2.

Thermodynamics of Corrosion
The tendency for any chemical reaction, including corrosion, is measured by the ΔG.
Mg + H2O +1/2O2 J Mg(OH)2 ΔG° = -142,600 cal
Cu + H2O +1/2O2 J Cu(OH)2 ΔG° = -28,600 cal
Au + 3/2H2O +3/4O2 J Au(OH)3 ΔG° = +15,700 cal

Tendency to corrosion : Mg > Cu ≫Au

• 2.1 Electrode Potential

Consider what happens when a metal electrode M is dipped into a solution containing the
metal ions M+. The concentration of M+ in the metal is much larger the in the solution, which
creates a chemical driving force that tends to equalize the concentration. A charge
separation occurs as a result of the metal’s tendency to oxidize.

M ↔ Mz+ (s) + ze- (M) : Dynamic equilibrium.

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 M↔Mz+ (s) + ze- (M) : Dynamic equilibrium.

+
e-
+
Zn Cu
+
+ + +
Pull ? + +
+ + +
Push? + +
+ + + +
+ + + +
+ +
++ + + + +
Metal WATER
+ water
Forces of ionization

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Charge transports across M/S interface

IHP OHP IHP OHP

Gch G

ΔGc*
ΔGa*
M

Metal Electrolyte M+ M

10Å
G = Gchem +Gelec
Gelect = Gchem +zFΦ ΔG*
+ + M M+
- +
E = φM - φs + 0
- φS Metal Solution
+
- + +
- +
φM +
Helmholtz Gouy Chapman zFE
Double Layer Layer

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Depending on the nature of Metal/Solution
system, one of two cases may occur.
Negative charge on
electrode
• Case I : Negative electrode potential e-
+ e- +
more metal dissolution + — +
-
+ e
 + + +
+ + +
Electron excess electrode +
+ + +
M M+z(S) + ze-(M) + + e-
+

Positive charge on
electrode
• Case II: Positive electrode potential
more deposition of metal ion + +
 + + +
+
Electron-depletion electrode + + ++ +
+ +
M M+z(S) + ze-(M) + +
+ +

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 The potential difference : Electrical double layer (EDL)
Helmholtz Model
+
+
At the electrode/electrolyte interface, a charge
+
M S separation between the metal surface and the
+
electrolyte occurs. The spatial region corresponding to
φM the charge separation is called the electrical double
layer (EDL).
φS

Outer
EDL is usually separated into two parts, the compact
x
Helmholtz plane double layer (Helmholtz layer) and the diffuse layer.
Stern Model The charge at the interface establish an electric field.
+ Within the compact layer, the electric field reaches the
+ order of 108 to 109 V-m-1, and hence has an influence
+ on the charge transfer reaction. Since corrosion is an
+
M + S electrochemical process involving the charge transfer
Scattered ions reaction, its rate is significantly influenced by the
φM 'Stuck' electrode potential or the electric field across the
ions double layer.
φS
Cdl x

RF Equivalent Circuit

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2.2 The Potential difference
We can analyze the potential at the interface by separating the electrode from the solution,
but with the charges of the metal and the solution frozen in position. Think that a positive
charge at great distances from the isolated electrode experiences a Coulomb potential that
varies inversely with distance.

z Volta potential or the outer potential, ψ +

+
z Surface potential, χ +
z Galvani potential, φ +
+
+
+

2.3 Electrochemical potential

When a charged species is added to a system in which the electrical potential is Φα :
Electrochemical potential ,

μi(α) = μi(α) + NAzieΦα =μi(α) + ziFΦα (1)

,where μi(α) = (∂G/∂ni)T,P,ni≠I chemical potential for i species in α phase

NA = Avogadro's number
F = Faraday constant = 96485 C/mol

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 The driving force for the electrochemical reaction;
ΔG= Σ niμi( final state ) - Σ niμi( initial state ) (2)

Properties of the electrochemical potential

For uncharged species : μi = μi
For any substance : μi = μi° + RT ln ai
For pure phase at unit activity : μ i = μ i°
For electron in a metal : μe = μe° - FΦM
For equilibrium of the species between phases α and β : μiα = μiβ Δφ (M,S)

2.4 The interfacial potential difference

For a reduction reaction at metal/metal ion electrode interface ;
M+z + ze- J M (3)
M+Z
apply eq.(2) to eq.(3) :
M+Z
ΔG = μM(M) – { μ M+z(S) + zμ ze-(M) } =0 at equili (4)
M+Z
M+Z
where, μM (M) = μM : M atoms are uncharged
μM+Z (S) = μM+Z + zFΦs
M+Z
μe- (M) = μe° - FΦM (5) M+Z M +Z

φ (S) φ (M)

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 (5) J (4):

ΔΦ = ΦM - ΦS = 1/zF ( μM+z + μ°ze- - μM )

where, μM+z = μ°M+z +RT ln aM+z ,

ΔΦ = 1/zF ( μ°M+z + μ°ze- - μ°M ) + (RT/zF) ln aM+z

= ΔΦ °+ (RT/zF) ln aM+z (6)

Electrode potential : E = ΔΦ,

E = E° + (RT/zF) ln aM+z (7)

• For the gas/inert metal electrode : G+⏐G2⏐Pt

G+ + e-  1/2G2
E = E° - (RT/F) ln (f1/2G2 /aG+) (8)

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z The ion⏐insoluble salt⏐metal electrode , X-⏐MX⏐M :

Consists of a metal M covered by a porous layer of insoluble salt

MX, the whole immersed in a solution containing X- ions ; the
electrode as a system of two interfaces.

M+(s) + e-(M) Q M : at the metal/salt interface,

MX Q M+(s) + X-(S) : at interface between X-(S)
and X-(Salt)

Overall equil. : MX(s) + e- Q M(M) + X-(S)

( M : metal, s : salt, S : solution)

μMX + μe-(M) Q μM(M) + μX-(S)

μMX + μe-(M) - FΦ(M) Q μM(M) + μX-(S) - FΦ(S)

ΔΦ(M,S) = (1/F) { μMX + μe-(M) - μM(M) - μX-(S)}

ΔΦ(M,S) = (1/F) { μ°MX + μe-(M) - μ°X-(S) } – (RT/F) ln aX-

E = E° - (RT/F) ln ( aproduct / areactant ) = E° - (RT/F) ln aX-

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z Liquid junction potential : potential difference at an electrolyte – electrolyte boundary
At an interface between two different solution, mass transport occurs to mix the solutes
until the two solutions are identical.

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2.5 Electrochemical Cell
- Galvanic Cell : a cell that produces
electricity as a result of the
spontaneous cell reaction

- Electrolytic cell : a cell in which non

spontaneous reaction is driven by an
external power source.

Electron Flow
2.6 Notation of a cell

Zinc Copper
Zn(M)⏐ ZnSO4(aq,m1) || CuSO4(aq,m2) | Cu(M) Salt Bridge
Z C
n u
e
e e
e
2+
Cu
SO42-
2+
SO42-
Zn

ZnSO4 (aq) CuSO4 (aq)

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2.7 How to determine the cell emf & reaction direction

For the cell : M⏐M+z(aq) || N+z(aq)⏐N

Cell reactiom ; M + N+z → M+z + N

1) Write the right-hand electrode reaction as a reduction reaction:

N+z + ze- ⇔ N ............ ER

2) Write the left hand electrode reaction as a reduction reaction:

M+z + ze- ⇔ M ..........…EL

3) Subtract Right-Left to get both the cell reaction and the cell emf :
Cell reaction: R-L, M + N+z → M+z + N
Cell emf : Ecell = ER – EL

4) Then, using the relation : ΔG = -zFEcell

|ΔG| = Charge passed × Reversible potential difference
= zF|E|
If Ecell > 0, cell reaction direction : L → R
if Ecell < 0, cell reaction direction : R → L

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2.8 Measurements of E.M.F
The potential difference of a cell measured at equilibrium ( no current flow ) and
between platinum terminals is called the electrochemotive force of the cell.

 Contact potential difference between two metals

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2.9 Standard Electrode Potential
The potential of a single electrode never
appears in the thermodynamics expression
for measurable quantities. Since only
difference are significant, one electrode
may arbitrarily be assigned the zero value,
and all others referred to it.

Standard hydrogen electrode :

S.H.E : H+ ( aH+ = 1 ) | H2 ( f = 1 atm ) , Pt
E°( H / H2 ) = 0

The Standard electrode potential of all other

electrodes is obtained by forming a cell in
which the S.H.E is on the left and the
electrode under investigation in on the right.
The ions and gases involved in the second
electrodes are brought to unit activity ;

E° (cell) = E°R – E°L (S.H.E.) = E°R

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Reduction scale of standard electromotive potential at 25 oC

ACTIVE NOBLE
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  The Reversible Electrode

The Reversible electrode is characterized by an Noble

electrochemical reaction that can be reversed when
the electrical current changes direction ; Cu2+ Stable
Copper Corrosion

For the case of Cu2+/Cu electrode at equilibrium, ECu2+/Cu

At small anodic current : Cu → Cu2+ + 2e- Cu Metal Stable
By reversing the current : Cu2+ + 2e- → Cu
Therefore, Eeq = Erev Active

2.10 Corrosion Tendency

The tendency for any chemical reaction, including corrosion, is measured by the ΔG.

 Nernst Equation
For the electrochemical reaction : lL + mM +…. → qQ + rR +….

ΔG = (qGQ + rGR + ...) - (lGL + mGM + ....)

ΔG°= (qG°Q + rG°R +...) - (lG°L + mG°M + ..)

Since GQ - G°Q = RT ln aQ ,for q mols of Q, q(GQ - G°Q) = q RT ln aQ

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 ΔG - ΔG° = RT ln [Πaproduct/Πareactant]
Now | ΔG | = charge that passed × reversible potential difference
= -zF|E| or ΔG = -zF|E| and ΔG°= -zF|E°|

E=E°-(RT/zF) ln [Πaproduct/Πareactant] : Nernst Equation.

[Ex 1.] Consider Zn immersed in the acid solution and find the corrosion tendency of Zn ;

Cathodic Reaction : 2H+ + 2e- ⇔ H2L ER = EH+/H2 (1)

Anodic Reaction : Zn2+ + 2e- ⇔ Zn EL =EH+/H2 (2)

ER = E°R – (0.059/2) log (PH2/aH+2) (3)

EL = E°L – (0.059/2) log (1/aZn+2) (4)
H+
Zn2+ H+
H2
¨ We can’t measure the Ecell through this
experiment because anodic site and cathodic site H+
are almost same and changes with time. H+
e-

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 The Ecell can be measured by constructing an
electrochemical cell : e-

+ –
Zn|Zn+2(aZn+2=0.01) || H+(pH = 2)|H2|Pt
Cell reaction : (1) – (2) : Zn + 2H+ → Zn+2+ H2↑
Assuming that : aH+ =1, PH2=1, aZn+2=1 for simplicity, Zn
H2 Bubble
Pt
2+
Zn
Ecell= E°R - E°L = E°H+/H2 – E°Zn2+/Zn 2H+
The standard hydrogen electrode(SHE) is chosen to have Zn2+
zero potential Acid

SHE : E°H+/H2 =0, H+(aH+ =1)|H2(PH2=1)|Pt

Ecell = 0 - E°Zn2+/Zn= 0.763 V

[Ex. 2] Determine whether zinc will corrode in a 0.01M ZnCl2 solution acidified to pH=2.
Solution : construct an electrochemical cell corresponding to the corrosion reaction given:

Zn|Zn+2(aZn+2=0.01) || H+(pH = 2)|H2|Pt

R......2H++2e- →H2
L.......Zn+2 +2e-→ Zn
cell rx. : Zn + 2H+ →Zn+2+ H2
Ecell=ER-EL= [E°H+/H2 - 0.059/2 log (PH2/aH+ =1)] - [E°Zn2+/Zn+ 0.059/2 log aZn+2] = 0.675 V
Ecell>0, thus ΔG<0 : cell reaction is spontaneous as written.
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2.11 Types of Cell in Corrosion
1) Galvanic cell : A potential difference exists when two dissimiliar metals, electrically
connected, are immersed in a corrosive solution.
• mother phase - impurities or precipitates
• iron pipe connected to copper pipe
• annealed metal - cold worked metal
• grain - grain boundary :μgb >μM, μ⊥ >μM, where μM represents the chemical potential of 1 mole of normal
atoms. In this regard, metallic glass is more corrosion resistant than is polycrystalline metal.

2) Concentration Cells : Cells having two identical electrodes each in contact with a solution of
different concentration.

• salt conc. cell : Cu |Dil.CuSO4 || Con. CuSO4 | Cu • Differential aeration cell

e- N2 e- Air
– + –
• differential +:
aeration cell

Cu Cu Fe Fe

Dil. CuSO4 Conc. CuSO4 Dil. NaCl Dil. NaCl

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At both electrode for the differential aeration cell :
anodic reaction : Fe → Fe2+ + 2e-
cathodic reaction : O2 + 2H2O + 4e- → 4OH-

For the cathodic reaction :

ER = E ° - (0.0592/4) log (aOH-4/PO2) =0.401 - (0.0592/4) log (aOH-4/1)
EL = 0.401 - (0.0592/4) log (aOH-4/0.001)
Ecell = ER - EL = (0.0592/4) [log1 + log3] = 0.044V
Therefore,right electrode is cathode and left electrode is anode.

Determination of the Ecell is as follows :

Cathode : R :1/2 O2+H2O+2e- → 2OH-....E°R=0.401V
Anode : L : Fe+2 + 2e- →Fe............E°L= -0.440V
Cell rx. :R-L : Fe +1/2 O2 + H2O → Fe+2+ 2OH-

E°cell=0.841V
E cell = 0.841V - (0.059/2) log [aFe+2aOH-2/aFePO21/2aH2O]
= 1.28V by assuming that : aFe+2 =0.1, pH=7.0, PO2 = 0.2 atm

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2.12 Experimental Measurements of Electrochemical Potential.
Electrochemical cell consists of two half cells.By making one of the half cells a
known or reference half cell, we are able to isolate the second for measurement
and study. The reference half cell is commonly called the reference electrode.

ηa >ηb
Erev ηa
• Reference electrode : An electrode having a
relatively fixed value of potential regardless of the a) Good ref.
ηb

Potential E
environment in which it is used & should have the electrode
following characteristics :
- stability
- reversible potential b) Poor ref.
electrode
- low polarizability
Log i

• The potential difference of a cell is measured when there is no flow of current

and the cell is operating reversibly. This is achieved by using a high impedance
voltmeter, or potentiometer that has a negligible input current.
• The standard hydrogen electrode (E°H+/H2=0) : the primary reference electrode
• Secondary reference electrodes are more conveniently used in the great
majority of experimental measurements.

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1) The saturated calomel
electrode(SCE) : most popular ref.
electrode for laboratory use.

Hg, Hg2Cl2/Cl-(aq. saturated KCl),  Type of Reference Electrode

Half cell rx.: Hg2Cl2 + 2e- = 2Hg + 2Cl-
Ecal = 0.268 - 0.059 log (Cl-)

2) The siver-siver chloride electrode :

preferred for use at high temperature.

Ag, AgCl(s)/Cl-(aq. saturated KCl),

Half cell rx.: AgCl + e- = Ag + Cl-
EAg/AgCl = 0.222 - 0.059 log (Cl-)

3) Cu-saturated CuSO4 electrode :

commonly used in field.

Cu/Cu+2(aq. saturated CuSO4) :

Half cell rx.: Cu+2 + 2e- = Cu
ECu+2/Cu = 0.340 - 0.0295 log (Cu+2)

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