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THERMODYNAMIC ASPECTS OF CORROSION

Let’s consider corrosion of two metals (copper and iron) in a reducing acidic solution with
pH= 0, free from dissolved oxygen.

The half cell potentials of these two metals under standard conditions are:

Cu+2 + 2e = Cu Eo= 0.337 V O2 + 2H2 O + 4e = 4OH- Eo= 1,229 V

Fe+2 + 2e= Fe Eo= -0.440 V Cu+2 + 2e = Cu Eo= 0,337 V
2H+ + 2e = H2 Eo= 0 V
Since in this solution the only available cathodic Fe+2 + 2e= Fe Eo=-0,440 V
half cell reaction is: Zn+2 + 2e = Zn Eo= -0,76 V
!"! + !" → !! !!!!!!! Eo= 0 V Al+3 + 3e = Al Eo= - 1,63 V

Copper will not corrode, Iron will corrode in this solution ∆!° = −!"!°!"## !
However, when dissolved oxygen is present both metals
Will corrode

Nernst equation is used for calculation of the half-cell potential under non-standard conditions

!" !!! . !!!

! = !° − 2.303 !"# ! ! !
!" !! . !!
In corrosion the concentration of the metal ions is taken as 10-6 mol/l for calculation of the half-
cell potential of anodic reactions with Nernst equation
COST MP 1407 training course - Mustafa Ürgen Brno 13.04.2016 17 / 58

THERMODYNAMIC ASPECTS OF CORROSION

When solution pH increases the nature of corrosion products changes.

On most of the metals in neutral or near neutral solutions corrosion products are
no more in ionic form-solid reaction (oxides- hydroxides) products starts to form.
This formation and character of these products starts to control corrosion process.

The stability region of these products and also ionic species dependent on half-
cell potential and pH can be calculated by the help of thermodynamic principles.

Potential-pH diagram are very useful for this purpose since it is possible to
visualize the stability region of corrosion products and their relation with the
stability region of water in one glance

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THERMODYNAMIC ASPECTS OF CORROSION

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KINETIC ASPECTS OF CORROSION- MIXED POTENTIAL THEORY

For determination of the kinetics of electrochemical corrosion the relations obtained through
mixed potential theory are used.

Wagner Wagner
Traud Traud

Ec, rev Ec, rev

Emix Ecorr

Ea, rev Ea, rev

Log I mix

All you have to do for this adaptation is to change Emix to Ecorr and imix to icorr
!!"## !!!"#,! !!"## !!!"#,!
!!"## =!! = !! = !!,! !"# !"
= !!,! !! ! !"
!"!!!"## "
!! − !! = !!"# ≠ !!"## !!!"#$!!"#$%&'()!!!"#$%&!''(!
! = !! − (!!"## − !!"#,! )!where!!!!! = !"!"## − !!"" !
! = !! − (!!"## − !!"#,! )!where!!!!! = !"!"## − !!"" !
! !
!!"# =!! − !! = !!"## !"# − !!"## !"# −!( )"
!" !"

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CORROSION RATE DETERMINATION

Tafel Extrapolation
!
!!"# ≅ !! = !!"## !"# !!"#!!"#!!!"#$%!&#'&()!"!!! >> !! !
!"

Corrosion currents determined by these

methods are converted into corrosion rate
expressions such mm/year by using faraday law

Polarization resistance method (low field approximation):

!". !" !
!! = !. !"! !
!" + !" !"#$$

!". !" !
!!!"" = !. !"! !
!" + !" !"

Y. Tan, Heterogeneous electrode proceesses and localized corrosion, Wiley Pub. 2013
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EVANS DIAGRAMS
Role of pH and io
Examples of EVANS diagrams

Control mechanisms (schematic)

LL Shreir, R.A Jarman, GT Burnstein, Corrosion Vol.1 3rd edn Butterworth Heineman, 2000.
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EVANS DIAGRAMS

LL Shreir, R.A Jarman, GT Burnstein, Corrosion Vol.1 3rd edn Butterworth Heineman, 2000.
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EVANS DIAGRAMS

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CORROSION IN ACIDIC SOLUTIONS

Fe= Fe +2 + 2e
2H+ + 2e = H2
Zn= Zn+2 + 2e
2H+ + 2e = H2

Both anodic and cathodic reactions are activation controlled and takes place on the
same metal

Rate of corrosion is controlled

By the dissolution kinetics of metal into ionic form
By the reduction kinetics of hydrogen ion reduction

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CORROSION IN NEUTRAL SOLUTIONS

Fe= Fe +2 + 2e
O2 + 2H2 O + 4e = 4OH-
Iron hydroxides form
!!! + !!! !! + !" → !!!! !(!"#$%&'!!"#!!"#!"$%&!!"#$%&"'!)!
By the formation of insoluble corrosion
This reaction is concentration polarization products:
controlled. The rate of corrosion is started to be controlled
• Stirring the solution will increase the by the nature of them.
oxygen content of the solution and
change Erev of the reaction If the corrosion products form a impervious
• and also increase iL homogeneous layer on the surface corrosion
rate decreases even stops

However if they are not protective corrosion

does not stop and may even be accelerated
(oxygen corrosion)
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CORROSION CELLS

Corrosion Cells

Micro Macro corrosion cells

corrosion cells Anode –cathode sites separable

Temperature
Concentration
Galvanic cells Difference
cells cells

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MICRO CORROSION CELLS

• Takes place on the same metal
• Anodic and cathodic sites are not distinguishable
• They are interchangable
• The potential differences cretad by the structural differences of the metal determines anodic
and cathodic sites.
• Point defects
• Line defects (dislocations, twins, stacking faults)
• Grain boundaries
• Orientation differences of grains (domains)
• Inclusions
• Surface roughness
Energetically more stable sites acts as the cathode sites and cathodic reactions takes place on
them and vice versa
Resultant corrosion is relatively homogeneous

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MACRO CORROSION CELLS

METAL ION CONCENRATION CELLS

Nernst equation

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MACRO CORROSION CELLS

OXYGEN CONCENTRATION CELLS
One of the most important type of cell formation
Pitting, Crevice

It is also named as oxygen paradox.

The regions where dissolved oxygen concentration is

high acts as cathodic sites PARADOX

E
io, O2 /OH-
on Fe
Erev,
O2 /OH- on
Fe Corrosion potential for high O2
content is more positive
E corr, for
high O2
Ecorr high O2 >Ecorr low O2
E corr for
low O2 Cathode Anode
Erev,
Fe++/Fe

icorr icorr
low O2
logi
high O2
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MACRO CORROSION CELLS

Drop experiment:
Drop a a dilute salt solution on a steel plate. Solution contains
• an indicator that gives blue color when comes in contact with ferric ions
• And another indicator that gives pink color when comes into contact with OH- ions
What will be your observations?

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MACRO CORROSION CELLS

These cells form as a results of corrosion potential
Galvanic Cells differences between them
The metal or alloy of the couple with a more negative
corrosion potential acts as the anode of the system.
Corrosion potential series of metals and alloys is named as
Electron flow galvanic series.
Note that the position of metal in this series can vary
Current substantially when compared to EMF series
CATHODE
ANODE

ELEKTROLTYE

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MACRO CORROSION CELLS

Galvanic Cells Let’s select two metals from galvanic series: Cu and Steel
Introduce the couple in sea-water.
According to their positions copper will be the cathode and
steel will be anode when coupled.
Thus cathodic reaction will take place on Cu
Electron flow
!!! + !!! !! + !" → !!!! !(!"#$%&'!!"#!!"#!"$%&!!"#$%&"'!)!

Current

Anodic reaction
Fe= Fe+2 + 2e
CATHODE
ANODE

ELECTROLYTE

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MACRO CORROSION CELLS

Kinetics of Galvanic Corrosion:

Graphical presentation of galvanic couple (EVANS diagram)

io, H+/H io, H+/H

on Zn on Pt
Erev,
H+/H on
Zn

E corr,
couple

E corr
Zn

Erev,
Zn++/Zn on
Zn

icorr Zn icorr logi

Couple
Fe –Zn couple both corroding

Zn –Pt couple one corroding

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MACRO CORROSION CELLS

Kinetics of Galvanic Corrosion
Parameters effective on Galvanic coupling
• Anode/Cathode area ratio
• Potential difference between anode and cathode ?
• The cathodic reaction kinetics on the cathodic metal of the couple
• Conductivity of the electrolyte

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PASSIVITY

There are two types of passivity:

1. Mechanical passivity

This type of passivity occurs when the corrosion products formed are solid and
insoluble and forms a thick protective layer on the metal.
Examples: ZnO formation on Zn in neutral pH environments, Lead sulphate
formation on Pb in sulfuric acid, MgF formation on Mg in HF acid.
Explainable by thermodynamic principles (see potential-pH diagrams)

2. Chemical/electrochemical passivity:
This type of passivity occurs under unexpected conditions with respects to
thermodynamic considerations. (e.g passivity of iron in nitric or sulphuric acid). It
is not observed for all metals. Mainly transition metals and their alloys posses
such an ability. As a result of this type of passivity very thin (in the 1-10 nm range)
protective layers form, which decreases the corrosion rate of the metal several
order of magnitudes in log scale

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PASSIVITY
Let’s consider behavior of pure iron in 1 N sulfuric acid under anodic polarization

Anodic polarization of the metal clearly indicates that at a specific potential named as
passivation potential (Epp), corrosion rate of the metal decreases. According to this figure a
metal can behave active – passive and transpassive. How it will behave depends on the
kinetics of cathodic reaction (next slide)

The mechanism of passivity is still not clear. There are several theories put forth for the explanation of the
phenomenon. People who are interested with the details of this topic may start with reading “Passivity” chapter
of Shreir’s Corrosion book
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PASSIVITY
Even though we can show that ordinary steel can behave passive in low pH
solutions, we do not observe that behavior under real conditions.
Critical current for passivation (icr) is another important
parameter for passivity.
When we look at the critical current requirement for
passivation of iron we see that it is very high (in A/cm2) range.
It is not possible to find cathodic reactions that will supply such
high oxidizing power. Thus lowering Icr is an important issue
for keeping metals passive in real conditions.

For steels this is achieved by alloying them with a metal with low icr,
namely Cr.

Introduction of Cr higher than 11 % results in the formation of a new

family of steels –Stainless steels.

We should keep in mind that relying on passivity of metal for corrosion

protection can be misleading especially in environments that contain
chloride ions.

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