ELECTROCHEMISTRY

BY
PRATIK
SUDRA

What is electrochemistry?
Electrochemistry is the study of

chemical reactions which take

place at the interface of an
electrode usually a solid, metal
or semiconductor and an ionic
conductor , the electrolyte.
Electrochemistry deals with the
interaction between electrical
energy and chemical change.

History of
electrochemistry
English chemist john Daniel and

physicist Michael faraday both credited

as founders of electrochemistry today.
The first germen physicist Otto von
Guericke created the electric
generater,which produced static
electricity by applying friction in the
machine.
The English scientist William Gilbert
spent 17 years experimenting with
magnetism and to a lesser extent
electricity.

Michael
faraday

john
Daniel

The french chemist charles francois de

cisternry du fay had discovered two types of

static electricity.
William Nicholson and Johann Wilhelm Ritter
succeeded in decomposing water into
hydrogen and oxygen by electrolysis.
Ritter discovered the process of
electroplating.
William Hyde Wollaston made improvements
to the galvanic cells.
Orsteds discovery of the magnetic effect of
electrical currents and further work on
electromagnetism to others.

Michael Faraday's experiments led him to

state his two laws of electrochemistry and

john Daniel invented primary cells.
Paul Heroult and Charles M.Hall developed an
efficient method to obtain aluminum using
electrolysis of molten alumina.
Nernst developed the theory of the
electromotive force and his equation known as
Nernst equation, which related the voltages of
a cell to its properties.
Quantum electrochemistry was developed by
Revaz dogonadeze and his pupils.

Oxidation-Reduction
The term redox stands for reduction-oxidation
It refers to electrochemical processes

involving electron transfer to or from a

molecule or iron changing its states.
The atom or molecule which loses electrons is
known as the reducing agent.
The substance which accepts the electrons is
called the oxidizing agent.

Balancing redox
reactions
Acidic medium
Example of manganese reacts with sodium bismuthate
Unbalanced reaction:

Mn2+(aq) + NaBiO3(s) Bi3+(aq) + MnO4(aq)

Oxidation:

4 H2O(l) + Mn2+(aq) MnO4(aq) + 8 H+(aq)

+ 5 e
Reduction:
2 e + 6 H+(aq) + BiO3(s) Bi3+(aq) + 3
H2O(l)
8 H2O(l) + 2 Mn2+(aq) 2 MnO4(aq) + 16 H+(aq) + 10 e
10 e + 30 H+(aq) + 5 BiO3(s) 5 Bi3+(aq) + 15 H2O(l)
Reaction balanced:

14 H+

+ 2 Mn2+

+ 5 NaBiO

7 H O + 2 MnO

+5

 Basic medium
Example of reaction between potassium permanganate

and sodium sulfite.

Unbalanced reaction:
KMnO4 + Na2SO3 + H2O MnO2 + Na2SO4 + KOH
Reduction:
3 e + 2 H2O + MnO4 MnO2 + 4 OH
Oxidation:
2 OH + SO32 SO42 + H2O + 2 e
6 e + 4 H2O + 2 MnO4 2 MnO2 + 8 OH
6 OH + 3 SO32 3 SO42 + 3 H2O + 6e
Equation balanced:
2 KMnO4 + 3 Na2SO3 + H2O 2 MnO2 + 3
Na2SO4 + 2 KOH

Neutral medium
Method to complete combustion of propane.
Unbalanced reaction:

C3H8 + O2 CO2 + H2O

Reduction:
4 H + + O2 + 4 e 2 H 2 O
Oxidation:
6 H2O + C3H8 3 CO2 + 20 e + 20 H+
20 H+ + 5 O2 + 20 e 10 H2O
6 H2O + C3H8 3 CO2 + 20 e + 20 H+
Equation balanced:
C3H8 + 5 O2 3 CO2 + 4 H2O

Standard electrode
potential
To allow prediction of the cell potential,

tabulations of standard electrode potential are

available.
Tabulations are referenced to the standard
hydrogen electrode.
The standard hydrogen electrode undergoes the
reaction

 Standard electrode potentials are usually

tabulated as reduction potentials.

The reactions are reversible and the role of
particular electrode in a cell depends on the
relative oxi./red. Potential of both electrodes.
The cell potential is then calculated as the
sum of reduction potential for cathode and
the oxidation potential for anode.
For example, the standard electrode
potential for a copper electrode is:

Gibbs free energy and cell potential

Though cell potential Cell and get electricity

n faraday in the cell:

For standard cell, this equation can we written
Though produce of electric energy converted

into electric work,

Electrical resistivity
It is an intrinsic property that quantities how

strongly a given material opposes the flow of

electrical current.
Many resistors and conductors have a uniform
cross section with a uniform flow of electric
current and made of one material
The electrical resistivity defined

Electrical conductivity
The reciprocal of electrical resistivity, and

measures a materials ability to conduct an

electric current.
It is commonly represented by
Conductivity is defined as

Conductivity SI units of Siemens per meter.

Molar conductivity
Molar conductivity is defined as the

conductivity of an electrolyte solution divided

by the molar concentration of the electrolyte,
and so measures the efficiency with which a
given electrolyte conducts electricity in
solution.
From definition, the molar conductivity

 Two cases should be distinguished:

Strong eletrolyte and weak electrolyte
For strong electrolyte
Salts, strong acids and strong bases, the

molar conductivity depends only weakly on

concentration.

For weak electrolyte

The molar conductivity strongly depends on

concentration.
The more dilute a solution, the greater its
molar conductivity, due to increased ionic
dissociation.
For weak electrolyte obeys Oswald's dilulation
law.

Kohlrauschs law of independent

migration of ions
High accuracy in dilute solutions, molar

conductivity is composed of individual

contributions of ions.
Limiting conductivity of anions and cations are
additive, the conductivity of a solution of a
salt is equal to the sum of conductivity
contributions from the cation and anion

Battery
Many types of battery have been

commercialized and represent an important

practical application of electrochemistry.
Early wet cells powered the first telegraph and
telephone systems, and were the source of
current for electroplating.
The zinc-manganese dioxide dry cell was the
first portable, non-spill able battery type that
made flashlights and other portable devices
practical.

 The mercury battery using zinc and mercuric

oxude provided higher levels of power and

capacity than the original dry cell for early
electronic devices.
Lead-acid battery was secondary battery.
The electrochemical reaction that produced
current was reversible, allowing electrical
energy and chemical energy to be
interchanged as needed.
Lead-acid cells continue to be widely used in
automobiles.

 The lithium battery, which does not use water

in the electrolyte, provides improved

performance over other types.
Rechargeable lithium ion battery is an
essential part of many mobile devices.

Corrosion
Corrosion is the term applied to steel rust

caused by an electrochemical process.

Corrosion of iron in the form of reddish rust,
black tarnish on silver, red or green may be
appear on copper and its alloys, such as
brass.

Prevention of corrosion
Coating
Metals can be coated with paint or other less

conductive metals.
This prevents the metal surface from being
exposed to electrolytes.
Scratches exposing the metal substrate will
result in corrosion.

 Sacrificial anodes
The method commonly used to protect a

structural metal is to attach a metal which is

more anodic than the metal to be protected.
This forces the structural metal to be catholic
thus spared corrosion. it is called sacrificial.
Zinc bars are attached to various locations on
steel ship hulls to render the ship hull catholic.
Other metal used magnesium.

Electrolysis
The spontaneous redox

reactions of a conventional
battery produce electricity
through the different
chemical potentials of the
cathode and anode in the
electrolyte.
Electrolysis requires an
external source of electrical
energy to include a chemical
reaction , and this process
takes place in a compartment
called an electrolytic cell.

Electrolysis of molten
sodium
chlorine
When molten, the salt sodium chloride can
be electrolyzed to yield metallic sodium
and gaseous chlorine.
This process takes place in a special cell
named Downs cell.

This process can yield large amounts of

metallic sodium and gaseous chlorine, and

widely used on mineral dressing and
metallurgy industries.

Quantitative electrolysis and Faradays

law
Quantitative aspects of electrolysis were

originally developed by Michel faraday .

Faraday is also credited to have coined the
terms electrolyte.
Electrolysis among many others while
studying analysis of electrochemical reactions.
Faraday advocate of the law of conservation

of energy.

First law
The mass of products yielded on the electrodes

was proportional to the the value of current

supplied to the cell, the length of time the current
existed, and the molar mass of the substance
analyzed.
The amount of substance deposited on each
electrode of an electrolytic cell is directly
proportional to the quantity of electricity passed
through the cell.

Second law
The amounts of bodies which are equivalent

to each other in the ordinary chemical action

have equal quantities of of electricity naturally
associated with them.
The quantities of different elements deposited
by a given amount of electricity are in the
ratio of the chemical equivalent weights

Applied aspects of electrochemistry

Industrial electrolytic processes
Electrochemical Reactors
Batteries
Fuel cells
Some Electrochemical Devices
Electrochemical Methods of Analysis

Branch of
electrochemistry
Photo electrochemistry
It is subfield of study within physical

chemistry.
The interest in this domain is high in the
context of development of renewable energy
conversion and storage technology.
The effects of luminous radiation on the
properties of electrodes and on
electrochemical reactions are the subject of
photo electrochemistry

Semiconductors electrochemistry
Semiconductor material has a band gap and

generates a pair of electron and hole per

absorbed photon if the energy of the photon is
higher than the band gap of the semiconductor.
This property of semiconductor materials has
been successfully used to converted solar energy
into electrical energy by photovoltaic devices.
Semiconductor-electrolyte interface
When a semiconductor comes into contact with a
liquid, to maintain electrostatic equillibrium
There will be a charge transfer between the
semiconductor and liquid phase,if formal redox
potential of redox species lies inside
semiconductor band gap.

 At thermodynamic eqilibrium, the fermi level of

semiconductor and the formal redox potential of

redox species and between interface
semiconductor.
This introduce n-type semiconductor and p-type
semiconductor.
This semiconductor used as photovoltaic device
similar to solid state p-n junction devices.
Both n and p type semiconductor can used as
photovoltaic devices to convert solar energy into
electrical energy and are called photoelectrical
cells

Boielectrochemistry
It is branch of electrochemistry and

biophysical chemistry concerned with topics

like cell electron-proton transport, cell
membrane potentials and electrode reactions
of redo enzymes.
Bioelectrochemistry is a science at the many
junctions of sciences.

Nanoelectrochemistry
Nanoelectrochemistry is a branch of

electrochemistry that investigates the electrical

and electrochemical properties of materials at
the nanometer size regime.
Nanoelectrochemistry plays significant role in
the fabrication of various sensors, and devices
for detecting molecules at very law
concentrations.

 The term electrochemical nanostructuring can

be used to mean different things.

This term is employed to refer to generation at
will of nanostructure on electrode surface,
involving a given positioning with a certain
precision
The term nanostructure is used to describe the
generation of nanometric patterns with move or
less narrow size distribution and a periodic or
random ordering on the surface.
But without control on the spatial location of
the nanostructure.

Application of electrochemistry
There are various extremely important

electrochemical processes in both nature and

industry.
The coating of objects with metals or metal
oxides through electro deposition and the
detection of alcohol in drunken drivers through
the redox reaction of ethanol.
Diabetes blood sugar meters measure the
amount of glucose in the blood through its redox
potential.

 The generation of chemical energy through

photosynthesis in inherently an electrochemical

process.
Production of metals like aluminium and titanium
from their ores.
For Photo electrochemistry
Artificial photosynthesis
Regenerative cell or Dye-sensitized cell
Photo electrochemical splitting of water

For Boielectrochemistry
Some of different experimental techniques

that can be used to study bioelectrochemical

problems.
Ampermetic of biosensors
Biofuel cells
Bioelectrosynthesis

Thank

you