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 Michael
founders of electrochemistry today. faraday

 The first germen physicist Otto von

Guericke created the electric
generater,which produced static
electricity by applying friction in the
john
machine. t Daniel
 The English scientist William Gilbert spen
17 years experimenting with magnetism
and to a lesser extent electricity.
 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.
 Orsted’s 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:
Mn 2+ 3+ –
(aq) + NaBiO3(s) → Bi (aq) + MnO 4 (aq)
 Oxidation:
4 H 2 O (l) + Mn2+ → MnO – + 8 H+ + 5 e–
(aq) 4 (aq) (aq)
 Reduction:
2 e– + 6 H + + BiO – → Bi3+ +3H O
(aq) 3 (s) (aq) 2 (l)

8 H 2 O (l) + 2 Mn2+ → 2 MnO – + 16 H + + 10 e–

(aq) 4 (aq) (aq)
10 e + 30 H
– + + 5 BiO – → 5 Bi 3+ + 15
HO
(aq) 3 (s) (aq) 2 (l)

 Reaction
14 H + + 2 balanced:
Mn2+ + 5 NaBiO → 7 H 2 O (l) + 2 MnO 4 – (a q ) + 5 Bi3+ (aq) +
(aq) (aq) 3(s)
5 Na+
 Basic medium
 Example of reaction between potassium permanganate and
sodium sulfite.
 Unbalanced reaction:
KMnO4 + Na2SO3 + H 2 O → MnO 2 + Na2SO4 + KOH
 Reduction:
3 e– + 2 H 2 O + MnO 4 – → MnO 2 + 4 OH –
 Oxidation:
2 OH – + SO32– → SO42– + H 2 O + 2 e–
 6 e– + 4 H 2 O + 2 MnO 4 – → 2 MnO 2 + 8 OH –
 6 OH – + 3 SO32– → 3 SO42– + 3 H 2 O + 6e –
 Equation balanced:
2 KMnO4 + 3 Na2SO3 + H 2 O → 2 MnO 2 + 3 Na2SO4 + 2 KOH
 Neutral medium
 Method to complete combustion of propane.
 Unbalanced reaction:
C3H8 + O 2 → CO2 + H 2 O
 Reduction:
4 H + + O 2 + 4 e– → 2
H2 O
 Oxidation:
6 H 2 O + C3H8 → 3 CO2 +
20 e– + 20 H +
20 H + + 5 O 2 + 20 e– →
10 H 2 O
6 H 2 O + C3H8 → 3 CO2 +
20 e– + 20 H +
 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
 2 H (aq)
+
+2e →H –
2
 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:
Cell d i a g r a m
Pt ( s ) | H 2 (1 a t m ) | H + (1 M ) || C u 2 + (1 M ) |
C u (s)
E° c e l l = E° r e d (cathode) – E° r e d ( a n o d e )
Gibbs free energy and cell
potential
 Though cell potential Cell and get electricity n
faraday
in the
cell: = - n F E cell
For standard cell, this equation can we
written
G
0
= -RTlnK=-nFE cell
0

 Though produce of electric energy converted

into electric work,
Wmax= Welectrical= -nFEcell
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 material’s ability to conduct an electric current.
 It is commonly represented by σ
 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.
Kohlrausch’s 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

Λ =v+ Λ +
0
m
0
+
vΛ 0
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
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

DowRnea’sctcioenlslt.hat t a k e pl a c e at D o w n ' s cell a re the

foal tl how
C o di en g(reduction):
A n o d e (oxidation):
2 N a + (l) + 22Cel–– →
→ 2ClN2 (ag(l)
) + 2 e
–

Ov e ra l l reaction: 2 N a + + 2 C l – (l) → 2 N a(l) + C l 2 (g )

 This process can yield large amounts of metallic

sodium and gaseous chlorine, and widely used
on mineral dressing and metallurgy industries.
Quantitative electrolysis and Faraday’s
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.
m=
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
Semiconductor’s 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