Electroanalytical Techniques

Electroanalytical techniques:
Electroanalytical methods are a class of techniques in analytical chemistry which study

an analyte by measuring the potential (volts) and/or current (amperes) in an electrochemical
cell containing the analyte.
Classification of electroanalytical methods:
The electroanalytical methods are divided into categories according to the

electric parameters that are measured. The major electroanalytical methods include
potentiometry, amperometry, conductometry, electrogravimetry, voltammetry (and
polarography), and coulometry. The names of the methods reflect the measured electric property
or its units.
1. Potentiometry: Potentiometry measures electric potential (or voltage) while maintaining

a constant (normally nearly zero) electric current between the electrodes.
2. Amperometry: Amperometry monitors electric current (amperes) while keeping the
potential constant.
3. Conductometry: Conductometry measures conductance (the ability of a solution to carry
an electric current) while a constant alternating-current (AC) potential is maintained
between the electrodes.
4. Electrogravimetry: Electrogravimetry is a gravimetric technique similar to the classical
gravimetric methods, in which the solid that is weighed is deposited on one of the
electrodes.
5. Voltammetry: Voltammetry is a technique in which the potential is varied in a regular
manner while the current is monitored. Polarography is a subtype of voltammetry that
utilizes a liquid metal electrode.
6. Coulometry: Coulometry is a method that monitors the quantity of electricity
(coulombs) that are consumed during an electrochemical reaction involving the analyte.
Electrochemistry:
Electrochemistry is the study of electricity and how it relates to chemical reactions. In

electrochemistry, electricity can be generated by movements of electrons from one element to
another in a reaction known as redox or oxidation-reduction reaction. OR
Electrochemistry is the study of chemical processes that cause electrons to move. This movement
of electrons is called electricity, which can be generated by movements of electrons from one
element to another in a reaction known as an oxidation-reduction ("redox") reaction.
Electrode:
An electrode by definition is a point where current enters and leaves the electrolyte. When the c
urrent leaves the electrodes it is known as the cathode and when the current enters it is known as
the anode. Electrodes are vital components of electrochemical cells. They transport produced ele
ctrons from one half-cell to another, which produce an electrical charge.
Electrode processes:
What processes are going on?
An electrode is a metal whose surface serves as the location where oxidation-reduction equilibriu
m is established between the metal and what is in the solution. The electrode can either be an ano
de or a cathode. An anode receives current or electrons from the electrolyte mixture, thus becomi
ng oxidized. When the atoms or molecules get close enough to the surface of the electrode,
electrolyte, donates electrons. This causes the atoms/molecules to become positive ions.
Since the reference electrode has a constant makeup, its potential is fixed. Therefore, any change
s in the cell are ascribable to the working electrode. We say that we observe or control the potent
ial of the working electrode with respect to the reference, and that is equivalent to observing or c
ontrolling the energy of the electrons within the working electrode. By driving the electrode to m
ore negative potentials (e.g., by connecting a battery or power supply to the cell with its negative
side attached to the working electrode), the energy of the electrons is raised. They can reach a lev
el high enough to transfer into vacant electronic states on species in the electrolyte. In that case, a
flow of electrons from electrode to solution (a reduction current) occurs (Figure a). Similarly, the
energy of the electrons can be lowered by imposing a more positive potential, and at some point
electrons on solutes in the electrolyte will find a more favourable energy on the electrode and wil
l transfer there. Their flow, from solution to electrode, is an oxidation current (Figure b).
What is an electrode made of?
An electrode has to be a good electrical conductor so it is usually a metal. Now what this metal is
made out of is dependent on whether or not it is involved in the reaction. Some reactions require
an inert electrode that does not participate. An example of this would be platinum in the SHE rea
ction(described later). While other reactions utilize solid forms of the reactants, making them the
electrodes. An example of this type of cell would be:
Cu(s)|Cu(NO3)2(aq) (0.1M)||AgNO3(aq) (0.1M)|Ag(s)
Cu(s)|Cu2+ (0.1M)||Ag+ (0.1M)|Ag(s)
(left side is the anode) (right side is cathode)
(In the above cell set up: the outside components are the electrodes for the reaction while the inn
er parts are the solutions they are immersed in)
Fundamentals of electrolysis
Electrochemical cells
An electrochemical cell is a device that can generate electrical energy from the chemical reaction
s occurring in it, or use the electrical energy supplied to it to facilitate chemical reactions in it. Th
ese devices are capable of converting chemical energy into electrical energy, or vice versa. A co
mmon example of an electrochemical cell is a standard 1.5-volt cell which is used to power man
y electrical appliances such as TV remotes and clocks.
Such cells capable of generating an electric current from the chemical reactions occurring in the
m care called Galvanic cells or Voltaic cells. Alternatively, the cells which cause chemical reacti
ons to occur in them when an electric current is passed through them are called electrolytic cells.
Electrochemical cells generally consist of a cathode and an anode. The key features of the cathod
e and the anode are tabulated below.
Cathode Anode
Electrons are consumed here Electrons are liberated here
A reduction reaction occurs in the cathode of an electr

An oxidation reaction occurs here
ochemical cell
Electrons move into the cathode Electrons move out of the anode
General convention dictates that the cathode must be represented on the right-hand side whereas
the anode is represented on the left-hand side while denoting an electrochemical cell.
Types of Electrochemical Cells

The two primary types of electrochemical cells are
1. Galvanic cells (also known as Voltaic cells)
2. Electrolytic cells
The key differences between Galvanic cells and electrolytic cells are tabulated below.
Galvanic Cell / Voltaic Cell Electrolytic Cell
Chemical energy is transformed into electrical e Electrical energy is transformed into chemical
nergy in these electrochemical cells. energy in these cells.
An input of energy is required for the redox re

The redox reactions that take place in these cells
actions to proceed in these cells, i.e. the reacti
are spontaneous in nature.
ons are non-spontaneous.
In these electrochemical cells, the anode is nega

These cells feature a positively charged anode
tively charged and the cathode is positively char
and a negatively charged cathode.
ged.
The electrons originate from the species that un Electrons originate from an external source (s
dergoes oxidation. uch as a battery).

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Electroanalytical techniques:

Electroanalytical methods are a class of techniques in analytical chemistry which study

Classification of electroanalytical methods:

The electroanalytical methods are divided into categories according to the

1. Potentiometry: Potentiometry measures electric potential (or voltage) while maintaining

Electrochemistry is the study of electricity and how it relates to chemical reactions. In

What processes are going on?

Cu(s)|Cu(NO3)2(aq) (0.1M)||AgNO3(aq) (0.1M)|Ag(s)

Cu(s)|Cu2+ (0.1M)||Ag+ (0.1M)|Ag(s)

(left side is the anode) (right side is cathode)

Electrons are consumed here Electrons are liberated here

A reduction reaction occurs in the cathode of an electr

Types of Electrochemical Cells

Galvanic Cell / Voltaic Cell Electrolytic Cell

An input of energy is required for the redox re

In these electrochemical cells, the anode is nega

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