Module 3

Electrochemistry - Corrosion
 Electrochemistry
Deals with the production of electric current
through chemical reactions
or

the chemical reactions produced by passing

electric current
 Electrochemistry
• Batteries
• Corrosion
• Industrial production of
chemicals such as Cl2, NaOH,
F2 and Al
• Biological redox reactions

The heme group

 Electrochemistry
Study of redox reactions at an electrode.

• Obtaining electricity directly from a spontaneous (∆G < 0) reaction.

• Using an electric current to drive a non-spontaneous (∆G > 0)

reaction.

Electrochemical cells:
• systems utilizing a redox reaction to produce or use electrical energy
 Oxidation Number
Hypothetical charges called oxidation numbers to atoms with polar
covalent bonds.

The general idea is to assign the shared electrons in each bond to the
more electronegative element.

H O H
(+1) (−2) (+1)

N(−3) H3(+1)

C(+4) O3(−2)
• Oxidation numbers are assigned to each element in a chemical
reaction to help us learn which element is oxidized and which is
reduced.

• If, in a reaction, the oxidation number of an element increases

(becomes more positive), the element is being oxidized. On the other
hand, if the oxidation number of an element decreases, the element is
being reduced.

• The oxidizing agent is reduced, whereas the reducing agent is

oxidized.

• Oxidation: loss of electrons (OIL)

• Reduction: gain of electrons (RIG)

• Oxidizing agent: accepts electrons (reduced)

• Reducing agent: donates electrons (oxidized)
 Oxidation – Reduction Reaction
Consider metallic zinc reacting with chlorine gas to form zinc chloride:

Zn(0) + Cl2(0) 🡪 Zn(+2) + Cl2(–1)

The oxidizing agent that gains electrons is chlorine, and the reducing
agent that loses electrons is zinc.

Use Oxidation numbers for balancing reactions. The goal is to keep the
total number of electrons lost in the oxidation equal to the total number
gained in the reduction.

Assignment:
Balance the following reaction in both basic and acidic medium:
Fe2+ + Cr2O72- 🡪 Cr3+ + Fe3+
 Redox Reactions
• The energy producing reactions in industry as well as in the body.
• The core of a redox reaction is the passing of one or more electrons
from one species to another.

• Oxidation and reduction occur simultaneously.

4Al(0) + 3O2(0) 🡪 2Al2(+3)O3(–2)

6 CO2 + 6 H2O 🡪 C6H12O6 + 6 O2 (Photosynthesis)

 Redox Reactions
Oxidation Half-Reaction:
Zn(s) → Zn2+(aq) + 2 e–.
The Zn loses two electrons to form Zn2+.

Zn(s) + Cu2+ (aq) → Cu(s) + Zn2+ (aq)

Reduction Half-Reaction:
Cu2+(aq) + 2 e– → Cu(s)
The Cu2+ gains two electrons to form copper.
 Redox Reactions
Zn(s) + Cu2+ (aq) → Cu(s) + Zn2+ (aq)
 Electrochemical Cells

The basic experimental setup which realizes electron transfer in redox

reactions is called an electrochemical cell.

Devices in which an electric current (a flow of electrons through a

circuit) is either

• produced by a spontaneous chemical reaction (Galvanic cell)

• used to bring about a non-spontaneous reaction (Electrolytic cell)

Electrochemical Cell
 Components
• Electrodes:
Any solid on whose surface oxidation-reduction reactions occur.

Anode: oxidation half-reaction takes place;

Zn(s) → Zn2+(aq) + 2 e–
Oxidation of metal releases metal ions into the solution, leaving behind the
electron at the surface of the metal electrode.

Cathode: reduction half-reaction occurs;

Cu2+(aq) + 2 e– → Cu(s)

Movement of metal ions from the solution to the electrode leads to accumulation
of positive charge at the surface of the electrode.

o Active electrodes: participate in redox

o Inactive: sites of oxidation and reduction.
 Components
• Electrolyte:
mixture of ions involved in reaction or carrying charge. Internal
conducting environment that allows ions to migrate between both half
cells so as to preserve electro neutrality.

• Salt bridge:
completes circuit (provides charge balance). Serves as a bridge to
complete the electric circuit and maintain electro neutrality in the
electrolyte.
 Cell Representation
• Phase boundaries are represented by “ | ”, and salt bridge is represented by “ | | ”.

• No phase boundary, then use “ , ”.

• Anode Half-Cell || Cathode Half-Cell

• Electrode | Anode Soln || Cathode Soln | Electrode

Zn (s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s)

Ox Red
Anode: Zn (s) → Zn2+ (aq) + 2e-
Cathode: Sn4+ (aq) + 2e- → Sn2+ (aq)

Zn (s) | Zn2+ (aq) || Sn4+ (aq), Sn2+ (aq)

Types of Electrodes
 Cell Representation

Zn(s) | Zn2+(aq) || H+(aq) | H2(g) | Pt(s)

Galvanic/Voltaic Cells
Electrochemical Cells
Electrochemical Cells

Standard Hydrogen Electrode

Electrolytic Cells
Electrolytic Cells
 Electrochemical Cells

Galvanic cell Electrolytic cell

Concentration cell Fuel cell

 Electrode Potential
• Oxidation at one electrode and reduction at the other electrode.

• Can think of the cell as consisting of two half-cells joined together by an

external circuit for flow of electrons and an internal pathway for
migration of ions to maintain electroneutrality.

• Each half-cell has a potential difference depending on the electrode

reaction, Electrode Potential (E).

• Oxidation potential: tendency to lose electron

• Reduction potential: tendency to gain electron

 Electrode Potential
• Individual half-cell potential are not directly measurable, so we use reference
half-cell potential.

• Usually measured w.r.t. a standard hydrogen electrode (SHE) as anode.

• Defined as Standard Electrode Potential, Eº: unit molar

concentration (1 atm for gases) at 250 C.

• The standard half-cell potentials are determined from the H2

difference between the two electrodes. in

• The standard hydrogen electrode is assigned an arbitrary

value of exactly 0.00 V.
H+ Cl-

1 M HCl
Electrode Potential
 Electrochemical Series

To maintain uniformity, convention is that half-cell potentials are always

defined for the reduction direction.
 Electrochemical Series
• When selecting two half-cell reactions the more negative value will form the
oxidation half-cell.

• Consider the reaction between zinc and silver:

Ag+ (aq) + e– → Ag (s) E° = 0.80 V
Zn2+ (aq) + 2 e– → Zn (s) E° = – 0.76 V

• Therefore, zinc forms the oxidation half-cell:

Zn (s) → Zn2+ (aq) + 2 e– E° = – (–0.76 V)
 Cell Potential

• Cell potential ECell = ERight – Eleft Reduction on the Right

At Anode: M → Mn+ + n e–
At Cathode: Mn+ + n e– → M

• Cell potential = Reduction potential of reduction half-cell + oxidation

potential of the oxidation half-cell

• Oxidation potential = -1 x Reduction potential

E°cell = E°cathode- E°anode

Cu(s) | Cu2+ || Cl- | AgCl(s) | Ag(s)

E0Cell = 0.337 – 0.222 = 0.115 V

Zn/Cu Electrochemical Cell
+

Zn(s) ---> Zn2+(aq) + 2e- Eo = +0.76 V

Cu2+(aq) + 2e- ---> Cu(s) Eo = +0.34 V
---------------------------------------------------------------
Cu2+(aq) + Zn(s) ---> Zn2+(aq) + Cu(s)
Eo = +1.10 V
 Cell Voltage
Assume I- ion can reduce water.
2 H2O + 2e- ---> H2 + 2 OH- Cathode
2 I- ---> I2 + 2e- Anode
-------------------------------------------------
2 I- + 2 H2O --> I2 + 2 OH- + H2

Assuming reaction occurs as written,

E˚ = E˚cat+ E˚an= (-0.828 V) - (- +0.535 V) = -1.363 V

Minus E˚ means rxn. occurs in opposite direction

(the connection is backwards or you are recharging the battery)
 Zn (s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s)

Ox Red

• Spontaneous reactions 🡪 electrons flow from left to right.

• Cell voltage ΔV = VR – VL

• Electromotive Force (EMF), E, of a cell is the potential difference of the

cell measured under the condition of no electric current flow.
 EMF

• The “pull” or driving force on electrons

• Measured voltage (potential difference)
 EMF

• Apply current via potentiometer in either direction of the cell. If EMF

changes slightly upon reversing the current direction, cell is
reversible.

• In reversible cell, the chemical reaction can process in either

direction, depending upon the flow of current.

• If E > 0, spontaneous reaction and non-spontaneous if E < 0.

• Can be related to Gibbs free energy, G.

• Consider a cell in which n moles of electrons are transferred from left to
the right electrode.

• Charge magnitude = Qe x NA = 96485 C mol-1 (Faraday constant, F).

• If ΔV > 0, amount of work by electrons = n F ΔV

• For a reversible cell, this work = n F E0

• ΔG = – wnon PV = – n F E0

ΔG0 = – n F E0
• EMF depends on the concentrations of reactant and products in the cell
reaction.
 Problem

• Calculate ΔG0 for the following reaction:

Cu+2(aq)+ Fe(s) 🡪 Cu(s)+ Fe+2(aq)

• Fe+2(aq) + 2e-🡪 Fe(s) E0 = 0.44 V

• Cu+2(aq)+2e- 🡪 Cu(s) E0 = 0.34 V

 Cell Potential, Ecell
• E0cell > 0 ΔG0 < 0 Spontaneous

• E0cell < 0 ΔG0 > 0 Non-spontaneous

• E0cell = 0 ΔG0 = 0 Equilibrium

E0cell: cell potential under standard conditions

• elements in standard states (298 K)
o solutions: 1 M
o gases: 1 atm

Ecell: cell potential under non-standard conditions?

 The Nernst Equation
•

Nernst’s equation for single electrode

 The Nernst Equation

M1 + M2n+ → M2 + M1n+
 Ni|Ni2+ (0.01M)||Cu2+ (0.5M)|Cu
Write the electrode reactions and calculate the EMF of the cell at 298 K
(Std. reduction potentials of Ni and Cu are -0.25 and 0.34 V respectively.)

Solution:

1. Find Anode and Cathode

2. Anode reaction; Cathode reaction; Cell reaction
3. Nernst Equation
 0
Calculating E cell

E0cell = E0cathode - E0anode

Br2(aq)+2V3+ +2H2O(l) → 2VO2+(aq)+ 4H+(aq)+ 2Br-(aq)

Given: E0cell = +1.39 V

E0Br2 = +1.07 V

What is E0V3+ and is the reaction spontaneous?

 Problem
Calculate the voltage generated in the following cell at 298 K:
Mn | Mn2+ (0.1M) || Fe2+ (1M) | Fe

(Std. reduction potentials of Fe and Mn are -0.40 and -1.18 V respectively.)

Solution:

1.Find Anode and Cathode

2.Anode reaction; Cathode reaction; Cell reaction
3.Nernst Equation
A cell is constructed by coupling a zinc electrode dipped in 0.5 M ZnSO4 and a Nickel
electrode dipped in 0.05 M NiSO4. Write the cell representation and cell reaction.
Calculate the EMF of the cell at 298 K.
(std. red. Potentials of Zn and Ni are -0.76 and -0.25 V resp.)

Solution:

1. Find Anode and Cathode

2. Anode reaction; Cathode reaction; Cell reaction
3. Nernst Equation
 Concentration Cell
Consider the following cell:
Ag | Ag+ (0.01M)||Ag+ (1M)|Ag
calculate the EMF of the cell at 298 K

Solution:
Corrosion

Patina
 Corrosion
• Corrosion is the deterioration or destruction and consequent loss of a
solid metallic material due to chemical, electrochemical and other
reactions of the exposed material surface with the surrounding
environment.

• Corrosion represents a return of metals to their more natural state as

minerals (oxides).

• Deterioration of metals through oxidation- usually but not always- to

their oxides.

• For example, when exposed to air, iron rusts, silver tarnishes, and
copper and brass acquire a bluish-green surface called a patina.
 Corrosion
Why are metals not found in their free state?

ENERGY Element Element Ore Formula

•Bauxite •Al2O3.2H2O
Aluminium •Cryolite •Na3AlF6
•Corundum •Al2O3

OR Zinc
•Zinc blende
•Calamine
•ZnS
•ZnCO3
•Zincite •ZnO
E •Haematite •FeO3
METAL Iron
•Magnetite
•Iron Pyrites
•Fe3O4
•FeS2
•Spathic Iron Ore •FeCO3

•Malachite •CuCO3•Cu(OH)2
Copper •Chalcopyrite •CuFeS2
•Copper Glance •Cu2S

•Tin Pyrites •Cu2FeSnS4

Tin •Cassiterite •SnO2

Silver Silver Glance •Ag2S

Why do metals undergo corrosion?

Why most metals undergo corrosion but not Au, Ag and Pt.
 Consequences of Corrosion

✔ Due to formation of corrosion product over the machinery, the efficiency of

the machine gets lost.

✔ The products are contaminated due to corrosion.

✔ The corroded equipment must be replaced frequently.

✔ Plant failure due to corrosion.

✔ Corrosion releases toxic products, health hazard, etc.

 Basics of Corrosion
Corrosion is essentially the oxidation of metal

Need:
1. An Anode (where oxidation is taking place)
2. A Cathode (where reduction is taking place)
3. Conductive electrolyte
4. Electrical contact between the Anode and Cathode
 Basics of Corrosion
Corrosion is essentially the oxidation of metal
 Different Theories of Corrosion

Corrosion

Chemical Electrochemical
or or
Dry Corrosion Galvanic
or
Wet Corrosion

55
 Dry or Chemical corrosion
Dry corrosion is due to the attack of metal surfaces by the atmospheric
gases such as oxygen, hydrogen sulphide, sulphur dioxide, nitrogen,
inorganic liquids etc.

There are three (sub-classification) main types of dry corrosion;

1. Oxidation corrosion (or) corrosion by oxygen

2. Corrosion by other gases

3. Liquid – Metal corrosion.

 Oxidation Corrosion

• Oxidation corrosion is brought about by the direct attack of oxygen at low or

high temperatures on metal surface in the absence of moisture.
• Alkali metals like (Li, Na, K, etc) and alkaline-earth metals (Mg, Ca, Sr, etc) are
rapidly oxidized at low temperature.
• At high temperature, almost all metals (expect Ag, Au and Pt) are oxidized.

M2+
O2-

Metal M2+ O2- Atmosphere

Mn+
O2-

MO (Metal oxide)
 Oxidation Corrosion
The nature of oxide film formed on the metal surface plays in important role in
oxidation corrosion.

• Stable oxide layer: a protective coating and no further corrosion can occur.
Example: Al, Sn, Pb etc.

• Unstable oxide layer: mainly produced on the surface of noble metals, which
decomposes back to the metal and oxygen.

Example: Pt, Ag, etc.

• Volatile oxide layer: The oxide layer volatilizes as soon as it is formed, leaving the
metal surface for further corrosion.

Example: Molybdenum oxide.

• Porous oxide layer: Metal oxides having pores and cracks allow penetration of
oxygen to the underlying metal, resulting in the complete conversion of metal into
its oxide.
Example: Rust
The ratio of the volume of the oxide formed to the volume of the metal
consumed is called “Pilling-Bedworth ratio”.

VOxide Moxide x ρ metal

RPB = =
VMetal Mmetal x ρ oxide

1. If RPB < 1, the oxide layer is porous and non-protective.

e.g. Oxides of alkali and alkaline earth metals

2. If RPB > 1, the oxide layer is Protective or non-porous.

e.g. Oxides of heavy metals such as Sb,V, W, etc

3. If RPB = 1, there will be protective oxide film formation.

e.g. Oxides of Al, Pb, Ni, Cr etc

 Corrosion by Other Gases
• Corrosion by other gases such as Cl2, SO2, H2S, CO2, F2 or NOx

• The extent of corrosion depends upon the chemical affinity between

metal and the gas.

• In dry atmosphere, these gases react with metal and form corrosion
products which may be protective or non-protective.

• Protective: Intensity or extent of attack decreases after layer formed.

Dry Cl2 reacts with Ag and forms AgCl

• Non-protective: Continuous Attack

SnCl4 is volatile
Corrosion by hydrogen
 Liquid– Metal Corrosion
This is due to the chemical action of flowing liquid metal at high temperature on
the surface of another metal.

The corrosion reaction involves

• Dissolution of a solid metal by a liquid metal

• Liquid metal may penetrate in to the solid metal.

Al

Ga

Gallium is corrosive
Liquid metal
Solid metal base to Aluminium
 Wet or Electrochemical Corrosion
Wet corrosion occurs under the following conditions,

• When two dissimilar metals are in contact with each other in the
presence of an aqueous solution or moisture.

• When conducting liquid is in contact with metal.

Zn undergoes corrosion

Electrolyte Electrolyte
Anodic

Zn, Anode Fe, cathode

EoZn = -0.76V EoFe = -0.44V Cathodic
Fe undergoes corrosion
 Wet or Electrochemical Corrosion
When one part of the metal acts as anode and the other as cathode and
corrosion occurs and the following electrochemical reactions occur.

At anode: oxidation or dissolution of metal takes place at this electrode releasing

electrons

M 🡪 M2++ 2e-

At cathode: Reduction takes place using the electrons released at the anode.

Depends on the nature of the corrosive environment.

• Hydrogen evolution type corrosion (Acidic solutions)

• Hydroxide ion formation corrosion (Neutral/alkaline medium)
 H2 evolution corrosion
If the corrosive environment in acidic in nature, hydrogen gas is evolved

Acidic environment: Cathodic H+Cl- H+Cl-

part
2H+ + 2e- H2

Fe Fe2+ + 2e-

Fe metal: Anodic part

As per the following reaction occurring at the cathode

2H+ + 2e- H2
 Formation of OH- Type Corrosion
• Anode: Fe undergoes dissolution to Fe2+ with the liberation of electrons.

• Cathode: Liberated electrons follow from anode to cathode, where dissolved O2 is

consumed to form OH- ions.
½ O2 + H2O + 2e- → 2 OH-

Fe2+ + 2 OH- → Fe(OH)2

Fe(OH)2 + 2 H2O + O2 → 4 Fe(OH)3 Or Fe2O3

Atmosphere: Neutral electrolyte

H2O O2
H2O O2
H2O O2
Fe(OH)3
Fe2+ 2e-

Iron oxide film

Fe metal (cathodic) )part) Crack (anodic part)

Fe Fe2+ +2e-
Corrosion occurs
 Examples for Wet corrosion – Types/Forms

Electrochemical Corrosion

Differential Metallic or
Localized
Bimetallic
• Pitting
Galvanic
• Stress Corrosion
• Waterline Corrosion More negative electrode
potential act as an anode
• Concentration Corrosion
• Inter-granular Corrosion
• Fatigue Corrosion 67
 Inter-granular corrosion
• Metals and alloys have micro-structures that are made up of grains, and
these grains have boundaries. Intergranular corrosion is an attack along or
near the boundaries of several grains while the rest of the grain remains
unaffected. This type of attack is caused by local differences in
composition.

• When it is severe it causes loss of strength and ductility.

 Pitting corrosion
• Pitting occur when there is break in protective oxide layer and imperfections
on the underlying metal.
• Caused by localized mechanical damage, chemical damage to a metals oxide
film, or poor application of protective coating.
• ”Pits” or “holes” range from deep cavities of small diameter to shallow
depression.
 Waterline corrosion
• Occurs when a metal is exposed to varying concentration of oxygen or any
electrolyte on the surface of the base metal.
Example
• Metals partially immersed in water (or) conducting solution (called water line
corrosion).
• If a metal is partially immersed in a conducting solution the metal part above the
solution is more aerated and hence become cathodic.
• On the other hand, the metal part inside the solution is less aerated and thus,
become anodic and suffers corrosion.

Zn
Water rod
line More oxygenated part (Cathodic
part)
1/2O2 + H2O + 2e- 2OH-
Brine solution
Zn2
+

Less oxygenated part (anodic part)

Zn2
+ Zn Zn2+ +2e-
ZnCl2 Undergoes corrosion

Zn2+ + 2OH- Zn(OH)2

 Stress Corrosion
• Metal develop internal stress during manufacturing process.
• Area under stress is high energy---- tend to oxidize--- ANODE
• Stress free area---- Cathode
 Fretting Corrosion

• Fretting corrosion occurs when metals slide over each other and cause
mechanical damage to one or both.
• During relative movement of metals, two process may occur, (i)
frictional heat is generated, which oxidize the metal to form oxide
films. (ii) removal of the protective films resulting in exposure of fresh
surface to corrosion attack.
• This can be avoided by using harder materials, minimizing friction by
lubrication or by proper designing of the equipment.
 Corrosion Fatigue

• Corrosion fatigue is the ability of metal surface to withstand repeated

cycle of corrosion. The metal surface is stressed and simultaneously
attacked by the corrosive media.
• Pits indicating corrosion are formed initially, which further develops in to
cracks.
• The protective surface oxide film reduces corrosion. Under cycling or
repeated stress conditions, rupture of protective oxide films takes place
at a higher rate than at which new protective films can be formed. So the
rate of corrosion is enhanced.
 Oxygen concentration Corrosion
• It is due to the presence of oxygen electrolytic cell.

• i.e. diff in the amount of oxygen in solution at one point exists

when compared to another.

• Corrosion is accelerated when the O2 is least, for example, under

gasket, stuffing boxes etc.
 GALVANIC CORROSION
• When two different metals are in contact with each other in the presence of an
aqueous solution (or) moisture, galvanic corrosion occurs.
• The more active metal (with more negative electrode potential) acts as anode and
the less active metal (with less negative potential) acts as cathode.

e.g. Steel screw in a brass marine hardware corrodes.

• This is due to galvanic corrosion. Iron (higher position in electrochemical series) as
anode, is attacked and corroded, while Copper (lower in electrochemical series)
acts as cathodic and is not attacked.

Fe undergoes corrosion

Electrolyte

Fe, Anode Cu,

EoZn = cathode
-0.44V EoCu =
+0.34V
 Bolt and nuts made of the same metal is preferred, Why?

It is preferred in practice, because galvanic corrosion is avoided due to

homogeneous metals (no anodic and cathodic part).

Rusting of a screw
in an door knob
 Chemical vs Electrochemical corrosion

Chemical Corrosion Electrochemical Corrosion

It occurs only in dry condition It occurs in the presence of moisture or
electrolyte
It is due to the direct chemical attack of It is due to the set up of a large number
the metal by the environment of cathodic and anodic areas
Even a homogeneous metal surface gets Hetergeneous surface or bimetallic
corroded contact is required for corrosion
Corrosion products accumulate in the Corrosion occurs at the anode, while
same place, where corrosion occurs. products formed elsewhere
Chemical corrosion is self-controlled It is continuous process
It follows adsorption mechanism It follows electrochemical reaction
Eg. Formation of mild scale on iron Eg. Rusting of iron in moist atmosphere
surface
 Biological Corrosion
• The role of biological corrosion may be explained by sulphate
reducing bacteria in slightly acidic or alkaline soils.

Reducing bacteria
Hydrogen Calcium
Sulphate Sulphite Sulphite
Anaerobic

On Iron in
Soil

Iron Sulphide
Corrosion pdt
Galvanic Series
Factors Affecting the Rate of Corrosion

1. Position of the metal in EMF series

More the diff. more the corrosion
2. Purity of the metal
Pure less prone
3. Relative area of Anode and Cathode Nature of the metal

Low anodic area and high cathodic area

Steel rivets in Cu plate
4. Physical state (Stress) on the metal
5. Solubility of corrosion product
6. Nature of the metal oxide (corrosion
product) formed
Like volatile?

80
 Factors influencing corrosion
• Solution pH.
• Oxidizing agent.
• Temperature.
• Velocity.
• Surface Films.
• Other Factors.
 Solution pH
• Metals such as iron dissolve rapidly in acidic solution. In the middle pH
range (4 to 10), the conc of H+ ions is low. Hence, the corrosion rate is
controlled by the rate of transport of oxygen.

• Certain amphoteric metals dissolve rapidly in either acidic or basic

solution. E.g. Al and Zn.

• Noble metals are not affected by pH. E.g. gold and platinum.

• H+ ions capture electrons and promote anodic corrosion.

 Oxidizing agents
⚫ Oxidizing agents accelerate the corrosion of one class of materials,
whereas retard another class.

⚫ Oxidizing agents such as oxygen react with hydrogen to form water. Once
hydrogen is removed, corrosion is accelerated. E.g. copper in NaCl

⚫ Oxidizing agent retard corrosion due to formation of surface oxide films,

which makes the surface more resistant to chemical attack.

⚫ Thus a balance between the power of oxidizing agent to preserve the

protective layer and their tendency to destroy the protective film determine
the corrosion of metal.
 Temperature
• Rise in temp increase rate of corrosion.

• Increase in temp reduce the solubility of oxygen or air. The released

oxygen enhances the corrosion.

• Increase in temp induces phase change, which enhance the rate of

corrosion. At high temp organic chemicals are saturated with water. as
temp decreases, water gets condensed.
Corrosion and its Control

Inter-granular Corrosion
1.
Control
Materials selection
of corrosion
2. Alteration of the Environment
3. Proper Design of articles – Avoid Crevice and sharp bends
4. Cathodic protection methods:
a) Sacrificial Anodic Protection
b) Impressed Current Cathodic Protection method
5. Anodic protection method:
6. Corrosion Inhibitors:
a) Anodic inhibitors
b) Cathodic inhibitors
c) Vapour phase inhibitors
7. Protective coating:
a) Electroplating and electro-less plating
b) Physical vapour deposition
c) Chemical vapour deposition
 Materials selection
Materials selection

• Using Pure Metals: Impurity in metal causes heterogeneity that leads

to corrosion.

• Using Metal alloys: Corrosion resistant

Example: Cr in Fe or steel produces stable oxide film, which protect the
steel from further corrosion.

• Large anodic area of the metal

• position of the metals in the galvanic series

 Alteration of the Environment
Typical changes in medium are:

– Lowering temperature –

– Removing oxygen or oxidizers – De-aeration or Hydrazine

– Removing Moisture: Dehumidification by silica gel or Alumina

– Alkaline neutralization– Acidity decrease

 Proper Design
• Wall thickness – allowance to
accommodate for corrosion effect.

• Avoid excessive mechanical stresses and

stress concentrations in components
exposed to corrosive mediums, especially
when using materials susceptible to SCC.

• Metallic Contact: Avoid galvanic contact

• Avoid crevices – e.g weld rather than rivet

tanks and other containers, proper
trimming of gasket, etc.
 Cathodic Protection methods

• The principle involved in cathodic protection is to force the metal to

be protected to behave like a cathode.

• Since, there will not be any anodic area on the metal, corrosion will
not occur.

There are two types of cathodic protection

• Sacrificial anodic protection method

• Impressed current cathodic protection method

 SACRIFICIAL ANODIC PROTECTION METHOD
• In this method, the metallic structure to be protected is made cathode by
connecting it with more active metal (anodic metal).
• So that all the corrosion will concentrate only on the active metal
• The artificially made anode thus gradually gets corroded protecting the
original metallic structure
• Hence this process is otherwise known as sacrificial anodic protection.
 Examples of sacrificial anode:
• This method is used for the protection of ships and boats.
• Sheets of zinc and magnesium are hung around the hull of the ship
• Zinc and magnesium being anodic to iron get corroded.
• Since they are sacrificed in the process of saving iron (anode), they are called
sacrificial anodes

Insulated copper wire

Sacrificial Zn or
Ship hull Mg
 IMPRESSED CURRENT CATHODIC PROTECTION
• In this method, an impressed current is applied in the opposite direction to nullify
the corrosion current and convert the corroding metal from anode to cathode
• This can be done by connecting negative terminal of the battery to the metallic
structure to be protected
• Positive terminal of battery is connected to an inert anode. Inert anode used for
this purpose is graphite (or) platinised titanium.
 Anodic Protection Method
• The principle involved in anodic protection is to force the metal to be
protected to behave like a “more anodic”.

• Used for metals which form protective layer, like Al, Cr, Ni etc.

• In this method, a predetermined potential is applied to the metal specimen and

the corresponding current changes are observed.

• During the initial stage, the current increases indicating the dissolution of the
metal.

• When the current reaches a critical point, passivisation occur, i.e., the oxide
layers set in suitable oxidizing environment. The potential at the critical point
is called passivating potential.

• Above this passivating potential, the current flows decreases to a very small
value called passivating current, the minimum protective current density
required to maintain passivisation.

• At this stage, an increase in potential will not be corrode the metal since the
later is in highly passive state.
 CORROSION INHIBITORS
A corrosion inhibitors is a substance which when added to in small
quantities to the aqueous corrosive environment effectively decreases the
rate of corrosion of the metal.

Inhibitors are classified in to three types,

1. ANODIC INHIBITORS
2. CATHODIC INHIBITORS
3. VAPOUR PHASE INHIBITORS
 ANODIC INHIBITORS
• Chromates, phosphates, tungstates of transition elements, inhibit the anodic
corrosion reaction by forming sparingly soluble compound with a newly
produced metal ion.

• They are absorbed on the metal surface forming a protective film or barrier
thereby reducing corrosion rate.

• This kind of corrosion rate is not fully reliable since certain areas left uncovered
by the film can produce severe corrosion.

Inhibitor
Iron metal rod immersed in
NiCrO4
corrosive medium

corrosive medium
Protective metal
chromate layer Ni2+ CrO42- + Fe3+ 🡪 Fe2(CrO4)3
Iron (III) Chromate
 CATHODIC INHIBITORS
• In acidic solution, the main cathodic reaction is evolution of hydrogen.
2H+(aq) +2e- → H2 (g)

• In an acidic solution, the corrosion can be controlled by slowing down the

diffusion of H+ ions through the cathode.

• This can be done by adding organic inhibitors like amines, pyridine, azoles, etc.
They absorb over the cathodic metal surface and act as a protective layer.

Cathode

H2

2e-
Anode
Fe2+

2H+

2H+ 2Cl-
• In a neutral solution, the cathodic reaction is,

H2O + ½ O2 + 2e- → 2OH-(aq)

• The formation of OH- ions is only due to the presence of oxygen.

• By eliminating the oxygen from the medium, the corrosion rate can be reduced.

• O2 can be removed by adding some reducing agents like, N2H4, Na2SO3 or by

de-aeration.

• Salts of Zn, Mg, Ni are employed as they form insoluble metallic hydroxide
which forms impermeable self barriers.
 VAPOUR PHASE INHIBITORS
Vapour phase inhibitors are organic substances which readily sublime
and form a protective layer on the metal/material surface.

Example : 1. Dicyclohexyl ammonium nitrite 2.

Benzotriazole

Mainly used for metal corrosion

Benzotriazole is an effective corrosion
protection such as automobiles,
inhibitor for copper and its alloys by
internal combustion engines,
preventing undesirable surface
machine tools and tools, spare parts.
reactions. It forms a passive layer, by
It forms a thin protective layer
forming a complex with copper
which can be removed easily
Protective coatings/Metallic coatings

100
 Protective coatings
Thick film coating methods Thin film coating methods

• Electroplating Physical &

• Galvanising Chemical vapour
• Tinning deposition.
• Metal cladding

Organic Coating
 Sample (or) substrate Preparation
• Mechanical cleaning :– To remove loose scale and rust, using hammer,
wire-brushing, grinding and polishing.
• Sandblasting :– To clean large surface areas in order to produce enough roughness
for good adherence of protective coating, using sand with air stream at 25-100
atm.
• Solvent Cleaning :– To remove oil, grease, rust using organic solvents like alcohol,
xylene, toluene, hydrocarbons followed by cleaning hot water or steam.
• Alkali Cleaning : To remove old paints that are soluble in alkaline medium using
chemicals like NaOH, Na3PO4 etc. After cleaning, the metal is washed with 1%
chromic acid solution.
• Acid pickling and etching: Base metal is dipped inside acid solution at a higher
tempt for a long duration. Acids used are HCl, H2SO4, H3PO4, HNO3, under dilute
conditions.
 Metallic coatings
Anodic coating – Galvanization:

It is produced by anodic coating metals (Zn, Al, Cd) on the surface of

base metal (Fe) based on the relative negative electrode potential.

Crack

Zn film

Steel (or) Fe EoFe = -0.44V

 Cathodic Coating

It is produced by cathodic coating metals (Sn, Cu, Ni) on Fe surface based

on the relative positive electrode potential of coat metal.

Crack
Sn film

Steel (or) Fe EoFe = -0.44V

 Methods for Metallic Coating

1. Hot dipping
2. Metal cladding
3. Electroplating
4. Cementation
5. Vacuum metalizing
6. Metal spraying
 Hot Dipping
• It is one of the common method of applying metallic coating on the surface of
base metals.
• Hot dipping is a process of coating the base metal by immersing it in the
molten liquid of the metal to be coated.
Examples: Galvanizing and Tinning
 Galvanization process
NH4Cl flux to
avoid ZnO
formation
Hot air Galvanized
Steel sheet Steel Sheet
Pair of Hot
rollers

Annealing
chamber
250oC

Hot air

Washing bath Molten Zn at Excess Zn

Dil. H2SO4 at 60 Collector
– 90oC 425 – 430oC

• Coating of Iron pipes, screws, bolts, wires, etc.

• Poisonous for utensils that store food stuffs
 Tinning
Tinned
ZnCl2 flux to Steel Sheet
Steel sheet avoid SnO
formation

Hot rollers

Dil. H2SO4 at
60 – 90oC
Molten Sn Palm oil
Acid Pickling

• Used for the coating of steel, Cu and brass sheets that store food
stuffs.
 Metal Cladding
• It is the process of sandwiching the base metal between two thin layers of
coating metal by hot-rolling the composite to produce a firm bonding.

• The coat metals are usually metals of least reactivity (Cu, Ni, Ag, Pt, Ti)

• The cladding layer should be very thin and its thickness is only 5% of the total
composite metal.

• Duraluminium (90% Al and Cu, Mg, Mn) sandwiched between Al sheets and
hot rolled to produce Alclad composite which is free from stress corrosion

109
 Electroplating
Electroplating is the process in which the metal to be coated is deposited
on the base metal (substrate) by passing a direct current in the presence
of electrolytic solution containing the soluble salt of the metal to be
coated.

Objectives of electroplating:
(i) To increase the resistance to corrosion and chemical attack of the
plated metal.
(ii) To obtain a polished surface
(iii) To improve hardness and wear resistance

Uses :
(i) It is often used in electronic industries for making printed circuit
boards, edge connectors, semiconductor lead-out connection
(ii) It is also used in the manufacture of jewelry, refrigerator, electric iron
etc.
 Electroplating of Cu
• The base metal to be plated is made cathode of an electrolyte cell, whereas the anode is
either made of the coating metal itself or an inert material of good electrical conductivity.
• If the anode is made of coating metal itself in the electrolytic cell, during electrolysis, the
concentration of electrolytic bath remains unaltered, since the metal ions deposited from
the bath on cathode are replenished continuously by the reaction of free anions with the
anode.
 DC battery

Cu (Anode) Steel object

+ ve Cu2+
Cu2+ (cathode) (-ve)

Cu2+ SO42-
Cu deposited
surface

Process
Ionization reaction of electrolyte:
CuSO4 Cu2+ + SO42- ; H2SO4 2H+ + SO42-

On passing current:
Cu2+ + 2e- Cu (at cathode)
Cu + SO42- CuSO4 + 2e- (at anode)
 Thin-Film Depositions
• PVD Coating (Physical Vapor Deposition)
• CVD Coating (Chemical Vapor Deposition)

lead frame gold wire

bonding pad

chips connecting pin

 Physical Vapour Deposition
In PVD, materials are first evaporated and then condensed to form a
solid material on the target at higher temperatures.

Evaporation Techniques:

• Evaporative deposition: In which the material to be deposited is

heated.

• Cathodic Arc Deposition: High-power electric arc discharged at

Source to produce highly ionized vapor to be deposited.

• Electron beam physical vapor deposition: In which the material

to be deposited is heated to a high vapor pressure by electron
bombardment.

• Sputter deposition: In which a glow plasma bombards the material to

be deposited.
 Deposition process
• Clean the substrate or object to be coated with solvent and acid pickling then dry
the substrate by hot air blower
• Clean the chamber, load the substrate in to the PVD chamber at the substrate
holder also place the source metal to be coated inside the chamber
• Heat the source metal (beyond melting point), sublimed vapour condensed on the
substrate surface which is kept at room temperature
PVD Chamber

Substrate
TiN film
View Port

Heater

N2 / H 2 Suction valve
Ti Metal
2000oC
To vacuum pump
 Chemical Vapour Deposition
• In typical CVD, the substrate is exposed to one or more volatile
precursors, which react and/or decompose on the substrate surface to
produce the desired deposit.

• Frequently, volatile by-products are also produced, which are removed by

gas flow through the reaction chamber.

Polysilicon

SiH3Cl → Si + H2 + HCl, SiH4 → Si + 2 H2

Silicon dioxide

SiH4 + O2 → SiO2 + 2 H2
SiCl2H2 + 2 N2O → SiO2 + 2 N2 + 2 HCl
Si(OC2H5)4 → SiO2 + byproducts

Silicon nitride

3 SiH4 + 4 NH3 → Si3N4 + 12 H2

 Organic Coating
• Organic coatings act as a protective barrier against corrosion and
oxidation.

• These are durable coatings applied to a substrate for their decorative or

specific technical properties.

• Organic coatings depend primarily on their chemical inertness and

impermeability.

• Various types of organic coatings are available for industrial purposes

including primers, adhesive cements and topcoats (enamel, varnish and
paints).

• Organic coatings are easy to apply with the help of brushes, sprays, rollers,
dips, or by electrostatic means.

• The coating cures or dries by evaporation or loss of solvent,

polymerization and oxidation.
 Charging a Battery
When you charge a battery, you are forcing the electrons backwards
(from the + to the -). To do this, you will need a higher voltage
backwards than forwards. This is why the ammeter in your car often
goes slightly higher while your battery is charging, and then returns to
normal.