PART C CORROSION KINETICS

I. Corrosion Rates

II. Corrosion Reactions Mechanism

III. Polarization in Corrosion Study

IV. Experimental Measurement of Corrosion

V. Passivity



1. Corrosion Rates
The rate of electron flow to or from a reacting interface is a
measure of the reaction rate
nF
ItM
m =
m = mass reacted (g)
I = current (amp)
t = time (s)
M = molar mass (g/mol)
n = number of electrons in electrode reaction
F = Faradays constant (96485 Coul /mole of electrons)
For a corrosion reaction:
I. Corrosion rate (based on metal loss):
nF
iM
tA
w
r = =
r = corrosion rate of metal (mass/area/time)
{usually mdd: mg/dm
2
/d}
w = mass loss or reacted (g)
i = current density (amp/cm
2
) NOTE: i=i
CORR
A = electrode surface area (cm
2
)
nF
ItM
w =
i = I/A
This rate expression is useful for uniform corrosion.
Corrosion Rate (mass/area/time) for an Alloy:

an equivalent weight (M/n) is used in calculating corrosion rate:
nF
iM
tA
w
r = =
f
i
= mass fraction of i
th
element
n
i
= electrons exchanged in the i
th

element
M
i
= Molar mass (= atomic weight) of i
th

element
N
eq
= number of equivalents in unit mass
of alloy
EW = equivalent weight of alloy
Example:
For 304 stainless steel (Cr 19%, n=3; Ni 9.25%, n=2; Fe 71.75%, n=2)

N
eq
=
0.19
( )
3
( )
52.00
( )
+
0.0925
( )
2
( )
58.71
( )
+
0.7175
( )
2
( )
55.85
( )
= 0.03981
M/n = EW =1/ N
eq



|
.
|

\
|
=
|
|
|
.
|

\
|
=
i
i
M
n
f
n
M
f
N
i
i
i
i
eq
EW =1/ 0.3981 = 25.12 r = i .EW/F (mdd)
II. Penetration Rate (Corrosion rate based on thickness):

r
p
= Penetration rate (length/time)
C = Conversion factor including Faradays constant.
i = current density of corrosion reaction (A/cm
2
)
= density of metal (g/cm
3
)

C = 0.129 {r in mpy mpy : mils/year
1 mil = 0.001 inch}
C =3.27 {r in mm/yr}

n
iM
C rp =
Example: What is r (mpy) for iron (=7.87 g/cm
3
) which is
equivalent to a corrosion current density of of 1 A/cm
2
?

Solution: r = 0.129 [(55.84)(1) / ((2)(7.87)] = 0.46 mpy
For metals and For alloys
] [ i
i i
i
f
n
M
Ci rp

E =
Explanation:
For single metal:
r
p
=r /

(length/time) = (mass/area/time) / (mass/volume)
volume = area x length

r
p
= (i M/n F)/ = (i M/n F)
r
p
= (i/F)(C) (M/n.) = (C i) (M/n.) C = unit conversion factor
r
p
= 0.129 i (M/n.) mpy

For alloys:

Replace (M/n.) by (f
i
.M
i
/n
i
.
i
) in the last equation above:

r
p
= 0.129 i (f
i
.M
i
/n
i
.
i
)
2. Corrosion Reactions Mechanism
Graphical representation of the processes occurring
at an electro-chemical interface.

The corrosion reaction consists of two types of processes:

1. Charge transfer reactions e.g.
anodic M
lattice
M
+
surface
+ e
M
+
surface
M
2+
surface
+ e
---------------------------------
M
lattice
M
n+
surface
+ n e
cathodic
O
2 surface
+ 2H
+
+ 2e H
2
O
2 surface
H
2
O
2 surface
+ 2H
+
+2e 2H
2
O
surface
-----------------------------------------------
O
2 surface
+ 4H
+
+ 4e 2H
2
O
surface

2. Mass transport of ions or molecules involved in the reaction e.g.
anodic M
n+
surface
M
n+
solution
cathodic O
2 solution
O
2 surface

H
2
O
surface
H
2
O
bulk solution


I. Activation Control:
The case when corrosion is controlled by charge transfer
reactions.
Either the anodic charge transfer OR the cathodic charge can be
the controlling (rate limiting) step.
The anodic reactions and the cathodic reactions in a system can
be studied INDIVIDUALLY by electrochemical methods.
II. Mass Transfer Control:
If the cathodic reagent at the corrosion site (e.g., dissolved O
2
in
the O
2
reduction reaction) is in short supply, mass transfer of the
reagent can become rate limiting.
Then, the cathodic charge-transfer reaction is fast enough to
reduce the concentration of the reagent at the surface corrosion
site to a value less than that in the bulk solution.
Rate Limiting Step in Corrosion Reactions

Activation control Mass transfer control
Reagent: O2, H+, OH-, H2O, Fe2+,
The rate of any electrochemical reaction (ECR) is
limited by various physical and chemical factors.

Thus, the reaction is said to be polarized or
retarded by these factors.

Polarization is also known as over-voltage or
over-potential.

A
is anodic polarization and

c
is cathodic
polarization.


3. Polarization in Corrosion Study
Components of Polarization
There are three possible components:
1) Activation over-potential (
act
)

: Commonly encountered in anodic
charge transfer reactions (metal oxidation):
M
surface
= M
n+
surface
+ n e
-

2) Concentration polarization (
conc
): Commonly encountered in
cathodic reactions, particularly oxygen and hydrogen reductions:




3) Resistance polarization (
R
) OR Potential drop. 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.



2H
+
+ 2e

= H
2
2H
2
O+ 2e

= H
2
+ 2OH

Theoretically, total polarization at an electrode is the

sum of the three components: activation, concentration
and resistance polarizations:

TOTAL
=
act
+
conc
+
R

The actual polarization is normally limited to one or the
sum of two components. This is based on the relative
amounts of these components which makes an over-
potential negligible at a given electrode.

In many cases,
Act
is the only significant polarization
component at the anode while
Conc
is the only
significant polarization component at the cathode.



act
occurs when some step in the half-cell
reaction controls the rate of charge transfer.


act
is commonly found in anodic (oxidation)
reactions, e.g. metal dissolution.

act
is
positive (anodic) if net current is dissolution
(oxidation):

negative (cathodic), if net current is
deposition (reduction).
3.1 Activation Polarization
At each electrode of corrosion cell there is a partial
current. The anodic current, i
a
, is given by:

) exp(
) exp( .
*
exp )
} * {
exp(
RT
zF
i i
RT
zF
RT
G
zFA
RT
zF G
zFA i
A
A A
f
o
a
f
a
q |
q | q |
=
A
=
A
=
Similarly, the cathodic current, i
c
, is
)
) 1 (
exp(
RT
zF
i i
C
o c
q |
=
The net current of cell is the difference between the
two partial currents:

)}
) 1 (
exp( { )} exp( {
RT
zF
i
RT
zF
i i i i
C A
o
o c a net
q | q |
= =
This is the Butler-Volmer (B-V) equation

expressing the relation between
the net anodic current flowing at the electrode, i
net

and
the over-potential, , at that electrode.

Reaction Progress Coordinate
Metal Ion
Energy Hump
Energy profile for equilibrium at an electrode
G*
G* is the
activation Gibbs
free energy
F
r
e
e

E
n
e
r
g
y

C
o
o
r
d
i
n
a
t
e

M M
z+
+ z e
-
+
= 0.5
I
o
I
o
NOTATION of B-V equation:

R = universal gas constant;
T = absolute temperature;
z

= number of electron transferred in electrochemical reaction
( valency)
F = Faraday constant (96,485 Coul/mol)

A
= over-potential (polarization) at the anode

C
= over-potential (polarization) at the cathode
= symmetry factor representing energy peak, usually taken as 0.5
i
o
= exchange current density (a constant for the system).

The first term in {brackets} in B-V equation, above, describes the
forward (metal dissolution, anodic) reaction while the second term
in {brackets} describes the reverse (metal deposition, cathodic)
reaction.
NOTE: z is used in place of n to avoid confusion with
Tafels Equation (based on B-V equation)
If the polarization is anodic, with
A
> 0.1 V, the value of i
c
is
insignificant. Making the approximation i
net
i
a
, the equation
becomes:

] [exp
RT
zF
i i i
A
o a net
q |
= =
If the polarization is cathodic with > -0.1 V, i
a
is insignificant
and with approximation i
net
i
c
,

then

Since and z are constants for a given electrode process at
constant temperature (usually room temperature, e.g. 25
o
C), this
equation can be re-arranged as
=
A
+
C
= a + b log i

Combine both equations, total over-potential is:
These are forms of Tafels Equation
o
a
a
i
i
b A log = q
o
c
c
i
i
b C log = q
zF
RT
b
a
|
303 . 2
=
zF
RT
b
c
) 1 (
303 . 2
|
=
The relationship between over-potential and current density
(reaction rate) for the two half-cell reactions: Tafels equation plot
q
a
=anodic over-potential
q
c
=cathodic over-potential

b
a
=anodic Tafel constant
b
c
=cathodic Tafel constant

(units of b: V/decade where
decade is interval between two
quantities having the ratio
of 10 to 1)

i
a
=anodic current density
i
c
= cathodic current density

i
o
=exchange current density
o
a
a a
i
i
b log = q
o
c
c c
i
i
b log = q
(i
o
depends on surface conditions and is a measured quantity)
Mixed Potentials Theory
Net current density on freely-corroding electrode
must be zero.

Therefore potential (E
corr
) will be that at which
anodic and cathodic current densities are equal
(lines intersect) and opposite.

Sometimes called a mixed equilibrium Potential
because the system is not at true electro-
chemical equilibrium.

1. Combined Electrodes
Zinc corrodes in an acid solution. Anodic and cathodic reactions take
place simultaneously on the surface:

Zn= Zn
2+
+2e

2H
+
+ 2e

= H
2
Anodic
Cathodic
The two half-cell potentials:
2
2
/
/
H H
Zn Zn
E
E
+
+
cannot exist separately on a conductive surface

They must change to a common intermediate potential called:

the mixed potential or corrosion potential E
corr


Anodic and cathodic half-cell reactions present
simultaneously on a corroding zinc surface.

Polarization of anodic and cathodic half-cell reactions for zinc in acid
solution to give a mixed potential, E
corr
, and a corrosion rate (current
density), i
corr
.
Evans Diagrams

In the Evans diagram, the intersection of the two polarization curves
occurs @ the corrosion current, i
corr
(as shown in the previous plot)..

The exchange currents, (i
o
)
a
and (i
o
)
c
, can be obtained by extrapolating
the Tafel lines back to the equilibrium potentials (E
rev
)
a
and (E
rev
)
c


The origin (i = 0) is not shown on a logarithmic plot.

The bigger the difference in equilibrium potentials (bigger E
rev
),
the bigger the value of i
corr
(greater the corrosion rate)

2. Prediction of Corrosion Tendency
Standard potentials of Fe and Zn oxidation:

Fe Fe
2+
+ 2e

(-0.44V SHE)
Zn Zn
2+
+ 2e

(-0.76V SHE)
Zn corrosion would be more prevalent than Fe corrosion based on
thermodynamic considerations (emf series of potentials).

However, due to kinetics considerations:

- low exchange current density for hydrogen reduction on zinc
(10
-9
A/cm
2
) compared to that of H
2
reduction on iron (10
-6
A/cm
2
),
and
- lower exchange current density for zinc dissolution (10
-8
A/cm
2
)
compared to iron dissolution (10
-6
A/cm
2
),
the corrosion rate of Fe is faster than that of zinc: i
corr, Fe
> i
corr, Zn

Note: lower i
o
means higher (see Tafels equation)
Conclusion: Iron is better a catalyst for H
2
evolution from acid than Zn.


N.B. Currents must balance for the coupled reactions. Current densities
are equivalent to currents when surface areas are accounted for.
Comparison of
electrochemical
parameters for iron
and zinc in acid
solution,
demonstrating the
importance of i
o
on
determination of
corrosion rates.
3. Effect of an Oxidizer
What happens if we add an oxidizer with a half-cell electrode
potential much more noble than any others present (e.g.
adding ferric-ferrous salts to a metal M in an acid solution).

Experimental observations:
1. Corrosion potential E
corr
shifts to more noble
(positive) values
1. Corrosion rate increases
2. Hydrogen evolution rate is reduced

Use charge conservation and find E
corr
as the point where the
two oxidation and reduction current densities are equal.
Total rate of reduction is the sum of all three reduction reactions at
any given potential

Total rate of oxidation is the sum of all three oxidation reactions at
any given potential

E
corr
is defined by the intersection of the total oxidation and total
reduction lines

In this example, at E
corr
the metal oxidation is the only oxidation so
the total oxidation current density is the corrosion rate

The total reduction current is the sum of the iron and hydrogen
reduction

Determine the mixed potential E
corr
for a corroding metal M exposed
to acid solution with a second oxidizer, Fe
3+/
Fe
2+
, present.

Rates of reduction ( and ) and oxidation (i
corr
) from above.
2
H H
i

+ + +

2 3
Fe Fe
i
What if the exchange current density from an oxidizer is very low?
In this case, there would be no measurable effect and the corrosion
potential would not change. No effect on corrosion when oxidizer of
low i
o
is added to an acid.


NOTE: the thermodynamic driving force remains the same
; but the kinetics change !
Exchange currents on Zn and Pt are different: 1. E
Corr,couple
> E
Corr,Zn

2. H
2
evolution on Zn decreases. 3. i
Corr,couple
>
iCorr,Zn
( )
+ +
= A
2
2
/ /
) ( ) (
Zn Zn
e
H H
e therm
E E E
4. Effect of Coupling Active Metal to a Noble Metal

Isolated zinc corrodes in acid
Zn Zn
2+
+ 2e
2H
+
+2e H
2
Platinum is inert in acid.
When Zn & Pt are coupled:
zinc corrosion increases
H
2
evolution occurs on platinum rather than on
zinc:
Activation polarization of H
2
reduction
H2/Pt
is less
than
H2/Zn

Pt is a good catalyst for H2 evolution; Zn is not.


The more active metal corrodes faster when coupled, more noble metal
corrodes slower;
The more active metal becomes anode, more noble becomes cathode.

N.B. Actual rates depend on Tafel slopes, exchange currents, etc.
without detailed information we only predict trends.

5. Effect of Galvanic Coupling
The more efficient the hydrogen evolution process (i.e., the higher the exchange
current), the larger the effect of galvanic coupling
Pt is more efficient a cathode for H
2
evolution than Au
Comparison of zinc-platinum and zinc-gold couples (equal areas).
6.
7. Effect of Electrode Area Ratio
Galvanic corrosion of zinc-platinum couples at different cathode (Pt) areas
CONCLUSIONS:

Increasing cathode area increases corrosion rate, or
Increasing cathode area / anode area increases corrosion rate
To control corrosion, cathode area / anode ratio should be low
(i
a
= I/A
a
; high corrosion current when low anode area).

REMINDER:

Corrosion [mixed] potential are determined by point where total
oxidation rate equals total reduction rate.
Rates of individual processes are determined by mixed potential.