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Degradation of Materials: Metals

This document discusses the degradation of metals through corrosion processes. It introduces electrochemical concepts like the electrochemical series (EMF series), galvanic series, corrosion cells, and Pourbaix diagrams. The EMF series lists standard electrode potentials but does not account for environmental factors, while the galvanic series provides actual measured potentials for metals in a given environment. Pourbaix diagrams show the thermodynamic stability of a metal as a function of potential and pH. They can predict the predominant species of a metal under certain conditions but do not provide kinetic information.

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Oliver Tabell
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61 views17 pages

Degradation of Materials: Metals

This document discusses the degradation of metals through corrosion processes. It introduces electrochemical concepts like the electrochemical series (EMF series), galvanic series, corrosion cells, and Pourbaix diagrams. The EMF series lists standard electrode potentials but does not account for environmental factors, while the galvanic series provides actual measured potentials for metals in a given environment. Pourbaix diagrams show the thermodynamic stability of a metal as a function of potential and pH. They can predict the predominant species of a metal under certain conditions but do not provide kinetic information.

Uploaded by

Oliver Tabell
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

Degradation of Materials

Metals

EMF Series
Standard potentials of metals in contact with its ions in

equilibrium at a concentration equal to unit activity

Anode = metal which is more active in EMF series

EMF Series

Limitations of EMF Series


Does not take into account other chemicals making the metal

more active
Does not consider thin films formed on metals that might make
them more noble
Alloys are not included

Galvanic Series
Metals and alloys with their actual measured potentials in a

given environment

positions of metals in the series depend on the environment

Galvanic Series
Platinum
Gold
Graphite
Titanium
Silver
316 Stainless Steel (passive)
Nickel (passive)
Copper
Nickel (active)
Tin
Lead
316 Stainless Steel (active)
Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium

Based on Table 17.2, Callister


6e. (Source of Table 17.2 is
M.G. Fontana, Corrosion
Engineering, 3rd ed.,
McGraw-Hill Book Company,
1986.)

Thermodynamic Basis of Cell Potential


Recall the relationship:

G
E =
nF

However, Gibbs Free Energy is related to


activity/concentration of the reactants and
products

wA + xB yC + zD
G = G o + RT ln Q
aCy aDz
Q= w x
a A aB

Thermodynamic Basis of Cell Potential

Nernst Equations:

RT
E=E
ln Q
nF
o

At T = 298.15K

RT
log Q
E = E 2.303
nF
o

0.0257
ln Q
E=E
n
o

0.0592
E=E
log Q
n
o

Pourbaix Diagrams
Summary of

thermodynamic data in the


form of potential-pH
diagrams
Relates electrochemical and
corrosion behavior of any
metal in H2O
Devised by Marcel Pourbaix

Advantages
Shows specific conditions of

potential and pH under


which metal either reacts or
not

Disadvantages
Not an indication of rate of

reaction
Derived for specific
temperature and pressure
Derived for selected
concentration of ionic
species
Most consider only pure
substances

Key Features
Vertical lines separate species related by acid-base equilibria
Non-vertical lines separate species related by redox reactions
Horizontal lines separate species in redox equilibria not involving

hydrogen or hydroxide ions.


Diagonal boundaries separate species in redox equilibria in which
hydroxide or hydrogen ions are involved.

Uses
Any point on the diagram will give thermodynamically stable

form of the element for that E and pH


Ex) at E=0.8V and pH=14 for iron
Predominant species is FeO42-

The diagrams give a visual representation of the oxidizing and

reducing abilities of the major stable compounds of the element

Limitations
1. Diagrams are drawn for equilibrium situations (derived for specific temperature

and pressure conditions and selected concentrations of ionic species).


2. Most diagrams consider pure metals in simple solutions - for example the above

diagram applies to pure water and pure iron only.


3. The pH used on diagrams is the pH of the solution in contact with the metal, not the

bulk solution.
4. No information on corrosion kinetics is provided by these thermodynamically

derived diagrams.

Quiz
What does thermodynamics tell us about corrosion?
What is the driving force for corrosion and how is it related to cell potential?
The absolute potential of an electrode can be measured using a voltmeter.
(True/False)
4.
Give two examples of inert or noble metals.
5.
What information can an EMF series or Galvanic series provide?
6.
How is the EMF series different from the Galvanic series?
7.
What are the four components of a corrosion cell?
8.
The removal of any of the four components will stop the corrosion reaction.
(True/False)
9.
Explain how tarnished silver can be cleaned using an Al foil and hot water.
10. Write the step-by-step procedure in calculating the Ecell of a corrosion cell
1.
2.
3.

Quiz
How can the corrosion of steel in water be stopped given

that at pH 7 the steel develops a potential of -0.5V, just inside


the Fe2+ region. Provide three methods.

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