MM 453

MM435_Corrosion, Degradation and Protection
Fall-2018
By
Ramzan Abdul Karim
GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY
FACULTY OF MATERIALS & CHEMICAL ENGINEERING

Contact Details
Office : G-09, FMCE
Phone Ext.: 2309
ramzan.karim@giki.edu.pk
Office visiting hours (Fall 2018)
Monday 09:00-10:30
Tuesday 09:00-10:00
Wednesday 10:00-11:30
Friday 14:30-16:00
Please ask in anticipation via email for meetings other than these timings..!
MM-435_Corrosion, Degradation and Protection 2

Course outline
1. Introduction: Corrosion definition and basics, Corrosion Science and Engineering, Corrosion
Environments, Corrosion Damage, Corrosion Classification, , Electrochemical Aspects of corrosion.
Role of a corrosion engineer.
2. Corrosion Kinetics and Thermodynamics: The Driving Force of Corrosion, Gibbs free Energy of
Chemical Reactions, Rate of Corrosion Factors Effecting Corrosion Rate, Modern electrochemical
theory and thermodynamics of corrosion, electrochemical cell, Electrode potential/emf series,
Nernst equation, Pourbaix diagrams for Fe system, electrode kinetics, passivity, Polarization and
types, Ohmic drop at electrolyte/metal interface, exchange current density and its measurement,
3. Common types of Corrosion: Corrosion types and their preventive measures, weld decay, selective
leaching/dealloying, dezincification, graphitization, velocity induced corrosion, Mechanically
assisted attack, stress corrosion cracking, Hydrogen damage and embrittlement, Microbiologically
influenced corrosion.
4. Corrosion Monitoring: Salt spray/fog test, corrosion rate (MPY) and penetration rate calculations,
electrochemical corrosion testing, limiting current density, polarization diagrams (Evans diagram)
and corrosion data analysis,Tafel extrapolation, Tafel slopes determination from polarization curve,
linear polarization resistance (LPR), potentiodynamic and potentiostatic polarization resistance,
electrochemical impedance spectroscopy (EIS).
5. Corrosion of Ceramics and Degradation of Polymers
6. Corrosion Protection: Measures of corrosion control, cathodic protection, anodic protection, types
of coatings, corrosion inhibitors, Corrosion control by design…etc.
Learning Outcomes
Blooms
Learning Outcome PLOs Taxonomy
Level
Students will:
Be able to relate the basic principles & practices of corrosion, its
CLO_1 thermodynamics, and chemistry of corrosion, kinetics and PLO1 C3
factors involved in corrosion.
Be able to evaluate the corrosion behavior of materials by using
the laws of thermodynamics and kinetics of corrosion and by
CLO_2 PLO2 C5
modern corrosion analysis tools and techniques to finally
develop the ways to control the corrosion.
Be able to analyze the risks of corrosion damages by applying
the knowledge of the mechanisms of various types of corrosion
CLO_3 PLO3 C4
and develop solutions to control and avoid/minimize the overall
corrosion by applying corrosion preventive strategies.
Text & Reference Books

1. Pierre R. Roberge, Ph. D., P.Eng, “Corrosion Engineering Principles and
Practice” 1st Edition,, McGrawHill, 2008.
2. Zaki Ahmad, “Principles of Corrosion Engineering and Corrosion Control”
Elsevier, 2006
3. H. Uhlig and W. Revie, “Corrosion and Corrosion Control” Wiley, 4th Edition,
New York, 2008.
4. Mars Fontana, “Corrosion Engineering” , 1987. McGraw Hills.
4
MM-435_Corrosion, Degradation and Protection
Grading Criteria
Assignments/Case Studies ( 2/4 ) = 4%
Quizzes ( Six ) = 20%
Midterm Exam = 30%
Course Project = 6%
Final Exam = 40%
General Instructions
• 80% Attendance to Qualify for Exams
• Come within the first five minutes of the class
• Note down your own attendance
• Not to proxy for any one
• No retake of quizzes/exams..!
• Not to sleep, talk, or make disturbance in the class
• Be precise, to the point, brief, explicit in examination
• Use dimensions and units
• No Exchange of calculators and other stuff during quizez and exams 5
Corrosion
“It is an interaction between a material, usually a metal, and its environment that
results in deterioration of the material, and the environment.”
It is the oxidation of a metal due to an ELECTROCHEMICAL reaction. The oxidizing agent is

most often O2 (atmospheric corrosion) or H+ (chemical corrosion) or both. 6
Corrosion
Corrosion is based on the Latin word “corrodere” which means to eat away
“It is an interaction between a material, usually a metal, and its environment that results
in deterioration of the material, and the environment.”
(A Groysman, Corrosion for everybody, 2010)
OR
It is extractive metallurgy in reverse.
OR
An electrochemical process between a metal/non metal and its environment that leads to
the deterioration of properties of the material
(MG Fontana, Corrosion Engg. 1987)
Think about:
• Dissolution of sugar and salt in water
• Burning (oxidation) of wood or paper Corrosion..??
• Dissolution of metals in hydrochloric acid,

• Oxidation of metals in a furnace/atmosphere Corrosion..??
7
Corrosion Product
Rust a reddish brown “corrosion product” formed

on iron (Fe) surfaces
For deterioration of other metals, the term “corrosion product” is used, and not “rust”.
For example,
white corrosion products are formed on aluminium and zinc,
blue and blue-green on copper,
green on nickel,
pink on cobalt, etc.
8
Corrosion Product
• Can we always observe a corrosion product?

NO..!
Sometimes pits in a metal surface
as a result of the reaction between a

metal and the environment, but we
do not see the corrosion product.
9
Problems due to Corrosion
Metals lose their:
 Pleasant appearance,
 Dimensions
 Mechanical, thermal, and optical properties

Corrosive Environments
Corrosion Vs. Environment
Magnitude of Corrosion depends upon the sensitivity of a certain metal/alloy to a
specific Environment
Common Types of Environments

1) Air and humidity
2) Water (fresh, distilled, salt and marine)
3) Atmospheres (Natural/urban/marine/ industrial
steam and gases (Cl2, NH3, H2S, SO2 etc)
4) Acids
5) Alkalies
6) Liquids
7) Soils
High temperatures and pressures…???

They usually become causes of more severe corrosion
11
Corrosion Classification
The corrosion may be wet or dry corrosion in simple classification
(based on state of the environment).
Wet Corrosion ( liquid / aqueous solutions / electrolyte)

Dry Corrosion (No liquid, gases / vapours)
Dry and moist chlorine…??? (steel / titanium)

Dry chlorine is noncorrosive to ordinary steel but in moisture,
chlorine rapidly and severely attacks steels, and other metals and
alloys.
The reverse is true for titanium.
12
Corrosion Science and Engineering
•Corrosion Science covers theories, laws and explanation of

corrosion phenomena confirmed by the observations or experiments.
Corrosion science is a ‘knowing why’ of corrosion.
•Corrosion Engineering is the application of science and art to

prevent or control corrosion damage safely and economically.
Corrosion engineering is ‘knowing how’ to control/prevent corrosion.
13
Corrosion Science and Engineering
What a Corrosion Engineer should be capable of?  Well acquainted with corrosion
science and corrosion engineering.
Corrosion engineer should know:
Chemical, metallurgical, physical and
mechanical properties of materials.
Practices and principles of corrosion
Nature of corrosive environments
Corrosion problems by corrosion

testing
Design of the engineering structure.
Corrosion prevention and control

methods
14
Corrosion Damages
• Plant shutdowns:
• nuclear plants,
• process plants, unexpected corrosion failure How to avoid..??
• power plants and plant shutdown
• refineries
• Loss of products:
• Containers
• storage tanks, Leakage due to unexpected
• fuel tanks corrosion failure
• water and oil transportation lines
25% of H2O is lost due to leakage problems..!!
• Loss of efficiency:
Insulation of heat exchanger tubing's and pipelines due to corrosion
products…thus loosing the heat exchanging efficiency
15
Corrosion Damages
• Contamination:
• Corrosion products may contaminate chemicals, pharmaceutical packaged goods,
etc. with dire consequences to the consumers.
• The market value of a product depends on its purity and quality.
• A very small amount of corrosion may introduce certain metals ions in the solution
which may catalyse the decomposition of the product.
• Nuclear hazards:
• The Chernobyl disaster (1986) is a continuing example of transport of radioactive
corrosion products in water, fatal to human, animal and biological life.
• Appearance:
• Structures have to be painted in order to avoid the rust appearance which is
unpleasing to the eyes.
• Outside surfaces of buildings are often made of stainless steel Al or Cu for the
sake of appearance and corrosion prevention.
16
Corrosion Damages
• Maintenance and operating costs
• Substantial cost savings can be made in plants by using of corrosion resistant
materials in construction.
A poor choice of joining materials e.g. a bolt can lead to heavy costs.
e.g. Failure of a small component may lead to the destruction of the entire
structure.
• Design engineer and corrosion engineers must collaborate to devise a
combined strategy for an efficient corrosion prevention protocol because:
It is easier and cheaper to erase line on a drawing than to repair or replace a
failed equipment in the plant.
• Effect on safety and reliability:

• Handling of hazardous materials such as toxic gases, HF, concentrated sulfuric
and nitric acids, explosive and flammable compounds, radioactive
substances, and chemicals at high temperature and pressure demand the use
of construction materials that minimize corrosion failures.
• Health:
• Depletion of resources…!!! 17
Managing Corrosion Risk
Corrosion Risk managing Stages:
• Design Stage,
• During Operation (maintenance and control)
18
Question?
How Chromium (Cr) will protect Iron in stainless steel when

Cr is only 13% compared to Fe >50% ?
Ans:
Basically as the steel first corrodes the iron will be lost into
solution while the chromium oxide (Cr2O3) will stay on the
surface.
After a few atomic layers have been oxidised the surface
will be covered by a continuous layer of chromium oxide.
Although the steel is corroded on the atomic level, it
appears stainless.
19
Why Corrosion Occurs
Corrosion….
Extractive metallurgy in reverse..!!

Corrosion product of iron (Fe),
Primary: Fe(OH)2 (or more likely FeO·nH2O),
Secondary:
• Fe2O3·H2O {Fe(OH)3} or hydrous ferrous oxide,
red-brown rust, called hematite.
• Fe3O4·H2O or hydrated magnetite,

most often green
• Fe3O4 or magnetite
black.
21
Why Corrosion Occurs??
Pt, Au (noble metals) = stable in most corrosive environments,
Whereas,
Fe and Zn corrode in the same environment.
How can we predict if a particular metal will corrode

under specific conditions/environments?
Answer lies in the study of thermodynamics of corrosion

process..!!
Gibbs Free Energy
22
Corrosion….
Why it occurs…??

Driving force behind a chemical reaction
G o   ni .G of ( products)   ni .G of (reac tan ts )
• If
GT  o
o
Reaction will be spontaneous and corrosion is more likely

• If
G T  oo
The corrosion reaction will not occur.
• There is also the yellow light situation, when
G T  o o
Which means that the sum of chemical potentials

(Gibbs energies) of reactants equals the sum of chemical potentials of
products. In other words chemical equilibrium is established.
24
Occurrence of corrosion……….. ∆ G
The rate of corrosion…………????
25
How can we predict if a particular metal will corrode
under specific conditions?
(∆G) tells us that if a certain chemical process can occur

spontaneously under certain environmental conditions or not.
∆ G = − nFEocell
26
Electrochemical Nature of Corrosion
Zn
Acidity and Alkalinity (pH)
Zn  2 HCl  ZnCl2  H 2
Zn  2 H   2Cl   Zn 2  2Cl   H 2
chloride ions……don’t take part directly
Bubbling, or “plating out of

hydrogen” on zinc immersed
in 0.1 M HCl solution.

Daniel Cell
This situation leads to a Galvanic Corrosion Cell

(bimetallic corrosion)

Corrosion of Fe, Mechanism

Anodic/Corrosion Reactions for other metals
Generalized Anodic Reaction
Cathodic Reactions
aerated


Corrosion of Zn in HCl

Corrosion of Zn in aerated HCl
Anodic Reaction
Cathodic Reactions

Corrosion of Mg in neutral water

Surface Area Effect

Next Topics:
Introduction to different forms of corrosion
Corrosion Cells
36
Anodic/Corrosion Reactions for common metals
Generalized Anodic Reaction
Cathodic Reactions
aerated


Corrosion of Zn in HCl

Corrosion of Zn in aerated HCl
Anodic Reaction
Cathodic Reactions

Corrosion of Mg in neutral water

Surface Area Effect

Forms of Corrosion
1. Uniform Corrosion, 5. Intergranular Corrosion,
2. Galvanic Corrosion, 6. Selective leaching,
3. Crevice Corrosion, 7. Erosion–Corrosion and
4. Pitting Corrosion, 8. Stress Corrosion

Forms of Corrosion
Uniform Corrosion
Corrosion that occurs with equivalent intensity over the entire exposed surface
It often leaves behind a scale or deposit.
In a microscopic sense, the oxidation and

reduction reactions occur randomly over
the surface.
Examples include general rusting of steel

and iron.
This is probably the most common form of

corrosion.

Forms of Corrosion
Galvanic Corrosion
Galvanic corrosion occurs when two metals or alloys having different compositions are
electrically coupled while exposed to an electrolyte.
More reactive metal in the particular environment

experiences corrosion; the more inert metal, the
cathode, is protected from corrosion.
Examples:
Steel screws corrode when in contact with brass
in a marine environment
Copper and steel tubing are joined in a domestic

water heater, the steel corrodes in the vicinity of
the junction.

Forms of Corrosion
Crevice Corrosion
this type of corrosion occurs in crevices

and recesses or under deposits of dirt or
corrosion products where the solution
becomes stagnant. Corrosion preferentially
occurring at these positions is called
crevice corrosion
Causes: concentration gradients in

electrolyte cause some areas high in ion
concentrations that accelerate oxidation
This plate was immersed in seawater, crevice corrosion has occurred

at the regions that were covered by washers.

Forms of Corrosion
Pitting Corrosion
Pitting is another form of very localized corrosion attack in which small pits or holes are formed.
They ordinarily penetrate from the top of a horizontal surface downward in a nearly vertical direction.
The mechanism for pitting is same as for crevice

corrosion, in that oxidation occurs within the pit itself

Forms of Corrosion
Intergranular Corrosion
Occurs in specific alloys – precipitation of corrosive specimens along grain
boundaries and in particular environments
e.g. : Chromium carbide forming in SS, leaving adjacent areas depleted in Cr

Forms of Corrosion
Erosion Corrosion
Erosion–corrosion arises from the combined action of chemical attack and
mechanical abrasion or wear as a consequence of fluid motion.
Causes: abrasive fluids impinging on surfaces

Commonly found in piping, propellers, turbine
blades, valves and pumps

Forms of Corrosion
Selective Leaching
one element or constituent is preferentially removed as a
consequence of corrosion processes
• Occurs in alloys – e.g., in Brass, Zinc is electrically active

and is removed, leaving behind porous Copper
(dezincification of brass)
• Occurs in other metals, such as Al, Fe, Co, Cr

Forms of Corrosion
Stress Corrosion Cracking
results from the combined action of an applied
tensile stress and a corrosive environment
Cracks grow along grain boundaries as a result

of residual or applied stress or trapped gas or
solid corrosion products
e.g., brasses are sensitive to ammonia
Stress levels may be very low
A bar of steel bent into a horseshoe shape using a nutand-bolt assembly.
While immersed in seawater, stress corrosion cracks formed along the bend
at those regions where the tensile stresses are the greatest.

Hydrogen Embrittlement
Various metal alloys, specifically some steels, experience a significant reduction in
ductility and tensile strength when atomic hydrogen (H) penetrates into the material.
• Metals loose strength when Hydrogen is absorbed

through surface, especially along grain boundaries
and dislocations
• Often occurs as a result of decorative plating
• High strength steels particularly susceptible

Corrosion Cells
Types of Corrosion Cells

Daniel Cell
This situation leads to a Galvanic Corrosion Cell

(bimetallic corrosion)

Corrosion Cells
Basic Components of a corrosion cell:
1. Anode
All these components should be present in an
2. Cathode electrochemical corrosion cell
3. Electrolyte
4. Electrical connection

Corrosion Cells
1. Galvanic Cells
2. Concentration Cells
3. Differential Temperature Cells
4. Stress Cells
5. Microbial Cells
6. Electrolytic Cells

Corrosion Cells - Galvanic Cells
Galvanic corrosion cell is developed between two dissimilar metals

Whenever a copper pipe service line is directly connected to a cast iron gas
or water main, a galvanic cell is formed:
• the soil is the electrolyte,

• the copper service line is the cathode,
• the iron main is the anode
Copper fitting
Iron
58
Galvanic Cell
59
Solution…???
Galvanic Cell
60
Corrosion Cells -Concentration Cells
• Concentration Cells
(a) Differences in compositions of the soil.
(b) Differences in moisture content of soils.
(c) Variation in the amount of oxygen in soils.

Corrosion Cells -Concentration Cells
• Dissolved salts in a soil environment can be complex mixtures and include compounds of aluminum,
calcium, magnesium, and other metals combined with sulfates, chlorides, hydroxides.
• Chloride ions, for example, can be quite aggressive toward steel
Chloride Rich Areas…… Anode
Chloride Starved Areas….Cathode
62
Corrosion Cells – Concentration + Galvanic Cells
• The main difference in the environment surrounding the steel anchor is due to the variation of pH
between the soil typically acidic and the basic pH in the concrete anchorage (pH > 10).
• Because this higher pH is protective to steel, it naturally follows that the steel in concrete becomes
the cathode drawing an anodic current from the adjacent steel in the soil.
Galvanic Cell
Concentration Cell
Low pH/acidic Areas…… Anode
High pH/basic Areas….Cathode
63

Corrosion Cells –
Differential Aeration: Oxygen Concentration Cells
• Generally, oxygen enables a corrosion reaction by maintaining a cathodic
reaction
• Corrosion can further be promoted where there is a difference in the

concentration of dissolved oxygen (DO) even between two points of the same
metal surface. O Concentration Cell
2
Oxygen Rich Areas…… Cathode

Oxygen Starved Areas….Anode
64
Corrosion Cells –
Differential Aeration: Oxygen Concentration Cells
65
Corrosion Cells – Temperature Cells
• The hot pipe near the compressor is the anode

• The cooler pipe down the line is the cathode
• The soil is the electrolyte
• The pipe itself is the connecting circuit
66
Corrosion Cells – Stray current cells
In stray current cells the energy comes from an electrical current external to the
corrosion site.
Possible sources of energy for such cells:
• a distant generator,
Deliberate
• a cathodic protection rectifier on some other line
• a direct-current transmission line

Accidental
• a street car system, or an electric railway
67
Presence of Stray Currents:
68
Presence of Stray Currents:
69
Corrosion Cells – Stress cells
Anode established by residual internal stress often produced by cold work
Solution….??
Stress Relieving….!!

Corrosion Cells – Microbial Corrosion Cells (MIC)
Microorganisms tend to attach themselves to solid surfaces, colonize and form
biofilms which may in turn produce an environment at the biofilm/metal interface
radically different from the bulk environment in terms of pH, dissolved oxygen, organic
and inorganic species.

Corrosion Cells – Surface Film cells

Corrosion Cells – Electrolytic Cells
They may consist of all the basic

components of galvanic cells and
concentration cells
plus
an external source of
electrical energy.
This is used for Cathodic

Protection of Metals
73
Visualizing Corrosion Cells
The existence and location of anodes and cathodes in a corrosion cell can be
demonstrated by the changes in color of certain reagents.
Cathode Anode
Anode
Cathode

Visualizing Corrosion Cells
The existence and location of anodes and cathodes in a corrosion cell can be
demonstrated by the changes in color of certain reagents.
Cathode Anode
Anode Cathode

Next Topics….!!
Electrode Potential
Cell Potentials
Free Energy & Thermodynamics
Electrochemical & Galvanic Series

Electrode Potentials
Standard Electrode Potential
A standard potential refers to the potential of pure metal measured with reference to a
hydrogen reference electrode called as Standard Hydrogen Electrode (SHE).
OR
If the substances taking part in the process are in their standard states, such that the
activities of the metallic ions are equal to unity or gases are at 1 bar pressure, the
potentials obtained are called ‘Standard Electrode Potentials’
What is Standard Hydrogen Electrode (SHE)…..????

Standard Hydrogen Electrode ( SHE )
SHE is arbitrarily assigned a potential of exactly 0.0000 volt
and is used as a reference
Platinized platinum
78
THE ZINC-SHE CELL: a special cell
Zinc electrode is
the anode SHE is the
cathode
Zn (s) + 2H+ (aq, 1M)  Zn2+ (aq, 1M) + H2(g, 1 atm)

79
Zn – SHE Cell
ox. anode
red.cathode
overal reaction
Ecell = E (anode) + E (cathode)

Once measured the electrode potential and the accompanying reaction are reported in
the reduction form
Zn2+ + 2e-  Zn E0 = - 0.763 V written as reduction
and not
Zn  Zn2+ + 2e- E0 = + 0.763 V written as oxidation
80
Zn – SHE Cell
The standard Zn electrode behaves as anode when combined with SHE
and the measured potential of the cell is called standard oxidation
potential for Zn Zn2+
The convention is to report all electrode potentials in the reduction form as given
below ! !
E0reduction
The standard reduction potentials of electrodes are tabulated along with

reduction half-reactions.
81
Standard Reduction Potential table
82
COPPER-SHE CELL
SHE is the Cu electrode is

anode the cathode
H2 (g, 1atm) + Cu2+ (aq, 1M)  Cu (s) + 2H+(aq, 1M)

83
THE COPPER-SHE CELL
Notice:
SHE works as anode when combined with Cu/Cu2+ electrode
SHE works as cathode when combined with Zn/Zn2+ electrode
84
85
Cell Potential / emf
The potential difference between the two electrodes of a voltaic cell ( Ecell)
Also known as the electromotive (“causing electron motion”) force, or emf.
Also called the voltage of the cell (because emf/potential is measured in volts)
86
Determining Standard State Cell Potentials
Predict the natural (spontaneous) direction of redox reactions.
spontaneous ?
Zn + Cu2+  Zn2+ + Cu Cu + Zn2+  Cu2++ Zn
Zn displaces Cu2+ or Cu displaces Zn2+ ? ?
Find the standard cell potential for an electrochemical cell with the following cell reaction.
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
l. Choose the appropriate half-reactions from the table
; Eº = - 0.763 v
; Eº = + 0.337 v
2. Choose the half reaction with the more +ve (or less - ve) Eo as the spontaneous
reaction on the cathode (reduction):
87
.
3 Reverse the other half-reaction and its potential to make it oxidation
Zn  Zn2+ + 2 e ; +0.763 [notice sign of the potential]
.
4 Balance the number of electrons if necessary
Cu2+ + 2 e-  Cu ; +0.337 Zn  Zn2+ + 2 e- ; +0.763
5.Add the half-reactions and the associated potentials.
Cu2+ + 2 e  Cu +0.337 V (st. red. potential)

Zn  Zn2+ + 2 e +0.763 V (st. Ox. potential)
Zn +Cu2+ Zn2+ + Cu ; E0cell =+1.100 V (+ve means favoured)

88
89
Predicting which species oxidizes which
one ?
In an acidic solution under standard conditions,
will Sn4+ ions oxidize NO to NO3 ions,
-
or
-
will NO3 ions oxidize Sn2+ to Sn4+ ions
NO3- + 4H+ +3e  NO + 2H2O +0.96 V ( from table )

Sn4+ + 2e → Sn2+ +0.15 V ( from table )
2 (NO3- + 4H+ +3e- NO + 2H2O) + 0.96 V (red)
3 (Sn2+ Sn4+ + 2e- ) - 0.15 V (ox)
2 NO3- +8H+ + 3Sn2+  2NO +4H2O+ 3Sn4+ ; E0cell = +0.81 V
90
Next Topics….!!
Free Energy & Thermodynamics
Electrochemical & Galvanic Series
Reversible electrode Potentials
Nernst Equation

Free Energy, G
How to calculate G
G  G( products)  G(reac tan ts )

Example:-
Solution:-

Example Problem
Calculate the standard enthalpy change for the following reaction at 298 K
when the standard enthalpies of formation are:
Solution

Example Problem
For the given reaction:
Deduce the direction in which the reaction would be feasible at 300K and 1200 K,
when all reactants and products are in their standard states (i.e. unit activities)
and the given values of enthalpies and entropies are:
Solution
As there is positive value of Gibbs Energy for the reaction at 300 K, the reaction
proceeds from right to left in the reverse direction at 300 K.
As there is negative value of Gibbs Energy for the reaction at 1200 K, the reaction
proceeds from left to right in the forward direction at 1200 K.
Free Energy and Corrosion Cells
The amount of work done by a cell is equal to the quantity of electrical energy which it
generates under constant pressure, temperature and concentration of the reaction.
In an electrochemical reaction, electrical energy available is equal to the product of

potential of the cell and the quantity of electricity involved
Net work done by the cell is given as:

Electrical energy = volts × amperes × time
= E×Q
= E×nF
(Work can only be performed if the free energy of the cell is decreased)
Where
For standard states:

Example Problem
Determine standard Reaction Potential for the following cell:
when we are given:
Solution

EMF and Galvanic Series: EMF Series
EMF Series:
a) EMF series lists only metals (little
engineering application). Alloys not included
b) Electrode potentials listed calculated from

thermodynamic principles (corrosion
potentials are more relevant).
c) Equilibrium potentials with concentrations

at unit activity (Exact prediction of galvanic
coupling not possible).
d) Predicts only tendency to corrode (Role of

passive films and oxidation kinetics not
predicted).
e) Effect of environment not predicted

EMF and Galvanic Series: Galvanic Series
Galvanic Series:
a) Instead of standard electrode potentials, actually

measured rest potentials of metals and alloys in
a given environment arranged with respect to
nobility and activity.
b) Effect of coupling of metals and alloys on

corrosion rate can be predicted.
Certain anomalies..!!
a) e.g: Stainless steels (active and passive)
b) Galvanic series is generally good for stagnant

conditions and not for turbulent conditions.

99
Reversible Electrode Potential
If a metal is immersed in a solution of its own ions, such as zinc in ZnSO4
solution, or copper in CuSO4 solution, the potential obtained is called the
reversible potential (Erev).
How to Calculate Reversible Electrode Potential..??

Nernst Equation…!!

Nernst Equation
The contribution made by one mole of any constituent, A, to the total free energy, G, of a mixture is GA, which may
be represented by:
relationship between free

MM-435_Corrosion, Degradation and Protection energy and equilibrium constant
101
Nernst Equation
Nernst equation expresses the emf

of a cell in terms of activities of
products and reactants taking
place in the cell reaction
Nernst Equation

Nernst Equation
Nernst equation expresses the emf of a cell in terms of
activities of products and reactants taking place in the
cell reaction
Nernst Equation

Nernst Equation
Example:
OR

Nernst Equation
Example:
Also the cell potential can be written as the sum of two half cells potentials as:
105
Problem:
Calculate the reversible potential for a zinc electrode in contact with ZnCl2 when the
activity of zinc is a Zn2+ = 10−3
Solution:

Sign conventions for Cell potentials:
; Eº = - 0.763 v
; Eº = + 0.337 v
E = 0.337 + 0.763
E = 1.1 v
Daniel Cell

Sign conventions for Cell potentials:

Nernst Equation
What if reacting species are

in gaseous form??
Nernst Equation
Nernst equation expresses the emf of a cell in terms of

activities of products and reactants taking place in the
cell reaction
Problem:
Show that for the reduction reaction giv
Solution:

Problem:
In the cell reaction given below, what is the ratio of the activities of ionic species
required to make the polarity reverse? Standard reduction potentials of Fe & Sn are
-0.441 and -0.140 respectively.
Solution:
Now

Problem:
The emf of a cell made of Zn (anode) and H2 electrode (cathode) immersed in 0.7 M
ZnCl2 is +0.690 volts. What is the pH of the solution? Given that activity coefficient (γ)
for Zn2+ is 0.6133. [ E˚(Zn)= - 0.762, R = 8.314 J/(mol·K), F = 96490 C, T = 298◦ K ]
Solution:

Problem:
Calculate the theoretical tendency of nickel to corrode (Ecell) in de-aerated water of pH= 8.
Assume the corrosion products are H2 and Ni(OH)2 and the solubility product of Ni(OH)2 is
1.6×10−16. Use IUPAC sign conventions for the electrode reactions involved.
-
[E˚(Ni)= 0.250, R= 8.314 J/(mol·K), F= 96500 C, T= 298◦ K ]
Solution:

Next Topics….!!
 Liquid Junction Potential

 Reference Electrodes
 Pourbaix Diagrams

Liquid Junction Potential
Liquid Junction Potentials---occur at the boundary between two solutions that
have different ionic compositions---
This potential difference is caused by:
1. The migration of ions (diffusion) from one electrolyte to another electrolyte.

2. Different rate of diffusion of oppositely charged ions.
Example:
Concentrated Dilute
Concen. HCl // dil. HCl.
 Both H+ and Cl− ions diffuse from

concentrated HCl to dilute HCl.
 The H+ ion moves faster and, therefore,
the dilute solution becomes positively
charged due to ingress of H+ ions from
the stronger acid solution.
 And the more concentrated solution thus
acquires a relative negative charge due
to increase of Cl− ions in the remaining
solution

Reference Electrodes:
Standard Hydrogen Electrodes:

Ag/AgCl Electrode:

The Colomel electrode (Hg/Hg2Cl2)

Cu/CuSO4 Electrode:

Ohmic Drop (IR drop):
The IR drop is the ohmic voltage that results from
the electric current flow in ionic electrolytes,
When the reference electrode for
measurement of potential is placed in the
electrolyte, an electrolytic resistance exists
along the line between the test and the
reference electrode.
Because the ionic current flows through an

electrolyte resistance an ohmic voltage drop
is also automatically included in the Current Interruption method
measurement of potential When there is no current flow there cannot be
any IR drop. However, when a current is flowing
IR drop is included in the measurement.
At a certain time, t, the current is interrupted so
that I=0, hence IR is also zero. The test electrode,
therefore, shows a potential free from IR drop.
Hence
IR drop Removal Methods: current interruption provides a good method for
measurement of IR free cell potential.
a. Extrapolation Method
b. Current Interruption Method
122

MM 453

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MM435_Corrosion, Degradation and Protection

Ramzan Abdul Karim

GHULAM ISHAQ KHAN INSTITUTE OF ENGINEERING & TECHNOLOGY

FACULTY OF MATERIALS & CHEMICAL ENGINEERING

MM-435_Corrosion, Degradation and Protection 2

5. Corrosion of Ceramics and Degradation of Polymers

Text & Reference Books

It is the oxidation of a metal due to an ELECTROCHEMICAL reaction. The oxidizing agent is

• Dissolution of metals in hydrochloric acid,

Rust a reddish brown “corrosion product” formed

• Can we always observe a corrosion product?

Sometimes pits in a metal surface

as a result of the reaction between a

Metals lose their:

 Mechanical, thermal, and optical properties

MM-435_Corrosion, Degradation and Protection 10

Common Types of Environments

High temperatures and pressures…???

Wet Corrosion ( liquid / aqueous solutions / electrolyte)

Dry and moist chlorine…??? (steel / titanium)

The reverse is true for titanium.

•Corrosion Science covers theories, laws and explanation of

Corrosion science is a ‘knowing why’ of corrosion.

•Corrosion Engineering is the application of science and art to

Corrosion engineering is ‘knowing how’ to control/prevent corrosion.

Practices and principles of corrosion

Nature of corrosive environments

Corrosion problems by corrosion

Design of the engineering structure.

Corrosion prevention and control

• The market value of a product depends on its purity and quality.

• Effect on safety and reliability:

How Chromium (Cr) will protect Iron in stainless steel when

Extractive metallurgy in reverse..!!

MM-435_Corrosion, Degradation and Protection 20

Corrosion product of iron (Fe),

Primary: Fe(OH)2 (or more likely FeO·nH2O),

• Fe3O4·H2O or hydrated magnetite,

Fe and Zn corrode in the same environment.

How can we predict if a particular metal will corrode

Answer lies in the study of thermodynamics of corrosion

Gibbs Free Energy

MM-435_Corrosion, Degradation and Protection 23

Reaction will be spontaneous and corrosion is more likely

The corrosion reaction will not occur.

• There is also the yellow light situation, when

Which means that the sum of chemical potentials

The rate of corrosion…………????

(∆G) tells us that if a certain chemical process can occur

chloride ions……don’t take part directly

Bubbling, or “plating out of

MM-435_Corrosion, Degradation and Protection 27

This situation leads to a Galvanic Corrosion Cell

MM-435_Corrosion, Degradation and Protection 28

MM-435_Corrosion, Degradation and Protection 29

Generalized Anodic Reaction

MM-435_Corrosion, Degradation and Protection 30

MM-435_Corrosion, Degradation and Protection 31

MM-435_Corrosion, Degradation and Protection 32

MM-435_Corrosion, Degradation and Protection 33

MM-435_Corrosion, Degradation and Protection 34

MM-435_Corrosion, Degradation and Protection 35

Introduction to different forms of corrosion