Corrosion Kinetics

4.
Corrosion Kinetics
At the electrode/electrolyte interface, a charge separation between the metal surface and the
electrolyte occurs. The spatial region corresponding to the charge separation is called the
electrical double layer. It is usually separated into two parts, the Helmholtz layer or compact
double layer and the Gouy-Chapman layer or diffuse layer. 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, and hence has an influence on the charge transfer reaction. Since corrosion is an
electrochemical process involving the charge transfer reaction, its rate is significantly
influenced by the electrode potential or the electric field across the double layer.
4.1 The electrical double layer
An electrode becomes positively charged relative to the solution nearby if electrons leave it
and decrease the local cation concentration in the solution. The most primitive model of the
interface is that it is an electric double layer consisting of a sheet of positive charge at the
electrode surface and a sheet of negative charge next to it in the solution (or vice versa). The
behavior of ions in the vicinity of the electrode is affected by the electric force arising from the
charge on the electrode and by thermal motion.
http://corrosion.kaist.ac.kr
A. Helmholtz Model B. Gouy-Chapman Model C. Stern Model
Cdl
RF
X Charge transfer reactions occur
across the compact double layer
Equivalent Circuit
and the influence of the diffuse
layer is usually neglected.
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.
¾ The variation of potential with distance ¾ The origin of the distance-independence of the outer potential.
from an electrode that has been separated
(a) Far from the electrode, a point charge experiences a
from the electrolyte solution without there
potential arising from a wide area but each contribution is weak.
being an adjustment of charge.
(b) Close to the electrode, the point charge experiences a
potential arising from a small area but each contribution is strong.
The Electrical analogue of double layer
The electrical double layer is characterized by two layers of opposite charge facing each other,
as in a capacitor. The electrical current can, however, pass across the metal-solution interface,
although there is some resistance to it. The electrode can then be represented by an electrical
analogue composed of a capacitor parallel to resistance RF called Faradaic resistance. The RF
is called also the polarization resistance or charge-transfer resistance.
Cdl
e-
e- M+z
e-
e- M+z RF
M e- S
Electrical double layer Equivalent Circuit
When an electrical current is impressed on the electrode, the RF must be overcome. This
generates additional voltage and causes a shift in the electrode potential. At rest(open
circuit), The electrode has a charged layer; in the absence of an electric current, the
capacitor Cdl is charged. The current impressed on the electrode, it, is divided into two parts.
it = iF + ich
When iF : Faradaic current
ich : current of charge accumulated in the capacitor
Usually iF ≫ ich .
The electrode potential is proportional to the charge Q of the double layer. Thus, the
electrode potential changes under an electric current across the double layer ;
E = Eeq + η(i)
η(i)= the additional voltage due to the current flow.
ich Cdl
it
RF
iF
Electrode-Electric Analogue
4.2 Charge transfer overpotential or Activation polarization
For charge transfer reaction in metal/solution interface:
M(in lattice) → M+z (hydrated in sol.) + ze-
Actually, M, lattice
↓
M, adsorbed
↓
M+z, sol.
The metal atoms on the electrode surface are in energy wells associated with the lattice
structure, and in order to pass into the solution they have to overcome the activation energy.
Gch G = Gchem +Gelectro
ΔGc*
M ΔGa* G
Metal Electrolyte M+
10Å
OHP ΔG*
IHP
M M+
+ + +
Gelect +
φS +
+ +
φM +
+ X
IHP OHP
Helmholtz Gouy Chapman
Double Layer Layer
E = φM - φs
The chemical free energy change due to the dissolution or deposition of the metal is balanced
by an equivalent quantity of electrical work done by the ions in crossing the electric field
imposed by the equilibrium electrode potential.
M ⇔ M+z + ze- ..... at equilibrium or reversible potential.
Reaction rate = k x Concentration

= amount produced per unit area per unit time = moles/ cm2sec
• The rate of metal dissolution or reduction may be expressed as a current density (A/cm2)
according to the Farady’s law ;
i=Q/At = zFm/At ,
where z = number of electrons,
M = number of moles
F = Farady’s constant (=96500 C/mole)
A = Surface area on which reaction take places.
At the equilibrium electrode potential, the flux of charge through the double layer is the same in
both directions and we call this the exchange current density, io.
At equil., ia = ic =io ,and anodic reation rate = cathodic reaction rate = io/zF
Anodic rx. rate = ka x CM = f CM exp (-ΔG*/RT)

where , ka = rate constant = f exp (-ΔG*/RT)
CM = concentration of surface active atom
f = frequency of activated complex ≈ 1012/sec
exp (-ΔG*/RT) = Probability of reaction
k = f (pool reactant species) (probability of reaction)
3Å
Let's calculate CM approximately.

If the lattice constant is 3Å, the number of surface atoms :
Ns = (1016Å2/cm2)/(9Å2/atom) ≈ 1015 atoms/cm2
Thus, the moles of atoms/cm2=Ns/NA (NA =Avogadro' No.)
However, surface atoms adjacent to the crystal defects have a higher probability of reaction
than others or more active;
Fraction of surface atoms which are likely to be surface active, = 10-3 to 10-4 depending on
crystal structure, defect density and grain size.
Therefore, CM =α(Ns/NA) = moles of surface active atoms/cm2
ia = io = zF x (anodic reaction rate) = zFf CM exp (-ΔG*/RT)
Cathodic rx. rate at equil. = ic/zF = kc [CM+zVL]

=f[CM+zVL]exp (-ΔG*/RT)
where, CM+z= conc. of metal ion at OHP
VL = volume of the double layer/cm2 ≈ 10-8 cm3
Thus, ic = io = zFf[CM+zVL]exp (-ΔGc*/RT)
• ΔG* can be changed in electrochemical reactions by externally applied potential (Eapp). The
change in electrode potential from the equil. value to acquire a net current ( ie, externally
measurable value) is called polarization.
ie = f(Eapp-Eeq) = f(η)
ie,a
e-
1) Anodic polarization
ia
M M+z + ze- ………at Eapp > Eeq
ic M+z
ie,a = ia – ic = f(ηa) M
where Eeq = reversible potential or equil. potential
ηa = Eapp-Eeq : anodic overpotential or
anodic overvoltage : Eapp > Eeq
ie,c
2) Cathodic polarization e-
ic
M M+z + ze- ............. at Eapp < Eeq
ia
M+z
ie,c = ic –ia = f(ηc) M
ηc = Eapp-Eeq cathodic overpotential or
cathodic overvoltage.
: Eapp < Eeq
If anodic polarization is applied to the metal electrode, what happens to the energy well
curve? The energy of M(metal) increases by zηaF and the metal ions become more
unstable (high energy state).
At Equilibrium,
ia = ic = io
ΔG* G
M M+ After anodic polarization
(1-β)zηaF
ΔGa* ie,a = ia - ic > 0
β 1-β
M ΔGc*
zηaF Anodic Polarization
ηa >0 zηaF
βzηaF
ΔG*
0 M M+
0 (1-β)zηaF
β 1-β
Metal β 1-β Solution Metal Solution
0 1
0 1 IHP OHP
IHP OHP
For anodic reaction, ΔG*a= ΔG* +(1-β)zFηa - zFηa = ΔG* - βzFηa
For cathodic reaction, ΔG*c = ΔG* + (1-β)zFηa
ia = zFfCM exp (- ΔG*a/RT)

= zFfCM exp - (ΔG*- βzFηa)/RT
= zFfCM exp - (ΔG*/RT) exp (βzFηa/RT)
=io exp (βzFηa/RT)
ic = zFf[CM+zVL]exp (- ΔG*C/RT)
= zFfVLCM+zexp (- ΔG* /RT) exp [-((1-β)zFηa)/RT]
= io exp [-(1-β)zFηa/RT]
ie,a = ia- ic = io{exp (βzFηa/RT) - exp [-((1- β)zFηa)/RT]} ............ Volmer- Butler equation.
1) for ηa> 0.03 V ...........high field approximation.

ie,a ≅ ia = io exp (βzFηa/RT)
for ηa< - 0.03 V .......cathodic polarization

ie,c = ic- ia ≅ ic = io exp [-((1- β)zFηa)/RT]
¨At sufficiently large overpotential, the η – ie relationship becomes exponential.
2) when ηa is very small, ..... |ηa|<0.01 V.....low field approximation
By using : ex = 1 + x + x2/2.....= 1 + x , when x≪ 1,
ie,a = io{ exp (βzFηa/RT) - exp [-((1- β)zFηa)/RT]}

= io (zFηa/RT) ............a linear relationship between ηa and ie,a .
ie,a
ia
η
ic
ie,c
4.3 Polarization Diagram ( Evans diagram)
o. Polarization : An electrode is no longer at equil. when a net current flows from or

to the surface. The extent of potential change caused by net current to or from an
electrode, measured in volts, is overpotential (η).
η = f ( ie )
Anodic current
1) For anodic polarization ηa
ie,a = ia - ic Ba=2.3RT / βzF
= io{ exp (βzFηa/RT) - exp [-((1- β)zFηa)/RT]} =0.059 / βz
= io exp (βzFηa/RT) at high field approx. E ER

Bc= -2.3RT / (1-β)zF
ηa = 2.3RT/βzF log ie,a - 2.3RT/βzF log io = -0.059 / (1-β)z
= Ba log ie,a/io ................ Tafel equation. ηc
2) For cathodic polarization Cathodic current
ie,c = ic - ia ≅ ic
= io exp [-((1- β)zFηa)/RT] log io log |io|
at high field approx.
ηc = -2.3RT/(1- β)zF log ie,c/io where, io = exchange current density
= Bc log ie,c/io Er = equil. potential, or rest potential
Ba, Bc : Tafel constant, -0.05 V<B< 0.15 V
4.4 Concentration Polarization
One of the assumptions in the derivation of the Volmer- Butler eq. is the uniformity of
concentration near the electrode. This assumption fails at high current densities because
migration of ions towards the electrode from the bulk is slow and may become rate
determining. A larger overpotential is then needed to produce a given current because the
supply of reducible or oxidizable species has been depleted. This effect is called conc.
polarization.
For reduction reaction:

M+z + ze- ⇔ M
Er = E° + RT/ZF ln CB .................(1)
When a passage of external current is made through the cell, the interfacial conc. changes to
a value of CS, resulting in change of electrode potential.
Conc.
M+z + ze- ⇔ M M M+Z
Ep = E°+ RT/zF ln CS .......................(2) CB
Conc. overvoltage, CS
ηc = Ep - Er =RT/zF ln Cs/CB ..……...(3)
δ : Nernst Layer
OHP
IHP
Fick's 1st law : J= -D ∂C/∂x = -D (CS - CB)/δ = i/zF
where D= diffusivity of M+z ion , δ = Nernst layer, about 0.1mm.
therefore, i = DzF/δ (CB -CS).........................(4)

When CS → 0, i → iL : limiting current density,
Thus, iL = DzFCB/δ ..................................….(5)

(5) → (4) i = iL (1 - CS/CB), CS/CB = (1 - i/iL) ...........................(6)
(6) → (3) ηc = RT/zF ln (1 - i/iL) = 0.059/z log (1 - i/iL) at 298 K.......(7)
iL is increased by
• higher solution concentration, CB;
• higher temperature which increases
diffusivity, D;
• higher solution agitation, which decreases
δ.
Concentration polarization only becomes
important when the current density
approaches iL
For anodic dissolution process :
M M+z + ze-
During corrosion, conc. polarization for anodic dissolution can be ignored because
an unlimited supply of metal atoms is available at the interface. But, at high
corrosion rates, the conc. of M+z ion in the anolyte is significantly increased and
exert a back e.m.f. which results in anodic conc. polarization.
+
ηA
iL +
M +
Tafel (Linear Kinetics)
Tafel Region
+
+ +
+
+ + +
+ + +
M + + +
log ia Conc. polarization
4.5 Combined Polarization
E
ηT = ηct + ηc
Er
At low reaction rates, ηct controls the reaction rates. ηct
At high reaction rates, ηc controls the reaction rates. io Ba
1) for anodic dissolution,ηc is small; ηC

ηdiss. = Ba log i/io
2) for reduction process;
ηred. = Bc log i/io + 2.3RT/zF log(1 - i/iL) log ic iL
4.6 Resistance Overvoltage
• Resistance Overvoltage (ηR) arises from the passage of electric current through an
electrolyte solution (with low conductivity) surrounding the electrode. This iR drop may be
offset by closing the tip of Luggin capillary to the surface of the electrode.
• Significant when surface oxide films forms on the electrode surface as a result of
electrochemical reaction.
ηR = i(Relectrolyte + Rfilm)
4.7 Mixed Potential Theory
- presented by Wagner and Traud in 1938.

- based on the following hypotheses;
1) All free corrosion reactions involve at least one anodic and one cathodic process.
2) During the corrosion of an electrically isolated metal, the total partial anodic current must
equal to the total partial cathodic current :
ΣAa ia = ΣAc ic at E = Ecorr
3) For metals, the electrical(Galvani) potential of the metal at the anodic site is equal to that at
the cathodic site due to their very low resistivities. This may not be valid for semiconductors,
particularly if the anodic and cathodic sites are widely separated.
Consider Zn undergoing active corrosion in a deaerated HCl solution at 25°C:
Anodic reaction : Zn2+ + 2e- Zn

Er,Zn = EZn2+/Zn + 0.059/2 log aZn2+
= – 0.763 + 0.059/2 log 10-6 2H+ H2
Zn2+ H+
= – 0.763 – 0.177 = – 0.94 V.
2e- Cl-
Cathodic reaction : 2H+ + 2e- H2 Zn
Er,H2 = EH2+/H + 0.059/2 log PH2/aH+
= – 0.059 V at PH2= 1 atm and pH =1
For hydrogen reduction reaction,

Er,H2 = – 0.059V, io,H+/H2(on Zn) = 10-11A/cm2, Bc = 0.12 V/decade
For Zn oxidation,
Er,Zn = – 0.94V, io,Zn2+/Zn= 10-7A/cm2, Ba =0.06 V/decade
+0.2
0
Er,H2 = – 0.059
E (SHE) V -0.2
ηC
io,H+/H2 (Zn) 2H+ +2e- →H2
-0.4
Zn→Zn2+ +2e-
-0.6
Ecorr
-0.8 ηA
-1.0 Er,Zn = – 0.94 icorr
io,Zn2+/Zn
10-10 10-8 10-6 10-4 10-2 10-0
log |i| A/cm2
• A mixed electrode is an electrode or metal that is in contact with two or more oxidation-
reduction systems.
• Corrosion potential(Ecorr) and corrosion current density(icorr) are determined at the point
where the total rates of oxidation and reduction are equal.
icorr = the rate of Zn dissolution = iH2 (Zn) at Ecorr
4.8 Importance of exchange current density
Consider the corrosion of iron in deaerated acid solution.
1) For Fe oxidation :
Fe2+ + 2e- ← Fe ............E°Fe2+/Fe = – 0.44 V
Er,Fe = E°Fe2+/Fe + 0.059/2 log aFe2+
= – 0.44 + 0.059/2 log10-6
= – 0.62 V
io,Fe2+/Fe = 10-6 A/cm2
Ba =0.08 V/decade
2) For hydrogen reduction : Fe2+

2H+ + 2e- → H2
H2
Er,H2 = – 0.059 pH =–0.059 V at pH=1 H2O
io,H+/H2(on Fe) = 10-6 A/cm2 2H+ H+
Bc = – 0.15 V/decade
f Comparison of corrosion behavior between Zn and Fe
1) Er,Zn = – 0.94V < Er,Fe = – 0.62 V

2) icorr,Fe > icorr,Zn
This is due to the lower exchange current density for hydrogen evolution on Zn compared to
that on Fe. i,e io,H+/H2(Zn) < io,H+/H2(Fe)
+0.2
H2→2H+ +2e-
0 Er,H2 Fe→Fe2+ +2e-
-0.2
io,H+/H2
Ecorr
-0.4
icorr
-0.6 Er,Fe
-0.8
io,Fe2+/Fe Fe2+ +2e-→Fe 2H+ +2e- →H2
10-10 10-8 10-6 10-4 10-2 10-0
Ecorr = corrosion potential, rest potential, open circuit potential, mixed potential
Hydrogen overvoltage = Ecorr – Er,H2 = Ecorr – ( – 0.059pH)
f The exchange current density ( io,H+/H2) for hydrogen evolution reaction is highly sensitive to
the nature of the metal substrate on which the reaction occurs, and are markedly reduced by
the presence of trace impurities such as arsenic, sulfur, and antimony compounds.
f For corrosion of metals in acid.
ηH2 = Ecorr – ErH+/H2 = Ecorr + 0.059pH

ηH2 (Zn) < ηH2 (Pt) at i = i1
In the electrical analogue of double layer
RF (Zn) > RF (Pt)
f Exchange current density, io (A/cm2) depends on :

• electrode composition
• redox reaction
• temperature
• surface roughness
4.9 Effect of oxidizer
The driving force for corrosion is

increased by the addition of a stronger
oxidizer that is a redox system with a
half cell electrode potential much
more noble than that of any others
present.
Consider the corrosion of metal M in
an acid containing Fe3+.
Fe3+ Fe2+
Fe3+ H2O
H2 H+
2+
Fe
2e-
2H+
• Ecorr is determined by the point at which the total rate of oxidation equals the total rate of
reduction.
icorr = iM→M+ = iFe3+→Fe2+ + iH+→H2
The addition of an oxidizer to an acid solution :

1) shifts corrosion potential in the noble direction,
2) increases the corrosion rate from i'corr to icorr,
3) decreases hydrogen evolution from i'corr to iH+→H2.
• The effect of an oxidizer on the corrosion rate is dependent on its redox potential and its
exchange current density.
4.10 Effect of concentration polarization
At low cathodic polarization the reduction process is activation controlled, but at high
polarization it is diffusion or concentration controlled.
ηdiss. = Ba log i/io
ηred. = Bc log i/io + 2.3RT/zF log(1 - i/iL)
A common example of corrosion controlled by concentration polarization is iron or steel in

dilute aerated sea water. The cathodic process is reduction of dissolved oxygen. The
maximum solubility of dissolved oxygen in water is relatively low, about 8ppm at ambient
temperature.
O2 + 2H2O + 4e- → 4OH-
¨ iL = 100μA/cm2
ioH+/H2(M)
Ecorr,C
Ecorr,B ioC+/C
Ecorr,A ioB+/B
ioA+/A
iL log |i|
In this system, icorr=iL, For different metals; A, B and C,

depending on conc., temperature and icorr is equal to iL.
velocity.
4.11 Experimental Polarization Curves

Corrosion Kinetics

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4.

4.1 The electrical double layer

Gch G = Gchem +Gelectro

M ⇔ M+z + ze- ..... at equilibrium or reversible potential.

Reaction rate = k x Concentration

Anodic rx. rate = ka x CM = f CM exp (-ΔG*/RT)

k = f (pool reactant species) (probability of reaction)

Let's calculate CM approximately.

ia = io = zF x (anodic reaction rate) = zFf CM exp (-ΔG*/RT)

Cathodic rx. rate at equil. = ic/zF = kc [CM+zVL]

Thus, ic = io = zFf[CM+zVL]exp (-ΔGc*/RT)

ia = zFfCM exp (- ΔG*a/RT)

1) for ηa> 0.03 V ...........high field approximation.

for ηa< - 0.03 V .......cathodic polarization

¨At sufficiently large overpotential, the η – ie relationship becomes exponential.

ie,a = io{ exp (βzFηa/RT) - exp [-((1- β)zFηa)/RT]}

o. Polarization : An electrode is no longer at equil. when a net current flows from or

= io exp (βzFηa/RT) at high field approx. E ER

2) For cathodic polarization Cathodic current

For reduction reaction:

therefore, i = DzF/δ (CB -CS).........................(4)

Thus, iL = DzFCB/δ ..................................….(5)

1) for anodic dissolution,ηc is small; ηC

4.6 Resistance Overvoltage

- presented by Wagner and Traud in 1938.

ΣAa ia = ΣAc ic at E = Ecorr

Anodic reaction : Zn2+ + 2e- Zn

For hydrogen reduction reaction,

-1.0 Er,Zn = – 0.94 icorr

icorr = the rate of Zn dissolution = iH2 (Zn) at Ecorr

Consider the corrosion of iron in deaerated acid solution.

2) For hydrogen reduction : Fe2+

1) Er,Zn = – 0.94V < Er,Fe = – 0.62 V

10-10 10-8 10-6 10-4 10-2 10-0

f For corrosion of metals in acid.

ηH2 = Ecorr – ErH+/H2 = Ecorr + 0.059pH

f Exchange current density, io (A/cm2) depends on :

The driving force for corrosion is

icorr = iM→M+ = iFe3+→Fe2+ + iH+→H2

The addition of an oxidizer to an acid solution :

A common example of corrosion controlled by concentration polarization is iron or steel in

In this system, icorr=iL, For different metals; A, B and C,

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