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?

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
Rusting

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

Rust on an iron surface

Corrosion Science and Engineering

Corrosion

Science Study of the chemical and metallurgical processes that occur during corrosion. Engineering Design and application of methods to prevent corrosion.

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
Formation Corrosion

of cell is essential for 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
Electrodes

are pieces of metal on which an electrochemical reaction is occurring anode is an electrode on which an anodic or oxidation reaction is occurring

An

A

cathode is an electrode on which a cathodic or reduction reaction is occurring

Electrochemical Cell
electrons

ELECTRON PATH

HCl ANODE

CATHODE

ELECTROLYTE
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Electrochemical Cell (cont.)

Corrosion of a Metal in Acid

Metal
M e
-

HCl solution M+n e

-

H+ H+ H+ H+

H+ H2 ClCl-

Anodic Rxn

M+n + n en/2 H2
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Cathodic Rxn nH+ + n e-

Corrosion of a Metal in Aerated Water or Aerated Basic Solutions

Metal
M eH2O O2

M+n OH-

Aerated H2O or Basic Solution

Anodic Rxn

M+n + n en OH11

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

Acids and Bases

An

acid is a substance that produces excess hydrogen ions (H+) when dissolved in water examples are HCl, H2SO4 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

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

Platinum Platinum

does not react with acids is known as a noble metal

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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 Pt C HCl
metal metal ions + electrons
(negligible cathodic rxn on Zn relative to that on Pt)

Zn A

Zn Zn2+ + 2e-

hydrogen ions + electrons hydrogen gas

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2H+ + 2e- H2

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 + 2OHPt 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
Hydrogen

or

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
Oxidation

reactions Produce electrons Examples

Zn Zn2+ + 2eFe Fe2+ + 2eAl Al3+ + 3eFe2+ Fe3+ + eH2 2H+ + 2eH2 + 2OH- 2H2O + 2e2H2O O2 + 4H+ + 4e4OH- O2 + 2H2O + 4ezinc corrosion iron corrosion aluminium corrosion ferrous ion oxidation hydrogen oxidation in acids hydrogen oxidation in water or bases oxygen evolution in acids oxygen evolution in water or bases
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Cathodic Reactions
Reduction

reactions Consume electrons 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

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

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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Home Exercise Problems

Prbs. 1, 4, 8, 10 and 11 of Chapter 1 in Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996.

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Faradays Law
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
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Faradays Constant
One

mole of metal (MW g) contains Avogadros number (61023) of metal atoms each mole of metal will produce n times that many number of electrons on the electron is 1.6 10-19 C (coulomb) one mole of metal will produce a charge of n 96500 C C/equivalent is known as Faradays constant (also in units of J/Vequivalent) 1 A (ampere) = 1 C/s, 1 J = 1 CV
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Hence

Charge Hence 96500

Conversions:

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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