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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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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
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:
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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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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.
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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
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.
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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.
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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.
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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..)
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The Voltammogram
Typical values
E1/2 (V)
Ion
-0.38
Pb2+
-0.46
Tl+
-0.58
Cd2+
-0.99
Zn2+
-2.12
Na+
-2.14
K+
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Switching potential
Sweep rate
Edc = Einitial + t
Initial potential
Switching potential
A = B + e-
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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 ]
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;
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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Hills and
Scharifker model
Oxide formation
Oxide reduction
Au OHads OH- Au +
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