Free Energy Curves and

Activation Free Energy

Electrode Kinetics: Charge transfer control (Activation Polarizatio

kf kb

v = k C(0,t) = i/nFA

mole/cm2-s = cm/s × mole/cm3 = (coul/s)(mole/coul)(1/cm2)

Chemical Reactions involving
Heterogeneous Electron Transfer (ET)

mass transport
A A
electrode

ET

mass transport
A- A-
 Metals and Semiconductors

A simplified diagram of the electronic band structure of metals,

semiconductors, and insulators
Schema8c effect of the increase in chain length (conjuga8on) on the Molecular Orbitals for
alkenes. The energy-level spliEng highlights the decrease of energy transi8ons from
HOMO to LUMO with increasing conjuga8on length. The bandgap of polyacetylene depends
on both the number of monomers n and the effec8ve conjuga8on length in the polymer
Heterogeneous ET Processes

e- A+

Ef

Electrode Solution
WhatWhat
do do
you control by applying a poten6al to an electrode?
you actually control by applying a potential to an electrode?
The highest occupied electron level in the electrode is the Fermi-level. Electrons
The highest occupied electron level in the electrode is the Fermi-level.
are always transferred to or from this level.
Electrons are always transferred to or from this level.

Oxidation (anodic) Reduction (cathodic)

EF
E smaller
e-
EF
e- Eredox Eredox
EF
E larger
EF

larger potential (E or ϕM larger) smaller potential (E or ϕM smaller)

favors oxidation favors reduction

The energy of the redox couple in solution is not affected by the potential
The energy of
variation (nothe redoxlayer
double couple in solu8on is
corrections). not affected
Under by the poten8al
ideal conditions, a shift in
varia8on.
electrode potential only affects the position of the Fermi-level.
Under ideal condi8ons, a shiM in the electrode poten8al affects only the
posi8on of the Fermi-level.
Heterogeneous ET Reactions
 Electrode Reactions
Reduction Oxidation

- - LUMO
LUMO

HOMO
+ HOMO +

electrode solution electrode solution

Electrochemical reactions are all adiabatic

the donor level and the acceptor level must at the same
All theenergy
electrochemical
state reac6ons are adiaba6c
i.e.,Faraday’s lawthe
the donor and F =acceptor
96,485levels
C/molare at very close energy
 where ∆Gox ( E ) and ∆Gox ( E ) are molar Gibbs free energies of activation

depend on potential!

To understand how the heterogeneous redox reac8on proceeds in

Which tendency do you expect upon variation of potential? Let’s say the
detail upon varia8on of poten8al, we need to use the absolute rate
value of potential E is increased. Does the rate of the anodic reaction
theory increase or decrease? What about the cathodic reaction?
Ox + e (M)
Let’s consider the free energy profile:
Red

G activated
complex

reduction

E increases
oxidation

electron in metal, electron in solution, reaction

oxidized state reduced state coordinate

Charge transfer between reduced and oxidized state always proceeds via an ac8vated
intermediate complex.
Charge Thebetween
transfer height of the poten8al
reduced barrier
and oxidized depends
state always on the electrode
proceeds via
poten8al E.anIn the diagram,
activated the poten8al
intermediate is shiMed
complex. from the
The height of equilibrium
the potentialvalue (black
barrier
curves) to adepends
more posi8ve
on thepoten8al
electrode(blue curve).
potential E. In the following pictures, the
Note that only the state
potential corresponding
is shifted to the electrons
from the equilibrium value in the metal
(black curves)isto
affected
a moreby the
poten8al shiM.
 Effect of Applied Potential on the
The effect of applied potential on activation free energy
Activation Free Energy
Electrode Kinetics: Charge transfer control (Activation Polariza

kf kb Arrhenius Equation
!! ! !!! ‡
O+e- R k=κ ! !" !
ℎ
κ is a transmission coefficie
Reaction coordinate Reaction coordinate
h = 6.626 x 10-34 J-s
Apply E > E° (hence [E-E°] > 0). The ac8va8on barrier for the anodic k is in units of s-1
Apply and E > Eo so that (E-Eo ) > 0. The activation barrier for the anodic reaction
reac8on has been
has been reduced by reduced by a quan8tyand that(1-α)F(E-E°) andreduction
for the cathodic that forreaction
the !! ‡
!
cathodic
Has been reduc8on
increased byreac8on has been . increased by αF(E-E°) k = Α! !" !

v = k C(0,t) = i/nFA mole/cm2-s

ge in a one electron transfer at the interface without being involved in any other che
step,
O + e *± R (3.
3.3 Butler-Volmer Mo
ppose also that the standard free energy profiles along the reaction coordinate have
abolic shapes shown in Figure 3.3.2. The upper frame of that figure depicts the
h from reactants to products, while the lower frame is an enlargement of the reg
r the transition state. It is not important for this discussion that we know the shape
se profiles in detail.
In developing a theory of electrode kinetics, it is convenient to express poten
inst a point of significance to the chemistry of the system, rather than against an
rary external reference, such as an SCE. There are two natural reference points,
equilibrium potential of the system and the standard (or formal) potential of
uple under consideration. We actually used the equilibrium potential as a refere
nt in the discussion of the preceding section, and we will use it again in this sect
wever, it is possible to do so only when both members of the couple are present
t an equilibrium is defined. The Reaction coordinate
more general reference point is E° . Suppose
per curve on the + side of Figure 3.3.2 applies when the electrode potentia
 ewise, we have for the backward reaction
gage in a one electron transfer at the interface without being involved
cal step,
(3 2
For a generic redox reac8on O + e *± R
apter 3. Kinetics of Electrode Reactions
re / a is the anodic component to the total current. Thus the net reaction rate is
Suppose also that the standard0 5free energy profiles along the reaction
value is called the standard rate constant, k . The rate constants at other potentials c
parabolic
"net = shapes
vf vb shown= k fCoin (0,Figure
t) k3.3.2. The upper frame of that (3.2
bCR (0, t)= ^
fig
then be expressed simply in terms of k°:
path from reactants to products, while the lower frame is an enlarge
we have overallnear the transition state. It is not important for this discussion that (3.3. we
i = i c in idetail.
these profiles a
= nFA[k { C o ( 0, t) k bCR(0, t)] (3.2
In developing
N ote that heterogeneous a theory
reactions of electrode
are described kinetics,
differently thanit homogeneous
is convenient (3.3.1 to
on
againstvelocities
example, reaction a point ofinsignificance
heterogeneous to the chemistry
systems refer oftothe
unitsystem, rather
interfacial ar
Insertion
ce they have bitrary
units external
Butler-Volmer
of these relations
of molintos"reference,
equa.on
(3.2.8)
1
cm ~yields
2 such
. Thus as an SCE.
the heterogeneous
complete There
rate are
current-potential twocharacteristic
constantsnatural
must re ca
the concentrations
s of cm/ s, if the equilibrium potentialon whichofthey the operate
system are andexpressed
the standard (orcm
in mol/ forma
3
. Sin
interface cancouple
respond under
only consideration.
to its immediate Wesurroundings,
actually usedthethe equilibrium enter
concentrations poten
(3.3.1
expressions point in the discussion
are always of the preceding
surface concentrations, whichsection, and wefrom
may differ willthose
use itofag
k solution. H owever, it is possible to do so only when both members of the cou
Whereis
This relation
that f very
an inequilibrium
the exponen8al
important.func8on oris:a variation
isIt,defined. f=F/RT derived
The more from it,reference
general is used inpoint
the treis
ment of almost everycurve
upper problem on requiring
the + an side
account of heterogeneous
of Figure 3.3.2 applieskinetics.
whenSection
the ele3
UTLER
will cover VOLMER
some of its
equal MOD
E°'. TheELcathodic
to ramifications. OFTheseELECTRODE
results KIN ETICS
and theactivation
and anodic inferences derived from
energies are the the
The two component curves from the Butler-Volmer Law
considering a generic reference poten8al E1/2 instead of E°
100 Chapter 3. Kinetics of Electrode Reactions

1.0

0.8 — / ^
0.6
'/ ~~—Total current
0.4

100 200 300 400

1 I | I J I I
400 300 200 100 /7 T|, m V
E
eq / *

0.4
// °
, 0.6

0.8

Polariza8on curve from the Butler-Volmer

1.0
Law
Figure 3.4.1 Current overpotential curves for the system + e <=± R with a = 0.5, T = 298 K,
// c = / / a = // and / 0/// = 0.2. The dashed lines show the component currents ic and / a.

level regions, the current is limited by mass transfer rather than heterogeneous kinet
ics. The exponential factors in (3.4.10) are then moderated by the factors C Q (0, 0/ Q)*
and C R (0, t)IC^, which manifest the reactant supply.

3.4.3 Approximate Forms of the I IJ Equation

 3.4 Implications of the Butler Volmer Model for the One Step, One Electron Process 101

2
j, /

4b)
(a)

400 300 200 100

I
100 200 300 400
2

Figure 3.4.2 Effect of exchange current density on the activation overpotential required to deliver
net current densities. (a)jo = 1 0 A/ cm (curve is indistinguishable from the current axis),
Effect
(b)j0
= 10of6 the
A/ cmk2
° on
, (c)j0
10 9polariza8on
=the A/ cm 2. For all cases
curves
the reaction is + e : * R with a = 0.5
and = 298 . h

If the exchange current is very large, as for case (a) in Figure 3.4.2, then the system
can supply large currents, even the mass transfer limited current, with insignificant acti
vation overpotential. In that case, any observed overpotential is associated with changing
surface concentrations of species and R. It is called a concentration overpotential and
can be viewed as an activation energy required to drive mass transfer at the rate needed to
support the current. If the concentrations of and R are comparable, then E eq will be near
E® , and the limiting currents for both the anodic and cathodic segments will be reached
 o+ o+

Reaction coordinate
Figure 3.3.4 The transfer coefficient as an indicator of the symmetry of the barrier to reaction.
The dashed lines show the shift in the curve for + as the potential is made more positive.
support the current. If the concentrations of and R are comparable, then E eq will be near
E® , and the limiting currents for both the anodic and cathodic segments will be reached
within a few tens of millivolts of E° .
On the other hand, one might deal with a system with an exceedingly small exchange
current because k° is very low, as for case (c) in Figure 3.4.2. In that circumstance, no sig

2
j, /
/
8 a = 0.75— j f — a= 0 . 5
/

4 a = 0.25

2
' %
1 1 I 1 I I
^0 ** 1 1
200 150 100 5 0 ^ ^ 50 100 150 200
2
r\ , mV
/ / '

/ 4
/ /
6
/
/ i
i
i 8
i
#
/ *

Figure 3.4.3 Effect of the transfer coefficient on the symmetry of the current overpotential curves
for + e ?± R with T = 298 andy0 = " 6 A/ cm 2.
Effect of α on the polariza8on curves
100 Chapter 3. Kinetics of Electrode Reactions

1.0

0.8 — / ^
0.6
'/ ~~—Total current
0.4

100 200 300 400

1 I | I J I I
400 300 200 100 /7 T|, m V
E
eq / *

0.4
// °
, 0.6

0.8

1.0

Figure 3.4.1 Current overpotential curves for the system + e <=± R with a = 0.5, T = 298 K,
// c = / / a = // and / 0/// = 0.2. The dashed lines show the component currents ic and / a.

Effect of mass transport on the polariza8on curves

level regions, the current is limited by mass transfer rather than heterogeneous kinet
ics. The exponential factors in (3.4.10) are then moderated by the factors C Q (0, 0/ Q)*
and C R (0, t)IC^, which manifest the reactant supply.

3.4.3 Approximate Forms of the I IJ Equation