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ELECTROCHEMICAL

THERMODYNAMICS OF CORROSION
AND POURBAIX DIAGRAMS-UNIT-2
CHE-545-172
DR IME B.OBOT

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CHANGE OF GIBBS FREE ENERGY
 The tendency of any chemical reaction to go, including the
reaction of a metal with its environment is measured by Gibbs
free-energy change, ΔG.
 The more negative the value of ΔG, the greater the tendency for
the reaction to go.
Consider the following reaction at 25oC;
Mg(s) + H2O (l) +1/2O2→Mg(OH)2(s)ΔGo=-596.6kJ
Cu(s) + H2O(l) + 1/2O2→Cu(OH)2(s); ΔGo=-119.7kJ
The large negative value of the first equation indicates a pronounced
tendency for Mg to react with water and oxygen than Cu.
For the reaction:
Au(s) + 3/2H2O(l) + 3/4O2(g)→ Au(OH)3(s); ΔGo=+65.7kJ
The free energy is positive indicating that the reaction has no
tendency to go on at all.
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EMF OF A CORROSION CELL
The tendency for a metal to corrode can be
expressed in terms of the electrochemical
force (EMF) of the corrosion cell:
ΔG = -nFE
n= is the number of electrons, F is the Faraday
(96,500C/equivalent and E is emf in volts.
Note: 1cal = 4.184J.

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NERNST EQUATION-CALCULATING
HALF-CELL POTENTIAL
The general equation for a galvanic cell is:
lL + mM +……→qQ +rR +….---------------------1
l and m are moles of reactants and q and r are moles of
products
The corresponding ΔG for this reaction is given by the molal
free energy of products and reactants:
ΔG = (qGQ + rGR +…) – (lGL + mGM + ……)---2
A similar expression can be achieved for each substance in the
standard state, where the symbol Go indicates standard molal
free energy:
ΔGo = (qGoQ + rGoR +…) – (lGoL + mGoM + ……)…….3
If aL is the corrected concentration or pressure of substance L,
called its activity, the difference of free energy for L in any
given state and in the standard state is related to aL by the
expression:
l(GL-GoL) = lRT lnaL = RT ln alL ……………………………….4 4
Subtracting equation 3 from 2, we have:
ΔG- ΔGo = RT ln (aqQ.arR)/alL.amM) …….5
When the reaction is at equilibrium, there is no tendency for it to go
on, ΔG =0, and
(aqQ.arR)/alL.amM) =K …………………………6

Where K is the equilibrium constant for the reaction. Hence


ΔGo = -RTlnK……………………………7
On the other hand, when all the activities of reactants and
products are equal to unity, the log term becomes zero (ln 1=0),
and ΔG=ΔGo
Since ΔG =-nFE, it follows that ΔGo=nFEo, where Eo is the emf
when all reactants and products are in their states (activity
equal to unity).
Corresponding to equation 5, we have;
E = Eo – RT/nF ln (aqQ.arR)/alL.amM) …….8
Equation 8 is the NERNST EQUATION- It expresses the exact emf
of a cell in terms of activities of products and reactants of the
cell. 5
CALCULATING ELECTRODE POTENTIAL
Emf of a cell is an algebraic sum of two electrode potentials.
We have to calculate each of the two electrode potentials or the two half
potentials separately.
For example, for the electrode reaction:
Zn2+ + 2e− →Zn,
We have:

Zn2+=(molality × activity coefficient).Values of activity coefficients for various


electrolytes are listed in reference books;
Zn= the activity of metallic zinc (equals to 1)
φoZn is the standard potential of zinc, calculated values of standard
potentials φ ° at 25 ° C are listed in several reference books.
R, T and F have their usual meaning.

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THE HYDROGEN ELECTRODE AND
THE STANDARD HYDROGEN SCALE
Absolute Potentials of electrodes are not known
 The hydrogen electrode
If we assumed arbitrarily that the standard potential is measured by
electrode potential is zero for the reaction: immersing a piece of platinized
2H+ + 2e− → H 2 platinum in a solution saturated
Then, with hydrogen gas at 1 atm.
 The potential of the electrode
equals zero if the hydrogen ion
activity and the pressure of
where pH2 is the fugacity of hydrogen in hydrogen gas in atmospheres
atmospheres; are both unity- This is the
(H+ ) is the activity of hydrogen ions. standard hydrogen potential.
All values of electrode potentials, therefore, are  The half - cell potential for any
with reference to the hydrogen electrode. electrode expressed on this
By measuring the emf of a cell made up, for basis is said to be on the
example, of a zinc and hydrogen electrode in zinc normal hydrogen scale or on
salt solution of known activity of Zn 2+ and H + , the the standard hydrogen scale ,
standard potential, φ ° , for zinc can be calculated; sometimes expressed as φ H or
the accepted value is − 0.763 V. φ ( S.H.E. ).
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CONVENTION OF SIGNS AND CALCULATION OF EMF
The emf of a cell with two electrodes—zinc and the standard hydrogen electrode:
Pt; H2, H+, Zn2+; Zn; Subtrating the left hand side from the right hand side we can
write:
Zn 2++ H2→ Zn + 2H+ standard emf = -0.763V
ΔGo =-nFEo; is positive-reaction not thermodynamically possible.
On the other hand, for the cell;
Zn; Zn2+, H+, H2; Pt-standard emf = 0.763V
The corresponding reaction is Zn + 2H+ → Zn 2+ + H2,
ΔGo =-nFEo; is negative-reaction is thermodynamically possible.

Clearly, the standard reduction potential for zinc is opposite in sign to the standard
oxidation potential for zinc.
It was agreed at the 1953 meeting of the International Union of Pure and Applied
Chemistry that the reduction potential for any half - cell electrode reaction would be
called the potential
Thus, zinc has a negative reduction potential and is also the negative pole of a
galvanic cell of which the standard hydrogen electrode is the other electrode. It is
said to be negative to the hydrogen electrode.
If positive current through the electrolyte within the cell flows from left to right,
then the emf is positive, and, correspondingly, the left electrode is anode and the
right electrode is cathode. If current flows within the cell from right to left, the emf
is negative.
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CALCULATING THE EMF OF CU-ZN CELL
We can first write reduction half-reaction for left side as if it were cathodic reaction:
Cu2+ + 2e− →Cu; φo = 0.337V;
Φcu=0.337-0.0592/2 log 1/(Cu2+)
The reduction reaction for the right electrode is:
Zn2+ + 2e− →Zn; φo = 0.763V and;
Φzn= -0.763-0.0592/2 log 1/(Zn2+)
Overall reaction after subtraction:
Cu + Zn 2+ →Cu 2+ + Zn
Overall reduction potential for both cell is:
Φzn- Φcu= -1.100-0.0592/2 log (Cu2+/(Zn2+)
If the activities of Cu2+ and Zn2+ are chosen to be the same, the emf E is − 1.100 V.
Since the emf is negative, current flows spontaneously from right to left within
the cell.
This fixes the true polarity of the cell, with the left electrode, Cu, as positive
(cathode) and the right electrode, Zn, as negative (anode).
From the relation Δ G = − nFE , the free - energy change of is positive, and the
reaction is, therefore, not spontaneous as written, but goes instead in the opposite
direction.
In other words, when current is drawn from the cell, Cu2+ plates out on the copper
electrode, and the zinc electrode corrodes.
The emf, polarity, and spontaneous reaction can be determined for
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any cell for which half - cell reactions and standard potentials are known
MEASUREMENT OF pH
Hydrogen ion activity is commonly expressed, for
convenience, in terms of pH, defined as:
pH = −log(H+),
Hence for the half-reaction: 2H+ + 2 e− → H2, with pressure
equals to unity;
φH2 = −0.0592pH
Pure water contains equal amount of [H+] and OH-] at
equilibrium with undissociated water; H2O → H+ + OH−, it is
possible to calculate the activity of either the hydrogen ion or
the hydroxyl ion from the ionization constant, the value of
which at 25 ° C is 1.01 × 10− 14 .
Therefore, the pH of pure water at 25 ° C is
−log 1.01× 10−14 = 7.0
If (H+ ) exceeds (OH − ), as in acids, the pH is less than 7.
If the pH is greater than 7, the solution is alkaline.
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THE OXYGEN ELECTRODE AND
DIFFERENTIAL AERATION CELL
The oxygen electrode can be represented by platinized
platinum immersed in an electrolyte saturated with oxygen.
This electrode is particularly important to corrosion studies
because of its role in differential aeration cells in the
mechanism of crevice corrosion and pitting.
The equilibrium for such an electrode is expressed as:
1/2H2O + O2 + e- →OH- ; φoH =0.401V and
φO2=0.401-0.0592 log(OH-/PO21/4 )
This reaction, however, unlike the hydrogen electrode reaction,
is not strictly reversible under practical conditions of
measurement, and hence the measured potential may vary
with time and is not reproducible.
The observed potential tends to be less noble than the
calculated reversible value.
Nevertheless, it is useful to know the direction of expected
potential change as, for example, when oxygen pressure is
altered. 11
THE EMF SERIES
 The EMF Series is an
orderly arrangement of the
standard potentials for all
metals. The more negative
values correspond to the
more reactive metals.
 Position in the EMF Series
is determined by the
equilibrium potential of a
metal in contact with its
ions at a concentration
equal to unit activity.

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THE GALVANIC SERIES
 The Galvanic Series is an arrangement of metals and alloys
in accord with their actual measured potentials in a given
environment.
 Alloys and passive metals are included in the Galvanic
Series.
 In EMF Series only the active positions are possible and
only one EMF Series exists.
 There can be several Galvanic Series because of differing
complexing tendencies of various environments.
 In the Galvanic couple, the metal or alloy with the more
negative electrode potential is the anode. The metal or
alloy with the more positive electrode potential is the
cathode (same with emf)
 Galvanic series is measured vs SCE.
 The Ordering of series of metals in galvanic series may not
be the same as the order in Emf.
 The emf series cannot be used to predict the corrosion
tendencies of coupled metals in other environments
 Galvanic series should not be used to predict corrosion
tendencies in solutions which are very much different than
sea water (e.g. body fluid , HCl solution).
Galvanic series in seawater at 25oC
 Galvanic series only shows the tendencies to corrosion and
not the rates.
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WORKED EXAMPLE
 Question: Composite materials consisting of Mg containing graphite-
reinforcing fibers have been developed to increase the mechanical
strength of the light metal Mg. Will the introduction of graphite into
magnesium pose a problem if this composite material is used in sea
water?

 Solution: From the Galvanic Series Diagram, The electrode potentials of


graphite in seawater is approximately +0.25 V vs SCE. The electrode
potentials of Mg is -1.6 V vs SCE. Thus, in a magnesium-graphite couple,
magnesium will be the anode. Because of the large difference in the two
electrode potentials, there will be large galvanic effects between Mg and
Graphite. This couple should not be used in sea water unless the
composite material is provided corrosion protection, such as a barrier of
paint or some other organic coating.

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REFERENCE ELECTRODES
Saturated Calomel Electrode
 It is standard reference electrode
used in the laboratory.
 It consists of a pool of mercury
covered with a paste of mercury
and calomel (mercurous
chloride), immersed in an
electrolyte containing a solution
of potassium chloride.
 The half -cell reaction is

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Silver-silver chloride electrode
The silver-silver
chloride electrode
shown in is based on
the following redox
reaction:

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COPPER-COPPER SULFATE ELECTRODE
 The copper-copper sulfate
reference electrode consists of
copper metal immersed in a
saturated copper sulfate solution.
 A porous frit or wooden plug
serves as an electrolytic contact
with the cell.
 The electrode reaction is:

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EQUILIBRIUM POTENTIAL VALUES FOR
COMMONLY USE REFERENCE ELECTRODE

E vs SCE = E vs SHE-0.241
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CONVERSION FROM POTENTIALS BETWEEN
DIFFERENT REFERENCE ELECTRODE
Example: If the corrosion potential of steel in
seawater is -0.7 V (SCE), what is the potential
–in the SHE: -0.7+0.241= -0.459 V vs (SHE)
For Ag/AgCl: -0.7 + 0.222= -0.478 V vs (SHE)
Example: If the corrosion potential of Zn in
seawater is -0.9 V (SHE), what is the potential
-In the SCE: -0.9-0.241= -1.141 V (SCE)
–In Ag/AgCl: -0.9-0.222= -1.122 V (Ag/AgCl)
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BASIS OF POURBAIX DIAGRAMS
 Developed by Marcel Pourbaix
 Summary of thermodynamic data in the form of potential – pH diagrams,
which relate to the electrochemical and corrosion behavior of any metal
in water.
 They have the advantage of showing at a glance specific conditions of
potential and pH under which the metal either does not react
(immunity) or can react to form specific oxides or complex ions; that is,
Pourbaix diagrams indicate the potential – pH domain in which each
species is stable.
 Pourbaix diagram is useful in identifying potential – pH domains where
corrosion does not occur — that is, where the metal itself is the stable
phase.
 By controlling potential (e.g., by cathodic protection) and/or by adjusting
the pH in specific domains identified using Pourbaix diagrams, it may be
possible to prevent corrosion from taking place.
 For example, in the potential – pH domain labeled “ Fe (immunity), ” iron
is stable, and no corrosion is predicted.
 However, predictions using Pourbaix diagrams must be tested
experimentally and validated.
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POURBAIX DIAGRAM FOR WATER
The oxygen line, b ,
above which oxygen is
evolved.
The hydrogen line, a ,
below which hydrogen
is evolved from the
surface of an immersed
electrode.
Between these two
lines, water is stable.
Pourbaix diagram for water at 25 ° C.

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POURBAIX DIAGRAM FOR WATER
 Above line b , oxygen is evolved in accord with the reaction: H2O → 1/2O2 + 2H+ +
2e − .
For this equilibrium, the relationship between potential and pH is, from the Nernst
equation :

 Below line a , hydrogen is evolved in accord with the reaction: 2H + + 2e− → H 2 .


For this equilibrium, the relationship between potential and pH is, from the Nernst
equation:

 Below line a , represented by this equation, hydrogen gas is evolved from the
surface of an immersed electrode.
 Between lines a and b , water is stable.

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POURBAIX DIAGRAM FOR IRON
 At pH of 6.0 and electrode potential of
-0.4 vs SHE corresponds to a region of
corrosion.

 Three ways of protecting iron:


 Changing the electrode potential
below -0.7 vs SHE, forces iron into
immunity region (cathodic
protection).
 Keeping the electrode potential into
positive values above 0.0 vs SHE,
forces the iron into the region of
passivity (anodic protection).
 If we increase the pH above 8 or
higher, iron is in a region of passivity

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POURBAIX DIAGRAM FOR IRON

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WORKED EXAMPLE
 Problem: In an experiment of stress corrosion cracking of 4340 steel
(predominantly iron with minor amounts of Cr, Mn and Ni), the local pH of the
electrolyte contained within the stress-corrosion crack attain values of 3.0-4.0,
even though the pH of the bulk solution was approximately 7. The local electrode
potentials corresponding to the pH of 3 and 4 were -0.52 and -0.58V vs SCE
respectively. Is hydrogen embrittlement a possible mechanism of stress corrosion
cracking for this allow?
 Solution: First Convert Electrode potentials to the standard hydrogen scale. For
pH 3.0,
E vs SCE = E vs SHE-0.242
-0.52 = E vs SHE-0.242
E vs SHE = -0.52 + 0.242 = 0.28 V
Similarly, at pH 4, the electrode potential is:
E vs SHE = -0.58 + 0.242 = -0.34V
Each point (3.0, -0.28; and 4.0, -0.34) when superimposed under Pourbaix diagram
for water lie below the ‘a’ line for hydrogen evolution. Thus, hydrogen evolution is
thermodynamically possible. Accordingly, H atoms can be formed, and hydrogen
embrittlement is a possible mechanism of stress corrosion cracking for this alloy.
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POURBAIX DIAGRAM FOR Al
 The Pourbaix diagram of
aluminum,, indicates that
hydrargillite, Al2O 3· 3H 2O, is
the stable phase between
about pH 4 and 9. Indeed, this
film is considered to be
responsible for the successful
use of aluminum in many
structural applications.

 The diagram also predicts the


amphoteric nature of
aluminum, with corrosion
under highly acidic and highly
alkaline conditions and
protection by an oxide film
between about pH 4 and 9.

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WORKED EXAMPLE
 QUESTION: An Al-1% Mn Alloy immersed in 0.1 M sodium
citrate solution (pH 3.5) for 24 h displayed an electrode
potential of -1.25 V vs SCE. What behaviour is expected in
terms of corrosion, passivity, or immunity?
 SOLUTION:
Change potential to SHE:
E vs SHE = -1.25V + 0.242 V = -1.01 V
From the Pourbaix diagram of pure Al, the electrode
potential at pH of 3.5 corresponds to a region of corrosion
Assumptions: (a) The Pourbaix diagram for pure Al also holds
for Al alloy (1% Mn); (b) the system is in equilibrium after the
relatively short immersion period of 24 h.

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POURBAIX DIAGRAM FOR MAGNESIUM
 Mg 2+ is the stable species in solution over
most of the potential – pH range.
 The potential – pH domain in which
magnesium is stable is well below the domain
in which water is stable.
 Magnesium reduces water, and hydrogen
evolution is the cathodic reaction.
 Between pH about 8.5 and 11.5, a protective
film of oxide or hydroxide may provide some
protection.
 At pH greater than about 11.5, a stable fi lm
of Mg(OH) 2 protects magnesium from
corrosion.
 Because of the very active value of the
equilibrium potential of the reaction, Mg2+ +
2e − → Mg, magnesium cannot be prepared
by electrolysis of its aqueous solutions, which
would evolve hydrogen without forming
magnesium.
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POURBAIX DIAGRAM FOR ZINC
 The diagram is similar to
that of Al.
 Zn like Al undergo
dissolution in Acid
solution to form (Zn2+ )
and in basic solution to
form ZnO22-.
 Zinc has a high corrosion
rates at both low and
high pH and low
corrosion rates at
intermediate values.

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POURBAIX DIAGRAM FOR CHROMIUM
 The passivity of Chromium is
destroyed by increasing the
electrode potentials (at a given
pH).
 At pH =7 and an electrode
potential of -0.4 V vs SHE, the
chromium electrode resides in the
region of passivity.
 By increasing the electrode
potentials, the electrodes can be
shifted into the region of corrosion
(as Chromate ions).
 The phenomenon in which
corrosion occurs at a high
electrode potentials (beyond the
existence of passivity) is called
transpassive dissolution.

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POURBAIX DIAGRAM FOR COPPER
 An interesting feature is that
oxidation reactions of Cu
occur at electrode potentials
above the ‘a’ line for
hydrogen evolution. Thus
these two reactions are not
thermodynamically feasible:
Cu2+ + 2H+ → Cu2+ + H2 or
2Cu + H2O → Cu2O + H2
 Instead the following
reaction is favoured:
2Cu + 2H2O →Cu2O + 2H+ + 2e-

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POURBAIX DIAGRAM FOR ALLOYS
 Pourbaix diagram for Fe-
dotted lines superimposed
on Cr-solid lines at 25oC
(alloy).
 The cross-hatched area is the
region of stability of Fe2O3
and Cr2O3.
 It is possible to prevent the
corrosion of iron as Fe2+
around neutral pH through
the formation of Cr2O3.
 This form the basis for using
Cr in Fe (stainless steel) and
chromate passive corrosion
inhibitors.

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LIMITATIONS OF POURBAIX DIAGRAM
 Equilibrium is assumed. (But in practical cases, the actual
condition may be far from equilibrium.
 It gives no information on actual corrosion rates.
 It applies to single elemental metals only and not to alloys. For a
solid solution binary alloy, the Pourbaix diagram of the two
constituents may be superimposed as first approximation. For
Engineering alloys experimental Pourbaix diagrams may be
developed.
 Passivation is ascribed to all oxides and hydroxides regardless to
their actual protective properties. (corrosion may proceed by
diffusion of ions through the oxide film which is ignored by
Pourbaix diagrams)
 It does not consider localized corrosion by chloride ions.
 Conventional Pourbaix diagrams applies to temperature at 25oC.

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APPLICATIONS OF POURBAIX DIAGRAM

The resistance of metals to uniform corrosion


in aqueous solutions.
The basis for establishing the passivity of
metals over a wide range of conditions of pH
and potentials.
Evaluation of possible use of oxidizing
inhibitors.
Identification of the set of internal conditions
within a localized corrosion cell.
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