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Electro-Kinetics

Description of Electrochemical
Techniques
The technique is named according to the
parameters measured
E.g.
Voltammetry measure current and
voltage
Potentiometry measure voltage
Chrono-potentiometry measure voltage
with time (under an applied current)
Chrono-amperometry measure current
with time (under an applied voltage)

Electro-Kinetics

Movement of Ions
Butler Volmer Equation
Rotating Disc Electrode
Rotating Cylinder Electrode
Voltammetry
Cyclic Voltammetry
Chrono-potentiometry
Chrono-amperometry

Movement of Ions in Solution


Diffusion Movement under a concentration
gradient. If an electrochemical reaction occurs the
current due to this reaction is called, id , the
diffusion current.
Migration or Transport Movement of ions under
an electric field due to coulombic forces. If an
electrochemical reaction occurs the current due to
this reaction is called, im , the migration current.
Convection Movement due to changes in density
at the electrode solution interface. This occurs due
to depletion or addition of a species due to the
electrochemical reaction.

The Capacitance Current


The charging or capacitance current, ic , is due to
the presence of the electrical double layer and it
is always present. This current, of course, is not
related to any movement of ions.
Ic = Cdl x V
Where:
Cdl = the capacitance of the electrical double
layer
V = voltage scan rate
The capacitance current makes its presence felt
when measuring charge transfer (Faradaic)
processes at concentrations of 10 -5 M.

Diffusion
Molecular
diffusion, often
called simply
diffusion, is a net
transport of
molecules from a
region of higher
concentration to
one of lower
concentration by
random molecular
motion.

Migration or Transport
Is the fraction of current carried by the ions.
For example in a solution of copper sulphate the
transport number of Cu2+ is 0.4 and that of SO42- = 0.6.
t+ + t- = 0.4 + 0.6 = 1
Since the migration current depends on the ionic
strength of the solution it is usually eliminated by
addition of excess of an inert supporting electrolyte (100
1000 fold excess in concentration)
The current is carried by the inert supporting electrolyte
(e.g. NaCl , KNO3 etc) because the ions produced do
not undergo any electrochemical reaction the transport
current is effectively removed.
In excess inert supporting electrolyte, the current
measured due to the electro-active species of interest is
due only to diffusion which can be related to mass
transfer.

Voltammetry the following example shows how


the migration current is eliminated. Pb2+ + 2e Pb0
The supporting electrolyte
Ensures diffusion control of limiting currents by
eliminating migration currents
Table: Limiting currents observed for 9.5 x 10-4 M
PbCl2 as a function of the concentration of KNO3
supporting electrolyte
Molarity
of KNO3
0

Il
A
17.6

0.001

12.0

0.005

9.8

0.10

8.45

1.0

8.45

Voltammetry
The example shown is for the reduction of Pb2+
at an inert mercury electrode.
Pb2+ + 2e Pb(Hg)
At low inert electrolyte concentration a large
fraction of the total current is due to the
migration current, i.e. the currents due to the
electrostatic attraction of ions to the electrode.
For solution 1:
i migration im 17.6 8.45 = 9.2 A
i diffusion
id = 8.45 A

Ficks First Law of Diffusion


Fick's first law relates the diffusive flux
to the concentration field, by postulating
that the flux goes from regions of high
concentration to regions of low
concentration, with a magnitude that is
proportional to the concentration gradient
(spatial derivative).
In one (spatial)
J this
Dis
dimension,

Ficks First Law of Diffusion

J D
x
where
J is the diffusion flux in dimensions of [(concentration
of substance) length2 time-1], example mole (M) m-2 s1.
J measures the amount of substance that will flow
through a small area during a small time interval.
D is the diffusion coefficient or diffusivity in
dimensions of [length2 time1], example m2 s-1
(for ideal mixtures) is the concentration in
dimensions of [(concentration of substance) length 3],
example M m-3
x is the position [length], example m

Ficks First Law of Diffusion


D is proportional to the squared velocity of
the diffusing particles, which depends on
the temperature, viscosity of the fluid and
the size of the particles according to the
Stokes-Einstein relationship.
In dilute aqueous solutions the diffusion
coefficients of most ions are similar and
have values that at room temperature are
in the range of 0.6x10-9 to 2x10-9 m2/s.
For biological molecules the diffusion
coefficients normally range from 10-11 to
10-10 m2/s.

Ficks First Law of Diffusion


In two or more dimensions we must use, ,
the del or gradient operator, which
generalises the first derivative, obtaining
J = -D
The driving force for the one-dimensional
diffusion is the quantity -/x
which for ideal mixtures is the concentration
gradient. In chemical systems other than ideal
solutions or mixtures, the driving force for
diffusion of each species is the gradient of
chemical potentialDc
of this
species. Then Fick's

first law (one-dimensional


J i 1 i case) can be
RT x
written as:

Ficks First Law of Diffusion


Dc1 i
Ji
RT x

where the index i denotes the ith species,


c is the concentration (mol/m3),
R is the universal gas constant (J/(K mol)),
T is the absolute temperature (K), and
is the chemical potential (J/mol).

Butler-Volmer Equation
The Butler-Volmer equation is one
of the most fundamental
relationships in electrochemistry. It
describes how the electrical current
on an electrode depends on the
electrode potential, considering that
both a cathodic and an anodic
reaction occur on the same
electrode:

Butler-Volmer Equation

where:
I = electrode current, Amps
Io= exchange current density, Amp/m2
E = electrode potential, V
Eeq= equilibrium potential, V
A = electrode active surface area, m2
T = absolute temperature, K
n = number of electrons involved in the electrode reaction
F = Faraday constant
R = universal gas constant
= so-called symmetry factor or charge transfer
coefficient dimensionless
The equation is named after chemists John Alfred Valentine
Butler and Max Volmer

Butler-Volmer Equation
The equation describes two regions:
At high overpotential the Butler-Volmer
equation simplifies to the Tafel equation
E Eeq = a blog(ic) for a cathodic reaction
E Eeq = a + blog(ia) for an anodic reaction
Where:
a and b are constants (for a given reaction and
temperature) and are called the Tafel equation
constants
At low overpotential the Stern Geary equation
applies

Current Voltage Curves for Electrode


Reactions
Without concentration
and therefore mass
transport effects to
complicate the
electrolysis it is
possible to establish
the effects of voltage
on the current
flowing. In this
situation the quantity
E - Ee reflects the
activation energy
required to force
current i to flow.
Plotted below are
three curves for
differing values of io
with = 0.5.

Voltammetry
Although the Butler Volmer Equation predicts,
that at high overpotential, the current will
increase exponentially with applied voltage, this
is often not the case as the current will be
influenced by mass transfer control of the
reactive species.
Take the following example of the reduction of
ferric ions at a platinum rotating disc electrode
(RDE).
Fe3+ + e = Fe2+
The rotation of the electrode establishes a well
defined diffusion layer (Nernst diffusion layer)
The contribution of the capacitance current will
also be demonstrated in this example.

Effect of the Capacitance Current in Voltammetry. The reduction of


Ferric Chloride is carried out in the presence of 1 M NaCl to
eliminate the migration current.
(a)

10-5 M Fe3+ Fe3+ + e Fe2+


ild

Slope due to ic

Current

Applied Potential -Ve

10 M Fe
-3

3+

Fe

3+

+ e Fe

(b)

2+

ild
Current

Applied Potential -Ve

Note that the iE curve in Fig. (a)


is recorded at a much higher
sensitivity than in Fig. (b).

Charging Current or
Capacitance Current
Note that due to the presence of the
electrical double layer a charging or
capacitance current is always
present in voltammetric
measurements.

Butler-Volmer Equation

where:
I = electrode current, Amps
Io= exchange current density, Amp/m2
E = electrode potential, V
Eeq= equilibrium potential, V
A = electrode active surface area, m2
T = absolute temperature, K
n = number of electrons involved in the electrode reaction
F = Faraday constant
R = universal gas constant
= so-called symmetry factor or charge transfer
coefficient dimensionless
The equation is named after chemists John Alfred Valentine
Butler and Max Volmer

Butler Volmer Equation


While the Butler-Volmer equation is valid over the full
potential range, simpler approximate solutions can be
obtained over more restricted ranges of potential. As
overpotentials, either positive or negative, become larger
than about 0.05 V, the second or the first term of
equation becomes negligible, respectively. Hence, simple
exponential relationships between current (i.e., rate) and
overpotential are obtained, or the overpotential can be
considered as logarithmically dependent on the current
density. This theoretical result is in agreement with the
experimental findings of the German physical chemist
Julius Tafel (1905), and the usual plots of overpotential
versus log current density are known as Tafel lines.
The slope of a Tafel plot reveals the value of the transfer
coefficient; for the given direction of the electrode
reaction.

Butler-Volmer Equation
1 nF a
ia ` i0 exp

RT

at high anodic overpotential

nF c
ic ` i0 exp
RT

at high cathodic overpotential

ia and ic are
the exhange
current
densities for
the anodic
and cathodic
reactions

These equations can be rearranged to give


the Tafel equation which was obtained
experimentally

Butler Volmer Equation - Tafel Equation


c

RT
RT
ln i0
ln ic
c nF
c nF

0.059
0.059
log i0
log ic at 250 C for the cathodic process
cn
cn

0.059
0.059
a
log i0
log ia at 250 C for the anodic process
an
an
The equation is the well known Tafel equation
a b log i
and
0.059
a
ln io
n
0.059
b
n

Tafel Equation
The Tafel slope is an intensive parameter and does
not depend on the electrode surface area.
i0 is and extensive parameter and is influenced by
the electrode surface area and the kinetics or speed
of the reaction.
Notice that the Tafel slope is restricted to the
number of electrons, n, involved in the charge
transfer controlled reaction and the so called
symmetry factor, .
n is often = 1 and although the symmetry factor can
vary between 0 and 1 it is normally close to 0.5.
This means that the Tafel slope should be close to
120 mV if n = 1 and 60 mV if n = 2.

Tafel Equation
We can write:
RT

ln i i0 or b ln i i0
nF
where
2.303RT
b
the Tafel slope
nF
ln i 2.303 log i

Current Voltage Curves for Electrode


Reactions
Without concentration
and therefore mass
transport effects to
complicate the
electrolysis it is
possible to establish
the effects of voltage
on the current
flowing. In this
situation the quantity
E - Ee reflects the
activation energy
required to force
current i to flow.
Plotted below are
three curves for
differing values of io
with = 0.5.

Tafel Equation
The Tafel equation can be also written as:

where
the plus sign under the exponent refers to an
anodic reaction, and a minus sign to a cathodic
reaction, n is the number of electrons involved in
the electrode reaction k is the rate constant for the
electrode reaction, R is the universal gas constant,
F is the Faraday constant. k is Boltzmann's
constant, T is the absolute temperature, e is the
electron charge, and is the so called "charge
transfer coefficient", the value of which must be
between 0 and 1.

Tafel Equation
The following equation was obtained
experimentally

a b log i

Where:
= the over-potential
i = the current density
a and b = Tafel constants

Tafel Equation
Applicability
Where an electrochemical reaction occurs in two half
reactions on separate electrodes, the Tafel equation is
applied to each electrode separately.
The Tafel equation assumes that the reverse reaction
rate is negligible compared to the forward reaction
rate.
The Tafel equation is applicable to the region where
the values of polarization are high. At low values of
polarization, the dependence of current on polarization
is usually linear (not logarithmic):

This linear region is called "polarization resistance"


due to its formal similarity to Ohms law

Stern Geary Equation


Applicable in the linear region of the Butler
Volmer Equation at low over-potentials
icorr

Rp

Where
B the Tafel constant
a c

2.3 a c
R p the measured polarisation resistance
E i

Tafel Equation
Overview of the terms
The exchange current is the current at
equilibrium, i.e. the rate at which oxidized
and reduced species transfer electrons
with the electrode. In other words, the
exchange current density is the rate of
reaction at the reversible potential (when
the overpotential is zero by definition). At
the reversible potential, the reaction is in
equilibrium meaning that the forward and
reverse reactions progress at the same
rates. This rate is the exchange current
density.

Tafel Equation
The Tafel slope is measured experimentally;
however, it can be shown theoretically when
the dominant reaction mechanism involves
the transfer of a single electron that

2.303RT
b
F
T is the absolute temperature,
R is the gas constant
is the so called "charge transfer
coefficient", the value of which must be
between 0 and 1.

Levich Equation
The Levich Equation models the diffusion and
solution flow conditions around a rotating disc
electrode (RDE). It is named after Veniamin
Grigorievich Levich who first developed an RDE as
a tool for electrochemical research. It can be used
to predict the current observed at an RDE, in
particular, the Levich equation gives the height of
the sigmoidal wave observed in rotating disk
voltammetry. The sigmoidal wave height is often
called the Levich current.
In work at a RDE the electrode is usually rotated
quite fast (1000 rpm) in order to establish a well
defined diffusion layer.
The scan rate is relatively slow typically 2-5 mV s 1

Current Voltage Curve at a RDE


It is important to remember that in order to determine the
diffusion current and the mass transfer coefficient using
volatmmetry, excess inert supporting electrolyte must be
present to eliminate the migration current

Levich Equation
The Levich Equation is written as:

where
iL is the Levich current
n is the number of electrons transferred in the half
reaction
F is the Faraday constant
A is the electrode area
D is the diffusion coefficient (see Fick's law of diffusion)
w is the angular rotation rate of the electrode
v is the kinematic viscosity
C is the analyte concentration
While the Levich equation suffices for many purposes,
improved forms based on derivations utilising more
terms in the velocity expression are available. [1][2]

Rotating Disc Electrode

Levich Equation

Levich Equation

Levich Equation
It is important to note that the layer of solution
immediately adjacent to the surface of the
electrode behaves as if it were stuck to the
electrode. While the bulk of the solution is being
stirred vigorously by the rotating electrode, this
thin layer of solution manages to cling to the
surface of the electrode and appears (from the
perspective of the rotating electrode) to be
motionless.
This layer is called the stagnant layer in order to
distinguish it from the remaining bulk of the
solution. The act of rotation drags material to the
electrode surface where it can react. Providing the
rotation speed is kept within the limits that laminar
flow is maintained then the mass transport

Levich Equation RDE


The Levich equation takes into account both the
rate of diffusion across the stagnant layer and the
complex solution flow pattern. In particular, the
Levich equation gives the height of the sigmoidal
wave observed in rotated disk voltammetry. The
sigmoid wave height is often called the Levich
current, iL, and it is directly proportional to the
analyte concentration, C. The Levich equation is
written as:
iL = (0.620) n F A D2/3 w1/2 v1/6 C
where w is the angular rotation rate of the
electrode (radians/sec) and v is the kinematic
viscosity of the solution (cm2/sec). The kinematic
viscosity is the ratio of the solution's viscosity to

Current Voltage Curve at a RDE

Ilimiting vs (electrode rotational


velocity)

Levich Equation - RDE


The linear relationship between Levich current and the square
root of the rotation rate is obvious from the Levich plot. A
linear least squares fit of the data produces an equation for
the best straight line passing through the data. The specific
experiment shown, the electrode area, A, was 0.1963 cm 2, the
analyte concentration, C, was 2.55x106 mol/cm3, and the
solution had a kinematic viscosity, v, equal to 0.00916
cm2/sec. After careful substitution and unit analysis, you can
solve for the diffusion coefficient, D, and obtain a value equal
to 4.75x106 cm2/s. This result is a little low, probably due to
the poor shape of the sigmoidal signal observed in this
particular experiment.
The kinematic viscosity is the ratio of the absolute viscosity of
a solution to its density. Absolute viscosity is measured in
poises (1 poise = gram cm1 sec1). Kinematic viscosity is
measured in stokes (1 stoke = cm 2 sec1). Extensive tables of
solution viscosity and more information about viscosity units
can be found in the CRC Handbook of Chemistry and Physics.

Cyclic Voltammetry
Cyclic Voltammetry is carried out at a
stationary electrode.
This normally involves the use of an inert
disc electrode made from platinum, gold or
glassy carbon. Nickel has also been used.
The potential is continuously changed as a
linear function of time. The rate of change
of potential with time is referred to as the
scan rate (v). Compared to a RDE the scan
rates in cyclic voltammetry are usually
much higher, typically 50 mV s-1

Cyclic Voltammetry
Cyclic voltammetry, in which the direction
of the potential is reversed at the end of the
first scan. Thus, the waveform is usually of
the form of an isosceles triangle.
The advantage using a stationary electrode is
that the product of the electron transfer
reaction that occurred in the forward scan can
be probed again in the reverse scan.
CV is a powerful tool for the determination of
formal redox potentials, detection of chemical
reactions that precede or follow the
electrochemical reaction and evaluation of
electron transfer kinetics.

Cyclic Voltammetry

Cyclic Voltammetry
For a reversible
process
Epc Epa = 0.059V/n

The Randles-Sevcik equation


Reversible systems

The Randles-Sevcik equation


Reversible systems
12
i p 0.4463nFAC nFvD RT

i p 2.687 10 n v D AC
5

32 12

12

n = the number of electrons in the redox reaction


v = the scan rate in V s-1
F = the Faradays constant 96,485 coulombs
mole-1
A = the electrode area cm2
R = the gas constant 8.314 J mole -1 K-1
T = the temperature K
D = the analyte diffusion coefficient cm 2 s-1

The Randles-Sevcik equation


Reversible systems

As expected a plot of peak height vs the square root of the scan rate
produces a linear plot, in which the diffusion coefficient can be obtained
from the slope of the plot.

Cyclic Voltammetry

Cyclic Voltammetry

Cyclic Voltammetry

Cyclic Voltammetry Stationary


Electrode

Peak positions are related to formal potential of


redox process

E0 = (Epa + Epc ) /2
Separation of peaks for a reversible couple is
0.059/n volts
A one electron fast electron transfer reaction
thus gives 59mV separation
Peak potentials are then independent of scan
rate
Half-peak potential Ep/2 = E1/2 0.028/n
Sign is + for a reduction

Cyclic Voltammetry Stationary


Electrode
The shape of the voltammogram depends on the
transfer coefficient
When deviates from 0.5 the voltammograms
become asymmetric -cathodic peak sharper as
expected from Butler Volmer eqn.

Web Sites
http://calctool.org/CALC/chem/electro
chem/levich
http://www.calctool.org/CALC/chem/el
ectrochem/cv1

Tafel Equation
The Tafel slope is an intensive parameter and does
not depend on the electrode surface area.
i0 is and extensive parameter and is influenced by
the electrode surface area and the kinetics or speed
of the reaction.
Notice that the Tafel slope is restricted to the
number of electrons, n, involved in the charge
transfer controlled reaction and the so called
symmetry factor, .
n is often = 1 and although the symmetry factor can
vary between 0 and 1 it is normally close to 0.5.
This means that the Tafel slope should be close to
120 mV if n = 1 and 60 mV if n = 2.

Tafel Equation
We can write:
RT

ln i i0 or b ln i i0
nF
where
2.303RT
b
the Tafel slope
nF
ln i 2.303 log i

Evans Diagrams

Evans Diagrams

Evans Diagrams