Chronoamperometry (Current Determined with Time)

In the chronoamperometric experiment, we measure current (hence

‘amp-’) as a function of time (‘chrono-’). It is usual to commence
with the solution around the electrode containing only one redox
form of the analyte.

(a) The potential of the working electrode will be stepped from a

potential at which lets say only Tl+ is the stable form to a potential at
which only Tl3+ is the stable form. The rise in potential here is
essentially vertical. But for the requirement to charge the double layer
around the electrode. 𝑬𝟎𝑻𝒍𝟑+ −𝑻𝒍+ =1.252 V, so the potential 0 V before
+
the step is well cathodic (negative) and 𝑻𝒍 is the only stable redox
form, and no Tl3+ will form. The potential after the step is, e.g. 1.6 V,
+
i.e. it is well anodic of 𝑬𝟎𝑻𝒍𝟑+ −𝑻𝒍+ =1.252 V, to 𝑻𝒍𝟑 is the only stable
+ +
redox form here, thus causing 𝑻𝒍 to oxidize to 𝑻𝒍𝟑 .

(b) shows a trace of current against time in response to the potential

step. The trace shows a rapid rise in current, with this rise requiring
perhaps as long as a few thousands of a second (i.e. milliseconds). The
time between the potential step and the maximum is known as the
rise time. The current trails off smoothly after the rise time until,
eventually, it reaches zero. Such plots are often termed transients to
emphasize their pronounced time dependence.
Why do ‘double-layer effects’ cause a longer time delay in the current trace than in the potential trace?

The delay in reaching the maximum voltage in graph (a) is caused by charging of the double-layer, i.e. merely adjusting the
positions of the ions. In contrast, the time delay in reaching the peak in the current trace in graph (b) is caused by
electrochemical changes to the analyte within the double-layer, according to Faraday’s laws.

The Nernst Layer ('Depletion ' Layer)

Before the potential is stepped from, e.g. 0 to 1.6 V, the electrode will be surrounded by only 𝑻𝒍+ , the concentration of
which will be the same throughout the analyte solution.

Conversely, after the voltage is switched, 𝑻𝒍+ ions will be oxidized to 𝑻𝒍𝟑+according to the reaction, 𝑻𝒍+ → 𝑻𝒍𝟑+ + 𝟐𝒆− .
Very soon, the electrode will be surrounded with a layer of solution that contains no 𝑻𝒍+. It is said then to be depleted
of 𝑻𝒍+ . The volume around the electrode, which now contains no 𝑻𝒍+, is called the depletion region, the depletion layer
or sometimes, the Nernst layer. Its thickness is often given the symbol . As the length of time increases following the
potential being stepped, i.e. as the extent of electrolysis increases, so the thickness of the Nernst layer () increases.
If the electrode is surrounded with a layer that contains no 𝑻𝒍+ , why
is there any current at all at longer times?

The value of [𝑻𝒍+ ] in the solution bulk remains essentially constant

since only a tiny proportion of the overall amount of 𝑻𝒍+ is oxidized,
but at the surface of the electrode we can say, to a good 𝑻𝒍+
approximation, that [𝑻𝒍+ ] = 0. Very soon after the potential is stepped,
𝑻𝒍+ from the bulk diffuses toward the electrode, thereby attempting to
'even out' the concentration gradient, i.e. to replenish the 𝑻𝒍+ that
was consumed at the commencement of the step. We need to
recognize, however, that these thallium ions will not remain as 𝑻𝒍+ for
long as they will be oxidized 'immediately' to form 𝑻𝒍𝟑+ , i.e. as soon as 𝑻𝒍𝟑+
they impinge on the electrode. The end result is that a concentration
gradient will soon form after the potential has been stepped.

Each concentration is depicted as a function of the distance from the

electrode | solution interface where oxidation is effected: these curved
traces are often termed concentration profiles. Each of the figures
incorporate a series of Concentration profiles, drawn as a function of
time, to show how the Nernst layer increases in thickness during
electrolysis, because the extent of electromodifiation has increased
with time.
How much of the 𝑻𝒍+ will be converted to 𝑻𝒍𝟑+ if 𝑬𝒂𝒑𝒑𝒍. = 𝑬𝟎𝑻𝒍𝟑+ −𝑻𝒍+ ?

We will start by assuming that the activity coefficients of 𝑻𝒍+ (aq) and 𝑻𝒍𝟑+ (aq) are the same, in which case
activities and concentrations may be considered as being inter-changeable. If 𝑬𝒂𝒑𝒑𝒍. = 𝑬𝟎𝑻𝒍𝟑+ −𝑻𝒍+ then from
Nernst equation:

𝑹𝑻 𝒂𝑶 𝒔𝒖𝒓𝒇
𝑬𝑾𝑬 = 𝑬𝟎𝑶,𝑹 + 𝒍𝒏
𝒏𝑭 𝒂𝑹 𝒔𝒖𝒓𝒇

𝒂𝑶 𝒔𝒖𝒓𝒇
We see that = 𝟏. In other words, half of the thallium remains as 𝑻𝒍+ while the other
𝒂𝑹 𝒔𝒖𝒓𝒇
half has been converted to 𝑻𝒍𝟑+ .

This is an important result, namely that below a certain overpotential, not all of the analyte at the surface of
the electrode will be electro-modified at or above a crucial value of overpotential, , all of the material
around the electrode is converted. The associated current, if conversion is total, is then said to be limiting.
 The Cottrell Equation
For a quantitative description of the way that a chronoamperometric current trails off with time, we employ the
Cottrell equation, as follows:
𝑫
𝑰𝒍𝒊𝒎 = 𝒏𝑭𝑨𝒄
𝝅𝒕
1. where n is the number of electrons transferred in the reaction, 𝑶 + 𝒏𝒆 ⇌ 𝑹 , F is the Faraday constant, t is the time
lapsing after the potential was stepped and D is the diffusion coefficient.

2. We need to realize that the concentration term, C, here relates to the bulk concentration of analyte rather than the
local concentration. The adsorption or electrolysis will both cause differences such that 𝑪𝒔𝒖𝒓𝒇𝒂𝒄𝒆 𝒐𝒇 𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆  𝑪𝒃𝒖𝒍𝒌.

3. Note that this equation relies on the current being limiting, i.e. the potential must be stepped to an extreme
overpotential to ensure that 𝑰𝒍𝒊𝒎 ∝ 𝒄𝒂𝒏𝒂𝒍𝒚𝒕𝒆 .

4. If the potential is not sufficient for the current to be limiting, then it is usually found that I is still proportional to
−𝟏
𝒕 ൗ𝟐 , but a smaller concentration than 𝒄𝒂𝒏𝒂𝒍𝒚𝒕𝒆 needs to be included within the collection of proportionality constants.

5. If the wire has a length h and a diameter r , then the surface area A of the wire is given by: 𝑨 = 𝝅𝒓𝟐 + 𝟐𝝅𝒓𝒉. In
electroanalysis, the area is conventionally considered to have units of cm2. If the electrode is fractal, then the
electrochemical area, rather than the geometric area, is employed as 'A’.
6. The diffusion coefficient D can be thought of as the velocity of the analyte as it moves from the bulk of the solution
towards the electrode just prior to the electron-transfer reaction. Because D is a velocity, larger values of D relate to a
faster motion of analyte through the solution, while smaller values relate to slower motion.
The Cottrell equation is derived with the assumption that diffusion is the sole form of mass transport. How can we
confirm that it actually is?

𝐃 −𝟏ൗ
If 𝐈𝐥𝐢𝐦 = 𝐧𝐅𝐀𝐜 𝛑𝐭
equation holds then a graph of 𝐈𝐥𝐢𝐦 against 𝐭 𝟐 - a Cottrell plot - should be linear and pass through the
origin. By corollary, such Cottrell plots represent a simple test of whether diffusion is indeed the sole form of mass
transport: a non-zero intercept indicates that non-faradaic currents contribute to 𝐈𝐥𝐢𝐦.

The linear part of the Cottrell plot indicates those times at which diffusion is the sole form of mass transport - usually at
the shortest times. Any curvature in a Cottrell plot indicates that migration and/or natural convection are contributing to
the overall mass transport, perhaps in varying proportions.

(A) Chronoamperograms of (line a) 300 and (line b) 400 μM

vitamin B9 in the buffer solution (pH 9.0); (B) Cottrell plot for the
data from the chronoamperograms.
How are chronoamperometric experiments useful to the analyst?

Actually, chronoamperometry is not a commonly performed electroanalytical technique. Probably its most
common application is to determine the electrochemical area of an electrode if the concentration and
diffusion coefficient of the analyte are already known.

Additionally, it can often, however, be a good idea to perform chronoamperometric transients over a wide
range of times and voltages to ascertain those experimental conditions which do indeed yield a linear
Cottrell plot that passes through the origin, i.e. to ascertain those experimental conditions over which
diffusion is indeed the sole form of mass transport.

When determining a diffusion coefficient D from a Cottrell plot, it is important to determine the current for
as long a time as possible, in order to ensure reliability. With suitable precautions, as much as 10 s may be
possible.
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Voltammetry
Voltammetry is concerned with the study of voltage-current-time relationships during electrolysis carried out in a cell. It
involves studying the influence of changes in applied voltage on the current flowing in the cell, but in some
circumstances, the variation of current with time may be investigated.

Essentially, voltammetry is an I-V technique and electrolysis occurs at in microscale. It is a three electrode process: (1) a
working electrode at which the electrolysis under investigation takes place; (2) a reference electrode which is used to
measure the potential of the working electrode; and (3) an auxiliary electrode which, together with the working
electrode, carries the electrolysis current.

In some circumstances the working electrode may be a dropping mercury electrode (D.M.E.), and the auxiliary electrode is
a pool of mercury at the base of the cell: for this special case the technique is referred to as polarography. Hence
polarography is a subset technique of voltammetry. Indeed, the root ‘polar-’ of polarography implies polarization. We know
that polarization represents ‘the deviation of the potential of an electrode from its equilibrium value’.
The magnitude of the deviation is termed the overpotential, , and is defined according to the following equation:
 = 𝑬 – 𝑬𝒆𝒒
 can be either positive or negative. The overpotential  is seen to be positive during anodic electrochemistry and negative
during cathodic electrode processes.

Voltammetry Cell
The electrochemical changes of interest occur - the working electrode (WE).
The reference electrode (RE) is kept at equilibrium.
The counter electrode (CE) is only included in the circuit to facilitate current passage at
the WE. It is rare to monitor the potential of the CE.

The potential of the WE is measured with respect to the RE and the current through
the WE is determined with respect to the CE.

Schematic representation of
If current flows through the working electrode, then it also flows through the counter
a cell used for voltammetry
electrode. From Faraday ’s laws, such a current flow implies that material must have
been formed at the counter electrode (CE). It is unwise to assume that the products of
electrode reaction at the CE are benign, so the CE should be excluded from the
solution bulk. In practice, a satisfactory extent of exclusion is achieved by placing it in
a separate compartment within the electrochemical cell, but with electrolytic contact
between the CE compartment and the main body of the cell being achieved via a
sinter or frit.

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During any voltammetry experiment, the potential of an electrode is varied while we simultaneously monitor the current
that is induced. This occurs as a result of the electrode being polarized, that is, its potential is forced away from its
equilibrium value.

Why does current flow when the potential is altered, i.e. what is the cause of the voltammetric current?

In voltammetry, electrochemical measurement is non-equilibrium (or ‘dynamic’), i.e. those for which 𝟎. No current
passes through the cell during an equilibrium electrochemical experiment, and the activities of the electroactive species in
solution will obey the Nernst equation.

Equilibrium is disrupted when we force charge to flow through an electrode. Such charge flow is accompanied by electron
uptake (reduction) or electron loss (oxidation) by the electroactive analyte at the electrode, thus causing the
concentrations to change - and hence the activities will change also. (These changes explain why voltammetry is a dynamic
experiment.)

The alteration of the potential at the electrode | solution interface is caused due to the conversion of material from its
reduced to its oxidized forms (or back) i.e. 𝑶 + 𝒏𝒆 ⇌ 𝑹 and following Nernst Eq.
𝑹𝑻 𝒂𝑶 𝒔𝒖𝒓𝒇
𝑬𝑾𝑬 = 𝑬𝟎𝑶,𝑹 + 𝒍𝒏
𝒏𝑭 𝒂𝑹 𝒔𝒖𝒓𝒇
where ‘surf’ here relates to the surface of the working electrode alone.

This idea of current flowing as a function of polarizing the electrode (shifting its potential away from equilibrium) lies at
the very heart of voltammetry.

𝒂𝑶 𝒔𝒖𝒓𝒇
If the ratio depends on the potential of the working electrode, and we measure the current through
𝒂𝑹 𝒔𝒖𝒓𝒇
this electrode as a function of that potential, how is it possible to simultaneously monitor both the current
and potential through the same electrode?

In fact, we don’t monitor two variables through the same electrode. Instrumentally, we employ a
feedback loop within the voltage source (that is, the potentiostat or polarograph).

The potential at the working electrode is maintained, by the circuitry of the voltage source, at its desired
value by causing charge to flow.

The potential is a function of the ratio of oxidized and reduced forms of the electroactive material,
according to the Nernst equation.

Experimentally, then, the potential of the working electrode is monitored with respect to the reference
electrode, while the current measurement is actually performed via the counter electrode.

2
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Techniques which come under the general heading of voltammetry are:

(a) polarography (d.c. and a.c.);
(6) anodic stripping voltammetry;
(c) chronopotentiometry.

POLAROGRAPHY
Basic Principle
If a steadily increasing voltage is applied to a cell incorporating a relatively large quiescent mercury anode and a minute
mercury cathode (composed of a succession of small mercury drops falling slowly from a fine capillary tube), it is
frequently possible to construct a reproducible current voltage curve. The electrolyte is a dilute solution of the material
under examination in a suitable medium containing an excess of an indifferent electrolyte (base or ground solution, or
supporting electrolyte) to carry the bulk of the current and raise the conductivity of the solution, thus ensuring that the
material to be determined, if charged, does not migrate to the dropping mercury cathode.

Heyrovsky and Shikata developed an apparatus which increased the applied voltage at a steady rate and simultaneously
recorded photographically the current-voltage curve. Since the curves obtained with this instrument are a graphical
representation of the polarisation of the dropping electrode, the apparatus was called a polarograph, and the records
obtained with it, polarograms.

Inlet and outlet tubes are provided to the ce11 for expelling dissolved oxygen from the
solution by the passage of an inert gas (hydrogen or nitrogen) before, but not during,
an actual measurement - otherwise the polarogram of the dissolved oxygen will appear
in the current-voltage curve. P is a potentiometer by which any e.m.f. up to 3 volts may
be gradually applied to the cell, and R is a pen recorder. It may be mentioned that
under these conditions the current-voltage curve is really a current-cathode potential
curve.

All the positively charged ions present in the solution will be attracted to the negative
working electrode by (a) an electrical force, due to the attraction of oppositely charged
bodies to each other, and by (b) a diffusive force, arising from the concentration gradient
produced at the electrode surface. The total current passing through the cell can be
regarded as the sum of these two factors.

The working electrode, being perfectly polarisable, assumes the correspondingly

increasing negative potential applied to it; from A to B practically no current will pass
through the cell. At B, where the potential of the micro-electrode is equal to the
deposition potential, the current suddenly commences to increase and the working
electrode becomes depolarised by the metal ions, which are then discharged upon the
electrode surface to form metal; consequently a rapid increase in the current flowing
through the cell will be observed.

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At the point C the current no longer increases linearly with applied potential but approaches a steady limiting value
at the point D: no increase in current is observed at higher cathode potentials unless a second compound able to
depolarise the working electrode is present in the solution.

At any point on the curve between B and C (usually spoken of as the polarographic wave) the number of metal ions
reaching the micro-electrode surface as a result of migration and diffusion from the main bulk of the solution always
exceeds the number of metal ions which react at and are deposited upon the electrode.

At the point C the rate of supply of the metal ions from the main bulk of the solution to the working electrode surface
has become equal to the rate of their deposition. Hence, at potentials more negative than point D, the concentration of
undischarged metal ions at the micro-electrode surface is negligibly small relative to the metal ion concentration in the
bulk of the solution; no further increase in current passing through the electrolytic cell can be expected, since the
limiting current is now fixed by the rate at which metal ions can reach the electrode surface.

A number of polarisable micro-electrodes have been used in determining current-voltage curves, but the most
satisfactory is a slowly growing drop of mercury issuing, under a head of 40-60 cm of mercury, from a resistance-glass
capillary (0.05-0.08 mm in diameter and 5-9 cm long) in small, uniform drops.

Advantages of dropping mercury electrode

The dropping mercury electrode has the following advantages.

(a) Its surface is reproducible, smooth, and continuously renewed; this is conducive to good reproducibility
of the current potential curve and eliminates passivity or poisoning effects.

(b) Mercury forms amalgams (solid solutions) with many metals.

(c) The diffusion current assumes a steady value immediately after each change of applied potential, and is
reproducible.

(d) The large hydrogen overpotential on mercury renders possible the deposition of substances difficult to
reduce, e.g. the alkali metal ions, aluminium ion and manganese(II) ion. (The current-potential curves of
these ions are inaccessible with a platinum micro-electrode.)

(e) The surface area can be calculated from the weight of the drops.

The dropping mercury electrode may be applied over the range +0.4 to about - 2.0 volts with reference to the S.C.E. Above
+0.4 volt mercury dissolves and gives an anodic wave; it begins to oxidise to mercury(I) ion. At potentials more negative
than about - 1.8 volts vs S.C.E., visible hydrogen evolution occurs in acid solutions and the usual supporting electrolytes
commence to discharge.

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The factors affecting the limiting current in DME

(1) Residual (or condenser) current: Mercury is unique in remaining electrically uncharged when it is dropping freely
into a solution containing an indifferent electrolyte, such as potassium chloride or potassium nitrate. If a current-voltage
curve is determined for a solution containing ions with a strongly negative reduction potential (e.g. potassium ions), a
small current will flow before the decomposition of the solution begins. This current increases almost linearly with the
applied voltage, and it is observed even when the purest, air-free solutions are used, so that it cannot be due to the
reduction of impurities. In practice, one often finds that the indifferent electrolyte contains traces of impurities so that
small, almost imperceptible currents are superimposed upon the condenser current and that must be subtracted from
the total observed current.

(2) Migration current: Electro-active material reaches the surface of the electrode largely by two processes. (1) one is the
migration of charged particles in the electric field caused by the potential difference existing between the electrode
surface and the solution and (2) the other is concerned with the diffusion of particles. the migration current can be
practically eliminated if an indifferent electrolyte is added to the solution in a concentration so large that its ions carry
essentially all the current. An indifferent electrolyte is one which conducts the current but does not react with the
material under investigation, nor at the electrodes within the potential range studied. the concentration of the added
electrolyte ('supporting electrolyte') must be at least 100-fold that of the electro-active material.

(3) Diffusion current: When an excess of supporting electrolyte is present in the solution the electrical force on the
reducible ions is nullified; this is because the ions of the added Salt carry practically all the current and the potential
gradient is compressed or shortened to a region so very close to the electrode surface that it is no longer operative to
attract electro-reducible ions. Under these conditions the limiting current is almost solely a diffusion current.

Diffusion limiting current

Under the condition when current is solely a diffusion current, it is called diffusion limiting current. Ilkovic examined the
various factors which govern the diffusion current and deduced the following equation:
𝟏 𝟐 𝟏
𝑰𝒅 = 𝟔𝟎𝟕𝒏𝑫 𝟐 𝑪𝒎 𝟑 𝒕 𝟔 𝒘𝒉𝒆𝒓𝒆

𝑰𝒅 = the average diffusion current in microamperes during the life of the drop.
𝒏 = the number of faradays of electricity required per mole of the electrode reaction.
𝑫 = the diffusion coefficient of the reducible or oxidizable substance expressed as cm2 s-1
𝑪 = its concentration in mmol.L-1
𝒎 = the rate of flow of mercury from the dropping electrode expressed in mg.s-1
𝒕 = drop time in s.
The constant 607 is a combination of natural constants, including the Faraday constant; it is slightly temperature-dependent
and the value 607 is for 25 ⁰C.

The Ilkovic equation is important because it accounts quantitatively the linear dependence of the diffusion current upon n
and C. Thus, with all the other factors remaining constant, the diffusion current is directly proportional to the concentration
of the electro-active material - this is of great importance in quantitative polarographic analysis.

The diffusion current 𝑰𝒅 depends upon several factors, such as temperature, the viscosity of the medium, the composition
of the base electrolyte, the molecular or ionic state of the electro-active species, the dimensions of the capillary, and the
pressure on the dropping mercury.
𝟐 𝟏
The product 𝒎 𝟑 𝒕 𝟔 (Capillary constant) is important because it permits results with different capillaries under otherwise
𝟐 𝟏
identical conditions to be compared: the ratio of the diffusion currents is simply the ratio of the 𝒎 𝟑 𝒕 𝟔 values.

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Polarographic maxima
Current-voltage curves obtained with the dropping mercury
cathode frequently exhibit pronounced maxima, which are
reproducible and which can be usually eliminated by the addition of
certain appropriate 'maximum suppressors’ which are generally
surface-active substance, such as a dyestuff, gelatine, or other
colloids. These maxima Vary in shape from sharp peaks to rounded
humps, which gradually decrease to the normal diffusion-current
curve as the applied voltage is increased.

The function of any maximum suppressor is probably to form an

adsorbed layer on the aqueous side of the mercury-solution interface
which resists compression; this prevents the streaming movement of
the diffusion layer (which is believed to be responsible for the current
maximum) at the interface.

To measure the true diffusion current, the maxima must be eliminated

or suppressed.

Half-wave potentials
The salient features of a typical current-applied voltage curve (polarogram) are shown here:

The conventional method of drawing the current-voltage curves is to

plot the applied e.m.f. as abscissae reading in increasing negative
values on the right: current is plotted as ordinates, cathodic currents
(resulting from reduction) being regarded as positive and anodic
currents negative.
1. The height of the curve (wave height) is the diffusion current, and
is a function of the concentration of the reacting material.
2. The potential corresponding to the point of inflexion of the curve
(half-wave potential) is characteristic of the nature of the reacting
material.
3. This is the essential basis of quantitative and qualitative
polarographicanalysis.
4. The current flowing increases as the mercury drop becomes larger
and then abruptly decreases when the drop falls, the recorder trace
in fact has a saw-tooth appearance, especially at the upper end.

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Underlying theory
The electrode is a cathode when a reduction can take place at its surface, and an anode when oxidation occurs at its
surface. The reductant differs from the oxidant merely by n electrons, and together they form an oxidation-reduction
system.
𝑶 + 𝒏𝒆 ⇌ 𝑹 … … . . (𝟏)
Considering the reversible reduction of an oxidant to a reductant at a dropping mercury cathode, the electrode potential
is given by :
𝑹𝑻 𝒂𝑶
𝑬 = 𝑬𝟎 + 𝒍𝒏 … … … . (𝟐)
𝒏𝑭 𝒂𝑹
where 𝒂𝑶 and 𝒂𝑹 are the activities of the oxidant and reductant respectively as they exist at the electrode surface.
Substitution of the concentrations for activities will not introduce any appreciable error and equation (2) may therefore be
written as:
𝑹𝑻 𝑶𝒔
𝑬 = 𝑬𝟎 + 𝒍𝒏 … … … . (𝟐)
𝒏𝑭 𝑹𝒔

Here, 𝑬𝟎 is the standard potential of the reaction against the reference electrode used to measure the potential of the
dropping electrode, and the potential E refers to the average value during the life of a mercury drop.
Before the commencement of the polarographic wave only a small residual current flows, and the
concentration of any electro-active substance must be the same at the electrode interface as in the bulk of the solution.
As soon as the decomposition potential is exceeded, some of the reducible substance (oxidant) at the interface is
reduced, and must be replenished from the body of the solution by means of diffusion.
If the applied potential is increased to a value at which al1 the oxidant reaching the interface is reduced, only
the newly formed reductant will be present; the current then flowing will be the diffusion current.

The current I at any point on the wave is determined by the rate of diffusion of the oxidant from the bulk of the solution
to the electrode surface under a concentration gradient [O] to [O]s. Thus,
𝑰∝ 𝑶 − 𝑶𝒔
Or 𝑰 = 𝑲 𝑶 − 𝑶 𝒔 …………………. 𝟒

When 𝑶 𝒔 is reduced to almost zero, equation (4) may be written: 𝑰 = 𝑲 𝑶 = 𝑰𝒅 … … … … … (𝟓)

where 𝑰𝒅 is the diffusion current.
𝑰 𝑰
From equations (4) and (5), it follows that: 𝑶 𝒔 = 𝒅 … … … (𝟔)
𝑲
If the R is soluble in water and none was originally present with the oxidant, it will diffuse from the surface of the
electrode to the bulk of the solution. The concentration of [Red], at the surface at any value of 1 will be proportional to
the rate of diffusion of the reductant from the surface of the electrode to the solution under a concentration gradient [R],
and hence also the current:
𝑰 = 𝒌 𝑹 𝒔………. 𝟕

The constants K and k may be evaluated from the Ilkovic equation.

Now substituting in equation (3), we have:

𝑹𝑻 𝑲 𝑹𝑻 𝑰𝒅 − 𝑰 𝑹𝑻 𝑰𝒅 − 𝑰
𝑬 = 𝑬𝟎 − 𝒍𝒏 + 𝒍𝒏 = 𝑬𝟏 + 𝒍𝒏 ………….. 𝟖
𝒏𝑭 𝒌 𝒏𝑭 𝑰 𝟐 𝒏𝑭 𝑰
𝑹𝑻 𝑲
Where 𝟎
𝑬𝟏 𝟐 = 𝑬 − 𝑬 𝒂𝒏𝒅 𝑬 = 𝒍𝒏
𝒏𝑭 𝒌

𝑹𝑻 𝒌
𝑬𝟏 𝟐 can be expressed as 𝑬𝟏 𝟐 = 𝑬𝟎 + 𝒍𝒏 Where 𝒌 and 𝑲 are the diffusion coefficient of the R and O, respectively.
𝒏𝑭 𝑲

7
 17-11-2022

When 𝑰 is equal to 𝑰𝒅 𝟐, equation (8) reduces to:

𝑰𝒅
𝑹𝑻 𝟐 = 𝑬𝟎 … … … … . . 𝟗
𝑬 = 𝑬𝟏 = 𝑬𝟎 + 𝒍𝒏
𝟐 𝒏𝑭 𝑰𝒅
𝟐

The potential at the point on the polarographic wave where the current is equal to one-half the diffusion
current is termed the half-wave potential and is designated by 𝑬𝟏 𝟐. 𝑬𝟏 𝟐 is a characteristic constant for a
reversible oxidation-reduction system and that its value is independent of the concentration of the
oxidant [O] in the bulk of the solution.

It follows from equations (8) and (9) that at 25 C:

𝟎. 𝟎𝟓𝟗𝟏 𝑰𝒅 − 𝑰
𝑬 = 𝑬𝟏 + 𝒍𝒐𝒈
𝟐 𝒏 𝑰

This equation is known as Heyrovsky-Ilkovic represents the potential as a function of the current at any
point on the polarographic wave, it is sometimes termed the equation of the polarographic wave.

The half-wave potential is also independent of the electrode characteristics, and can, therefore,
serve for the qualitative identification of an unknown substance.

Heyrovsky-Ilkovic plot

How do we determine 𝑬𝟏 𝟐 accurately?

It is sometimes possible to determine 𝑬𝟏 𝟐 just by inspection,
that is, find the potential at which the current is exactly half
f the diffusion current 𝑰𝒅. In practice, however, such values
of 𝑬𝟏 𝟐 are not particularly accurate, so we need an
alternative approach. We use the Heyrovsky-Ilkovic equation
as follows:
𝑹𝑻 𝑰𝒅 − 𝑰
𝑬 = 𝑬𝟏 + 𝒍𝒏
𝟐 𝒏𝑭 𝑰

where all terms are familiar, and where 𝑰 is the current at

the potential 𝑬.

In order to obtain 𝑬𝟏 𝟐 from the above equation, we plot a

graph of 𝒍𝒏 𝒅
𝑰 𝑰
against E. The intercept on the x-axis Logarithmic analysis of a polarographic wave by
𝑰 using the Heyrovsky-Ilkovic method. The intercept
gives then an accurate value of 𝑬𝟏 𝟐 . The intercept on the x- on the x-axis is an accurate value of 𝑬𝟏 𝟐 for the
axis is 𝑬𝟏 𝟐 . Fe2+, Fe couple in water.

8
 17-11-2022

Does the gradient of a Heyrovsky -1lkovic graph have any significance?

𝑰𝒅 𝑰
From the way that the Heyrovsky -Ilkovic equation is written, the gradient of a graph of 𝒍𝒏 as ‘𝒚’
𝑰
𝒏𝑭 𝒏𝑭
against 𝑬 as ‘𝒙’ should be . If the gradient of the graph is indeed then we can say that the electrode
𝑹𝑻 𝑹𝑻
reaction is likely to be reversible in the electrochemical sense.

𝒏𝑭
If the gradient is too low, however, then we can imply that the ( ) term has been modified, i.e. that the
𝑹𝑻
reaction at the DME is electrochemically irreversible, such that a variant of the Heyrovsky-Ilkovic equation
now needs to be employed, as follows:
𝑹𝑻 𝑰𝒅 − 𝑰
𝑬 = 𝑬𝟏 + 𝒍𝒏
𝟐 𝒏𝑭 𝑰

where a is a constant (having a value in the range 0 <  < 1 ). A wholly reversible electron-transfer process
has a value of  = 1.

Determination of Stability Constant and Co-ordination Number of Metal Complexes

If the reaction at the indicator electrode involves complex ions, satisfactory polarograms can be obtained only if the
dissociation of the complex ion is very rapid as compared with the diffusion rate, so that the concentration of the simple ion is
maintained constant at the electrode interface.
Let us consider the reaction
𝑀 + 𝑛𝑒 + 𝐻𝑔 ⇌ 𝑀(𝐻𝑔)

. .
𝑬𝟏 𝟐 = 𝐸 + 𝑙𝑜𝑔 𝑎𝑛𝑑 𝐸 = 𝐸 + 𝑙𝑜𝑔
( )

Consider the general case of the complexation: 𝑀 + 𝑥𝐿 ⇌ 𝑀𝐿 =

𝑀𝐿
∴ 𝑀 =
𝐿

0.06 𝑀𝐿
∴ 𝐸 =𝐸 + 𝑙𝑜𝑔
𝑛  𝐿 𝑀(𝐻𝑔)

0.06 0.06 0.06 𝑀𝐿

=𝐸 − 𝑙𝑜𝑔 − 𝑙𝑜𝑔 𝐿 + 𝑙𝑜𝑔
𝑛 𝑛 𝑛 𝑀(𝐻𝑔)
0.06 𝑀𝐿
𝐸 =𝐸 + 𝑙𝑜𝑔
𝑛 𝑀(𝐻𝑔)

9
 17-11-2022

Now, let us recall the redox reaction: 𝑶 + 𝒏𝒆 ⇌ 𝑹 and compare with the reaction: 𝑴𝑳𝒏𝒙 + 𝒏𝒆 + 𝑯𝒈 ⇌ 𝑴 𝑯𝒈 + 𝒙𝑳
𝑰𝒅 𝑰 𝑰𝒅 𝑰
𝑶 𝒔 =  𝑴𝑳𝒏𝒙 =
𝑲 𝑲𝑳𝑶
𝑰 𝑰
𝑹 𝒔 =  𝑴(𝑯𝒈) = 𝑳
𝒌 𝒌𝑹

𝑴𝑳𝒏
Now put the values of 𝑴𝑳𝒏𝒙 and 𝑴(𝑯𝒈) in equation: 𝑬𝒄 𝑳 = 𝑬𝟎𝒇 + 𝒍𝒐𝒈 𝒙
we obtain
𝑴(𝑯𝒈)

𝟎. 𝟎𝟔 𝒌𝑳𝑹 𝟎. 𝟎𝟔 𝑰𝒅 − 𝑰
𝑬𝒄 𝑳 = 𝑬𝟎𝒇 + 𝐥𝐨𝐠 𝑳 + 𝒍𝒐𝒈
𝒏 𝑲𝑶 𝒏 𝑰
𝑳
𝟎. 𝟎𝟔 𝒌 𝑹
∴ 𝑬𝟏 = 𝑬𝟎𝒇 + 𝒍𝒐𝒈 𝑳
𝟐 𝑳 𝒏 𝑲𝑶
𝟎.𝟎𝟔 𝒌 𝟎.𝟎𝟔 𝒌𝑳
So, 𝑬𝟏 𝟐 = 𝑬𝟏 𝟐 − 𝑬𝟏 𝟐 = 𝑬𝒐 + 𝒍𝒐𝒈 𝑹 − 𝑬𝟎𝒇 − 𝒍𝒐𝒈 𝑹𝑳
𝑳 𝒏 𝑲𝑶 𝒏 𝑲𝑶
considering, K/k does not change on complexation, we get:
𝟎. 𝟎𝟔 𝟎. 𝟎𝟔
𝑬𝟏 = 𝒍𝒐𝒈 + 𝒍𝒐𝒈 𝑳 𝒙
𝟐 𝒏 𝒏

𝟎. 𝟎𝟔 𝟎. 𝟎𝟔𝒙
𝑬𝟏 =
𝒍𝒐𝒈 + 𝒍𝒐𝒈 𝑳
𝒏𝟐 𝒏
Thus, plot of 𝑬𝟏 𝟐 vs. 𝒍𝒐𝒈 𝑳 will give  and x, from the intercept and slope, respectively.

Why is 𝑬𝟏 𝟐 shifted by complexation?

A fraction of the electrons on the metal cation help form the new bonds created during the complexation
process. With a different electron density on the central cation, the energy needed to reduce the metal
will be different before and after the complexation reaction.

Example-1: Cadmium ion is reduced at a DME and the diffusion current measured as 24.3 A. Previously, a sample of
2.0 x 10-4 mol dm-3 Cd2+ was analysed at the same DME with the same drop time, and the diffusion current was then
found to be 15.2 A. What is the concentration of the sample? (Assume that the residual current was known, and has
been subtracted for both samples.)

Ans.: From straightforward ratios: 𝑰𝒅𝟏 𝑪𝟐 = 𝑰𝒅𝟐 𝑪𝟏

𝑰𝒅𝟐
𝑪𝟐 = × 𝑪𝟏
𝑰𝒅𝟏

𝟐𝟒.𝟑 𝟒 𝒎𝒐𝒍. 𝒅𝒎 𝟑
and therefore: 𝑪𝟐 = × 𝟐. 𝟎 × 𝟏𝟎 𝟒 𝒎𝒐𝒍. 𝒅𝒎 𝟑 = 𝟑. 𝟐 × 𝟏𝟎
𝟏𝟓.𝟐

10
 Cyclic Voltammetry
In polarography, we have measured i-V curves and acquired information
about analyte from diffusion limiting current.

More information can be gained in a single experiment by sweeping the

potential with time and recording the i-E curve directly.

This amounts, in a qualitative way, to traversing the three-dimensional i-t-E

realm. Usually the potential is varied linearly with Time (i.e., the applied
signal is a voltage ramp) with sweep rates 𝒗 ranging from 10 mV/s ( 1 V
traversed in 100 s) to about 1000 V is with conventional electrodes and up
to 106 V using an ultramicroelectrode (UME).

In this experiment, it is customary to record the current as a function of

potential, which is obviously equivalent to recording current versus time.
The formal name for the method is linear potential sweep
chronoarnperornetry, but most workers refer to it as linear sweep
voltammetry (LSV). A portion of the i-t-E surface for a
Nernstian reaction. Potential axis is
Cyclic voltarnrnetry (CV), is a reversal technique and is the potential-scan in units of 59/n mV.
equivalent of double potential step Chronoamperometry.
Cyclic voltammetry has become a very popular technique for initial electrochemical studies of new systems and has
proven very useful in obtaining information about fairly complicated electrode reactions.

The principal difference between polarography and voltammetry is the nature of the working electrode (WE).

In polarography, a dropping-mercury electrode (DME) is used as the WE, while the WE employed during
voltammetry is usually solid. Like polarography, voltammetry is a microanalysis technique, so only a small proportion
of the solution is ever modified by the processes occurring at the electrode.

(a) Cyclic potential sweep and (b) Resulting cyclic voltammogram.

 Cyclic Voltammetry

The potential of the working electrode is ramped at a scan rate of v. The resultant trace of current against potential is
termed a voltammogram. In linear sweep voltammetry (LSV), the potential of the working electrode is ramped from
an initial potential Ei to a final potential Ef.

During cyclic voltammetry, the potential is similarly ramped from an

initial potential Ei but, at the end of its linear sweep, the direction of the
potential scan is reversed, usually stopping at the initial potential Ei (or
it may commence an additional cycle). The potential at which the
reverse occurs is known as the switch potential (E). Almost universally,
the scan rate between Ei and E is the same as that between E and Ei.
Values of the scan rates 𝒗𝒇𝒐𝒓𝒘𝒂𝒓𝒅 and 𝒗𝒃𝒂𝒄𝒌𝒘𝒂𝒓𝒅 are always written as
positive numbers.
A linear-sweep voltammogram for the
reduction of a solution-phase analyte,
𝑶 + 𝒏𝒆 ⇌ 𝑹, depicted as a function
of scan rate.
 Cyclic voltammogram (CV).
There is seen to be a peak formed in both the forward and reverse
sides of the CV. These peaks are of similar shape and, if fully
reversible, their magnitudes will be identical.

Oxidation has occurred during the forward part of the CV, with
oxidation taking place during the reverse part.

If the scan was ‘going negative’ from Ei, then reduction would occur
during the forward part of the scan, and oxidation during the
reverse.

As with other forms of voltammetry, the magnitude of the current

is proportional to concentration, so the equality between Ip(forward)
A voltammogram for a simple solution-phase and Ip(back) (where ‘p’ represents ‘peak’) implies a quantitative
couple: such a plot is known as a cyclic retrieval of electromodified material (which follows from Faraday’s
voltammogram (CV) for wholly reversible laws).
system.
At the completion of the CV, when the potential has returned to Ei,
there is still a slight current, indicating that a small amount of
material (around the electrode) has still not been reduced. This
slight residual current would dissipate to zero if we were to force
the potential of the electrode to more negative potentials beyond Ei.
What is meant by ‘reversible’ in the context of the above CV?

Diagnostic tests for the electrochemical reversibility of a redox couple, carried out by using cyclic
Voltammetry.

1. Ipc = Ipa
2. The peak potentials, Epc and Epa, are independent of the scan rate v
3. E0 is positioned midway between Epc and Epa , so E0 = (Epc + Epa)/2
4. Ip is proportional to v1/2
5 . The separation between Epc and Epa , is 59 mV/n for an n-electron couple.

A couple fulfilling all of the criteria will probably be reversible. The couple is almost certainly not reversible if one or more
of these criteria are not fulfilled.
As a 'bottom-line' definition, the CV will look like that shown
here only if:

( i ) the ratio of activities of the oxidized and reduced forms of

the redox couple satisfies the Nernst equation for the
potential of the working electrode

(ii) the rate of electron transfer, ket, is extremely fast.

In practice, we mean fast' such that the rates of analyte

diffusing to and from the electrode are limiting.
Thus for a reversible wave, 𝑬𝒑 is independent of scan rate, and 𝒊𝒑 (as well as the current at any other point on the
/
wave) is proportional to 𝒗𝟏 𝟐. The latter property indicates diffusion control and is analogous to the variation of id
− 𝟏 /𝟐
with 𝒕 in chronoamperometry. A convenient constant in LSV is ip/v1/2c (sometimes called the current
/𝟐 /
function), which depends on 𝒏𝟑 and 𝑫𝟏 𝟐. This constant can be used to estimate 𝒏 for an electrode reaction, if a
value of 𝑫 can be estimated, for example, from the LSV of a compound of similar size or structure that undergoes
an electrode reaction with a known 𝒏 value.
 Data Interpretation of CV Analytical Electrochemistry 2d Ed Jospeh Wang
The cyclic voltammetry is characterized by several important parameters. Four of these observables, the two peak
currents, and two peak potentials, provide the basis for the diagnostics developed by Nicholson and Shain for analysing
the cyclic voltammetry response.

Reversible systems:
The peak current for a reversible couple (at 25 0C) if given by Randles-Sevcik equation:
𝟑 𝟏 𝟏
𝒊𝒑 = (𝟐. 𝟔𝟗 × 𝟏𝟎𝟓 )𝒏𝟐 𝑨𝒄𝑫𝟐 𝒗𝟐

Where n is the number of electrons, 𝑨 is the electrode area (in cm2), 𝑪 is the analyte concentration (in mol.cm-3), 𝑫 is the
diffusion coefficient (in cm2.s-1), and 𝒗 is the scan rate (in V.s-1). Accordingly, the current is directly proportional to
concentration and increase with the square root of the scan rate. The ratio of the reverse-to-forward currents, 𝒊𝒑, 𝒓/𝒊𝒑, 𝒇,
is unity for a simple reversible couple.

This peak ratio can be strongly affected by chemical reactions coupled to the redox process. The current peaks are
commonly measured by extrapolating the preceding baseline current.

The position of the peaks on potential axis (𝑬𝒑) is related to the formal potential of redox process. The formal potential
for a reversible couple is centered between 𝑬𝒑𝒂 and 𝑬𝒑𝒄:
𝑬𝒑𝒂 + 𝑬𝒑𝒄
𝑬𝟎 =
𝟐
The separation between the peak potential (for a reversible couple is given by:

𝟎. 𝟎𝟓𝟗
∆𝑬𝒑 = 𝑬𝒑𝒂 − 𝑬𝒑𝒄 = 𝑽
𝒏

Thus, the peak separation can be used to determine the number of electrons transferred and as a criterion for a
Nernstian behaviour. Accordingly, a fast one-electron process exhibits a ∆𝑬𝒑 of about 59 mV.

Both the cathodic and anodic peak potentials are independent of the scan rate. It is possible to relate the half-peak
potential (𝑬𝒑/𝟐 , where the current is half of the peak current) to the polarographic half-wave potential 𝑬𝟏/𝟐 :

𝟎. 𝟎𝟐𝟖
𝑬𝒑/𝟐 = 𝑬𝟏/𝟐 ± 𝑽
𝒏
The sign is positive for a reduction process.
 For multielectron-transfer (reversible) processes, the
cyclic voltammogram consists of several distinct
peaks if the 𝑬𝟎 values for the individual steps are
successively higher and are well separated. An
example for mechanism is the six-step reduction of
the fullerenes C60 and C70 to yield the hexaanion
products 𝑪𝟔− 𝟔−
𝟔𝟎 𝒂𝒏𝒅 𝑪𝟕𝟎 .

Cyclic voltammetry for C60 and C70 in an acetonbitrile-

toluene solution.
 Irreversible and quasi-reversible systems:
For reversible processes (those with sluggish electron exchange), the individual peaks are reduced in size and widely
separated. Totally irreversible systems are characterized by a shift of the peak potential with the scan rate:
𝟏
𝑹𝑻 𝒌𝟎 𝒏𝑭𝒗 𝟐
𝑬𝒑 = 𝑬𝟎 − 𝟎. 𝟕𝟖 − 𝒍𝒏 𝟏/𝟐 + 𝒍𝒏
𝒏𝑭 𝑫 𝑹𝑻
Where alpha is the transfer coefficient and 𝒏 is the number of electrons involved in the charge-transfer step. Thus, 𝑬𝒑
occurs at potentials higher than 𝑬𝟎 , with the over potential related to 𝒌𝟎 and . Independent of value of 𝒌𝟎 , such peak
displacement can be compensated by an appropriate change of the scan rate. The peak potential and half-peak potential
(at 25 0C) will differ by 48/𝒏 mV. Hence, the voltammogram becomes more drawn-out as  decreases.

The peak current is given by:

𝟏 𝟏 𝟏
𝒊𝒑 = (𝟐. 𝟔𝟗 × 𝟏𝟎𝟓 )𝒏(𝒏)𝟐 𝑨𝒄𝑫𝟐 𝒗𝟐
Is still proportional to the bulk concentration, but will be lower in
height (depending upon the value of ). Assuming a value of 0.5, the
ratio of the reversible-to-irreversible current peaks is 1.27 i.e. the
peak current for the irreversible process about 80% of the peak for a
Cyclic voltammograms for irreversible reversible one.
(Curve A) and quasi-irreversible (Curve b)
redox processes.
 Randles-Sevcik equation to determine the concentration of analyte
If the electrolyte composition is constant in terms of temperature,
solvent, swamping electrolyte, etc., then we can use the Randles-
Sevcik equation to determine the concentration of analyte by the
construction of a suitable calibration curve shown here.

Note that all values of Ip were determined at a constant scan rate v.

Such curves should yield accurate values of concentration (to within a
few %) in the range c. 1 mol dm-3 down to as low as mol.dm-3 at the
lower extreme. Below the lower concentration limit, the non-faradic
Plot of peak current (Ip) in a voltammogram
current resulting from charging of the electrode double-layer (either linear-sweep or cyclic) against analyte
becomes comparable in magnitude to Ip. The extreme low- concentration. The linear portion obeys the
Randles-Sevcik equation, while the horizontal
concentration portion of the graph therefore appears as a horizontal plateau at low Canalyte, plateau es is usually
plateau, implying that Ip becomes independent of concentration. In caused by non-faradaic components of Ip, such
as double-layer charging.
fact, this plot can yield an approximate Value Of Idouble-layer charging by
taking the I value for the horizontal portion.
Alternatively, the CV can be drawn as a function of the scan rate u (see the Figure). Note here how the magnitude of the
peak current increases with the increasing scan rate.

−𝟏ൗ
A plot of Ip as 'y' against 𝒗 𝟐 as 'x' is often called a Randles-Sevcik plot. Such plots should be linear and pass
through the origin. The gradient of the linear portion of a Randles-Sevcik plot can be employed to determine the
concentrations of analyte if the diffusion coefficient D is known accurately. Unfortunately, D is not independent of
analyte and is often quite unknown. Note, however, that a Randles-Sevcik plot is one of the best ways of determining
an experimental value of D if a literature value is unavailable, provided that the electrode reaction is fully reversible.
The primary use of CV is as a tool for fundamental and diagnostic studies that provides qualitative information about
electrochemical processes under various conditions.
Consider CV of the shown pesticide parathion. The switching
potentials were about -1.2 V and +0.3 V. The initial forward scan
started at 0.0 V, not at +0.3 V. Three peaks are observed.

1. First one is cathodic peak results from a four-electron

reduction of parathion to give hydroxylamine derivative.
− +
𝑵𝑶𝟐 + 𝟒𝒆 + 𝟒𝑯 → 𝑵𝑯𝑶𝑯 + 𝑯𝟐𝑶

2. The anodic peak at B arises from oxidation of the

hydroxylamine to a nitroso derivative
+
𝑵𝑯𝑶𝑯 → 𝑵𝑶 + 𝟐𝑯 + 𝟐𝒆 +

3. The cathodic peak at C results from the oxidation f nitroso

compound to the hydroxylamine as:
+ −
𝑵𝑶 + 𝟐𝑯 + 𝟐𝒆 → 𝑵𝑯𝑶𝑯