ELECTRO ANALYTICAL CHEMISTRY

Electro analytical chemistry encompasses a group of quantitative analytical methods that

are based upon the electrical properties of a solution of the analyte when it is made part of an
electrochemical cell.
Electrochemistry is the study of electrochemical changes or the interconversion of energy
as electricity. Electrochemical changes is either 'chemical reaction is applied to convert chemical
energy of a reaction directly into electrical energy' or 'electrical energy is used to cause chemical
reaction'.
There are two types of reactions. The reaction in which the free energy change of a
spontaneous chemical reaction is converted into electrical energy is called galvanic reactions.
The reactions in which the electrical energy from an external source is used to bring about
chemical reaction is called electrolysis.
Electrochemical cell is a device in which an electrochemical change takes place in the
system. There are two fundamental types of electrochemical cells (i) galvanic cell (ii) electrolytic
cell.
 Electroanalytical techniques include a group of instrumental techniques like
potentiometry, voltammetry, conductometry, coulometry, electrogravimetry in all of
those techniques there is interaction of electricity with matter and in all the above
mentioned techniques we measure the electrochemical properties like potential, current,
charge etc with help of different instruments like potentiometer, pH meter,
conductometer, voltammeter etc,.
 The use of electrical measurements for analytical purposes has found large range of
applications including analytical, environmental monitoring, industrial quality control &
biomedical analysis.
Why Electroanalytical Chemistry?
 Electroanalytical methods have certain advantages over other analytical methods.
 Electrochemical analysis allows for the determination of different oxidation states of an
element in a solution, not just the total concentration of the element.
 Electroanalytical techniques are capable of producing exceptionally low detection limits
and an abundance of characterization information including chemical kinetics
information. The other important advantage is its low cost.
Electrochemical Cell
 Oxidation-reduction or redox reactions take place in electrochemical cells. There are two
types of electrochemical cells. Spontaneous reactions occur in galvanic (voltaic) cells;
nonspontaneous reactions occur in electrolytic cells. Both types of cells contain
electrodes where the oxidation and reduction reactions occur. Oxidation occurs at the
electrode termed the anode and reduction occurs at the electrode called the cathode.
Electrodes & Charge:
 The interface through which electricity is exchanged with electrolyte solution is called
electrode. There are two types of electrodes anode & cathode. The anode of an
electrolytic cell is positive (cathode is negative), since the anode attracts anions from the
solution. However, the anode of a galvanic cell is negatively charged, since the
spontaneous oxidation at the anode is the source of the cell's electrons or negative charge.
The cathode of a galvanic cell is its positive terminal. In both galvanic and electrolytic
cells, oxidation takes place at the anode and electrons flow from the anode to the cathode.
Galvanic cells:
The reaction in which the free energy change of a spontaneous chemical reaction is
converted into electrical energy is called galvanic cell.
eg: Daniel cell

In the Daniel cell, copper and zinc electrodes are

immersed in a solution of copper(II) sulfate and
zinc sulfate, respectively. At the anode (negative
electrode), zinc is oxidized as per the following
half reaction:
Zn(s) → Zn2+(aq) + 2e−.

At the cathode (positive electrode), copper is

reduced as per the following reaction:
Cu2+(aq) + 2e−→ Cu(s)
Overall reaction is
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
 When two electrodes of a cell are dipped into the solution of their respective ions, there
are excess of electrons at the anode due to oxidation process and a deficient of electrons at the
cathode due to reduction process. Thus, cathode or positive electrode is at higher potential where
as anode or negative electrode is at lower potential. hence, the existence of a potential difference
called EMF cause the conventional current to flow from cathode to anode of the cell in the
external circuit where as the electrons move in the external circuit from anode to cathode of a
galvanic cell.
Electrolytic Cells:

The redox reaction in an electrolytic cell is non spontaneous. Electrical energy is required to
induce the electrolysis reaction. An example of an electrolytic cell is shown below, in which
molten NaCl is electrolyzed to form liquid sodium and chlorine gas. The sodium ions migrate
toward the cathode, where they are reduced to sodium metal. Similarly, chloride ions migrate to
the anode and are oxided to form chlorine gas. This type of cell is used to produce sodium and
chlorine. The chlorine gas can be collected surrounding the cell. The sodium metal is less dense
than the molten salt and is removed as it floats to the top of the reaction container.
Conductometric titration
 The titrations in which end point is determined by means of conductance measurements
are called conductometric titration
Potentiometric titration
 The variation of potential of an electron with the concentration of ions with which it is in
equilibrium can be used as an indicator to find the end point in volumetric analysis is
known as potentiometry.
EMF
 The difference of potentials between the electrodes of a cell which causes flow of current
from an electrode of higher potential to another at lower potential is known as
electromotive force or EMF or cell potential .

Electrochemical sensors
 An electrochemical sensor is a device that transforms electrical information into an
analytical useful signal.
 Composed of two basic components, a chemical recognition system and physiochemical
transducer which is a device that converts the chemical response into a signal that can be
detected by modern electric instrumentations.
Electrogravimetry
 The goal is to determine the amount of analyte present by converting it to a product that
is weighed as a deposit on one of the electrode.
 In most applications, the metal is deposited on a weighed platinum cathode, and the
increase in mass is determined. Some methods use anodic deposition such as the
determination of lead as lead oxide on platinum and of chloride as silver chloride on
silver.
Coulometric titrations

 In coulometric procedures, we determine the amount of analyte by measuring the quantity of

electrical charge needed for complete conversion to a product.
 The quantity of electrical charge required to convert a sample of an analyte quantitatiively to a
different oxidation state is measured.
Voltametry and amperometry

 A group of electroanalytical methods in which we acquire information about the analyte

by measuring current in an electrochemical cell as a function of applied potential.

 We obtain this information under conditions that promote polarization of a small

indicator or working electrode. When current proportional to analyte concentration is
monitored at a fixed potential, the technique is called amperometry.

Polarography
It is a particular type of voltametry in that the working microelectrode takes the form of a
dropping mercury electrode.

CONDUCTOMETRY TITRATIONS
 The titration in which end point is determined by means of conductance measurements,
are called conductometric titrations.
 They are based upon the principle that the conductance of an electrolyte solution
depends upon the number of ions, their charges and mobilities.
 The conductance of the solution changes with every addition of the titrant.
 At the equivalent point, a sharp change in conductance is observed.
 The end point can be conveniently obtained by extrapolation of straight lines obtained by
plotting conductance against volume, and finding out the point of their intersection.
Common ion effect
 The common-ion effect refers to the decrease in ionization of a weak electrolyte by the
addition to the strong electrolyte with an ion in common with the weak electrolyte.
Hydrogen sulphide (H2S) is a weak electrolyte. It is weakly ionized in its aqueous solution.
There exists an equilibrium between un-ionized molecules and the ions in an aqueous medium as
follows:
H2S ⇌ H+ + HS−
To the above solution of H2S , if we add hydrochloric acid, then it ionizes completely as
HCl → H+ + Cl−
This makes H+ a common ion and creates a common ion effect. Due to the increase in
concentration of H+ ions, the equilibrium of dissociation of H2S shifts to the left .Thus the ionization
of H2S is decreased.