ANALYTICAL

CHEMISTRY II
220401
Dr. Aysun DİNÇEL

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 Week-9

Electrochemical Methods
Electroanalytical Chemistry
ELECTROCHEMISTRY

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• Electrochemical sensors are used in amazing places
• For example,
• sensors measure pH, dissolved hydrogen,
• and dissolved hydrogen sulfide, species critical to understanding
geochemical reactions deep in the ocean crust, as well as
• biogeochemical processes in the near-vent environment

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• In this section the theory and methodology of electroanalytical
chemistry are explored
• Terminology and conventions of electrochemistry as well as
theoretical and practical aspects of the measurement of
electrochemical potentials and currents are presented.

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• Electroanalytical chemistry encompasses a group of qualitative and
quantitative analytical methods
• based on the electrical properties of a solution of the analyte when it
is made part of an electrochemical cell.

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• Electroanalytical techniques are capable of producing low detection
limits and a wealth of characterization information describing
electrochemically accessible systems.
• Such information includes the stoichiometry and rate of interfacial
charge transfer, the rate of mass transfer, the extent of adsorption or
chemisorption, and the rates and equilibrium constants for chemical
reactions.

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• electrochemical measurements are often specific for a particular
oxidation state of an element.
• For example, in electrochemical methods it is possible to determine
the concentration of each of the species in a mixture of cerium(III)
and cerium(IV), whereas most other analytical methods can reveal
only the total cerium concentration

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• A second important advantage of electrochemical methods is that the
instrumentation is relatively inexpensive.

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• A third feature of certain electrochemical methods, which may be an
advantage or a disadvantage, is that they provide information about
activities rather than concentrations of chemical species.
• Generally, in physiological studies, for example, activities of ions such
as calcium and potassium are more important than concentrations

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Electrochemical Cells
• A dc electrochemical cell consists of two electrical conductors called
electrodes, each immersed in a suitable electrolyte solution
• For a current to develop in a cell, it is necessary that the electrodes be
connected externally with a metal con-ductor, that the two
electrolyte solutions be in contact to permit movement of ions from
one to the other, and that an electron- transfer reaction can occur at
each of the two electrodes.

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 Cuo Cu2+ + 2e–
Ag+ + e–  Ago
shows an example of a simple
electrochemical cell It consists of a
silver electrode immersed in a
solution of silver nitrate and a copper
electrode in a solution of copper
sulfate.
The two solutions are joined by a salt
bridge, which consists of a tube filled
with a solution that is saturated with
potassium chloride or, sometimes, a
different electrolyte.

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• In these analytical techniques, measurement of
• potential,
• current, or
• charge to determine an analyte’s concentration or to characterize an
analyte’s chemical reactivity

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To understand electrochemistry
we need to appreciate five important and interrelated concepts:
(1) the electrode’s potential determines the analyte’s form at the
electrode’s surface;
(2) the concentration of analyte at the electrode’s surface may not be
the same as its concentration in bulk solution;
(3) in addition to an oxidation–reduction reaction, the analyte may
participate in other chemical reactions;
(4) current is a measure of the rate of the analyte’s oxidation or
reduction; and
(5) we cannot control simultaneously current and potential.

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Galvanic and Electrolytic Cells
Cuo Cu2+ + 2e–
Ag+ + e–  Ago
the sum of the two half-cell reactions shown
Cuo + 2Ag+  Cu2+ + Ago The net cell reaction
The voltage of this cell is a measure of the tendency for this
Reaction to proceed toward equilibrium.
Thus, when the copper and silver ion concentrations (actually, activities)
are 0.0200 M, the cell voltage is 0.412 V, which shows that the reaction is
far from equilibrium.
As the reaction proceeds, the voltage becomes smaller and smaller, and it
ultimately reaches 0.000 V when the system achieves equilibrium.
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 galvanic cells
• Cells,
• that produce electrical energy
are called galvanic cells

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 electrolytic cells
• In contrast,
• electrolytic cells consume electrical
energy.
• For example, the Cu-Ag cell can operate in
an electrolytic mode by connecting the
negative terminal of a battery or dc
power supply to the copper electrode and
the positive terminal to the silver
electrode,
• If the output of this supply is adjusted to
be somewhat greater than 0.412 V, as
shown, the two electrode reactions are
reversed and the net cell reaction is A cell in which reversing the direction of the current simply
• Cu2+ + 2Ag+  Cuo + Ago reverses the reactions at the two electrodes is termed a
chemically reversible cell.
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Anodes and Cathodes
• By definition, the cathode of an electrochemical cell is the electrode
at which reduction occurs, and the anode is the electrode where
oxidation takes place.
• These definitions apply to both galvanic cells and to electrolytic cells.
• ln galvanic cells the silver electrode is the cathode and the copper
electrode is the anode.
• On the other hand,
• in the electrolytic cell, the silver electrode is the anode and the
copper electrode the cathode because the half-cell reactions are
reversed.

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Electrode Potentials
• An electrode potential is defined as the potential of a cell in which the
electrode under investigation is the right-hand electrode and the SHE
is the left-hand electrode.

• the cell potential Ecell as Ecell = Eright + Eleft

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Electrode Potentials
• A system in which there is an oxidation or reduction is called as a
half-reaction (or half-cell).
• When two half reactions (an oxidation and a reduction) combine, a
redox reaction occurs.
• Thus, a complete (Overall) reaction (or full cell or galvanic cell (in
shortly cell) occurs.

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• voltammetry; It is an electroanalytical method based on current-
potential relationship.
• In this method, a working electrode and a large surface electrode
(reference) are immersed in a cell containing a solution of an
electroactive substance, and a potential is applied between it.
• a reaction occurs in the cell and a current is formed at the end of the
reaction.
• It is preferred that the working electrode has a small surface area so
that the current density at this electrode is large.

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• In the method; An electrolysis cell arranged according to these
features is filled with a suitable solution to be analyzed, and the
current passing through the cell is read by applying increasing
potential differences.
• A curve is obtained when the potential difference is plotted against
current.
• This curve is a current-potential curve and is called a voltammogram
or polarogram, depending on the type of electrode used.

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• The analysis method that uses current-potential changes is called
voltammetry or polarography.
• If the working (indicator) electrode used in the experiments is the
dropping mercury electrode, the method is called polarography,
• and if the working electrodes are solid electrodes, the method is
called voltammetry.

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• Summary of
• common
• electroanalytical
• methods

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Potentiometry

• Calomel Electrodes
• Calomel reference electrodes consist of mercury in contact with a
solution that is saturated with mercury(I) chloride (calomel) and that
also contains a known concentration of potassium chloride.

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• The ideal reference electrode has a potential that is known, constant,
• and completely insensitive to the composition of the solution under
study. In addition, this electrode should be rugged and easy to
assemble and should maintain a constant potential even when there
is a net current in the cell.

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Voltammetry
• Voltammetry is widely used by inorganic, physical, and biological
chemists for nonanalytical purposes, including fundamental studies of
oxidation and reduction processes in various media, adsorption
processes on surfaces, and electron-transfer mechanisms at
chemically modified electrode surfaces.

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Historically
• the field of voltammetry developed from
polarography, which is a particular type of
voltammetry that was invented by the
Czechoslovakian chemist Jaroslav Heyrovsky
in the early 1920s

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• Jaroslav Heyrovský was an inventor of
• the polarographic method, father of
• electroanalytical chemistry, recipient of
• the Nobel Prize (1959). His contribution
• to electroanalytical chemistry can not be
• overestimated. All voltammetry methods
• used now in electroanalytical chemistry
• originate from polarography developed by
• him. This instrument is saved in the museum of
J.Heyrovský Institute of Physical Chemistry
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• Polarography differs from other types of voltammetry in that the
working electrode is the unique dropping mercury electrode.
• At one time, polarography was an important tool used by chemists for
the determination of inorganic ions and certain organic species in
aqueous solutions.

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• Linear-sweep voltammogram for the reduction of a hypothetical
species A to give a product P.
• The limiting current i1 is proportional to the analyte concentration
and is used for quantitative analysis.
• The half-wave potential E1/2 is related to the standard potential for
the half-reaction and is often used for qualitative identification of
species.
• The half-wave potential is the applied potential at which the current i
is i1/2.

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Linear-sweep voltammogram

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• Linear-sweep voltammograms generally have a sigmoid shape and are
called voltammetric waves.
• The constant current beyond the steep rise is called the diffusion-
limited current, or simply the limiting current i1 because the rate at
which the reactant can be brought to the surface of the electrode by
mass-transport processes limits the current.
• Limiting currents are usually directly proportional to reactant
concentration. Thus, it may written
• i1 = kcA
• cA is the analyte concentration and k is a constant.

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• The potential at which the current is equal to one half the limiting
current is called the half-wave potential and given the symbol E1/2.

• A small current is observed before the electrode and the electroactive

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• diffusion current is proportional to
a) Viscosity,
b) Temperature,
c) The height of the mercury column, and
d) Concentration
Since those in a, b, and c are constant during the experiment, it can be
said that the diffusion current is directly related to concentration

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Use of voltammetry and polarography:
• Polarograms allow us to make both qualitative (qualitative) and
quantitative (quantitative) analysis of matter.
• Every electroactive substance has a certain half-wave potential under
certain conditions (such as certain electrodes and medium).
• Since half-wave potentials are characteristic for each electroactive
substance, it can be used in qualitative analysis.

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Concentration Profiles at Electrode Surfaces
• In quantitative analysis, the diffusion current is proportional to the
concentration.
• This dependence is given by the Ilkovic equation:

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Ilkovic equation
id (max) = 708 n D1/2 m2/3 t1/6 C

id = Diffusion current in microamperes

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• The average current is 6/7 of the maximum current at the end of the
drop life.
• If the Ilkovic equation is written for the average current, the
coefficient becomes 607:

• id (av) = 607 n D1/2 m2/3 t1/6 C

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• Since the other parameters are constant for the electrode and the
substance used in the Ilkovic equation, there is a linear relationship
between the id value and the concentration.
• Using this relationship, the amount of substance in the unknown
sample can be calculated based on the calibration equation to be
prepared with the help of standard solutions of the substance.

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The advantages of polarography
a) Since the hydrogen overvoltage on mercury is high, it can be used in
many analyzes.
b) Since it is renewed at any time, repeatable current flow is ensured.
The disadvantages are;
a) Mercury evaporates in its environment and the vapors are very toxic.
In researchers who are in contact with mercury vapors for a long time,
mercury passes into the blood through the respiratory tract and can
accumulate in the organism by soluble in oil. Symptoms such as tremors,
dizziness, anemia, memory weakness and hair loss occur in poisoning.

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b) The mercury used must be very pure and always Pure mercury is
hard to find. Therefore, it is necessary to carry out very difficult
purification processes.
c) It is a disadvantage that mercury is oxidized at a voltage more
positive than + 0.5 V. This limits the use of mercury as an anode.

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The most commonly used electrodes in
voltammetry
• Mercury electrodes; There are different types such as dropping
mercury, hanging mercury drop electrode, mercury thin film
electrode (mercury film is coated on metals).
• It has advantages due to obtaining repeatable results

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• solid electrodes; metal electrodes (conductive metals such as
platinum or gold, metal oxides such as tin oxide or iridium oxide),
carbon electrodes (electron transfer rates are slower than metal
electrodes. It is widely used because of its chemical inertness, low
residual current, high sensitivity.

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• Modified electrodes; It is formed by the presence of a layer on the
electrode surface that will allow the collection of molecules or ions.
• The accelerated electron reaction has advantages such as preventing
the poisoning of the electrode surface due to adsorption, providing
biocatalysis and selective permeability.

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• Micro Electrodes; electrodes with an electrode diameter of less than
25 µm.
• It is used for analysis of micro-scale volume samples and examination
of microscopic fields.

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• In this method;
• It is very important to mix the solution so that the electrode surface
always remains clean.
• Because, as a result of reduction and oxidation events on the
electrode surface, new compounds are formed and they have the
possibility of accumulating on the electrode surface.
• It is best to clean the electrode surface after each scanning.

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VOLTAMMETRY

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• Many of the limitations of traditional linear-scan voltammetry were
overcome by the development of pulse methods.
• the two most important pulse techniques, differential- pulse
voltammetry and square-wave voltammetry are developped

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