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Kinetics of Corrosion

Bob

Cottis

This presentation is copyright Bob Cottis 1997. All rights reserved. It may not be copied as a whole or in part in any form without prior written permission of the author.

Recommended Books
Corrosion

Engineering, Fontana Corrosion, Shreir

What is Corrosion?
Reaction

of a metal with its environment Aqueous corrosion


reaction with water (usually containing dissolved ions)
High High

temperature oxidation temperature corrosion

reaction with oxygen at high temperature


reaction with other gases

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

Corrosion of Zinc in Acid

Acids and Bases


An

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

base is a substance that produces excess hydroxyl ions (OH-) when dissolved in water
examples are NaOH, KOH

Corrosion of Zinc in Acid


Zinc

dissolves with hydrogen evolution Zn + 2HCl ZnCl2 + H2 known as a base or active metal

Zinc

One atom zinc metal plusof two molecules hydrogen reacts toof form one molecule of molecule zinc chloride plus one of hydrogen gas chloride (hydrochloric goes to acid)

Corrosion of Platinum in Acid


Platinum

does not react with acids Platinum is known as a noble metal

Connection of Platinum to Zinc Zinc and platinum Zinc and platinum not
electrons

current flows connected, no reaction and hydrogen is evolved on platinum on platinum

Zn

Pt

HCl
Zn 2HCl ZnCl 2H+ + 2e- H2 Zn + Zn2+ + 2e 2 + H2 metal + acid salt+ +electrons hydrogen hydrogen ions + electrons hydrogen gas metal metal ions

Connection of Platinum to Zinc


Zn + 2HCl ZnCl2 + H2 But we can separate metal dissolution and hydrogen evolution Zn Zn2+ + 2e2H+ + 2e- H2 These are known as electrochemical reactions One atom of zinc metal two electrons in the metal

one zinc ion in solution Reactions that involve both chemical change and the transfer of charge

External Current Applied to Platinum in Acid


Hydrogen evolved on negative electrode 2H+ + 2e- H2 Oxygen evolved on positive electrode + 2H2O O2 + 4H+ + 4e-

Acid - chemical species Pt Pt that produces hydrogen ions in water


HCl

Overall reaction
2H2O 2H2 + O2

External Current Applied to Platinum in Alkali


Hydrogen evolved on Oxygen evolved on + The product of [H times [OH ] - ] negative electrode positive electrode + -14, so is both 2H2O + 2e- H10 + 2OH- in pure water 4OH- O2 + 2H2O + 4e2
+] and [OH-] are 10-7. This [H + Alkali chemical species that Note that OH in Pt H and Ptare leads to the concept of pH , produces hydroxyl ions (OH+) equilibrium in water: which is defined as -log[H ] in water H2O H+ + OHHence pH = 0 is strong acid, 7 NaOH is neutral, andreaction 14 is strong Overall alkali 2H O 2H + O
2 2 2

External Current Applied to Platinum A piece of metal


in the solution
Hydrogen

or

evolution at one electrode 2H+ + 2e- H2 (acids) 2H2O + 2e- H2 + 2OH- (alkalis)

Oxygen evolution at the other electrode 2H2O O2 + 4H+ + 4e(acids) or 4OH- O2 + 2H2O + 4e(alkalis)

Faradays Law
Charge

is related to mass of material reacted in and electrochemical reaction: 2H+ + 2e- H2


Two hydrogen ions To produce one molecule of hydrogen gas

React with two electrons

Faradays Constant
One

mole of hydrogen ions (1 g) contains Avogadros number (6 1023) ions Hence electrons will react with each mole of hydrogen ions Charge on the electron is 1.6 10-19 C Hence one mole of ions requires 96500 C This is known as Faradays constant

Faradays Law
nFm Q M where Q charge (C) F Faraday' s constant (96500 C/mole) n number of electrons transferr ed m mass of metal oxidised (g) M atomic weight of metal (g/mole)

Electrodes
Electrodes

are pieces of metal on which an electrochemical reaction is occurring An anode is an electrode on which an anodic or oxidation reaction is occurring A cathode is an electrode on which a cathodic or reduction reaction is occurring

Anodic Reactions
Examples

Zn Zn2+ + 2eFe Fe2+ + 2eAl Al3+ + 3eFe2+ Fe3+ + eH2 2H+ + 2e2H2O O2 + 4H+ + 4e Oxidation reactions Produce electrons

zinc corrosion iron corrosion aluminium corrosion ferrous ion oxidation hydrogen oxidation oxygen evolution

Cathodic Reactions
Examples

O2 + 2H2O + 4e- 4OH2H2O + 2e- H2 + 2OHCu2+ + 2e- Cu Fe3+ + e- Fe2+ Reduction reactions Consume electrons

oxygen reduction hydrogen evolution copper plating ferric ion reduction

Metal Ion Hydrolysis


Note

that metal ions may react with water (a hydrolysis reaction) e.g. Al3+ + 3H2O Al(OH)3 + 3H+ or 2Al3+ + 3H2O Al2O3 + 6H+
Note

that in an electrochemical reaction, we have the same number of each atom on each side of the equation, and the same overall charge

Effect of Potential
Electrochemical

reactions involve transfer of

charge Hence, we expect that the voltage of the metal with respect to the solution will affect electrochemical reactions Voltage of metal with respect to solution is known as the electrochemical potential

Corrosion of zinc in acid


When

zinc is placed in acid the metal will start to dissolve and hydrogen will start to be liberated according to the potential of the metal Consider the anodic zinc dissolution reaction Zn Zn2+ + 2e-

Corrosion of zinc in acid


Electrochemical Potential If the potential is above Then the corrosion rate may bethe Corrosion Potential, then it will fall due to expressed as the 2+ + 2e- of electrons production Zn Zn If the corrosion current potential is below the Corrosion Potential, density, icorr Rate of Reaction At the Corrosion it will rise, due to As the then reaction involves Potential, E , we have a corr consumption of rate electrons transfer of charge, the stable mixed equilibrium of reaction may be as a current per + + 2e- H 2Hexpressed 2 unit area, or current density icorr Current density Rate of Reaction

Ecorr

How Fast will Corrosion Occur?


Corrosion

kinetics

Concerned with the rates of corrosion reactions


Mixed

potential theory:

The corrosion potential will be that potential at which the sum of all anodic (positive) and cathodic (negative) currents on the electrode is zero
Polarization

The change in potential that is caused by the passage of a current

Types of Polarization
Activation

Polarization

The polarization necessary for the electrochemical reaction to go at the given rate Given by Tafels Law:

i E Eo b log io

E = potential at current i Eo = potential at current io b = Tafel slope

E-log i and Evans Diagrams


Plot

E against E log |i|, then activation and i for the o o polarization gives a straight cathodic reaction line
Electrode Potential

Anodic reaction, Tafel slope Mixed equilibrium icorr for the Tafel slope E is corr and Cathodic reaction, expressed as occurs when sum of reaction positive corrosion slope is mV Tafel per decade all currents is zero negative Eo and io for the of current anodic reaction mV log (-i2) - log (-i1) log |current|

Concentration Polarization
Additional

polarization caused by drop in concentration of a reactant at the electrode surface As concentration falls, more polarization is needed to make the current flow Eventually, no more current can flow because no more reactant can reach the metal, and a limiting current is reached

Concentration Polarization
Oxygen

reduction is often affected by concentration polarization


Electrode Potential Rate of cathodic oxygen Rate of cathodic oxygen reduction without reduction with concentration polarization Limiting current density concentration polarization rate of reaction limited by availability of oxygen at the metal surface

log |current density|

Resistance Polarization
If

there is a resistance between the anode and the cathode in a cell, then the current flowing through that resistance will cause a potential drop given by Ohms Law: V = IR This is important for paint films and for high resistance solutions

Resistance Polarization
Electrode Potential
Resistance Polarization causes potential of anode and cathode to differ due to potential drop across solution, hence corrosion current is reduced

log |current density|

Passivation
When

a passive film is formed, this causes a marked drop in current density due to the resistance of the film and its effect as a barrier to diffusion This effect is seen on the anodic curve

Passivation
Electrode Potential The rate of corrosion will be When aRapid stable passive film rate of cathodic critically affected by the has formed, the current has reaction leads to passivation, cathodic curve Lower rate of cathodic a steady, low value the and low rate of corrosion But it slow may lead to and low Current fallsalso as passive reaction leads to the activity, passive current density Very cathodic reaction rate ofof corrosion? film starts to form the Active corrosion gives normal high rate corrosion leads to low rate of corrosion active-passive transition activation polarization

log |current density|

Polarization Curves
Iron

in hydrochloric acid
Electrode Potential

Anodic iron dissolution Cathodic hydrogen evolution

log |current density|

Polarization Curves
Iron

in sulphuric acid
Electrode Potential

Anodic iron dissolution (with active-passive transition) Oxygen evolution on passive film (or transpassive corrosion Cathodic hydrogen evolution as metal is oxidised to a higher oxidation state)

log |current density|

Polarization Curves
Iron

in aerated neutral NaCl solution


Electrode Potential

Cathodic oxygen reduction Anodic iron dissolution Cathodic hydrogen evolution

log |current density|

Effect of pH on reaction rate


Consider

hydrogen evolution reaction 2H+ + 2e- H2 The concentration of hydrogen ions will influence the rate of the reaction As the hydrogen ion concentration is increased (i.e. the solution made more acid), so the rate of the reaction increases Similarly the potential will influence the reaction - the more negative the potential the faster the reaction

Effect of pH and potential on rate of hydrogen evolution


Slower
Potential

Faster

pH

Effect of pH on reaction rate


On

platinum no metal dissolution will occur, but to balance the charge a reaction which creates electrons must occur If the solution contains dissolved hydrogen, the reverse of the hydrogen evolution reaction can occur: H2 2H+ + 2e-

Effect of pH on reaction rate


H2

2H+ + 2e-

This

reaction will go faster in alkaline solution (since H+ will be removed by H+ + OH- H2O)
reaction will go faster at more positive potentials (because electrons will be removed from metal)

This

Effect of pH and potential on rate of hydrogen oxidation


Oxidation Faster Reduction Slower Potential Oxidation Slower Reduction Rates equal Faster Electrochemical Equilibrium pH

Thermodynamic Equilibrium
2H+ + 2e- H2 The potential at which it occurs for a given solution composition is known as the equilibrium potential. The concentrations of reactants controls the rates of the forward and reverse reactions and hence the equilibrium potential

The Pourbaix (E-pH) Diagram


2.0 1.6 1.2 0.8 0.4 0.0 -0.4 -0.8 -1.2 -1.6

Potential

2H2O = O2 + 4H+ + 4eEquilibrium potential as pH increases Ofalls is stable 2 2H+ + 2e- = H2 Equilibrium potential falls as H2O is stable pH increases

H2 is stable pH = - log [H+]


0 7 14

Pourbaix Diagram for Zinc


Equilibrium for 2.0 Zn(OH)2 + 2OH ZnO22- + 2H2O 1.6 Equilibrium for 1.2 2+ + 2OH- Zn(OH) Zn 2 0.8 Zn(OH) stable 0.4 ZnO22solid Equilibrium for 0.0 Zn2+ Equilibrium stable for stable in - Zn + 2OH Zn(OH) + 2e 2 -0.4 Zn Zn2+ + 2e- solution in for solution Equilibrium -0.8 2Zn + 4OH ZnO2 + 2H2O + 2e-1.2 Zn metal stable -1.6 0 7 14
Potential
2

Pourbaix Diagram for Zinc Corrosion


2.0 1.6 1.2 0.8 0.4 0.0 -0.4 -0.8 -1.2 -1.6
possible with oxygen reduction Corrosion Corrosion is possible, but likely possible with to be stifled by solid hydrogen Zn(OH) Corrosion corrosion product stable evolution ZnO22Corrosion requires solid Corrosion is 2+ Zn stable stable in strong oxidising thermodynamically solution in solution agent impossible Passivity
2

Potential

Immunity Zn metal stable


0 7 14

Corrosion

Pourbaix Diagram for Gold


2.0 1.6 C 1.2 0.8 0.4 0.0 -0.4 -0.8 -1.2 -1.6 0
Passivity C corrode Gold Gold metalcant stable with oxygen reduction Immunity or hydrogen evolution

Potential

14

Pourbaix diagram for Copper


Will copper corrode in neutral waters?
Potential 2.0 No - hydrogen 1.6 evolution only Cu oxides 1.2 occurs below the stable 0.8 Cu2+ stable potential for copper 0.4 corrosion in solution 0.0 Usually it will just passivate,-0.4 but corrosion can occur -0.8 Cu metal stable in slightly acid -1.2 solutions -1.6 0 7 14
CuO22- stable in soln.

Will copper corrode in acid?

Pourbaix Diagram for Iron


2.0 1.6 Yes - there is a 1.2 reasonably wide Fe3+ 0.8 range of potentials 0.4 Fe oxides where hydrogen Yes - although iron can stable can be evolved and 0.0 form an oxide in neutral 2+ iron dissolved Fe stable -0.4 solution, it tends not to -0.8 form directly on the No - iron forms a solid Fe metal stable -1.2 metal, as oxide the potential at all potentials, is too low, therefore is and-1.6 will it passivate 7 14 not protective. 0
Potential

Will iron Will iron corrode corrode in in alkaline neutral waters? solution?

Will iron corrode in acid?

Pourbaix diagram for Aluminium


1.2 0.8 0.4 0.0 -0.4 -0.8 -1.2 -1.6 -2.0 -2.4

Potential

Al3+

Al2O3

AlO2-

Al
0 7 14

Limitations of Pourbaix Diagrams


Tell

us what can happen, not necessarily what will happen No information on rate of reaction Can only be plotted for pure metals and simple solutions, not for alloys