ELECTROCHEMISTRY

• Electrochemistry is the branch of science which deals with the

interconversions of chemical energy into electrical energy and vice
versa.
•
• Cells are of two types.
• Electrolytic cells
– It is a device which converts electrical energy into chemical energy.
– Non – spontaneous reactions take place.
– Example: Electrolysis of molten NaCl
• Electrochemical cell or Galvanic or Voltaic cells
– It is a device which converts chemical energy into electrical energy.
– The reactions are spontaneous.
– It involves redox reactions.
– Oxidation means loss of electrons and Reduction means gain of
electrons.
– Oxidation takes place at anode and reduction takes place at cathode.
 ELECTROCHEMICAL CELL OR GALVANIC OR VOLTAIC CELLS
• It is an electrochemical cell that converts chemical
energy into electrical energy by spontaneous redox
reaction within the cell.
• It generally consists of two different metals
connected by a salt bridge.
• Example: Daniel cell.
• It consists of two half cells i.e., one half-cell contains
a zinc metal electrode dipped in ZnSO4 solution and
other half-cell contains a copper metal electrode
dipped in CuSO4 solution.
 ELECTROCHEMICAL CELL OR GALVANIC OR VOLTAIC CELLS

• These two half cells are separated by a salt

bridge, and two electrodes are joined by wire.
ELECTROCHEMICAL CELL OR GALVANIC OR VOLTAIC CELLS
 Representation of a galvanic cell
• Galvanic cell is represented as follows:
• The anode half-cell is written on left hand side
and the cathode half-cell is written on right
hand side.
• The salt bridge is represented by two vertical
lines, separating the two half- cells.
• Galvanic cell:Zn/ Zn+2(1M)// Cu+2(1M)/Cu
 Electromotive force (EMF)
• The flow of electrons from one electrode to another
electrode is due to difference in electrode potential.
• The difference between two electrode potentials is
known as electromotive force of electrochemical cell.
• Where

• ECell - e.m.fof cell

• Eright - electrode potential of right-hand side electrode
• Eleft - electrode potential of left-hand side electrode.
 Electrode Potential

• Electrode potential is the tendency of metal

electrode to lose or gain electrons when it is
contact with its own ion solution. It is
represented by E.
• Electrode potentials are of two types.
• Oxidation Potential: It shows the tendency of
metal to lose electrons.
– Reduction Potential: It shows the tendency of metal to gain
electrons.
 Electrode Potential
– Reduction Potential:
– It shows the tendency of metal to gain electrons.
– For a metal both potentials have the same
numerical value with opposite signs.
• Standard electrode potential is the electrode potential
measured at standard conditions i.e at 298K and 1M
concentration of the electrolyte and 1atmosphere pressure. It
is represented by E0.
NERNST EQUATION (EXPRESSION FOR ELECTRODE POTENTIAL):

• Nernst equation gives the relationship

between the electrode potential and the
concentration of the electrolyte solutions.
• Consider a general redox reaction.
 Electrode Potential
• For a reversible reaction, free energy change
and equilibrium constant are related as

• Van’t Hoff’s equation ------ (1)

• Where ΔG is free energy change,
• ΔGo is standard free energy change,
• R is Gas Constant
• T is temperature
 Electrode Potential
• In a reversible reaction, the free energy
change is equal to its electrical energy
produced.
•
• And ------- (2)
• Where E is the electrode potential,
• Eo is the standard electrode potential,
• F is Faraday
Electrode Potential
 Significance:

• It is used for the determination of electrode

potential.
• Electrode potential depends on
• a) Concentration of ions b) Temperature
and c) Nature of the electrode
POTENTIOMETRY: POTENTIOMETRIC
TITRATIONS

• Potentiometry:
Potentiometry is a technique that is used in analytical chemistry,
usually to find the concentration of a solute in solution.

• Potentiometric Titration: The titration in which the equivalence or

end point of a reaction is determined with the help of measurement
of the electrode potentials is known as Potentiometric titrations.
• In this titration, there are two electrodes
• 1. Reference electrode 2. Indicator electrode
• For all titrations, Reference electrode is calomel electrode and
Indicator electrode may be different
POTENTIOMETRY: POTENTIOMETRIC
TITRATIONS
 POTENTIOMETRY: POTENTIOMETRIC TITRATIONS

Redox titrations:
• The emf of the electrode is determined by the activity
of the ratio of the substance being oxidized or reduced.
• Example for redox titration is titration between Fe 2+ ions
and K2Cr2O7.
• Ferrous solution is taken in the beaker and treated with
dil. H2SO4.
• Platinum and Calomel electrodes are dipped into the
solution, and they are connected to the potentiometer.
• A known volume of K2Cr2O7 solution is added from the
burette, stirred thoroughly and EMF of the cell is
recorded.
EMF of the cell increases with the decrease in
the concentration of Fe+2 ions in the solution.
The volume of K2Cr2O7 added is plotted against
EMF.
The steepest portions of the curve indicate the
equivalence point of the titration.
 Acid – base titrations:

• The acid solution is taken in a beaker and the Glass electrode

and Calomel electrode were dipped in the solution.
• The electrodes are connected to a potentiometer and the
EMF is measured.
• A known volume of standard alkali solution is added from the
burette, stirred thoroughly and EMF of the cell is recorded.
• EMF of the cell decreases with the increase in
the pH of the solution.
• The volume of alkali added is plotted against
EMF.
• The steepest portions of the curve indicate
the equivalence point of the titration.
 Advantages:
• Potentiometric titrations are also used for the
colored solutions where the use of indicator is
impossible.
• These are also used for precipitation titrations.
• Polybasic acids can also be titrated.
• All kinds of acid base titrations to be done
without using indicators(pH based).
• No need for the use of external indicators.
 CONCEPT OF CONDUCTIVITY
• Conductance (C):
• It is the ability of a substance to conduct electricity. It is the
reciprocal of resistance.
• Therefore, conductance
• Units: Ohm-1
•
• Specific Conductance ():
• It is the conductance of a material or solution occupying
one cm3 volume.

• Equivalent Conductance ( or ):

• The conductance of a solution containing one gram
equivalent of substance is known as equivalent
conductance.
• Molar Conductance (m or):
• The conductance of a solution containing one
mole of substance is known as molar
conductance.
 CONDUCTIVITY CELL

• A conductivity cell is a key component in

conductometry analysis, which is a device used to
measure the conductivity of a solution.
• The conductivity cell plays a crucial role in
facilitating the measurement of electrical
conductivity.
• Conductivity cells are constructed with a glass
tube which contains two platinum electrodes
coated with fine platinum powder.
CONDUCTIVITY CELL
• If the distance between two electrodes is ‘l’
and the area of cross section of electrodes is
‘a’ and the cell constant of the cell is given by
» Cell constant =1/a

• If the cell constant of the cell is known, then

the conductivity cell is used to determine the
conductivity of any solution.
 Advantages:

• Accuracy
• easy cleaning
• corrosion resistance
• affordable price
 CONDUCTOMETRIC TITRATIONS
• The titrations in which the equivalence point
or end point is determined with the help of
conductivity measurement are known as
Conductometric titrations.
• Procedure:
• A solution (titrant) is added from the burette
into a known volume of another solution
(titrate) taken in a beaker containing a
conductivity cell placed in a thermostat to
keep constant temperature.
 CONDUCTOMETRIC TITRATIONS
• The conductivity readings are taken after each
addition.
• When a titrant is added to a solution of titrate,
some ions of titrate are replaced by titrant,
causing change in conductance of the resulting
solution.
• The conductivity readings after each addition are
plotted against the volume of titrant added; two
linear curves are obtained; the intersection of the
curves gives an end point.
 Acid-base titrations:
• Conductometric titrations give excellent
results for acid – base titrations, because of
fast moving H+ ion and OH- ions.
• Strong acids and strong bases are highly
ionizable and give fast moving ions, hence
conductivity is more.
• Weak acids and Weak bases are poorly
ionizable and give slowly moving ions, hence
conductivity is less.
 Acid-base titrations:
• Weak acid or weak base gives strong
conjugate base or conjugate acid respectively.
• Strong conjugate acid or strong conjugate
base are also highly ionizable.
Strong Acid – Strong Base titrations
 Strong Acid – Strong Base titrations

• When HCl is titrated against NaOH, initial

conductivity of HCl is high due to HCl being
strong acid which gives fast moving H+ ions.
• By the addition of NaOH to HCl solution, some
of the fast-moving H+ ions are neutralized by
the OH- ions.
 Strong Acid – Strong Base titrations
• Hence the conductivity keeps on decreasing
until all H+ ions are neutralized by OH- ions.
• After the end point, conductivity increases by
the addition of NaOH due to fast moving OH-
ions.
Strong Acid – Strong Base titrations
Strong Acid – Weak Base titrations:
 Strong Acid – Weak Base titrations:

• When HCl is titrated against NH4OH, initial

conductivity of HCl is high due to HCl being
strong acid which gives fast moving H+ ions.
• By the addition of NH4OH to HCl solution,
some of the fast-moving H+ ions are
neutralized by the OH- ions.
 Strong Acid – Weak Base titrations:

• Hence the conductivity keeps on decreasing

until all H+ ions are neutralized by OH- ions.
• After the end point, conductivity remains
constant by the addition of NH4OH due to the
poor dissociation NH4OH.
Strong Acid – Weak Base titrations
Weak acid – strong base titrations
Weak acid – strong base titrations
• When CH3COOH is titrated against NaOH, initially
the conductivity of the solution is low because of
its poor dissociation.
• By the addition of NaOH, conductivity increases
slowly due to the formation of a strong conjugate
base called sodium acetate (CH3COONa).
• After the end point, conductivity increases by the
addition of NaOH due to fast moving OH - ions.
Weak acid – strong base titrations
Weak acid – weak base titrations
 Weak acid – weak base titrations
• When CH3COOH is titrated against NH4OH,
initially the conductivity of the solution is low
because of its poor dissociation.
• By the addition of NH4OH, conductivity increases
slowly due to the formation of a strong conjugate
base called sodium acetate (CH3COONH4).
• After the end point, conductivity remains
constant by the addition of NH4OH due to the
poor dissociation NH4OH.
Weak acid – weak base titrations
 Electrochemical Sensors

• Sensor
• A sensor is a device that detect events or
changes in quantities and provide a
corresponding output.
• The output is usually an electrical or an optical
signal
Electrochemical Sensors
Electrochemical Sensors
 Electrochemical Sensors
• Example
• A mercury thermometer convers the
measured temperature in to expansion and
contraction of a liquid which can be visualized
on the calibrated glass tube.
Electrochemical Sensors
 Electro chemical sensor

• Sensor which transforms the effect of the

electrochemical interaction analyte-electrode
into a useful signal are known as
electrochemical sensor.
 Electro chemical sensor

• Electrochemical sensors detect

the electrochemical reactions and measures
by using electrodes which is due to the
interaction between the sensing surface and
the analytes thereby converts this responsive
information to qualitative and quantitative
electric signals
Electro chemical sensor
 Electro chemical sensor
• Electrochemical sensors are
• Potentiometric sensor-potential is
measures(reference electrode and working
electrode)
• Amperometric sensors-current is measures
•
 Potentiometric sensors
• Potentiometric sensor is a type of
electrochemical sensor that may be used to
measure potential difference of an electrode.
 Potentiometric sensors
• The signal is measured as the potential difference
(voltage)between the working electrodes and the
reference electrode.
• The working electrode’s potential must depend
on the concentration of the analyte in the
solution or gas phase.
• In the potentiometric sensor the ion-selective
electrode is coupled with reference electrode to
complete the circuit and the sensor measure the
potential difference between two electrodes.
•
 Example
• Potentiometric sensor used in analysis of
glucose in blood
• Glucose undergo decomposition and gives H+
ions which is detected by PH electrode
• A potential difference is setup between glass
electrode and reference electrode which is
sense by potentiometric sensor which analyze
the glucose level in blood
Potentiometric sensors
 Examples:

• Ion-Selective Electrodes (ISE).

• Screen-Printed Electrodes.
• Ion-Selective Field Effect Transistors (ISFET).
• Solid-State devices
• Chemically modified electrodes (using, e.g.,
metal oxides or electrodeposited polymers as
sensitive layers).
 Applications:

• These are commonly used in various areas such

as
– Process Control Analysis
– Environmental Analysis
– Industrial Analysis
– Agricultural Analysis
– Medicinal Drug Analysis
– Water Analysis
– Health Monitoring
– Determination of Various Different Organic or
Inorganic Ions
 Applications:
• Potentiometric sensors are used for the determination of
drug molecules in biological samples.
• To find the concentration of a solute in solution.
• Nano materials play an important role in the fabrication
of chemosensors and biosensors
• The potentiometer is used in radio and television (TV)
receiver for volume control, tone control and linearity
control.
• The potentiometer is used in medical equipment .
 Amperometric Sensors

•
• Amperometric sensors are sensitive analytical
systems that measure current as a result of an
electroactive substance losing (oxidation) or
gaining (reduction) an electron while
undergoing an electrochemical reaction.
Amperometric Sensors
Amperometric Sensors
Amperometric Sensors
 Applications:

• The Amperometric devices continuously measure current

resulting from the oxidation or reduction of an
electroactive species in a biochemical reaction.
• The Amperometric sensor are used in
– Clinical diagnosis
– environmental monitoring
– Industrial applications
– food safety and quality
– bioanalysis
– ensure proper pressure levels
• Electrochemical sensors offer useful information needed
for precision agriculture such as pH and soil nutrient
content.
 Advantages of electrochemical sensors:

• Cheap to manufacture
• Simple to use
• Good sensitivity
• Good selectivity
• Robust design
 CELLS (OR) BATTERIES

• A cell is a device in which chemical energy is

converted into electrical energy.
• Many cells connected in series are called
batteries.
• Cells are of three types.
• Primary cells
• Secondary cells
• Fuel cells
 PRIMARY CELLS
•
• Cells in which electricity is continuously generated till
all the reactants are converted into products.
• These reactions are irreversible.
• Hence the cell becomes dead after the conversion of
reactants into products. Such cells cannot be charged.
 SECONDARY CELLS

• Secondary cells may be used through many

cycles of discharging and charging.
• Cell reactions are reversible.
• As and when required the cell can be discharged and
charged.
 ZINC –AIR BATTERIES

• Zinc air cells are composed of three parts Zinc

metal as anode, an air electrode as cathode and
an electrolyte KOH/NaOH.
• During discharge process, zinc oxidizes to zinc
ions and the reduction of oxygen to hydroxyl
ions.
• The hydroxyl ions migrate from the air cathode
to zinc anode to complete the cell reaction.
ZINC –AIR BATTERIES
ZINC –AIR BATTERIES
 Applications:

• A very small battery used in hearing aids.

• Larger batteries are used in cameras.
• A very large battery used in electric vehicles.
 LITHIUM ION BATTERY
• A lithium-Ion battery is a rechargeable
portable battery.
• In these cells, the electrodes are made up of
lithium cobalt oxide and graphite respectively
and electrolyte is either LiBF4 or LiClO4 or
LiPF6.
 LITHIUM ION BATTERY
• In these cells, oxidation and reduction
reactions do not take place, but transport of
Li+ ions from one electrode to another
electrode through the electrolyte.
• In this battery, lithium ions interchange
between two layers of graphite and LiCoO2.
LITHIUM ION BATTERY
 LITHIUM ION BATTERY
• During the charging process, lithium ions
move from LiCoO2 to graphite (C6).
• During the discharging process, lithium ions
leave move back from graphite to LiCoO2
• Thus, charging and discharging cycle is simply
migration of Li+ ions from one electrode to
another electrode with flow of electrons
through the external circuit.
 Applications:

• These are used in

• electronic devices like cameras, cell phones
• military
• space
• medical devices
 Advantages:

• It generates higher voltage than other types of

cells.
• These are less toxic and recycled.
 FUEL CELLS

• A fuel cell is an electrochemical cell which converts

chemical energy into electrical energy by available
oxidant.
• The fuel and oxidizing agents are continuously supplied
to the electrodes of the cell, at which they undergo
reactions.
• Fuel cells can supply current as long as reactants are
supplied.
• Fuel cells are characterized by
– High efficiency
– Low noise
– Free from vibration and pollution
 HYDROGEN – OXYGEN FUEL CELL

• Construction:
• Electrodes are made of two porous graphite
rods impregnated with fine powder of Pt or an
alloy of Pb with Ag or Ni.
• Electrolyte solution 2.5% KOH.
• H2 gas is passed through the anode and O2 gas
is passed through the cathode.
HYDROGEN – OXYGEN FUEL CELL
HYDROGEN – OXYGEN FUEL CELL
HYDROGEN – OXYGEN FUEL CELL
– The product discharged in water and the standard EMF of the
cell is Eo = 1.23V.
– A few such fuel cells are stacked together in series to make a
battery.
 Applications:

• They are used as auxiliary energy sources in

space vehicles, submarines etc.

• Because of light weight and pure drinking

water formation, they are highly useful in
space crafts.
 Advantages:

• The efficiency is high.

• Drinking water is produced for astronauts.
• No noise and thermal pollution.
• Maintenance cost is low.
 Disadvantages:

• The lifetime of fuel cells is not known accurately.

• Initial cost is high.

• The distribution of H2 is not proper.

 POLYMER ELECTROLYTE MEMBRANE FUEL CELLS ( PEMFC)

• A polymer electrode is a polymer matrix

capable of ion conduction by the movement
of charge between the anode and cathode.

• These cells contain three components, two

electrodes and a conductive electrolyte.
 POLYMER ELECTROLYTE MEMBRANE FUEL CELLS ( PEMFC)

• The electrodes are made up of platinum or

platinum alloy.

• The electrolyte is proton exchange polymer

membranes like Polyether ketones, Polyether
sulphones or Nafion (a copolymer of poly
tetra fluoro ethylene and poly sulfonyl
fluoride vinyl ester).
 POLYMER ELECTROLYTE MEMBRANE FUEL CELLS
( PEMFC)

• These are the electrochemical cells which

convert the chemical energy of fuel directly
into electrical energy.
• H2 gas is passed through the anode and O2 gas
is passed through the cathode.
POLYMER ELECTROLYTE MEMBRANE FUEL CELLS
( PEMFC)
POLYMER ELECTROLYTE MEMBRANE FUEL CELLS
( PEMFC)
 Advantages:

• Ecofriendly

• Low operating temperature

• Easy and safe to handle.

 Disadvantages:

• Expensive

• Applications:
• It is used in transportation.

• These are also used in stationary and portable

power generation.
 Question Bank

• What is meant by electrochemical cell? Derive an expression for the

measurement of electrode potential.

• What is potentiometric titration? Explain redox titration by using

potentiometry.

• What is conductometric titration? Explain acid base titration by

using conductometry.

• Define electro chemical sensor? Explain potentiometric sensors

with examples

• Explain amperometric sensors with examples.

 Question Bank

• Give an account of the construction, chemical reactions involved, merits and applications of
Lithium-ion batteries.

• Give an account of the construction, chemical reactions involved, merits and applications hydrogen
oxygen fuel cell.

• Give an account of the construction, chemical reactions involved, merits and applications of
polymer electrolyte membrane fuel cell.

• Give an account of the construction, chemical reactions involved, merits and applications of Zinc
air battery.

• Two halfreactions with E0 values are given below

• (i) Fe3+ +e– →Fe2+ ;E0 =+0.77V

(ii) Fe2+ +2e– →Fe;E0 =–0.44V
• The standard potential for the cell reaction 2Fe 3+ + Fe → 3Fe2+ will be.
 Question Bank

• Calculate the e.m.f of the following reactions at 250C

• Cu++ +Zn⇋Zn++ +Cu
• E0Zn(ox)=0.763V
• E0Cu(ox)=-0.337V.

• The potential of the cell Zn|Zn++(1M)||Cu++(0.1M)|

Cu at 250C is 1.1V calculate the potential of cell Zn|Zn+
+(0.5M)||Cu++(0.1M)|Cu at same temperature.