BASICS OF CORROSION

Reading Material: Chapter 1 in

Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996.

Dr. Ramazan Kahraman

Chemical Engineering Department
King Fahd University of Petroleum & Minerals
Dhahran, Saudi Arabia
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What is Corrosion?
z

Reaction of a metal with its environment

Aqueous corrosion
reaction with water (usually containing
dissolved ions)

High temperature oxidation

reaction with oxygen at high temperature
High temperature corrosion
reaction with other gases
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Examples of Corrosion
z Rusting

of steel
corrosion product (rust) is solid
but not protective
z Reaction of aluminium with
water
corrosion product is insoluble in
water, so may be protective
z Burning of magnesium in air
high temperature oxidation

Rust on an iron surface

Corrosion Science and Engineering

z Corrosion

Science
Study of the chemical and metallurgical
processes that occur during corrosion.

z Corrosion

Engineering
Design and application of methods to
prevent corrosion.

Why is Corrosion Happening?

Because metals want to go back to their stable states.
For Example, Fe is stable when it reacts with oxygen.
So, in the presence of a corrosive environment, Fe
tends to separate (decompose) from steel and reacts
with oxygen

Nature of Corrosion
z Formation

of cell is essential for corrosion

z Corrosion

cell comprises of the following

Anode (supplies e- - oxidation reaction)

Cathode (consumes e- - reduction reaction)
Electrolyte
Conductor (electron path)
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Electrodes
z Electrodes

are pieces of metal on which an

electrochemical reaction is occurring

z An

anode is an electrode on which an

anodic or oxidation reaction is occurring

zA

cathode is an electrode on which a

cathodic or reduction reaction is occurring

Electrochemical Cell
electrons

HCl
ANODE

ELECTRON
PATH

CATHODE

ELECTROLYTE
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Electrochemical Cell (cont.)

Corrosion of a Metal in Acid

HCl solution

Metal

M+n

M
e

H+

H2

H+
H+

Anodic Rxn

H+

H+

ClCl-

M+n + n e-

Cathodic Rxn nH+ + n e-

n/2 H2
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Corrosion of a Metal in Aerated Water or

Aerated Basic Solutions

Metal

M+n

M
e-

Anodic Rxn

Aerated H2O or
Basic Solution

H2O
O2

OH-

M+n + n e-

Cathodic Rxn (n/2)H2O + (n/4)O2 + ne-

n OH11

Acids and Bases

z An

acid is a substance that produces

excess hydrogen ions (H+) when dissolved
in water
examples are HCl, H2SO4
z A base (alkali) is a substance that
produces excess hydroxyl ions (OH-) when
dissolved in water
examples are NaOH, KOH
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Acids and Bases (cont.)

Note that H+ and OH- are in equilibrium in water:
H2O H+ + OHThe product of [H+] times [OH-] is 10-14, so in
pure water both [H+] and [OH-] are 10-7. This
leads to the concept of pH, which is defined as
-log[H+]
Hence pH = 0 is strong acid, 7 is neutral, and
14 is strong alkali
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Corrosion of Zinc in Acid

Zinc known as a base or active metal

Zinc dissolves with hydrogen evolution

Zn + 2HCl ZnCl2 + H2
z

But we can separate metal dissolution

and hydrogen evolution
Zn Zn2+ + 2e2H+ + 2e- H2

These are known as electrochemical

reactions
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Corrosion of Platinum in Acid

z Platinum

does not react with acids

z Platinum

is known as a noble metal

15

Zinc and Platinum in Acid Not Connected

Zinc and platinum not
connected, no reaction
on platinum
Zn

Pt

HCl
Zn + 2HCl ZnCl2 + H2
metal + acid salt + hydrogen
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Connection of Platinum to Zinc

(This is galvanic corrosion which will be studied in detail later)
electrons

Zinc and platinum

connected, current flows
and hydrogen is evolved
on platinum

Zn

Pt

C
HCl

Zn Zn2+ + 2e-

metal metal ions + electrons

(negligible cathodic rxn on Zn relative to that on Pt)

2H+ + 2e- H2

hydrogen ions + electrons hydrogen gas

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External Current Applied to Platinum in Acid

Hydrogen evolved on
negative electrode
2H+ + 2e- H2

Pt

Oxygen evolved on
positive electrode
+
2H2O O2 + 4H+ + 4ePt

HCl
Overall reaction
2H2O 2H2 + O2

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External Current Applied to Platinum in Alkali

Hydrogen evolved on
negative electrode
2H2O + 2e-
H2 + 2OH-

Pt

Oxygen evolved on
positive electrode
4OH- O2 + 2H2O + 4e-

Pt

NaOH
Overall reaction
2H2O 2H2 + O2

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External Current Applied to Platinum

A piece of metal
in the solution
z Hydrogen

or
z

evolution at one electrode

(acids)
2H+ + 2e- H2
2H2O + 2e- H2 + 2OH(alkalis)

Oxygen evolution at the other electrode

(acids)
2H2O O2 + 4H+ + 4eor 4OH- O2 + 2H2O + 4e- (alkalis)

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Anodic Reactions
z Oxidation

reactions
z Produce electrons
z Examples
Zn Zn2+ + 2e-

zinc corrosion

Fe Fe2+ + 2e-

iron corrosion

Al Al3+ + 3e-

aluminium corrosion

Fe2+ Fe3+ + e-

ferrous ion oxidation

H2 2H+ + 2e-

hydrogen oxidation in acids

H2 + 2OH- 2H2O + 2e-

hydrogen oxidation in water or bases

2H2O O2 + 4H+ + 4e-

oxygen evolution in acids

4OH- O2 + 2H2O + 4e-

oxygen evolution in water or bases

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Cathodic Reactions
z Reduction

reactions
z Consume electrons
z Examples
O2 + 2H2O + 4e- 4OHO2 + 4H+ + 4e- 2H2O
2H2O + 2e- H2 + 2OH2H+ + 2e- H2
Cu2+ + 2e- Cu
Fe3+ + e- Fe2+
Sn4+ + 2e- Sn2+

oxygen reduction in water/bases

oxygen reduction in acids
hydrogen evolution in water/bases
hydrogen evolution in acids
copper plating
ferric ion reduction
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Cathodic Rxns in Acidic & Basic Solns

z

Deaerated Acidic Solutions

2H+ + 2e- H2
Aerated Acidic Solutions
2H+ + 2e- H2
O2 + 4H+ + 4e- 2H2O
(presence of O2 further increases corrosion)
Deaerated Neutral or Basic Solutions
2H2O + 2e- H2 + 2OHAerated Neutral or Basic Solutions
O2 + 2H2O + 4e- 4OH(this reaction causes higher corr. rate)
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Corrosion Rate
z

Simplest and most useful technique for corrosion rate

determination is the Weight Loss Technique
Corrosion Rate = mass / exposed surface area . time
or
Corrosion Rate = avg. corrosion penetration depth / time
( = mass / density . surface area . time )

Common Corrosion Rate Units

gmd (grams of metal lost per square meter per day)
mm/y (average millimeters penetration per year)
mpy (avg. mils penetration per year, 1 mil = 0.001 in)
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Example
A carbon steel test specimen of dimensions
2-in 3-in 0.125-in with a 0.25-in hole for
suspending in solution is exposed for 120
hours in an acid solution and loses 150
milligrams. Calculate the corosion rate in
mpy and mm/y.

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26

Home Exercise Problems

Prbs. 1, 4, 8, 10 and 11 of Chapter 1

in Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996.

27

Faradays Law
z Charge

is related to mass of material

reacted in an electrochemical reaction:
M Mn+ + neOne metal ion

n mols of electrons
To produce one mol
of metal ion and
Reacts
28

Faradays Constant
z One

mole of metal (MW g) contains Avogadros number

(61023) of metal atoms

z Hence

each mole of metal will produce n times that

many number of electrons

z Charge

on the electron is 1.6 10-19 C (coulomb)

one mole of metal will produce a charge of n

96500 C

z Hence
z 96500

C/equivalent is known as Faradays constant

(also in units of J/Vequivalent)

z Conversions:

1 A (ampere) = 1 C/s, 1 J = 1 CV
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Faradays Law

Q
m= M
nF
where Q = charge (coulomb, C)
F = Faraday' s constant (96500 C/equivalent)
n = number of equivalents (mols of electrons) transferred
per mol of metal
m = mass of metal oxidized (g)
M = molecular (atomic) weight of metal (g/mole)

So, if Q is known, mass loss by corrosion can be determined.

The details of corrosion rate determination by electrochemical
techniques will be covered later.
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References

Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996.

Web Site of Dr. R. A. (Bob) Cottis.

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