Beruflich Dokumente
Kultur Dokumente
Butler
Max Volmer
Walter Nernst
Julius Tafel
F
i i0 exp
exp
RT
RT
iox ired
P
ne-
Oxidation or de-electronation.
P = reductant (electron donor)
Q = Product
ne-
Reduction or electronation.
A = oxidant (electron acceptor)
B = Product
Current (A)
dq
nFA
dN
nFAf
dt
Amount of
Faraday Material (mol)
Constant (Cmol-1)
Fig. 1(a)
Fig. 1(b)
P
ne-
ne-
Reduction or electronation.
A = oxidant (electron acceptor)
B = Product
Oxidation or de-electronation.
P = reductant (electron donor)
Q = Product
2H2 O 2e H2 g 2OH
O2 g 4H aq 4e 2H2 O c
Cu 2 aq 2e Cus d
2CH2 CHCN 2H2 O 2e
Pt H2 O PtO 2H 2e
2Cl aq Cl2 g 2e g
Fe s Fe 2 aq 2e
CH3OH H2 O CO2 6H 6e
(a) Simple outer sphere single step single electron transfer reaction. This reaction type serves as a prototype
in fundamental kinetic studies.
(b) The cathodic evolution of hydrogen. A much studied multistep, multielectron transfer reaction which
involves the formation of intermediate species adsorbed on the electrode surface.
(c) The electrochemical reduction of dioxygen. Much studied in fuel cell technology. Again a complex
reaction involving multiple electron transfer and the involvement of adsorbed intermediates.
(d) Metal electrodeposition.
Reference
electrode
Working
electrode
Counter (auxillary)
Electrode.
A aq
Baq
e
Energy of electrons
in metal increases
upon application of a
potential more negative
than the thermodynamic
equilibrium value.
n e-
LUMO
LUMO
EF
HOMO
Electron
energy
HOMO
Redox couple
in solution
Metallic electrode
Pictorial explanation of
current flow due to reduction.
Energy of electrons
in metal decreases upon
application of a potential
more positive than the
thermodynamic equilibrium
value.
Electron
energy
LUMO
LUMO
n e-
EF
HOMO
HOMO
+
Redox couple
in solution
Metallic
electrode
A survey of electrochemical
reaction types.
Electrochemical reactions
are usually complex multistep
processes involving the
transfer of more than one
electron.
In this course we focus on
simple single step ET
processes involving the
transfer of a single
electron.
The kinetics of simple ET
processes can be understood
using the activated complex
theory of chemical kinetics
(see SF Kinetics notes).
MT
ET
iC
CDL
RS
i
Faradaic
current
iF
Electrode
Resistance of
solution
i iC iF
RCT
Solution
Double layer charging
current always presen
in addition to
Faradaic current in
electrochemical
measurements.
E
k A exp
RT
d ln k
d ln k
RT 2
E A R
d
T
dT
1
/
ln k
Slope
1
T
EA
R
U 0
d ln K c
2
dT
P RT
TS
U 0 E E
R
P
E
R
U0
P
k
Kc
k
d k
d ln k d ln k U 0
dT ln k dT dT RT 2
P
Reaction coordinate
d ln k
E
dT
RT 2
d ln k
E
dT
RT 2
E
k aT m exp
RT
We can relate the latter expression to the Arrhenius parameters A and EA
as follows.
ln k ln a m ln T
E
RT
E
d ln k
2 m
E mRT
E A RT 2
RT
2
dT
T RT
E E A mRT
Hence
E
E
k aT m e m exp A A exp A
RT
RT
A aT m e m
Svante August
Arrhenius
A more
comprehensive
Picture of
chemical
reactivity is
given by
Transition State
Theory.
A BC ABC* AB C
V R Do 1 exp a R Re
Activated complex
Transition state
Energy
Ea
Reaction coordinate
Henry Eyring
1901-1981
Developed (in 1935) the
Transition State Theory
(TST)
or
Activated Complex Theory
(ACT)
of Chemical Kinetics.
Reaction co-ordinate
0
Our presentation to date has been couched in
Where G denotes the electrochemical Gibbs energy of
qualitative terms. We can of course get more
activation. Note that the term
has got units of s-1
quantitative but this has already been covered and is expressed in cm.
Hence k ' has got units of cm s-1 as it should.
adequately earlier on in the module by Prof.
Bridge. Now we have stated that chemical
activation occurs via collisions between molecules
and that reaction involves formation of a discrete
activated complex of transient existence. The
latter species represents a configuration in which
the reactant molecules have been brought to a
degree of closeness and distortion, such that a
small perturbation due to a molecular vibration in
an appropriate direction will transform the
complex to products. The overall rate of reaction
is then equal to the rate of passage of the
activated complex through the transition state.
The Activated Complex Theory has been
discussed earlier on but we will deal with a special
case of a unimolecular reaction at an electrode
surface. Since the reaction is heterogeneous we
must include a characteristic reaction layer
thickness which we label (the length of which is
of the order of a molecular diameter).
Hence for an interfacial electron transfer
reaction we have the following.
kB T
G 0
k
exp
h
RT
q nFAN k
f k Ea0
(3)
(1)
dN
dq
nFA k nFAf
dt
dt
(2)
F E E 0
0
k E k exp
k exp
RT
(4)
F
i i 0 exp
(5)
RT
i 0 FAk 0 a 0 b 0 1
(6)
e E i E e
(7)
k'E
A
B
k'-E
where we assume that the forward process is a deelectronation oxidation process and the reverse
reaction is an electronation reduction process .
Both processes involve the transfer of a single
electron . The net flux is given by :
f k E a0 k E b0
and the heterogeneous
constants are given by :
electrochemical
k E k 0 exp
k E k 0 exp 1
rate
F E E 0
0
RT
F
1 F
exp
i i 0 exp
RT
RT
This is the Butler-Volmer equation which is the
fundamental equation of electrochemical ET kinetics .
We recall that electrochemical equilibrium implied, on a
microscopic level, that the electronation and deelectronation fluxes were in balance . No net currents
passed across the electrode/electrolyte interface .
Now if a net current is passed, this balanced situation
is perturbed , a net current will flow in one specific
direction . One has a departure from equilibrium . The
greater the departure from equilibrium , the larger will
be the observed net reaction rate and the larger will
be the overpotential . Positive overpotentials
correspond to oxidation processes , negative
overpotentials to reduction processes . Zero
overpotential corresponds to equilibrium . This can be
summarised as follows.
0
0
DMT
ETK
Energy
Amount of
Barrier lowering
Transition state
Activated complex
Reaction
Flux
mol cm-2 s-1
=0
G0 *
Reactant
state
G *
Product
state
finite
dN
dq
nFA
nFAf
i
dt
dt
f k ' ET c0
Interfacial
reactant
Heterogeneous
concentration
ET rate constant mol cm-3
cm s-1
G * G0 * F
Total added
Electrical energy
Symmetry
factor
overpotential
E EN
Applied
potential
Thermodynamic
Nernst potential
f k ' ET c0
Apply Eyring eqn. from TST
k ' ET
G *
Z exp
RT
k T
Z B
h
Transmission
coefficient
overpotential
G * G0 * F
Electrochemical Gibbs energy
of activation
Characteristic ET
distance (molecular
diameter).
Symmetry
factor
k 'ET
G0 *
F
exp
Z exp
RT
RT
F
0
k ET exp
RT
i nFAf
Butler-Volmer Equation.
A(aq ) B (aq )
e
B(aq )
A(aq )
Normalised
potential
Net rate
Oxidation
and
i iox ired
Reduction
i i0 exp
exp 1
processes are
BV equation
microscopically
reversible.
Exchange
Reduction
Net current i at interface
Oxidation
Exchange current
current
component
reflects a balance between
component
provides a measure
iox and ired .
of kinetic facility
Thermodynamic
overpotential Nernst potential
Symmetry factor determines
of ET process.
how much of the input electrical
energy fed into the system will
0 1
F F E E N Exchange
i
FAk
a
b
0
current
affect the activation energy
RT
RT
barrier for the redox process.
Standard rate
Note 0< < 1 and typically = 0.5.
Applied
constant
potential
i i0 exp exp 1
reduction
oxidation
15
i iox i0 exp
Tafel Region
10
Linear Ohmic
region
= i/i0
The Butler-Volmer
equation describes
the shape of the
current density /
overpotential
characteristic of an
interfacial ET
reaction . Typical i
versus curves are
presented across for
typical values of the
exchange current
density . Note that
when = 0 the net
current i density is
zero and the reaction
is at equilibrium .
The current density
is seen to rise
rapidly when the
overpotential
deviates from its
equilibrium value of
zero . The rate of
current increase with
overpotential
depends on the
magnitude of the
exchange current
density and hence on
the value of the
heterogeneous
standard rate
constant .
i ired i0 exp 1
-5
-10
-15
-6
Tafel Region
-4
-2
F/RT
6
1/ 2
i 2i0 sinh
2
The situation in
terms of
potential energy
curves of the
type used in
transition state
theory are
presented
across.
ired iox
i ired
Net oxidation
iox ired
Net Reduction
i iox
15
10
= i/i0
5
0
iox ired
-5
i 0
-10
Equilibrium
-15
-6
i iox ired
-4
-2
F/RT
0.9
80
60
0.7
= i/i0
40
0.5
20
0
-20
-40 0.3
-60
0. 1
-80
-100
-6
-4
-2
F/RT
exp
i i0 exp
is large, typically > 120 mV.
iox ired
At high overpotentials we assume
that the ET reaction occurs in
If >> 0 then i iox : net de-electronation
the forward direction and the
or oxidation.
reaction occurring in the reverse
F
F
direction can be neglected.
i iox i0 exp
ln i ln i0
RT
Oxidation
log (i/i0)=log
10
log i
Reduction
Linear Tafel
Region
0.1
0.01
0.001
-8
d
RT
2.303
bA
F
d log i
d
RT
2.303
bC
1 F
d log i
-6
-4
-2
= F/RT
Exchange
Current evaluated
At = 0
Tafel approximation
not valid at low
overpotential
RT
RT
Tafel behaviour breaks down as
iox ired
0.
Taylor expansion at small x.
Tafel behaviour is characteristic
of totally irreversible (hard driven)
x2
expx 1 x
ET kinetics and will only be valid
2!
if the driving force for the
x2
exp x 1 x
electrode process is very large
2!
which will be the case at high
F
F
overpotentials.
exp
1
RT
RT
In the limit of low overpotentials
1 F 1 F F
1 F
exp
1
( < 10 mV) the exponential terms
RT
RT
RT RT
0
a linear relationship between current
RT
RT
RT
Linear
approximation
i i0
RT
Linear i versus
relation
Charge Transfer
Resistance
= i/i0
= F/RT
RT
d
RCT
di
i 0 i0 F
iRCT
Ohms Law
RCT
Interfacial ET
Low overpotential
situation:
Charge Transfer
Control
ETK
DMT
Large overpotential
situation :
Mass Transport
Control
DMT
ETK
Bulk Phase
Reactant
Bulk Phase
Reactant
Reactant at
electrode
Product at
electrode
Reactant at
electrode
Product at
electrode
1.0
i
J
nFA nF
Net flux
ET & MT
D
kD
= i / iD
0.5
MT
D
dc
f D k ET c0
c c0 k D c c0
dx 0
0.0
-6
-4
-2
= F(E-E0)/RT
ET
c
c0
k
1 ET
D
k ET k D c
f
k D k ET
f k ET c0
k ET k exp
0
Normalised
potential
1
1
1
f k ET c k D c
nFA
k ET k D 1 k D 1 k D
k ET
k ET
F E E
k ET k 0 exp
RT
fD
iD
kDc
nFA
fD
k
1 D
f
k ET
MT corrected
Tafel plot
i i
ln D
i
F E E0
iD
fD
f D f kD
1
1
0 exp
i
f
f
k
RT
f D f
iD i
kD F E E
ln
ln
ln 0
f
i
RT
k
ln( D0 )
k
ln k
D
0
k
F
RT
E E0
This is one form of the mass transport corrected Tafel equation. We see that a plot of ln (iD-i/i)
vs is linear . The slope of this plot yields - F/RT whereas the intercept directly
yields ln (kD/k0). Since kD may be readily evaluated, then the standard rate constant k0 may
be determined. This form of Tafel plot has been much used in the literature.
i0 FAk 0 a
A ne B
ln i0 ln FAk 0 1 ln a ln b
ln i0
1
ln a b
ln i0
lnb a
i
F
F
F F
ln
ln
i
i i0 exp
exp
exp
0
F
RT
RT RT
RT
1 exp RT
F
F
i0 exp
1 exp
RT
RT
Allen-Hickling Equation
Hence we see that a plot of ln i 1 exp F RT versus
should be linear, the slope yielding and the intercept at = 0 yielding i0 .
Energy of electrons
in metal decreases upon
application of a potential
more positive than the
thermodynamic equilibrium
value.
Electron
energy
LUMO
LUMO
n e-
EF
HOMO
HOMO
+
Redox couple
in solution
Metallic
electrode
Energy of electrons
in metal increases
upon application of a
potential more negative
than the thermodynamic
equilibrium value.
n e-
LUMO
LUMO
EF
HOMO
Electron
energy
HOMO
Redox couple
in solution
Metallic electrode
Pictorial explanation of
current flow due to reduction.
U( x) 0 x 0
U( x) U 0
0xa
U( x) 0 x a
In the latter a represents the width of the
rectangular barrier and U0 denotes the barrier
height ,
Total energy of particle
Incidence of particle
on barrier
Transmission of particle
Through barrier
Barrier width a
III
II
Barrier
Height U0
Distance
0
sinh 2 ka
PT 1
4
E
E
U0
U 0
Barrier Type
Barrier Width/
Tunneling
Probability
Parabolic Barrier
1.2 x10-4
10
10
9.1 x10-12
15
15
5.2 x10-21
20
20
6.0 x10-32
1.0x10-5
10
10
8.8x10-15
15
15
1.5x10-26
20
20
1.7x10-40
16E
16E
E
exp 2 ka
exp 2 ka
1
U0 U0
U0
2L
1/2
PT exp
2m U 0 E
2m U 0a 2 2
2 m U 0 E
sinh ka exp ka 2
PT
G
k E A exp
k BT
where G* is the Gibbs energy of activation . The preexponential factor is given by
A e n n
(Sutin 1982 ; Hupp and Weaver 1984 ) where e is the
electronic transmission coefficient and represents the
probability with which electron transfer will occur once the
transition state has been formed ( and so is equivalent to the
tunnelling probability) . Typically 0 e 1 . Also n (units :
s-1 ) is the nuclear frequency factor and is defined as the
frequency at which the configuration of nuclear co-ordinates
appropriate for electron transfer is attained . In other
words it represents the rate at which the reactant species in
the vicinity of the transition state is transformed into
products .
This factor depends on the mechanism of activation and will
include contributions from solvent re-organization and bond
stretching . Its value is typically in the range 0.5 - 1.0 x 1013
s-1 . Finally n is termed the nuclear tunnelling factor and is
a quantum mechanical correction which becomes important at
low temperature . All of these factors have been discussed in
detail in a recent review (Weaver 1987) .
2e
e
k E A exp
A exp
exp
4 k B T
4k BT
2k BT
e 2
k E A exp
k
T
4
B
k E
e 2
A exp
4k B T
We note that if
e
the quadratic term in the energy of activation
presented in the Marcus-Hush expressions
outlined above may be expanded to first order in
e and the heterogeneous electron transfer
rate constant for the forward de-electronation
process admits the form given on the left hand
side across.
G 1 G 0
2
G 0 2
where we note that G* is the activation energy for electron
transfer and G0 represents the standard Gibbs energy
change on proceeding from the reactant to the product state
which for an electrochemical reaction is given by - e . The
Gibbs energy of activation is given by (Albery 1975) :
G 0
G 0
*
G 1
4
4
2
G 0 e
the electron transfer kinetics are slow and as noted
in eqn.2.52. On the other hand when l is small and one
has fast electron transfer then the following three
cases must be considered . When
then .
Alternatively, if
G 0
then 1 . Finally, if
G 0
then 0 .