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24/09/2013

Rate of Reaction
Since the current, i, which represents the number of coulombs
of charge flowing per second, is stoichiometrically related to
the number of mole of (say) Cd2+ reacting per second, it is a
measure of the rate of the electrochemical reaction
v (mol s-1 cm-2) = i/nFA = j/nF
where n is the number of electrons transferred, F is Faradays
constant, A is the area of the electrode, and j = i/A is the
current density (A m-2).
Kinetics, rather than thermodynamics rule here!

Polarisation
Theoretically, an applied potential, Eappl, slightly in
excess of the cell emf would cause the reverse of the
spontaneous cell reaction to occur.
In practice, the applied potential may need to exceed
the cell emf by anything up to a couple of tenths of a
volt before this is achieved!
The departure of the electrode potential from the
equilibrium value on passage of a current is called
polarisation.

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Ideal Polarised Electrodes


An ideal polarised electrode shows a very large change
in potential upon the passage of a small current, and is
characterised by a horizontal i-E profile.
An inert electrode (eg., Hg, Pt, Au) in a solution
containing only electro-inactive species approaches this
ideal.
Ideal polarized (polarizable) electrode: An electrode is
called "ideal polarizable" if no electrode reactions can
occur within a fairly wide electrode potential range.
Consequently, the electrode behaves like a capacitor
and only capacitive current ( no faradaic current) is
flowing upon a change of potential. Many electrodes can
behave as an ideal polarized electrode but only within an
electrode potential range called the "double-layer range."
Also called "completely-polarizable electrode" and
"totally-polarized electrode." Contrast with ideal nonpolarizable electrode.

Ideal polarized (polarizable) electrode

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Ideal Nonpolarisable Electrode


The potential of an ideal nonpolarisable electrode does
not change on passage of current. It is an electrode of
fixed potential.
Nonpolarisable electrodes have a vertical i-E profile.
Reference electrodes (silver-silver chloride and SCE)
approach non-polarisability at low current densities.

Reference electrodes
Reference electrode is an electrode which has a stable and wellknown electrode potential
The Standard Hydrogen Electrode (SHE) forms the basis of the
thermodynamic scale of oxidation-reduction potentials
Based on
2H+(aq) + 2e- H2(g)
Often impractical to use
Large area required : platinised platinum
Cumbersome, can be hazardous

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Reference electrodes
Ag/AgCl (3M NaCl) is one of the most commonly used
Based on
AgCl(s) + e- = Ag(s) + Cl-(aq)

E = 0.220 V vs SHE
Unit activity at standard conditions
Ideal non-polarizable
electrode

For Ag/AgCl (3M KCl)


E = 0.196 V

Overpotential
The extent of polarisation is measured by
the overpotential,
= |E(i) - E(0)|,
the (absolute) difference between the cell
potential when there is no current flow,
E(0), and when there is current flow, i E(i).
The overpotential increases as the current
flowing through the system increases.

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Overpotential
Overpotential is always deleterious to
performance - it decreases the potential
available during discharge:
Edischarge = E(0) -
and increases the potential required for
charging:
Echarge = (Eappl) = E(0) +

Overpotential
An electrode reaction O + ne R can be thought of
as composing a series of steps:

mass transfer of O to and R away from the electrode


electron transfer at the electrode
chemical reactions before and after the electron transfer.
surface reactions - adsorption, desorption,
electrodeposition.

Overpotentials can be associated with each of these


steps. Overpotential serves as an activation energy
required to drive the processes at the rate reflected
by the current.
Overpotential means must apply greater potential
before redox chemistry occurs

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iR Drop
With the passage of a current, i, through
a cell of resistance R, there is a potential
drop, iR (Ohms Law), that has the same
effect as an overpotential - it decreases
the potential available during discharge:
Edischarge = E(0) - - iR
and increases the potential required for
charging:
Echarge = (Eappl) = E(0) + + iR

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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.

Butler-Volmer Equation
j = jc - ja = j0[e(1-)nF/RT - e-nF/RT]
where
jc and ja are the cathodic and anodic current densities;
j0 is the exchange current density at equilibrium, where the
rates of the forward (cathodic reduction) and reverse
(anodic oxidation) reactions are equal (but not zero);
and is the transfer coefficient (usually ca. 0.5)
The charge transfer coefficient signifies the fraction of the interfacial
potential at an electrode-electrolyte interface that helps in lowering the
free energy barrier for the electrochemical reaction. The electroactive
ion present in the interfacial region experiences the interfacial potential
and electrostatic work in done on the ion by a part of the interfacial
electric field. It is charge transfer coefficient that signifies this part that is
utilized in activating the ion to the top of the free energy barrier.

Remember is negative for reduction.

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a + b = 1

Small
For x<<1, ex = 1 + x, and the Butler-Volmer
equation becomes
j = j0(nF/RT) or = RTj/nFj0
There is a linear relationship between j and at
small overpotentials (< 10 mV).
This linear region is called "polarization
resistance" due to its formal similarity to Ohms
law

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Problem - Small
The exchange current density of a Pt|H2(g)|H+
electrode at 298 K is 0.79 mA cm-2. What
current flows through a standard electrode of
area 5.0 cm2 when the overpotential is 5.0 mV?
j = j0(nF/RT)
= (0.79)(1)(96485)(0.005)/(8.314)(298)
= 0.15 mA cm-2
i = 0.15 mA cm-2 x 5.0 cm2 = 0.75 mA.

Large Oxidation
For large either negative or positive, one of
the exponential terms in the Butler -Volmer
equation becomes negligible.
At large positive potentials (corresponding to
oxidation), the first term predominates and
j = j0e(1-nF/RT
or
lnj = lnj0 + (1- )nF/RT

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Large - Reduction
At large negative potentials (for reduction),
j = -j0e-nF/RT
or
ln(-j) = lnj0 - nF/RT
Remember is negative for reduction
Same form as the Tafel equation
= a + b logi

Large
The Tafel form holds when ja/jc < 0.01 (or vice-versa)
i.e., for ||>118/n mV.
If the electrode kinetics are fast (large j0), the current
will be limited by mass transfer by the time such a
large overpotential is applied, and the Tafel
relationship will not be observed.
When electrode kinetics are slow (small j0) and
activation potentials are required, the Tafel equation
holds.
Tafel behaviour is thus an indicator of totally
irreversible kinetics.

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Problem - Oxidation
A solution of 1 M KOH is electrolysed at
250C with a Pt electrode to produce O2 at
the anode. At an overpotential of 0.40 V,
the current density is 1.0 x 10-3 A cm-2.
What does j become when = 0.6 V?
Assume = 0.5 and n = 1.

Solution
Since >>RT/F, the Tafel equation applies.
lnj0 = lnj - (1-)nF/RT
= ln(1x10-3)- (0.5)(1)(96485)(0.4)/(8.314)(298)
= -6.91 - 7.79 = -14.7
j0 = 4.1 x 10-7 A cm-2.
lnj = lnj0 + (1-)nF/RT
= -14.7 + (0.5)(1)(96485)(0.6)/(8.314)(298)
= -14.7 + 11.7 = -3.0
j = 0.05 A cm-2

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Problem - Reduction
The exchange current density and transfer
coefficient for the reduction of H+ to H2 on Ni
are 6.3 A cm-2 and 0.58. What is the current
density at an overpotential of 200 mV?
ln(-j) = lnj0 - nF/RT
= ln(6.3) - (0.58)(1)(96485)(-0.2)/(8.314)(298)
= 1.84 + 4.52
= 6.36

(-j) = 578 A cm-2

or

j = - 578 A cm-2

Tafel Equation
The overpotential, , increases as the
current flowing through the system
increases.
Tafel (1905) found that the overpotential
is related to the logarithm of the current:
= a + b logi
where a and b are empirical constants.

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Tafel Plots
lnj = lnj0 + (1- )nF/RT from Butler Volmer
ln(-j) = lnj0 - nF/RT
from Butler Volmer
A plot of lnj versus has an anodic branch
with slope (1-)nF/RT and a cathodic branch
with slope - nF/RT. Both linear segments
extrapolate to an intercept of lnj0.
The transfer coefficient, , and the exchange
current density, j0, can thus be obtained.

Tafel plot: the plot of logarithm


of the current density against
the over potential.
Example: The following data
are the cathodic current
through a platinum electrode of
area 2.0 cm2 in contact with an
Fe 3+, Fe 2+ aqueous solution
at 298K. Calculate the
exchange current density and
the transfer coefficient for the
process. Slope is and
intercept is a (=ln i0).
In general exchange currents
are large when the redox
process involves no bond
breaking or if only weak bonds
are broken.
Exchange currents are
generally small when more
than one electron needs to be
transferred, or multiple or
strong bonds are broken.

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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.

Half-wave Potential, E1/2

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Half-wave Potential, E1/2


A plot of E versus ln{(iL - i)/i}
is a straight line of slope RT/nF, and an intercept of E1/2 on the
vertical axis.

A plot of E versus log10{(iL - i)/i}


is a straight line of slope 2.303RT/nF = 59.1/n mV at 250C, and an
intercept of E1/2 on the vertical axis

When DO = DR, E1/2 = E0.

Irreversible Processes

Voltammetric waves for irreversible processes are more drawn out than
reversible ones and their half-wave potentials, E1/2, are more extreme than
E0.

A quick test for reversibility is the Tomes


criteria:
|E3/4 - E1/4| = 56.4/n mV at 250C,

where the potentials E3/4 and E1/4 are those


for which i = 3iL/4 and iL/4, respectively.

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Practical details
Nearly every experiment requires the presence of a supporting electrolyte
minimises solution resistance
For CV experiments we use a 3 electrode setup
WE : working electrode : process of interest occurs
Typically Pt, Au, carbon, ITO, boron doped diamond
CE : counter electrode : Pt wire/coil/mesh, graphite rod
REF : Reference electrode
Dependent on solvent system
A potential is applied between WE and REF
Current is recorded between WE and CE.
Therefore a stable REF electrode is essential (eg Ag/AgCl, Calomel..)

Dropping Mercury Electrode

Clean, reproducible surface.


Large overpotential for 2H+ + e H2(g) (Eo = 0 V) means Hg electrode can
operate at more negative potentials than other electrodes. Good for
studying reduction reactions: Mn+ + ne = M(Hg).
Oxidation of Hg (~0.25 V vs SCE) means Hg electrodes not suitable for
studying oxidation.
Other working electrodes - C, Pt, Au

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The Voltammogram

At E < -0.6 V, only small residual currents flow.


At E ~ - 0.6 V, reduction of Cd2+ occurs: Cd2+ + 2e Cd(Hg) and Faradaic
current flows. Cd dissolves in Hg to form an amalgam.
The current plateaus as the rate of reaction (and hence the current) is
limited by the rate at which Cd2+ diffuses from the bulk solution to the
surface of the electrode to replace those that have been reduced.
At E > -1.2 V, reduction of H+ occurs.

Oscillations are due to growth and fall of Hg


drops.
As drop grows, area increases, more Cd2+
ions reach surface, and current increases.
Current quickly decreases as drop falls off

Typical values
E1/2 (V)

Ion

-0.38

Pb2+

-0.46

Tl+

-0.58

Cd2+

-0.99

Zn2+

-2.12

Na+

-2.14

K+

Note problem detecting


Na, K.
Modern instrumentation
and further development
of technique allows
analysis with excellent
limit of detection

Original polarographic spectrum developed


1920-30 by Heyrovsky
Note shift wrt table due to different RE, and E convention
reversed

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Switching potential
Sweep rate

Edc = Einitial + t
Initial potential
Switching potential

A = B + e-

What does this actually represent?


Point A: Only R is present in solution :
still below the redox potential of solution
species
Increase the electrode potential towards
the redox potential : R is converted to O.
As R is converted to O a concentration
gradient is setup at the electrode

Take the oxidation


of species R to O

Point B: R is instantaneously converted


to O
After point B the current is dependent on
the rate of mass transfer to the electrode
surface

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ferrocene
Data1B

0.000030

40

20

0.000025

I [A]

ip [A]

0.000020

-20

0.000015
-40

0.000010

-60
-1.2

0.000005

-0.9

-0.6

-0.3

0.0

0.3

0.6

0.9

E [V] vs Ag ref

0.000000
0.0

0.1

0.2

0.3

0.4

0.5

0.6

-1 1/2

sweep rate [V s ]

Randles Sevcik Equation

ip = 2.69 x 105 n3/2 A D1/2 v1/2 C


n : no of electrons
A : electrode area

D : diffusion coefficient
v : sweep rate

C : concentration

Develop a protocol
Find a suitable solvent for your analyte
Find a suitable supporting electrolyte (SE)
Run a background - SE + whatever (e.g., buffer, ligand,
acid, base..) with no analyte present
Run a simple CV with the analyte
Chosen a value of typically 50 or 100 mVs-1

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Many mechanisms
Identify some basic mechanisms

E
EE
EC
EC
EC2
CE
ECE

A+e=B
A + e = B; B + e = C;
A1 + e = B1; B1 = B2
A + e = B; B + P = A + Q
A + e = B; 2B = B2
Y = A; A + e = B
A1 + e = B1; B1 = B2; B2 + e = C2;

Use DigiSim or a simulator of choice to explore the behavior of


selected basic mechanisms.

Chronoamperometry
E2
Stationary electrode
Solution must be stationary and unstirred =
mass transport by diffusion

E
E1

Constant potential
Measure current vs time (t)

t (time)

Theory
Assume A = B + e- Both A and B are soluble
- Reversible reaction (electrochemically)
- Potential (E) set so oxidation or reduction goes
to completion at the electrode surface

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Can analyse it profile to


elucidate mechanism

Hills and
Scharifker model

Regarded as a model system


Double layer region

Oxide formation

Oxide reduction

Au H 2 O Au OH ads H eplace exchange reaction

Au OHads OH- Au +

OH - Au + O 2- Au 2+ H + e2AuO H 2O Au 2O3 2H + 2e-

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