CHAPTER 4

ELECTRODE KINETICS

4.1 POTENTIOSTATIC METHOD (TAFEL PLOTS)

The rate of each reaction is controlled in part by the rate of an electron transfer
reaction and in part by the rate of transport of a solution species into the near vicinity of
the electrode surface. In this section, only the case in which the electron-transfer step is
much slower then the mass-transport step will be considered. Under this assumption, the
solution is homogeneous and the surface concentration of electrocution species is equal to
its concentration in the bulk solution.
Consider an electron transfer process consisting of the single elementary step

R e O
-
= +
(1)

cathodic rate = k
c
C
O
(o,t)
(2)
anodic rate = k
a
C
R
(o,t)

where k
c
and k
a
are heterogeneous rate constants with units m s
-1
. If the concentrations
have units of mol m
-3
, then the rates have units of mol m
-2
s
-1
, the same units as flux.
The difference between the cathodic and anodic rates in the net flux of O and is
proportional to the net current

(3)
)] , 0 ( ) , 0 ( [ t C k t C k FA i
R a O c
=

The temperature dependence of the rate constants k
c
and k
a
from transition state
theory are equal:

(4)
RT
G
A k
c
c
*
exp

=
RT
G
A k
a
a
*
exp

=
(5)

where G
*
s are free energies of activation. At equilibrium, the net current must be
zero and the surface and bulk concentrations should be equal

RT
G G
k
k
t R
t C
a c
c
a
R
O
* *
0 ,
0 ,
ln
) , 0 (
) , 0 (
ln

= =
(6)

where k
c,0
and k
a,0
are the rate constants at zero current.

The ratio of the reactant and product concentrations at equilibrium is given by the
Nernnst equation

) ( ln
0
E E
RT
F
C
C
e
R
O
=
(7)

where E
e
and E
o
are the equilibrium and standard half-cell potentials.
Combining above equations we have

( )
o
e a C
E E F G G =
* *

(8) (8)

and is graphically shown in Figure (1). Assuming a simple linear relationship:

( )
o
e o c
E E F G G + =
* *

(9)

( )
o
e o a
E E F G G =
* *

(10)

where a and =1- are cathodic and anodic transfer coefficients and G is the
activation free energy for the process when E
e
=E
o


Figure 1 Free energy reaction coordinate-transfer process.




Assuming that G
*
o
is constant temperature, we have:

( )
RT
E E F
k k
o
e
c

=

exp
0 0 ,

(11)
( )
RT
E E F
k k
o
e
o a

=

exp
0 ,

(12)
RT
G
Z k
o
*
0
exp

=
(13)
The deviation of the half-cell potential from the equilibrium value is called the
overpotential or overvoltage, ()
(14)
+ =
e
E E
Thus, the cathodic activation energy changes by an amount F, while the anodic
activation free energy changes by an amount F.
The rate constants then differ from the equilibrium values according to the
relations:
RT
F
k k
c c

= exp
0 ,
(15)
RT
F
k k
o a a

exp
,
=
(16)
The net current is:
(17)
( ) ( )
(

=
RT
F
t C k
RT
F
t C k FA i
R o a O c

exp , 0 exp , 0
, 0 ,

or
( ) ( )
(

=
RT
F
C
t C
RT
F
C
t C
i i
R
R
O
O
o

exp
, 0
exp
, 0
* *
(18)

Where i
o
is the exchange current and is equal to the cathodic current and to the negative
of the anodic current at equilibrium:

( )
RT
E E F
C FAk i i
o
e
o o e c o

= =

exp
*
,

(19)

( )
RT
E E F
C FAk i i
o
e
R o e a o

= =

exp
*
,

(20)


For fast transport C
O
(0,t)= C
O
* and C
R
(0,t) = C
R
*

(

=
RT
F
RT
F
i i
o

exp exp (21)

where C
O
* and C
R
* are concentration of the electroactive in the bulk of the electrolyte.

The above equation is called Butler-Volmer equation. When the overpotential is
large, one of the exponential terms on Butler-Volmer equation will be negligible
compared with the other. For example, when the over potential is large and negative, the
anodic component of the current is negligible and we have:
RT F n
o c
a
e i i
/
=
(22)

RT
F n
i i
a
o

exp =
(23)
and
o
a
o
a
i
F n
RT
i
F n
RT
log
3 . 2
log
3 . 2

=
(24)
Introducing the notations:
c o
a
a i
F n
RT
= log 3 . 2

(25)
and
(26)
b i
F n
RT
o
a
= log 3 . 2

(27)
The potential current relationship becomes:
i b a
c c
log + =

This equation was first derived by Tafel and is known as Tafels equation; the
quantities a
c
and b
c
are called Tafel constants. Tafel constants. Tafel plots have been
long known to fit experimental data obtained in studies of activation overpotential (such
as the evolution of hydrogen and oxygen at various electrodes.)
Thus, the passage of the net current causes the potential to deviate from its
equilibrium value called the activation overpotential, . This overpotential caused by a
slow kinetic in the electron transfer reaction and must be distinguished from
concentration of oxidized and reduced species.
It is difficult to measure the activation overpotential without the other side effects.
In fact electrode processes are classified to be reversible if the activation overpotential is
immeasurable small and irreversible if the activation overpotential is measurable. Clearly,
the distinction between reversible and irreversible electrode processes is somewhat
artificial since it is highly dependent upon the conditions of the electrolysis. Whereas the
activation overpotential is readily measured when large and a very special techniques
must be employed to measure its value when small. In the later case the overpotential is
measured under conditions in which the electrochemical process is virtually completely
controlled by the rate of electrochemical reaction i.e., where the rate of mass transfer
toward or away from the electrode is effectively infinite. In practical measurements of
activation overpotential, care must be taken to avoid any surface concentration depletion,
by stirring and by obtaining potential measurements almost immediately after current
flow commence.
3.2 The Charge-Transfer Resistance (Polarization Resistance)
When n is small (in comparison to 0.0257/nn
a
and 0.0257/(1-a)nn
a
, the
exponential form of the Butler-Volmer equation can be expanded in the form
(28)
(

+ = ..... 1 .... 1
RT
F
RT
F
i i
o



Retaining only the first nonvanishing term, we have:

RT
Fi
i
o
=
(29)
o
ct
Fi
RT
R = (30)

The polarization resistance R
ct
is the effective resistance imposed at the electrode surface
by the finite rate of the electron-transfer process.
3.3 KINETICS OF HYDROGEN EVOLUTION

Consider the electrode process
(31)
( ) ( ) g H e aq H
2
2 2 = +
+

The mechanism is likely to involve reduction of hydrogen ions to give hydrogen
atoms adsorbed on the electrode surface:
(32)
H M e aq H M = + +
+
) ( (I)
and
(33)
2
2 MH H M = (IIa)

If the mobility of hydrogen atoms on the surface is slow H-H bond formation may
be connected with reduction of a second hydrogen near the adsorbed atom:
(34)
2
) ( MH e aq H H M = + +
+
(IIb)
and desorbed from the surface according to:

(35)
) (
2 2
g H M MH + = (III)

If step (I) is rate limiting, the anodic and cathodic transfer coefficients should be near .
The data given in Table (1) are consistent with step (I) being rate limiting for Pb, Hg, Zn,
Sn, Cd, Cu, Fe, and Ni. If step (IIb) is rate limiting, the mechanism is analogous to the
oxidation if iron and one can expect the cathodic transfer coefficient to be appeoximately
3/2 and the cathodic transfer coefficient to be . Step (IIb) is probably rate limiting for
Pt, Au, Mo and W.































REQUIRED EQUIPMENT AND SUPPLIED

Sodium sulphate
Sodium chloride
Boric acid
Ferrous sulphate
AISI 4340 steel
INCONEL 718 alloy
PAR Model 273 Potentiostat/Galvanostat
Interconnected by a IEEE-488 general Purpose
Interface Bus (GPIB) to an IBM PS/2

PROCEDURE

Objectives:
I. Determination if the Diagnostic Criteria for the Identification of the Mechanism
of Hydrogen Discharge on 4340 Steel and INCONEL 718.

1. Prepare 1 L of an electrolyte containing 1 M Na
2
SO
4
+ 0.4 M NaCl + 1M H
3
BO
3
,
pH=4.

The electrochemical cell employed for these studies should be a conventional
three-compartment design with contact between the working electrode compartment and
reference electrode via a Luggin probe. The polarization experiments should be carried
out using AISI 4340 steel and INCONEL 718 alloy electrode with geometric area of 0.5
cm
2
. The electrodes should be mechanically polished to a fine finish, activated in sulfuric
acid, washed with ethanol and cleaned in ultrasonic cleaning bath.

When current is applied to an electrode, the potential is shifted from its initial
value according to the Tafel equation. According to the mixed potential theory, the
dissolution of the metal or alloy using Tafel method is obtained by extrapolating the
linear portion of the vs i curves to the equilibrium or corrosion potential or is obtained
at the anodic and cathodic Tafel lines. In order to obtain the Tafel slopes;
(1) Measure (potentiostatically) using the above solution and PAR potentiostat, the
dependence of vs i. The polarization experiments should be carried out on AISI 4340
steel and INCONEL 718 electrodes by starting from 250 mV from E
o
and moving in the
anodic direction to 250 mV above E
o
.

(2) Obtain Tafel slopes (potentiodynamically) by using scan rates in the range of 0.1 to 5
mV/s. The experience should be carried out using the same solution on AISI 4340 and
INCONEL 718 electrodes by starting from 250 mV from E
o
and moving in the anodic
direction to +250 mV above E
o
.

II. Determination of the Rate of Anodic Dissolution of iron as a Function of pH.

2. Prepare 1 L of an electrolyte containing 0.5 M FeSO
4
+ 0.5 M Na
2
SO
4
. Study
potentiostatically and potentiodynamically using scan rates of (0.1 to 5mV/s) the rate of
anodic dissolution of AISI 4340 steel at pH=2.0, 3.0 and 4.0. Adjust the pH with 20 %
sulfuric acid.

Calculation Procedure

I A (1) Construct vs i diagram for hydrogen evolution and AISI 4340 steel dissolution
on oxygen free electrolyte containing 1 M Na
2
SO
4
+ 4.0 M NaCl + 1M H
3
BO
3
, pH=4.
(2) Compute [for AISI 43040 dissolution] the exchange current density (io).
(3) Compute the anodic (/logi).
(4) Compute the transfer number .
(5) Compute (i
o
) for hydrogen evolution reaction.
(6) Compute the cathodic (/logi).
(7) Compute the transfer number .
I B (1) Construct vs i diagram for hydrogen evolution and INCONEL 718 dissolution
in oxygen free electrolyte containing 1M Na
2
SO
4
+ 0.4 M NaCl + 1 M H
3
BO
3
, pH=4.
















(2) Compute [for INCONEL 718 dissolution] the exchange current density (i
o
).
(3) Compute the anodic (/logi).
(4) Compute the transfer number .
(5) Compute (i
o
) for hydrogen evolution reaction.
(6) Compute the cathodic (/logi).
(7) Compute the transfer number .

I C (1) From the data in Table (2) for the hydrogen Evolution Reaction (h.e.r.) calculate
the relative electrocatalytic activity of an AISI 4340 electrode with respect to that of a
INCONEL 718 electrode.




II (1) Compute the rate of anodic dissolution of AISI 4340 steel in 0.5 M FeSO
4
+ 0.5 M
Na
2
SO
4
at pH=2, 3.0 and 4.0.
(2) Compute the slopes at pH2.0, 3.0 and 4.0 and construct (vs log i) plots showing
the displacement of the Tafel lines at different pH.
(3) Compute the transfer number .
(4) Compute
|
|
.
|
\
|

pH
i log

.
(5) Explain why the process is first order in OH
-
(or 1 order in H
+
).
(6) Explain why is the cathodic branch Tafel plot is more difficult to evaluate.














Literature

1. D. T. Sawyer and J. L. Roberts, Jr. Experimental Electrochemistry, J. Wiley &
Sons, New York, (1974).
2. Mars G. Fontana, Corrosion Engineering, McGraw-Hill, Third Edition, New
York, (1986).
3. L. I. Antropov, Theoretical Electrochemistry, Mir Publishers, Moscow, (1978).
4. S. N. Popova, B. N. Popov, R. E. White and D. Drazic, Corrosion, 46, 12, 1007
(1990)