Electrode kinetics

Faradays Law :
nF
Ita
m =
I = current in A (1 A = 1 coulomb of charge/s)
m = mass reacted
a =atomic weight
F = Faradays constant = 96500 coulombs/equivalent
n = number of equivalents or e exchanged
t = time
Electrochemical reaction produce OR consume e
So, rate of e flow is a measure of rxn rate
Electrode Kinetics
Cu
a
Cu2
+
=1
Cu
2+
Cu
2+
Two equal and opposite partial currents due to flow of ions, one
leaving the electrode, other entering the electrode
i
1
= i
2
= i
0
, the exchange current density
Dynamic equilibrium at an electrode
Cu dissolution as Cu
2+
rate=r
1
Cu deposition from Cu
2+
, rate = r
2
No net change in G
If equilibrium is disturbed, a net current flows across
surface, and potential is displaced in a direction and
to an extent determined by the direction and
magnitude of current
Corrosion systems are not at equilibrium!
What happens when cells are short circuited?
Electrode Kinetics
If a cell is short-circuited,
net oxidation and reduction processes occur at the electrode surfaces, and
potentials of electrodes deviate from equilibrium potentials
Polarization: deviation from equilibrium potential resulting from a net
current
Magnitude of polarization: overvoltage,
log i
+
E
-
i
o,Zn/Zn+
E
o
Zn
X
Cu
Zn
a
Cu2
+
=1
a
Zn2
+
=1
i
+
E
-
Exchange Current Density, i
o
E
H/H+
i
o,
H
2
/H
+
,
Hg i
o,
H
2
/H
+
,
Pt
i
o,
H
2
/H
+
,
Fe
i
o,
H
2
/H
+
, Pt*
nF
i
r r
o
red ox
= = At equilibrium,
] [
] [
red
ox
i
o
is a f( redox rxn, electrode, , T, roughness)
The activation energy is the excess energy
that must be acquired to transform metal
atoms at the metal surface into solvated
metal ions.
* Activation polarization is a manifestation of the relative
changes in the activation energies for dissolution and
deposition, when equilibrium is disturbed.
** The polarization is positive, i.e., anodic, or negative,
i.e., cathodic, according to whether the net current is a
dissolution or deposition current.
*** It is always a component of the total polarization,
whether or not there are also significant contributions
from concentration and resistance effects.
Activation polarization
rate determining steps
rates of the electrochemical processes are controlled by the charge transfer
across the metal solution interface
specific activation energies are required to proceed
both anodic and cathodic rxn
log i
+

-
+
i
o,M/M+
o
a
i
i
log | q =
Activation Polarization
1. ion adsorption
2. e transfer
3. Molecule formation
Tafel Equation
Concentration Polarization
Hydrogen evolution rxn
What happens if rate of reduction is steadily increased?
diffusion in the electrolyte rate controlling
Only significant during reduction rxns
log i
+

-
Velocity
Concentration
Temperature
i
L
|
|
.
|

\
|
=
L
c
i
i
nF
RT
1 log 3 . 2 q
x
DnFC
i
B
L
=
Thickness of
diffusion layer
not apparent
i
L
= max. rate of
reduction possible
Combined Polarization
log i
+

-
|
|
.
|

\
|
+ =
=
+ =
L o
red
o
diss
c a T
i
i
nF
RT
i
i
i
i
1 log 3 . 2 log
log
| q
| q
q q q
i
L
Concentration
Polarization
For.
reactions
Mixed Potential Theory
Hypotheses
1. Any electrochemical rxn can be divided in to two or more partial
oxidation/reduction rxns
2. There can be no net accumulation of charge, during an electrochem. rxn
Mixed Electrodes
log i
+
E
-
i
o,
H
2
/H
+
E
H2/H+
E
corr
i
corr
E
o
Zn/Zn2
+
i
o
Mixed Electrodes
log i
+
E
-
i
o,
H
2
/H
+
E
H2/H+
E
corr
i
corr
i
0
on Fe is higher than on Zn.
-Faster corrosion!
*emf series can not tell this!
Complex Environments
log i
+
E
-
i
o,
H
2
/H
+
E
H2/H+
Find net rates
- graphical additions
i
o,Fe3+/Fe2+
E
Fe3+/Fe2
+
i
corr
E
corr
i
corr
Corrosion under reduction diffusion
control
log i
+
E
-
i
L
Concentration
Polarization
i
o,M/M+
i
o,
H
2
/H
+
same principles
-M in weak acid solution
Passivity
Faradays Expt.
Conc HNO3 Dilute HNO3 Dilute HNO3
No Reaction No reaction Violent reaction
Passive state Active state
H
2
O Scratching/direct
immersion of Fe
corrosion rate drops by 10
4
10
6
loss of chemical reactivity under certain
environmental conditions
Passivity
I (log scale)
+
E
-
i
o,M/M+
Active
Passive
Transpassive
I
c
E
pp
E
M/M
+
Anodic dissolution of active-passive metal
Fe, Cr, Ni, Ti, and alloys
Passivity
I (log scale)
+
E
-
Effect of T, and [H
+
]
increasing
[H+] and T
i
p
Passivity
Anodic dissolution of active-passive metal
Fe, Cr, Ni, Ti, and alloys
log i
+
E
-
E
M/M
+
i
o,M/M+
i
01
i
02 i
03
A
B
C
D
E
1
2
3
E
pp
I
c
Most desirable
case: 3
Least desirable: 2
Position of nose:
at E
pp
,
cathodic rxn rate>
anodic dissolution rate
.for spontaneous
passivation
Small I
c
, and active
E
pp
Good
Modern Theory- Applications
Predicting Corrosion Behavior
Effect of oxidizers
When reduction is under diffusion control- effect of velocity
Galvanic coupling
A
anode
: A
cathode
effect
I (log scale)
+
E
-
Modern Theory- Applications
Predicting Corrosion Behavior
Effect of oxidizers
What if it was active metal?
i
o,M/M+
E
M/M
+
A
B
C
D
E
H
G
F
I
J
i
o
R
7
6
5
4
3
2
1
4 is required to
produce passivity
2 is required to
maintain
passivity
l
o
g

c
o
r
r
o
s
i
o
n

r
a
t
e
Conc. Oxidizer
A
C
B
G
D
J
I
H
F
E
surface
damag
e
Corrosion under reduction diffusion
control
log i
+
E
-
i
o,
H
2
/H
+
5 6 3
C
4
D
2
B
increasing velocity
i
o,M/M+
1
A
A
C
B
D
C
o
r
r
o
s
i
o
n

R
a
t
e
Effect of velocity
I (log scale)
+
E
-
i
o,M
A
1
i
o,
H
2
/H
+
4 5
A
C
B
D
C
o
r
r
o
s
i
o
n

R
a
t
e
increasing
velocity
2
B
3
C
D
log i
+
E
-
Galvanic Coupling
i
o,
H
2(Pt)
i
o,
H
2(Zn)
i
o,Zn
E
corr
i
corr(Zn)
E
M/M+
E
H2/H+
i
corr(Zn-Pt)
E
couple
log i
+
E
-
i
o,
H
2(Zn)
i
o,Zn
E
corr
i
corr(Zn)
E
M/M+
E
H2/H+
Galvanic Coupling
i
o,
H
2(Pt)
i
corr(Zn-Pt)
i
corr(Zn-Au)
i
o,
H
2(Au)
Comparison of Zn-Au and Zn-Pt
couples
log i
+
E
-
Galvanic Coupling between 2
corroding metals
i
o,
H
2(N)
i
o,N
E
M/M+
i
corr(N)
E
couple
i
o,
H
2(M)
E
H2/H+
i
o,M
i
corr(M)
i
corr(M-N)
i
corr(M-N)
log I (current)
+
E
-
i
o,
H
2(Zn,1cm
2
)
i
o,Zn,1cm
2
E
corr
i
A
E
M/M+
E
H
2
/H+
Galvanic Coupling
i
o,
H
2(Pt,10cm
2
)
i
C
i
B
i
o,
H
2(Pt,1cm
2
)
Area Effect
Exchange
current!
i
oH2,Pt
i
corr,Ti/Pt
i
oH2,Ti
i
corr,Ti
Spontaneous Passivation of Ti upon coupling to Pt
i
oH2,Pt
i
corr,Fe/Pt
i
oH2,Ti
i
corr,Fe
Enhanced Corrosion of Fe upon coupling to Pt
Alloy Evaluation
Anodic polarization curves
To compare quantitatively the
corrosion characteristics
To determine effect of alloying
additions
2-3 hrs required/specimen
Example
Given: i
L
for O
2
reduction 100 A/cm
2
Fe
Fe-18Cr (430L)
Fe-18Cr-8Ni (304L)
i
c
-too high
i
c
-low
Corrosion Prevention
Anodic Protection
log i
+
E
-
Protection Range
?
i
o,H2
i
corr,active
i
corr,Passiv
e
i
app4
i
app,C
i
o,H2
+
E
-
i
Anodic Protection
i
app (anodic)
= i
ox
- i
red
i
app(cathodic)
=i
red
- i
ox
Electrochemical Reactions
nFE G = A
ox
red
red
o
red
a
a
nF
RT
E E ln =
Nernst Equation
For non-standard
conditions
Limitation:
Only direction of reaction- no info about kinetics (rates)
sign of G is important!
(not magnitude)
Half-cell reduction
potential
Total cell potential
...
...
ln
reactant2 reactant1
2 1


=
=
a a
a a
Q
quotient reaction the is Q
Q
nF
RT
E E
product product
cell
o
cell
when,
activity 1 =
Common Name Electrode V vs NHE Notes
Saturated
Calomel
Electrode (SCE)
Hg/Hg
2
Cl
2
/sat. KCl +0.241 Probably the most common
electrode in the laboratory,
but use of mercury
presents safety hazards
Calomel Hg/Hg
2
Cl
2
/1 M KCl +0.280 Better temperature stability
than SCE
Mercurous
sulphate
Hg/Hg
2
SO
4
/sat.
K
2
SO
4
+0.640 Useful for avoiding Cl
-
contamination of test
solution
Hg/Hg
2
SO
4
/0.5M
H
2
SO
4
+0.680
Mercurous oxide Hg/HgO/1M NaOH +0.098 Good for alkaline solutions
Silver chloride Ag/AgCl/sat. KCl +0.197 Very easy to make, but
light sensitive
Copper sulphate Cu/sat. CuSO
4
+0.316 Very robust, commonly
used for cathodic
protection
Reference Electrodes
Half Cell Potential
When a metal M is immersed in an aqueous electrolyte, it
acquires a certain potential. If the activity of the metal ions M
++
in
the aqueous environment is unity, then the acquired potential is
known as standard potential
0.
Potential of each electrode can be calculated using Nernst
equation.
Example: Zinc Electrode
+
+
=
+
2
Zn
0
Zn
2
Zn
Zn
ln
2
Zn 2e Zn
F
RT

Hydrogen Electrode
It is assumed arbitrarily
that the standard
potential for the
following reaction is
equal to zero at all
temperatures
So
Standard Hydrogen Electrode
(SHE)
The potential of the electrode equals zero if the
hydrogen ion activity and the pressure of hydrogen
gas in atmospheres are both unity. This is the
standard hydrogen potential
The half - cell potential for any electrode is equal to
the emf of a cell with the standard hydrogen
electrode as the other electrode.
The half - cell potential for any electrode expressed
on this basis is said to be on the normal hydrogen
scale or on the standard hydrogen scale ,
sometimes expressed as
H
or ( S.H.E. )
Convention of Signs and Calculation of
EMF
V 763 . 0 Zn 2e - Zn
V 763 . 0 Zn 2e Zn
0 2
0 2
+ =
= +
+
+

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
Pt; H
2
, H
+
, Zn
2+
; Zn Cell
E
cell
= E
cathode
E
anode
= ??
Calomel Reference Electrode
Ag-AgCl Reference Electrode
Cu-CuSO
4
Half Cell
Number Line for Potential Conversion
Among Different Reference Electrode
Scales
Oxygen Electrode
Oxygen Electrode and Differential Aeration Cell
Consider two O
2
electrodes:
one in contact with O
2
at 1 atm
other in contact with O
2
at 0.2 atm
Oxygen Electrode and Differential Aeration Cell
The reaction is not thermodynamically possible as
written
Thus, the electrode 1 is cathode electrode 2 the
anode.
In a differential aeration cell, the electrode in lower
O
2
pressure acts as the anode and the one in higher
O
2
pressure acts as the cathode
Galvanostat
In the galvanostatic method, a fixed current is applied from a
constant current power source connected between the working
electrode and a counter electrode.
Counter electrode is usually made of some inert material such as
platinum. The change in potential induced in the working electrode
by the passage of current is measured against the reference
electrode.
In order to minimise the inclusion in the measured potential of any
potential drop occurring in the solution due to its resistance, i.e. an IR
drop, the reference electrode is brought into contact with the test
solution through a tube which ends in a fine capillary known as a
Luggin capillary.
This is placed close to the surface of the working electrode, though
no closer than twice the external diameter of the capillary to avoid
screening of the electrode from the flow of current.
In the potentiostatic method, as illustrated in Fig 1, the potential of the working
electrode is controlled at a fixed value with a potentiostat.
This instrument uses a feed-back circuit to pass appropriate currents to the working
electrode so that its potential measured against the reference electrode is
maintained at the desired value, regardless of variations in current corresponding to
changes in the rates of the corrosion reactions.
The potentiostatic method of polarisation has the advantage that it can follow more
closely the behaviour of metals during the formation and breakdown of passivating
films.
It primarily depends on the potential of the metal, and very large changes in
currents can occur at constant potential.
Potentiostat
A corroding metal in a solution takes up a potential, the corrosion potential, such
that the rate of the anodic reaction of metal dissolution is equal to the rate of the
cathodic reactions of hydrogen and/or oxygen reduction.
If the potential of the corroding metal is displaced slightly from the corrosion
potential, Ecorr, either by galvanostatic or potentiostatic polarisation, then the
potential E is initially a linear function of the current density i (the current per unit
area).
The linear relationship holds for a potential displacement of up to about 10 mV. The
slope of the linear polarisation curve dE/di is termed the polarisation resistance R
p
.
The polarisation resistance is inversely proportional to the rate of corrosion
expressed as the equivalent corrosion current density i
corr
, i.e.
where B is a constant. Measurements of the polarisation
resistance provide a valuable means of rapidly determining the
instantaneous rate of corrosion of a metal, as used in several
commercial instruments.
The value of the constant B can be determined from weight loss
measurements or from electrochemical data.
As the displacement of the potential of the metal from the
corrosion potential is increased beyond about 10 mV, the
polarisation curve increasingly deviates from the linear
relationship between potential and current.
A region is reached when the potential exhibits a linear
dependence on the logarithm of the current density as shown
in Fig 2.
This behaviour is characteristic of the occurrence of a single
electrochemical reaction on the metal surface, indicating that the
displacement of potential is so great that one of the corrosion
reactions, either anodic or cathodic depending on the direction of
potential change, has been retarded until its rate is negligible
compared to the rate of the reaction being accelerated.
The relationship between the observed potential E and current
density i is given by
The difference between the observed potential and the reversible
potential Er is the overpotential. The term io is the exchange current
density, i.e. the current density of the opposing reactions at the
reversible potential.
The constant b which is the slope dE/d log i of the polarisation curve
is termed the Tafel slope and is related to the kinetics of the
corrosion reaction.
For the cathodic reactions of hydrogen ion reduction or oxygen
reduction, the value of B is generally about 120 mV. For metal
dissolution reactions from active surfaces, values of b are generally
smaller and in the range 30 to 70 mV.