Voltammetry and Polarography

Lecture 4

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 Diffusion Controlled Processes

• The flux of material to and from the electrode

surface is a complex function of all three modes of
mass transport.
• In the limit in which diffusion is the only significant
means for the mass transport of the reactants and
products, the current in a voltammetric cell is given
by:

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where n is the number of electrons
transferred in the redox reaction, F is
Faraday's constant, A is the area of the
electrode, D is the diffusion coefficient for
the reactant, CbuIk and Cx=o are the
concentration of the analyte in bulk
solution and at the electrode surface, and 
is the thickness of the diffusion layer.
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• For the above equation to be valid, migration
and convection must not interfere with
formation of diffusion layer around the
electrode surface.
• Migration is eliminated by adding a high
concentration of an inert supporting
electrolyte to the analytical solution.
• The large excess of inert ions, ensures that
very few reactant and product ions will move
as a result of migration.

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• Although convection may be easily eliminated
by not physically agitating the solution, in some
situations it is desirable either to stir the
solution or to push the solution through an
electrochemical flow cell. Fortunately, the
dynamics of a fluid moving past an electrode
results in a small diffusion layer (stagnant
solution), typically of 0.001 ‑ 0.01 cm thickness,
in which the rate of mass transport by
convection is close to zero.

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 Voltammograms
For the reduction of an analyte A to give a product P
at a mercury film microelectrode (for example), the
microelectrode is connected to the negative
terminal of a linear potential scan generator,
cathodic currents are positive (by convention),
while anodic currents are negative. The figure
below represents the linear scan voltammogram
under hydrodynamic conditions:

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As seen from the figure, linear scan voltammograms
assume a sigmoidal curve called a voltammetric wave.
The constant current beyond the steep rise is called the
limiting current il, because it arises from the limitation
at which reactants are brought to electrode surface.
Limiting currents are proportional to concentration, and
thus are used in quantitative analysis.
il = kCA
Where CA is the analyte concentration, and k is a constant.
The potential at half the limiting current is called the half
wave potential (E1/2), a characteristic property of a
component.

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Obtaining a stable limiting current
Reproducible limiting currents can be obtained rapidly when:
1. The solution (or the microelectrode) be in continuous and
reproducible motion.
2. Or a dropping mercury electrode is used
3. Or the solution is forced through a flow cell comprising
the three electrodes (as in HPLC).

Linear scan voltammetry in which the solution is stirred or

the electrode is rotating is called hydrodynamic
voltammetry.

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 Hydrodynamic Voltammetry
• In hydrodynamic voltammetry the solution is stirred by
rotating the electrode, or using a stirrer.
• Current is measured as a function of the potential applied to
a solid working electrode.
• The same potential profiles used for polarography are used
in hydrodynamic voltammetry.
• The resulting voltammograms are identical to those for
polarography, except for the lack of current oscillations
resulting from the growth of the mercury drops.
• Because hydrodynamic voltammetry is not limited to DME
electrodes, it is useful for the analysis of analytes that are
reduced or oxidized at more positive potentials.

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 Hydrodynamic Voltammetry

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 What Happens During a Voltammetric
Experiment
1. The reactant is carried to the surface of the electrode by
one or more of the following:
• Diffusion
• Migration
• Convection
2. Migration is minimized using a supporting electrolyte (50-
100 times more concentrated than analyte), therefore
the fraction of current carried by the analyte through
migration approaches zero. That means that the rate of
migration of analyte to the electrode of opposite charge
becomes independent of applied potential.

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 Concentration Profiles at Microelectrode
Surface
Assume an electrode reaction:
A + ne D P
Taking place at a Hg coated microelectrode in a solution of A
containing an excess of a supporting electrolyte. Also, assume the
following:
CA : initial concentration of A in the bulk soln
CP : concentration of P in the bulk solution
CAo and CPo are concentrations of A and P at the thin layer adjacent to
electrode surface
In addition, P is insoluble in the mercury film. The reduction is rapid
and reversible (this means that the concentrations at electrode
surface can be calculated from Nernst equation), therefore:

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 0.0592 𝐶𝑝𝑜
𝐸𝑎𝑝𝑝𝑙 = 𝐸𝐴𝑜 − log − 𝐸𝑟𝑒𝑓
𝑛 𝐶𝐴0

Where the Eappl is the potential between the

microelectrode and the reference electrode. It
can also be assumed (since the microelectrode
is very small) that electrolysis will not change
the bulk concentration. Therefore, the bulk
concentration of A is unchanged and is equal
to CA while the concentration of P (CP) in the
bulk solution is practically zero.
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 Profiles for Planar electrodes in Unstirred
Solutions
In this case, mass transport of solute to electrode surface
occurs by diffusion.
Assume that a square wave potential is applied (E appl) to the
working microelectrode for a period of time (t). Also,
assume that Eappl is large enough that CPo /CAo is very large
(>1000).

Under this condition, the concentration of C Ao at the

electrode surface is zero, for all practical purposes, A is
immediately reduced as soon as it approaches electrode
surface.
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In the previous figure, the current rises to a peak
value, resulting in conversion of all A to P at the
electrode surface layer of the solution. Diffusion of
A from the bulk into this surface occurs which
results in more reduction of A. The current required
to satisfy the concentration of A in Nernst equation:
0.0592 𝐶𝑝𝑜
𝐸𝑎𝑝𝑝𝑙 = 𝐸𝐴𝑜 − log − 𝐸𝑟𝑒𝑓
𝑛 𝐶𝐴0

Decreases rapidly with time as A is required

to travel longer distances to reach the
surface. That is i a dCA/dx

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It is then clear that it is not
practical to obtain
limiting currents with
planar electrodes in
unstirred solutions,
because the current will
continually decrease
with time as the slopes
of the concentration
profiles become lower:
𝒅𝑪𝑨
𝒊 ∝
𝒅𝒙
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 Profiles of Microelectrodes in Stirred
Solutions
At any time, it can be assumed that the concentrations at the
stagnant solution, region adjacent to electrode surface and at low
potential, x, obey the equation:
Cpo = CA – CAo
At the half wave potential, the concentration of P is half that of A (at
the electrode surface), which means that:
Cpo = C A/2
However, applying a negative potential z or larger will make the
reduction of A complete, that no A will be present at the electrode
surface, therefore:
Cpo = CA, and will remain constant, resulting in a limited current,
regardless of applied potential.

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 Voltammetric Currents
In the stirred solution (or using a dropping mercury
electrode), the current at any point will depend on:
1. The rate of mass transport of A to the diffusion layer
(stagnant phase) by convection
2. The rate of transport of A from the outer edge of the
diffusion layer to the electrode surface
Since the concentration of P formed in the diffusion layer
is continuously swept away by convection, a continuous
current will be necessary to maintain the surface
concentrations of A and P to satisfy Nernst equation.

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Convection maintains a constant supply of A at
the outer edge of the diffusion layer,
therefore a steady state current results that is
determined by the applied potential:
𝑑𝐶𝐴
𝑖 = 𝑛𝐹𝐴𝐷𝐴 ( )
𝑑𝑥
Where i is the current in A, n is the number of moles, A is
the electrode surface area in cm2, DA is the diffusion
coefficient of A in cm2s-1, and F is the Faraday constant.

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dCA/dx is the slope of the initial part of the
concentration profile and can be
approximated to:
𝑑𝐶𝐴 𝐶𝐴 − 𝐶𝐴𝑜
=
𝑑𝑥 𝛿
𝑛𝐹𝐴𝐷𝐴
𝑖= (𝐶𝐴 − 𝐶𝐴𝑜 )
𝛿

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CAo becomes negligible at high negative
potentials, therefore it can be concluded
that:

This derivation is based on a simplified assumption

that the interface between the moving and
stationary layers is well defined, where as transport
of A ceases, its diffusion begins!!!

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 Polarographic Wave Equation
We have the two previous equations where:

Subtraction of the later from the first and

rearrangement gives:
𝑖𝑙 − 𝑖
𝐶𝐴𝑜 =
𝑘𝐴
Where CAO is the surface concentration of A
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The surface concentration of P can also be
expressed in a similar way:
𝐶𝑃 −𝐶𝑃𝑜
𝑖 = −𝑛𝐹𝐴𝐷𝑝
𝛿
Or:
𝑛𝐹𝐴𝐷𝑝 𝑜
𝑖= ሺ𝐶𝑃 ሻ
𝛿
≅ 𝑘𝑝 𝐶𝑃𝑜 , since Cp in bulk is practically zero

And thus: 𝑖
𝐶𝑃𝑜 =
𝑘𝑝

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Since we have: 0.0592 𝐶𝑝𝑜
𝐸𝑎𝑝𝑝𝑙 = 𝐸𝐴𝑜 − log 0 − 𝐸𝑟𝑒𝑓
𝑛 𝐶𝐴

Substitution for Cpo tio and CAo we get:

0.0592 𝑘𝐴 0.0592 𝑖
𝐸𝑎𝑝𝑝𝑙 = 𝐸𝐴𝑜 − log − log − 𝐸𝑟𝑒𝑓
𝑛 𝑘𝑃 𝑛 𝑖𝑙 − 𝑖

When i = il/2, we have Eappl = E1/2

And E1/2 = EAo –Eref since usually kA = kp, both log terms will equal zero

0.0592 𝑖
𝐸𝑎𝑝𝑝𝑙 = 𝐸1 − log
2 𝑛 𝑖𝑙 − 𝑖
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 Finding E and Number of Electrons involved

I
Id

Id  I
Id/2 lg
I

E1/2 E

The polarographic wave The linear relationship

 Pulsed Voltammetric Techniques
There are three main pulsed polarographic
techniques based on the excitation
waveform and the current sampling regime:

- Normal-Pulse Polarography
- Differential-Pulse polarography
- Square-Wave polarography

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 Why use pulse techniques?
The basis of all pulse techniques is the difference in the rate of the decay of
the charging and the faradaic currents following a potential step (or
"pulse"). The charging current decays exponentially, whereas the
faradaic current (for a diffusion-controlled current) decays as a function
of 1/(time)½; that is, the rate of decay of the charging current is
considerably faster than the decay of the faradaic current. The charging
current is negligible at the end of the potential pulse. Therefore, at the
end of the potential pulse, the measured current consists solely of the
faradaic current; that is, measuring the current at the end of a potential
pulse allows discrimination between the faradaic and charging currents.

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Reduction of the capacitive current during the pulse time

𝑡
∆𝐸𝐴 − ∆𝐸𝐴
𝑖𝑐 = 𝑒 𝑅𝐶 𝐷 or 𝑖𝑐 = 𝑒 −𝑘𝑡
𝑅 𝑅
iC Capacitive current
∆EA Pulse amplitude
R Discharge resistance
t Time after pulse application
CD Double layer capacitance
This means that the charging current decays exponentially
(ic = k”e-kt)

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Reduction of the capacitive
current during the pulse
time

iC Capacitive current
∆EA Pulse amplitude
R Discharge resistance
t Time after pulse
application
CD Double layer capacity of
working electrode
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 Cottrell Equation
For diffusion controlled processes at planar electrodes:

i = current, in unit A, n = number of electrons (to reduce/oxidize one

molecule of analyte), F = Faraday constant, 96,485 C/mol, A = area of the
(planar) electrode in cm2 , C = initial concentration of the reducible
analyte in mol/cm3; D = diffusion coefficient for analyte in cm2/s, and tm
= time in s.
OR:
The limiting Faradaic current is proportional to t-1/2, which is a slow decay as
compared to exponential decay of the charging current.

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• In addition, because of the short pulse duration, the
diffusion layer is thinner than that of DC
polarography (i.e., greater flux of analyte) and
hence the faradaic current is increased. The
resulting polarogram has a sigmoidal shape, with a
limiting current given by Cottrell equation:

where tm is the time after application of the pulse where the current is sampled

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The important parameters for pulse techniques are as
follows:
1. Pulse amplitude is the height of the potential
pulse. This may or may not be constant depending
upon the technique.
2. Pulse width is the duration of the potential pulse.
3. Sample period is the time at the end of the pulse
during which the current is measured.
4. Note that the end of the drop time coincides with
the end of the pulse width).

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 Normal Pulse Polarography (NPP)
• Normal-pulse polarography consists of a series of pulses of
increasing amplitude applied to successive drops at a
preselected time near the end of each drop lifetime.
Between the pulses, the electrode is kept at a constant
(base) potential at which no reaction of the analyte occurs.
The amplitude of the pulse increases linearly with each
drop.The current is measured about 40 ms after the pulse is
applied, at which time the contribution of the charging
current is nearly zero.

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In a reduction, if the Initial Potential is well positive of the
redox potential, the application of small amplitude pulses
does not cause any faradaic reactions, hence there is no
current response. When the pulse amplitude is sufficiently
large that the pulse potential is close to the redox potential,
there is a faradaic reaction in response to the potential pulse
(assuming moderately fast electron transfer kinetics), and
the magnitude of this current may depend on both the rate
of diffusion and the rate of electron transfer. When the
pulsed potentials are sufficiently negative of the redox
potential that the electron transfer reaction occurs rapidly,
the faradaic current depends only on the rate of diffusion;
that is, a limiting current has been attained.

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