝑁𝑎2𝐹𝑒𝑂2 + 𝐻2
This further gets converted to rust and makes the boiler materials more brittle (embrittles) at the stressed sites
6𝑁𝑎2𝐹𝑒𝑂2 + 6𝐻2𝑂 → 2𝐹𝑒3𝑂4 + 12𝑁𝑎𝑂𝐻
Factors Affecting the Rate of Corrosion:-

1. Nature of the metal: (Electrode Potential)

2. Nature of corrosion product:
3. Ratio of Anodic to Cathodic Areas:
4. Nature of medium:
• pH
• Temperature
• Conductivity
1. Nature of the metal: (Electrode Potential) :
• The ability of the Metal to undergo corrosion is dependent on the nature of the Metal.
• The metals with lower electrode potential values are more reactive than the metals with higher electrode
potential values.
• When two metals or alloys are in contact in the presence of an electrolyte, the metal that is higher in the galvanic
series undergoes corrosion. The rate and severity of corrosion depends on the difference in their position. Greater
the difference in the position of the two metals greater is the corrosion of the anodic metal
Example: The Metals like Mg, Zn etc. with low Electrode potential values are highly susceptible for corrosion. The
Nobel metals such as Ag, Au, Pt etc., with higher electrode potential values are less susceptible for corrosion.

2. Nature of corrosion product:

• Most metals form a layer of oxide on the surface as a corrosion product.
• If the surface oxide layer is adherent, stoichiometric , insoluble, non porous having low ionic and electronic
conductivity, then it acts as a protective film which prevents further corrosion.
• On the other hand if the corrosion product is non adherent, soluble, porous, unstable and conducting then
corrosion product does not prevent further corrosion and corrosion continues.
Examples : Metals like Al, Cr, Ti forms a protective layer of oxide (Al2O3, Cr2O3 , TiO2) on their surface which prevents
further corrosion of the metal. Metals like Zn, Fe, Cd, Mg ,etc. .do not form protective layer and are readily under
goes corrosion
3. Ratio of anodic to cathodic area:
• If the metal has large cathodic and small anodic area then the demand for electrons from cathode increases. As a result all
the electrons from anode gets consumed. This increases the rate of corrosion.
• If the area of cathode is smaller than the anodic region then the rate of corrosion decreases.
Example : If an iron sheet coated with tin has small pin holes, a small anode and a large cathode areas will form, which results
in intense localized corrosion. If zinc plating on iron peels off at some
points, the rate of corrosion of iron is low due to formation of large anodic and small cathodic areas

4. Nature of the Medium (Environment):

pH : If pH decreases rate of carrion increases
• If pH<3 rate of corrosion is high even in the absence of air due to evolution of hydrogen at the cathodic region.
• If pH is between 3-10, the rate of corrosion depends upon the presence of oxygen on the Cathodic area for reduction.
Higher the concentration of O2, higher the rate of corrosion.
• If pH>10, the rate of corrosion ceases due to the formation of protective coating of hydrous oxides on the metal.

Temperature:
• The rate of all chemical reactions increases with the increase in temperature, rate of corrosion also increases as temperature
rises.
• At higher temperatures, even the passive metal can become active and get corroded.
• However, differential aeration corrosion slows down at higher temperatures. This is because of the faster diffusion of O2 into
pits and crevices. Moreover, corrosion also occurs due to the formation of differential temperature cells
Conductivity :
If the medium to which the metal part is exposed is conductive, then it induces corrosion. If the electrical conductance of the
soil or medium is high, the rate of corrosion of metal is severe and fast
Corrosion Penetration Rate :
• Rate at which any metal or alloy deteriorates in a corrosive environment.
• It can also be defined as the amount of weight loss per year of a metal due to corrosion.
• It is a measure of reduction in thickness of a metal per year
• Unit of CPR : millimeters per year (mmpy) or mils per year (mpy)

𝑲 ×𝑾
𝑪𝑷𝑹 =
𝝆 ×𝑨 ×𝑻
Unit For numericals : convert the
Parameter Definition given data into the units given
mmpy mpy in table before solving the
𝑲 Constant 87.6 534 problem
𝑾 Total weight lost by metal mg mg
Ex : 1inch = 2.54 cm
𝝆 Density g/cm3 g/cm3 1 year = 365*24 Hrs etc.
Surface Area of exposed
𝑨 cm2 inch2
metal
Time taken for loss of
𝑻 Hour Hour
metal
1 . A sheet of carbon steel (1meter X 3meter) loses 80g due to corrosion over 120 days calculate Corrosion penetration rate in
mmpy and mpy (density of Carbon steel : 7.8g/cm3)
Unit
Parameter
mmpy mpy
𝑲 87.6 534

80g
80000mg
𝑾 = 80*1000mg
80000mg

𝝆 7.8 g/cm3 7.8 g/cm3

𝟑𝟎𝟎𝟎𝟎
= inch2 (1inch = 2.54cm)
𝟐.𝟓𝟒×𝟐.𝟓𝟒
1m * 3m = 100cm* 300cm
𝑨 𝟑𝟎𝟎𝟎𝟎 𝟏
= inch2 (1cm2 = 𝟐.𝟓𝟒×𝟐.𝟓𝟒 inch2)
=30000cm2 𝟐.𝟓𝟒×𝟐.𝟓𝟒

= 4650 inch2

120 days = 120*24 Hour

𝑻 2880 hours
= 2880 hours

𝐾 ×𝑊 𝐾 ×𝑊
𝐶𝑃𝑅 = 𝐶𝑃𝑅 = 𝑲 ×𝑾
𝜌 ×𝐴 ×𝑇 𝜌 ×𝐴 ×𝑇 𝑪𝑷𝑹 =
𝝆 ×𝑨 ×𝑻
CPR 87.6 x 80000 534 x 80000
= =
7.8 × 30000 × 2880 7.8 × 4650 × 2880

= 0.0104 mmpy = 0.409 mpy

Corrosion Control :
The various methods by which corrosion can be controlled and prevented are as follows
1. Cathodic and anodic protection
2. Protective Coatings

Cathodic Protection : In this technique the metal to be protected is made as a cathode by providing electrons from
an external source
1. Sacrificial Anode
2. Impressed Current Cathodic Protection
 Sacrificial anode :

a) Sacrificial anode method:

• In this method, the metal structure to be protected is connected to a more reactive metal (having lower reduction potential).
• For example, if an iron structure is to be protected it is connected to a metal like Zn or Mg.
• The more reactive metal behaves as an anode and the iron structure becomes cathodic
• Thus, the iron structure is protected and the anode undergoes corrosion.
• After sometime, the anode is corroded completely and is replaced with a fresh anode.
• The anode (Zn or Mg), which is sacrificed to protect the base metal is called the sacrificial anode
2. Impressed current cathodic protection

• In this method direct current is impressed (electrical current

applied from external source ) to nullify the corrosion
current and convert the corroding metal from anode to
cathode.
• The electrons are supplied from a source of Direct
current(DC).
• The positive terminal of the DC source is connected to the
anode and the negative terminal to the structure to be
protected.
• Anode is made of inert material like graphite, carbon,
stainless steel
Protective coatings : Inorganic coatings
In this method the surface of the base metal is converted in to a protective coating by
chemical reaction

1. Anodizing
2. Phosphating

Anodizing : Anodizing is a process of artificially forming protective passive oxide film on the
surface of metals such as Al, Mg, Ti, Zr, Ta, Cr, etc by electrochemical oxidation.

Phosphating : Coating of a metal with its metal phosphate by electrochemical oxidation in a

phosphoric acid medium is known as phosphating
• Aluminium is cleaned, degreased and polished
and taken as anode in an electrolytic cell.
• It is immersed in an electrolyte consisting of 5-
10% chromic acid.
• Steel or copper is taken as cathode.
• Temperature of the bath is maintained at 35°C.
• A current density of 100 Acm-2 or more is
applied which oxidizes outer layer of Al to Al2O3
that gets deposited over the metal.
• The passivity of aluminium is due to the
formation of a thin and compact layer of
aluminium oxide over the metal. This
phenomenon is known as anodizing or anodic
oxidation or anodic passivity
Phosphating :

1. The metal to be phosphated is taken as anode, an inert material is taken as

cathode
2. Phosphoric acid (H3PO4) is used as electrolyte
3. The metal to be phosphate is oxidized and the metal ions that are formed
react with phosphate (PO43-) ion to give Metal phosphate which is deposited
on the surface of the metal
4. pH ~ 1.8 to 3.2
5. NO3- and ClO3- are used as accelerators to speed up the process
6. Phosphate coatings are porous and are commonly used as base for paint to
impart good adhesion
Metal Finishing :
Metal finishing is the process employed to modify the surface properties of conducting and non
conducting materials by deposition of a layer of metal over it.

Technological importance of metal finishing:-

1. Imparting the metal surface to higher corrosion resistance.
2. Imparting improved wear and abrasion resistance.
3. Providing electrical and thermal conducting surface.
4. Imparting thermal resistance and resistance to impact.
5. Providing optical and thermal reflectivity.
6. In the manufacture of electrical and electronic components such as PCB’s, capacitors and
contacts
7. In electro framing of articles, electrochemical machining, polishing and etching.
8. To increase the decorativeness of metal surface.
9. In electrotyping and to build up material or restoration.
10. To improve solderability.
Metal finishing can be done either by electroplating or electroless plating.

Electroplating :
This method is employed to coat a layer of metal over the surface of another metal or alloy by applying electric current. the
metal to be plated is made cathode and placed in a bath containing the ions of the metal to be deposited. The anode is either
inert or made of the coating metal. When current is passed, the coating metal ions migrate and get deposited in the form of a
thin layer.
Ex: Chromium coating, Nickel coating

Electrolessplating :
The controlled deposition of layer of a metal from its salt solution on to a catalytically active surface of the material using a
suitable reducing agent without using electric current is called as electroless plating
Electroless Plating of Copper on PCB (Printed Circuit Boards):
1. The base is a plastic board is etched and conditioned by dipping in dil H2SO4
2. The surface is activated by dipping in SnCl2 containg HCl at 25°C followed by PdCl2
3. SnCl2 reduces the Pd2+ ions which are deposited on the surface of the board as metallic Pd
4. Pd acts as the catalyst to help deposit copper on the surface of the board from the Plating Bath
5. The required region is protected and the rest of the area is etched away to produce circuit pattern
6. The connection between two sides of the board is created by drilling holes in the appropriate region and repeating the process of
electroless plating
Metal Ion Solution CuSO4 12g/L

Plating Bath : Reducing Agent HCOOH 8g/L

EDTA
Complexing Agent 20g/L
(Ethylene Diamine Tetra Acetic acid)
Rochelle Salt 14g/L
Buffer (to Maintain pH)
NaOH 15g/L
Temperature 25°C
pH 11
− − −
Reactions : 2𝐻𝐶𝐻𝑂 + 4𝑂𝐻 → 𝐻𝐶𝑂𝑂 +2𝑒
𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢

Pd
−
Overall Reaction : 𝐶𝑢2+ + 2𝐻𝐶𝐻𝑂 + 4𝑂𝐻 → 𝐶𝑢 + 𝐻𝐶𝑂𝑂 +2𝐻2𝑂 + 𝐻2
Copper plating through the holes of a PCB board for connections in a Double Sided PCB

Copper Coating
Plastic Board

Copper is etched to produce tracks/ Circuit pattern Copper Coating

Drilling of holes Drilling of holes

Cu Plating in holes Cu Plating in holes