CHEM ENG 3029_7055

Materials Science and Engineering

 Lecture 6

Introduction to Corrosion and its Mechanisms

 Lecture Structure
Lecture 6 (Introduction to Corrosion and its Mechanisms) is divided into the following sections:
• L6.1 – Introduction to Corrosion
– Overview and Context
– Definition of Corrosion
– Importance of Corrosion in Engineering
– Cost of Corrosion
– Safety of Corrosion
• L6.2 – Introduction to Thermodynamics and Electrochemistry of Corrosion
– Thermodynamics of Corrosion
– Chemical and Free Energy
– Electrochemistry of Corrosion
– Predicting Corrosion: Standard EMF Series
• – Introduction to Types of Corrosion and Mechanisms
L6.3 – Formalisation of Corrosion
– Predicting and Monitoring Corrosion
– Formalisation Approach
– Thermodynamic Formalisation
– Electrochemical Potentials
– Electrochemical Double Layer
– Standard Hydrogen Electrode (SHE)
– Establishment of Electrochemical Potentials
• L6.4 – Electrochemical Series and Cell Potential
– Electrochemical Series
– Galvanic Series
– Reference Electrodes
– Cell Potential: Daniel Cell

Reference Book: W. D. Callister and D. G. Rethwisch, Materials Science and Engineering: An Introduction, John Willey & Sons ISBN: 9781119321590

Complementary Reference Book: P. A. Schweitzer, Fundamentals Of Corrosion: Mechanisms, Causes, and Preventative Methods, CRC Press ISBN:
9781420067705
 Lecture Structure
• L6.3 – Formalisation of Corrosion
– Predicting and Monitoring Corrosion
– Formalisation Approach
– Thermodynamic Formalisation
– Electrochemical Potentials
– Electrochemical Double Layer
– Standard Hydrogen Electrode (SHE)
– Establishment of Electrochemical Potentials
L6.3 – Formalisation of Corrosion
o Learning Objectives

✓ How to formalise electrochemical reactions (corrosion)

thermodynamically and electrochemically

✓ Introduction to electrochemical potential concept and

the standard hydrogen electrode

✓ How electrochemical potentials are established

University of Adelaide 5
L6.3 – Formalisation of Corrosion
• Predicting and Monitoring Corrosion
Basic concepts to prevent corrosion:
(i) Good (smart) design (materials, coatings, structural
design, etc.)
(ii) Role of E–pH diagram in understanding protection
mechanisms (i.e., those conditions where we can avoid or
reduce corrosion)
(iii) Cathodic and impressed current cathodic protection
(iv) Anodic protection
(v) Coatings
(vi) Inhibitors

University of Adelaide 6
L6.3 – Formalisation of Corrosion
• Formalisation Approach
– Introduce the basic thermodynamic concepts that underpin corrosion
– Gibbs free energy
– Nernst equation

– Identify the four conditions required for wet corrosion to occur

– Discuss the practicalities of measuring electrochemical potentials
– Standard electrochemical potential series and galvanic series
– Types of reference electrodes

– Introduce the electrochemical cell

– Cell potential calculations
– Mechanism for establishing a potential

University of Adelaide 7
L6.3 – Formalisation of Corrosion
• Thermodynamic Formalisation
Fe in CuSO4 solution

Mild steel
sample

10 g/100 ml
CuSO4 solution

What happens? Copper replates out of

solution onto the iron
University of Adelaide 8
L6.3 – Formalisation of Corrosion
• Thermodynamic Formalisation
Copper plating
– How does this happen? Half Reactions
• Fe Fe 2+ + 2e -
Iron is corroding

• Cu 2+ + 2e - Cu
Copper is replating (reducing)

Complete Reaction
Fe + Cu 2+ Fe 2+ + Cu

University of Adelaide 9
L6.3 – Formalisation of Corrosion
• Thermodynamic Formalisation
– Copper replating (reduction) is spontaneous therefore:

ΔG < 0
– Free energy is dependent on temperature:

ΔG = ΔGo +RTlnJ

Where J is: For the following reaction

jA + kB = lC + mD
University of Adelaide 10
L6.3 – Formalisation of Corrosion
• Thermodynamic Formalisation
– If the system reaches equilibrium:
– No net change in free energy
ΔG = 0
and J = K the equilibrium constant
ΔGo = -RTlnK
– For iron in copper sulphate solution:

Complete Reaction
Fe + Cu 2+ Fe 2+ + Cu

University of Adelaide 11
L6.3 – Formalisation of Corrosion
• Thermodynamic Formalisation
– Free energy of the reaction:
Concentration of solids is 1, then:

– Faraday showed:
ΔG = (-zF)E
E is measured in volts
F = 96,494 C·mol–1,
z is valency (2 in this case)

University of Adelaide 12
L6.3 – Formalisation of Corrosion

• Thermodynamic Formalisation
Free energy can be related to electrochemical potential:
– For standard conditions

ΔGo = (-zF)Eo

-zFE = -zFEo +

– Divide by -zF
E = Eo -
zF
University of Adelaide 13
L6.3 – Formalisation of Corrosion
• Thermodynamic Formalisation
– Equation can be written more generally as:

– Substituting values for R,T and F and converting to

log10
Nerst Equation

Pay attention that both products and

reactants are ions (no solids)
University of Adelaide 14
L6.3 – Formalisation of Corrosion
• Electrochemical Potentials
Metals corrode by loss of electrons (oxidation)
– For example:
M+ M+
M+
M+
Fe Fe2+ + 2e– M+ M+
M+
M M+ M+
Formation of ions M+ M+
M+
results in a loss of metal M+
M+ M+
M+

Solid metal Ions in solution

University of Adelaide 15
L6.3 – Formalisation of Corrosion
• Electrochemical Potentials
Equilibrium: Loss of electrons continues until driving
force is zero

Change in potential
with distance

M = M z+ + ze

University of Adelaide 16
L6.3 – Formalisation of Corrosion
• Electrochemical Potentials
Wet Corrosion Cell
• Four components
– Anode (+)
• Corrodes by loss of e-
M = Mz+ + ze- (oxidation)
» z = valency
– Cathode (-)
• Consumes e-
Mz+ + ze- = M (reduction)
» does not normally corrode
H+ + e- = H, 2H= H2
– Electrolyte solution
– Connections
Remove one component and
corrosion stops
University of Adelaide 17
L6.3 – Formalisation of Corrosion
• Electrical Double Layer
Interface or double layer (metal + solution) FACTS

M+ M+ • + ions (cations) set up

M+
M+ potential field
M+ M+
M+ • 1 volt across 10-10 m
M M+ M+
• This is a very strong field
M+ M+
M+ = 108 V/cm
M+
M+ • Hence there is a very
M+ M+
large accelerating force
on the electric charges
Potential difference f
How do we measure this potential force or
voltage?
University of Adelaide 18
L6.3 – Formalisation of Corrosion
• Standard Hydrogen Electrode (SHE)
Measuring Electrochemical Potential
Potential or Voltage
– Not an absolute value
– Can only be measured relative to another
substance (reference)
• Standard reference
• Hydrogen is chosen as the reference standard

University of Adelaide 19
L6.3 – Formalisation of Corrosion
• Standard Hydrogen Electrode (SHE)

University of Adelaide 20
L6.3 – Formalisation of Corrosion
• Establishment of Electrochemical Potentials
Iron (Fe) test sample vs SHE • Iron dissolves:

Fe Fe 2+ + 2 e-
• Hydrogen gas is formed:

H+ + e- H; 2H H2
• Overall reaction:

Fe + 2H+ Fe 2++ H2

University of Adelaide 21
L6.3 – Formalisation of Corrosion
• Establishment of Electrochemical Potentials
– Using the Nernst equation
  Fe2+   H  
E=E −
o RT
ln    2

zF   Fe  H +   2

   

– Now [H] = 1 Hydrogen standard electrode

[H+] = 1 0.5 mol/L sulphuric acid (H2SO4) solution
[Fe] = 1 metallic solid
z=2 valency of Fe

– Hence E=E −
0.059
o

2
(
log  Fe2+  )

University of Adelaide 22
L6.3 – Formalisation of Corrosion

• Establishment of Electrochemical Potentials

E = Eo - 0.059 log [Fe2+]

2
However [Fe2+] also = 1
– 1 M ferrous sulphate (FeSO4) solution

So: - 0.059 log [Fe2+] = 0

2
and E = Eo

The measured potential difference is the electrode

potential of iron under standard conditions

University of Adelaide 23