Unit-II

Electrochemical Energy Systems

Introduction, Electrode potential, Std Electrode Potential

-Origin of single electrode potential,
Galvanic Cell, -Signs and Conventions.
Nernst Equation and numerical problems.
Applications of Nernst Equation
-Potentiometric titrations, pH determination
Types of electrodes
Calomel electrode, Glass electrode
Determination of pH

Battery Technology
Classification, LiCoO2 battery

Fuel cells
Methanol-Oxygen Fuel cell
 content
• History
• Galvanic cell
• Representation of galvanic cell
• Types of galvanic cell
• Daniell cell
• Concentration cell
• Nerst Equation
 HISTORY....
Animal electricity

Luigi Galvani
Luigi Galvani discovered when copper and zinc were
connected together and then both touched to different parts
of a nerve of a frog leg at the same time, they made the leg
contract. He called it “Animal electricity”.
 VOLTAIC CELL

• The voltaic pile, invented by Alessandro Volta in the 1800s, consists

of a pile of cells similar to the galvanic cell. However, Volta built it
entirely out of non-biological material in order to challenge
Galvani's ‘animal electricity’ theory in favour of his own ‘metal-
metal contact electricity theory’.
THE LATER CELLS

•In 1836, John Frederich Daniel

invented the Daniel Cell.
•It consisted of a copper pot
filled with a copper
sulphate solution, in which
was immersed an unglazed
earthenware container filled Daniel Cell
with sulphuric acid and a zinc
electrode.

•Provided a voltage of roughly 1.1 volts.

• “Redox” reactions involve electron transfer from
one species to another
• Ox1 + Red2 → Red1 + Ox2
• Ox1 + ne- → Red1 (Reduction ½ reaction)
• Red2 → Ox2 + ne- (Oxidation ½ reaction)
• “Reducing agent” donates electrons (is oxidezed)
• “Oxidizing agent” accepts electrons (is reduced)
 Potential difference concept
• In an electrode , a metal
has tendency to either
undergo oxidation or
reduction which results in
formation of Helmholtz
electric double layer.
• Potential difference
developed at the interface
itself is known as electrode
potential.
“the potential developed at the interface between the metal and solution,
when it is in contact with a solution of its own ions”—”E”
SINGLE ELECTRODE POTENTIAL (E):
It can be defined as “the potential developed at the interface between the metal and
solution, when it is in contact with a solution of its own ions”

STANDARD ELECTRODE POTENTIAL (Eo):

“Standard electrode potential is the electrode potential when the electrode is in contact with
a solution of unit concentration; at 298K. If the electrode involves a gas then the gas at one
atmosphere pressure”
If the electrode system involves gaseous substances, they must be passed at a partial
pressure of one atmosphere.

EMF OF THE CELL (ECell):

“Emf is the potential difference between the two electrodes of a galvanic cell which causes
the flow of current from one electrode to other”
The cell potential is said to be large, when a given number of electrons travelling between
the electrodes can do a large amount of work. When the cell potential is small, the same
number of electrons can do only a small amount of work. The cell potential becomes zero,
when the overall cell reaction is at equilibrium and subsequently the cell can do no work.
EMF of a cell is the difference in the single electrode potentials of the two electrodes
constituting the cell.
Ecell = Ecathode- Eanode
or Ecell = ERight electrode – ELeft electrode
Eo cell = Eo cathode- Eo anode
 Standard Electrode Potential
the standard electrode potential (Eo) is defined as the potential developed at the
interface of the gas and solution containing its own ions when an equilibrium is
established between the gas at a pressure of 760 mm of Hg and the ions in solution of
unit concentration.
 Measurement of Single electrode potential
Whenever, the potential of any electrode say M|Mn+ is to be measured experimentally, it is
combined with the standard hydrogen electrode as given in the following
M|Mn+ || H+(1M)|H2(1atm), Pt

Potential of standard hydrogen electrode (SHE) has been arbitrarily fixed as zero.

The emf of the cell is measured by the

electronic voltmeter and the
measured emf will be equal to the
required potential of the electrode on
the hydrogen scale, by taking potential
of the hydrogen electrode as zero.

Eocell = Eo Reduction – Eo oxidation

=EoSHE – Eo Cu2+| Cu
0.36V = 0 – Eo Cu2+| Cu
Eo Cu2+/ Cu = - 0.36V
The potential of the cell assembly is found to
be 0.36V
Origin of electrode Potential
 WHAT IS A GALVANIC CELL..???
Source or use of
• Galvanic cell is an electricity
electrochemical cell that
converts chemical energy to
electrical energy.
• In galvanic cell the free energy
change of spontaneous
reaction is converted to
electricity.
• It is a cell which contains two
Electrode
electrodes connected by a salt salt bridge
bridge or electrolyte.
The salt bridge allows charge transfer through the solution and prevents mixing.
The spontaneous cell reaction generates the cell potential.
The cell potential depends on the half-reaction potentials at each electrode.
The Nernst equation describes the concentration dependence.
A battery is a voltaic cell. It goes dead when the reaction is complete (Ecell = 0).
 functions of salt bridge and
electrolyte
• It connects two half cells electrically.

• It helps in maintaining electrical neutrality.

• It minimises liquid junction potential.

• It minimizes polarisation.

• It may acts as electron carrier(fuel cell)

KCl or KNO3 is used because the ions have almost same migration
velocities.
When one of the solutions contains soluble silver, mercurous or
thallous salt, the KCl salt bridge cannot be employed.
 Representation of a galvanic cell
Cell notation..
• Anode is written on the left hand side; while cathode is written on right
hand side.
• Metals and electrolyte are separated by vertical line or a semicolon.
• The anode is written by writing the metal first and then the electrolyte.
Zn|Zn2+ or Zn:Zn2+
• The cathode is written by writing the electrolyte first and then the
metal.
Cu 2+|Cu or Cu2+:Cu
• The salt bridge is represented by two vertical lines separating two half
cells.
Zn|Zn2+||Cu2+|Cu
 Electrochemical series
• It is an arrangement of elements in decreasing
order of reduction potentials.
• It helps to know replacing tendency and standard
electrode potential.
• It helps to know spontaneity of the reaction.
• Classification

Electrochemical cells

Voltaic Cell Electrolytic cell

(Galvanic cell)

Chemical Cells Concentration cell Fuel cell

 TYPES OF GALVANIC CELLS...
1.CHEMICAL CELL.
• Ex: Daniell Cell
2.CONCENTRATION CELL.
• Ex: Ni|Ni2+cell
3.FUEL CELL.
• Ex: Hydrogen-oxygen fuel cell
 daniell cell...
• It is a type of galvanic cell which contains two
electrodes (copper and zinc) connected by a salt
bridge.
• It was invented by John Frederic Daniell in 1836.
• Salt bridge used normally contains mixture(jelly-
like) of potassium chloride(KCl), ammonium
nitrate(NH4NO3) and agar-agar.
• Zinc electrode is anode and copper electrode is
cathode.
 Cell notation and reactions
• Cell Notation:
Zn|Zn2+||Cu2+|Cu
• Reaction at anode:
Zn Zn2+ + 2e-
• Reaction at cathode:
Cu2+ + 2e- Cu
• Net Reaction:
Zn + Cu2+ Zn2+ + Cu Eo = 1.10V
WORKING OF DANIELL CELL..
WORKING OF DANIELL CELL..
 CONCENTRATION CELL
• It is a type of galvanic cell in which two similar
electrodes are dipped in solution containing their
own ions of different concentration.
• Here electrode dipped in lower concentration of
solution acts as anode and electrode dipped in
higher concentration solution acts as cathode.
• More is the concentration difference of cathode
and anode more is the emf of the cell.
WORKING OF CONCENTRATION
NICKEL CELL
 Cell notation and reactions
• Cell Notation:
Ni|Ni2+ [.001m] ||Ni2+ + [1m] |Ni
• Reaction at anode:
Ni Ni2+[.001m] + 2e-

• Reaction at cathode:
Ni2+ [1m] + 2e- Ni

• Net Reaction:
Ni2+ [1m] Ni2+[.001m] Eo = 0.0888V
 Nernst Equation
Nernst equation gives a relationship between single electrode potential and
standard electrode potential through concentration of metal ions at a
particular temperature.

Let us consider an assembly consisting of metal (M) dipped in its solution

(Mn+).The spontaneous electrode reaction is represented as,

Mn+ + ne- ↔ M
According to law of mass action,
K= [M]/ [Mn+ ] Here [M]=1
K=1/[ Mn+] ……………(1)

Where K is equilibrium constant

Free energy change (ΔG) of a system varies with temperature and concentration
of reactants and products.
ΔG= ΔGo + RT ln K (2)
This equation is called Van’t Hoff isotherm equation.
At equilibrium, electrical work done is maximum (Wmax).
Wmax= [no. of coulombs of charge X [Energy available per every
coulomb flowing across the interphase]
Wmax= nE F

For spontaneous reaction,

Wmax= -ΔG

ΔG= - nEF ……………….. (3)

ΔGo= - nEoF ………………. (4) Where Eo is standard electrode potential of

the system.

Substituting equations 1, 3 and 4 in 2 we get,

- nEF = - nEoF + RT ln 1/[ Mn+]

E=Eo – RT/nF ln 1/[ Mn+] E=Eo – 2.303RT log 1

nF [ Mn+]

At 298 K, the Nernst equation,

E=Eo – 0.0591 log 1

n [ Mn+]
Types of Electrodes
1. Metal-Metal Ion electrode:
A half cell of this kind consists of a metal dipped in a solution containing its
own ions. The half cell is represented as M/ Mn+ (oxidation)
The redox reaction at the electrode M Mn+ + ne
Example: Zn/Zn2+, Cu/Cu2+

2. Metal-Metal salt ion electrodes:

In this type of half cell, a metal is in contact with a sparingly soluble salt of
the same metal dipped in a solution containing anion of the salt.
Example: Calomel electrode Hg/HgCl2/Cl-
Silver- Silver chloride electrode Ag/AgCl(s)/Cl-

3. Gas electrode:
A gas electrode consists of a particular gas flushed around an inert
electrode (Pt), which is dipped in a solution containing ions to which it is
reversible. At the metal interface, there is equilibrium between gas and its
ions.
Example: Standard hydrogen electrode Pt/H2 (g) (1atm) H+
4. Oxidation –Reduction electrodes:
In this type of half cell, electrode potential arises due to the presence of both
oxidized and reduced species of the same metal at an inert electrode like Pt.
Example: Pt/Fe2+, Fe3+ Pt/Sn2+, Sn4+
5. Ion selective electrodes ( ISE):
“Ion selective electrode is one which selectively responds to a specific
ion in a mixture and the potential developed at the electrode is a
function of the concentration of that ion in the solution”

The electrodes that are able to respond to certain specific

ions only and develop a potential while ignoring the other
ions in a solution are called ion selective electrodes.

These electrodes are very sensitive in their response that

even in a solution containing small amounts of different
types ions, concentration of a particular ionic species in the
mixture can be measured.

Ex: Glass electrode

 APPLICATIONS of ISE:
✓ pH of the solution can be measured by using gas sensing
electrode
✓ It is used in determining the concentrations of cations like
H+, Na+, K+, Ag+, Li+
✓ Determination of total hardness of water
✓ Potentiometric determination of F- in drinking water
✓ Determination of concentration of anions such as
NO3-, CN-, Cl-, S2-
 Construction:
Ag
The glass electrode consists of a glass bulb
made up of special type of glass
(72% SiO2, 22% Na2O and 6% CaO)

which has low melting point and relatively

high electrical conductivity.

The glass bulb is filled with a solution of

Representation: constant pH (0.1M HCl) and insert with an
Ag/AgCl/ HCl (0.1M)/Glass Ag-AgCl electrode, which is the internal
reference electrode and also serves for the
external electrical contact.

The electrode dipped in a solution

containing H+ ions.
GLASS ELECTRODE:
▪ When two solutions of different pH values are separated by a thin
glass membrane, there develops a difference of potential between
the two surfaces of the membrane.
▪ The potential difference developed is proportional to the difference
in pH value.
▪ A glass electrode is an ion selective electrode where potential
depends upon the pH of the medium.
▪ A glass membrane of silicate glass is found to be sensitive to
hydrogen [H+] ions of an acidic solution.
▪ The membrane undergoes ion exchange reaction, the Na+ ions of
glass are exchanged for H+ ions. H+ + Na+ Gl- Na+ + H+ Gl-
 H+ + Na+Gl- Na+ + H+Gl-
A potential difference exists at the interface between glass (Na+ ions)
and the solution (H+ ions of solution). The magnitude of this difference
of potential is given by

EG = E°G + 0.0591 log [ H+]

EG = E°G - 0.0591 pH [ pH = -log [ H+] ]

The potential difference varies as the pH of the two solution varies.

In practice, the pH of one of the solution is made to remain constant
and therefore the potential varies with the pH of the analyte
solution.
Ex: Glass electrode
Working of Glass Electrode

• The surface of the glass membrane on both the sides gets

hydrated.
• Hydrogen ions get adsorbed on the hydrated surface
• The exchange of H+ ions for alkali ions takes place
• Some ions move through the dry layer by Frankel defect
mechanism
Analyte Solution HCl (0.1M)=C2 Ag-AgCl electrode
(C2)
E1
E2

Glass Membrane

The potential developed by the glass membrane Eb (Boundary potential) is given by

Glass membrane behaves as an electrochemical membrane. Hence, potential develops across

the membrane.
EISE= Eo+ 0.0591/n logC1 where E0 is constant
Video
Boundary potential: Whenever, a thin glass membrane is placed
between two solutions of different pH values, a potential difference
develops across the membrane. The potential difference, Eb at the
interface is referred to as the boundary potential. It is result of
potential difference developed across the gel layer of the glass
membrane between the two liquids.
 x

Membrane potentials: The cell potential difference

observed across an ion-selective membrane is called
membrane potential.
Expression for Glass electrode Potential
Let us consider the glass electrode dipped in a solution of concentration , C2 with respect to
H+. If C1 is the concentration of solution inside , the potential is given by

i) Potential developed by Ag/AgCl electrode in contact with 0.1M HCl ( E Ag/ AgCl = Eref)

ii) Potential developed by the glass membrane Em 0r Eb ( boundary potential is

EG= Eb+ E ref

Theoretically, Eb=0, when C1=C2.
However a small additional Easy potential contribution exists even if C1=C2
EG= Eb+ Eref + Easy

Now,
Eb= E2-E1
where E2 and E1 are the potential of the solution outside and inside respectively
According to Nernst,
Eb= E2-E1= 0.0591 log C2 - 0.0591 logC1
Eb= L+ 0.0591 logC2 or L+ 0.0591 log (H+)
where C1 is constant = concentration of H+ ions in the internal std solution
L=constant= - 0.0591 logC1
Eb= L- 0.0591 pH
Since C2= (H+), -log10(H+)= pH
Now

EG= Eb + Eref + Easy

EG= (L- 0.0591 pH) + E Ag/AgCl + Easy.
The potential of glass electrode is given by,

EG= EoG -0.0591 pH

where EoG = [L + E Ag/AgCl + Easy.] is constant for particular glass material

The above expression indicates that potential of a glass electrode EG varies with the pH
of the acidic solution.
Determination of pH of a given solution using Glass Electrode
The experimental activity has two stages Method -I
i) Determination of EoG

The given glass electrode is flushed with distilled water and bulb is wiped off using cotton.
It is then dipped in a solution of Known pH. The electrode is coupled with Satd. Calomel
electrode using salt bridge
The cell formed is represented as,
Pt, Hg / Hg2Cl2 / Satd. KCl / Known Solution // Glass membrane / HCl (0.1M) / AgCl / Ag

The cell is connected to VTVM and the emf is measured (Eknown)

E Known = EG-ESCE

At T=298K ESCE= 0.2412 V

EG= E known + E SCE

But EG= EoG- 0.0591 pH

As the pH is known EoG can be calculated

EoG= EG+ 0.0591 pH
ii) Determination of given pH using Glass Electrode
The glass electrode is removed, washed with distilled water and bulb is wiped off using
cotton.
It is then dipped in a solution of unknown pH and coupled using salt bridge with Satd.
Calomel electrode

Pt, Hg / Hg2Cl2 / satd. KCl / Test Solution // Glass /HCl (0.1M) / AgCl / Ag

Ecell= ECathode - Eanode

ECell= EG-ESCE
Ecell=(EoG-0.0591pH )-ESCE Where EoG =(K+EAg/AgCl +Easy)

Ecell= EoG-0.0591 pH-0.2422

EoG-ESCE- Ecell EoG- 0.2422-Ecell
pH = pH =
0.0591 0.0591
Determination of pH of a given solution using pH meter Method -II
Direct reading pH meters are widely employed for determining the pH of a solution and in
electrometric titrations.

Calibration of pH meter
This experimental activity carried out in place of determination of E0G value of the glass
electrode. The bulb of glass electrode washed is with distilled water and is wiped off using
cotton. It is dipped in a buffer solution .It is coupled with SCE.

Pt, Hg, HgCl2/ Satd KCl/ Buffer Solution/ Glass membrane/0.1M HCl/ Ag, AgCl

The terminals are connected to pH meter, the value is displayed to the pH value of the buffer.
The instrument is said to be calibrated and could be used to measure the pH directly.

Measurement of pH of the solution

Without switching the pH meter the glass electrode is removed from the solution washed
with distilled water and wiped off using cotton. It is now dipped in the solution whi=ose pH
is to be measured and connected to SCE through salt bridge.

Pt, Hg, HgCl2/ Satd KCl/ solution of unknown pH/ Glass membrane/0.1M HCl/ Ag, AgCl
The assembly is connected to pH meter It directly shows the pH of the solution.
 Determination of pH of a given solution using pH meter

Buffer of Known pH

Calibration of pH meter Measurement of pH of the solution

Pt, Hg, HgCl2/ Satd KCl/ Buffer Solution/ Pt, Hg, HgCl2/ Satd KCl/ solution of unknown
Glass membrane/0.1M HCl/ Ag, AgCl pH/ Glass membrane/0.1M HCl/ Ag, AgCl
Lab electrode
ADVANTAGES OF GLASS ELECTRODE:

• It is portable and easy to operate

•Equilibrium is attained easily and measurements are accurate
•It can be used for the measurement of pH of small volumes of liquid.
•It cannot be easily poisoned and can be used in presence of proteins,
oxidizing and reducing agents and in viscous media.
LIMITATIONS OF GLASS ELECTRODE:
❖ The glass membrane is very thin. Hence, electrodes are fragile
should be handled with care.
❖ It cannot be used in the presence of fluoride ions since they attack
the glass membrane
❖ Normal glass electrodes cannot be used for accurate measurements
of pH more than 9. It is due to alkaline error.
❖ Membrane offers some resistance and cannot be measured by
ordinary potentiometers.
REFERENCE ELECTRODES:

The electrodes of known potential, with reference to which the

potential of any other electrode can be measured, are called
reference electrodes.
There are two types of reference electrodes, namely
•Primary reference electrode, Ex: Hydrogen gas electrode
•Secondary reference electrode, Ex: Calomel electrode, silver-silver
electrode
Limitations or drawbacks of using hydrogen electrode as a reference
electrode:
✓ It is difficult to maintain hydrogen ion concentration always unity.
✓ It is difficult to pass hydrogen gas always at 1 atmosphere.
✓ The deposition of impurities on platinum foil causes hindrance in
maintaining the equilibrium between the gas and H+ ions.
✓ Hydrogen electrode cannot be used in solutions containing
oxidising agents such as nitrates, permanganates, ferric salts, etc.
SECONDARY REFERENCE ELECTRODES:

For the sake simplicity and to overcome the above difficulties,

there was a need for the development of secondary reference
electrodes. The potentials of these electrodes are known on the
hydrogen scale and are used in place of hydrogen electrode.
These electrodes can be easily set up.
CALOMEL ELECTRODE: (Saturated Calomel electrode-SCE)
Construction:
Calomel electrode consists of a long glass tube having two
side tubes as shown in figure. Highly pure mercury is placed at the
bottom of the tube and is covered by a paste of pure mercury, calomel
(Hg2Cl2) and potassium chloride solution. The electrical connection is
made by means of platinum wire sealed into another small glass tube
having little mercury at its bottom. The rest of the tube is filled with an
appropriate concentration of KCl solution saturated with calomel. The
calomel electrode can be connected to another electrode to make the cell
complete by means of a salt bridge.
 Electrode Reactions:
at 298K
The reaction that occurs at calomel electrode is,

½ Hg2Cl2(s) + e−  Hg(l) + Cl−(aq)

The calomel electrode is a reversible electrode,
behaves either as anode or as cathode depending on the
nature of the other electrode.

Representation: Hg|Hg2Cl2(sat), KCl(solution)

If the electrode behaves as
cathode, the electrode reaction is: If the electrode behaves as
anode, the electrode reaction is:
Hg2Cl2(s )→Hg2+2+2Cl-
Hg2+2 + 2Cl- → Hg2Cl2(s)
Hg2+2 +2e-→2Hg(l)
2Hg(l) →Hg2+2 +2e-
Hg2Cl2(s)+2e-→ 2Hg(l)+2Cl-
2Hg(l)+2Cl-→ Hg2Cl2(s)+2e-
The electrode potential may be represented by the Nernst equation as
 
E = E 0 − 0.0591 log Cl − at 298K
The electrode potential of calomel electrode depends on the
concentration of KCl solution with which the tube is filled. The
reduction potentials for the various KCl concentration at 25oC are,

0.1M KCl solution 0.3338V

1.0M KCl solution 0.281 V
Saturated KCl solution 0.2415V

The electrode potential decreases with increase in the

concentration of chloride ions.
ADVANTAGES OF CALOMEL ELECTRODE:
•It is simple to construct and operate.
•It gives reproducible electrode potentials.
•The cell potential does not vary much with temperature
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Engineering Chemistry
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 RV College
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Unit-II : ELECTROCHEMICAL ENERGY SYSTEMS
Engineering
AND ELECTRODE POTENTIAL

Lithium ion
battery

Nernst’s equation

Glass Fuel
electrod cells
e
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Applications of Nernst’s equation

 RV College
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Potentiometry
Electroanalytical technique is used
to determine the concentration of
given analyte

Principle: In potentiometric
titration, end point is detected
by measuring the change in
potential of a suitable electrode
during titration..n

Electrodes: Indicator electrode

(platinum) and Calomel electrode
(reference)
RV College
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Engineering

Estimation of Ferrous ion by Potentiometric

titration method using Potassium dichromate

A-Saturated Calomel Electrode

(SCE)
B-Indicator Electrode
C-Potassium dichromate
D-pH Meter with a mV scale
E-Magnetic stirrer
F = Magnetic Guide
.n

Analyte-Ferrous Sulphate solution

+ Sulphuric acid
Titrant-Potassium dichromate
Instrumentatio
n
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 RV College
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Engineering

Calculation
world
Volume of K2Cr207required for the reaction= V cm3
(From graph)
(NFAS = NIron)

NFAS = (NV) K2Cr2O7

VFAS

Report:
Amount of iron presented in 1000 cm3 of its solution =
NFAS x gram equivalent weight of Iron =
…………B
RV College
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the
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 Potentiometric titration
● Potentiometric titration is a volumetric method in which the changes in the emf between
two electrodes (referent and indicator electrode) on the addition of titrant of known
concentration (titrant) to a solution of unknown (analyte).

● The indicator electrodes is reversible with respect to one of the ions of analyte taking part
in the titration reaction but does not take part in the reaction. They are inert electrode
made up of Pt.

● During the course of the titration, the concentration of active ion in the analyte changes
thereby electrode potential of indicator electrode changes.

● Types of potentiometric titration for the determination of analytes in solutions include

acid-base, redox, precipitation, and complexometric.

Redox Titration: Fe2+ against Potassium dichromate

✓ The concentration of an ion such as Fe2+ can be found by titrating with a strong
oxidizing agent such as KMnO4 (Mn7+) or K2Cr2O7 (Cr6+).

• The titration is carried out in one side of a cell whose other half is a reference
electrode: Calomel electrode,
Pt| Hg | Hg 2+ (aq) | KCl ||
 Cell configuration:
Pt(s)| Hg+ (aq)|Hg2 Cl2 (s) | KCl || Fe3+(aq)| Fe2+(aq)| Pt(s)
E= EInd-ESCE
Procedure: –
Pipette out 25ml of FAS into a beaker, Add one test tube of dil.H2SO4 .The acid is added to
make the medium acidic.

Immerse calomel electrode-platinum electrode assembly into it. Connect the assembly to a
potentiometer and measure the potential.

Now we add the oxidizing agent and will note the reading of electrode potential. we will add
0.2ml of K2Cr2O7 each time here.
 Eind (E Fe3+ / Fe2+) = E0 Fe3+ / Fe2++ 0 .0591 log Fe3+ / Fe2+ where E0 Fe3+ / Fe2+ = 0.77V

Initially the left cell contains only Fe2+. As the titrant is added, the ferrous ion is
oxidized to Fe3+ according to the reaction.

K2Cr2O7 + FeSO4+7H2SO4→ Cr2(SO4)3 + 3 Fe2(SO4)3 +7H2 O + K2 SO4

Once the first drop of Cr6+ (K2Cr2O7) titrant has been added, the potential of the indicator
electrode is controlled by the ratio of oxidized and reduced iron ( ( Fe3+) / (Fe2+) )which causes
the potential to rise as more iron becomes oxidized.

Near the end-point the ratio changes very rapidly since a small quantity of added Cr6+ removes
considerable proportion of the few remaining Fe2+ ions.

When the equivalence point is reached, the Fe2+ will have been totally consumed and the
potential will then be controlled by the concentration ratio of cell couple Cr6+ / Cr3+

The end point is found not by measuring a particular cell voltage, but by finding what volume
of titrant gives the steepest part of the curve.
A titration curve has a characteristic sigmoid curve. The part of the curve that has the
maximum change marks the equivalence point of the titration.

The first derivative, ΔE/ΔV, is the slope of the curve, and the endpoint occurs at the
volume, V', where ΔE/ΔV has the maximum value.
Model Procedure

Transfer25 cm3 of FAS into a beaker. Add 2 t.t. of dil. H2SO4. Immerse calomel electrode &
platinum electrode assembly into it. Connect the assembly to a potentiometer and
measure the potential. Add K2Cr2O7 solution from burette in increments of 0.2 cm3
and measure the potential after each addition. Plot a graph ΔE / ΔV against volume of
K2Cr2O7and determine the equivalence point. From the normality of K2Cr2O7,
calculate the normality and the weight of FAS in the given solution
 x

Features of the titration curve

▪ the wave-like shape occurs because of the rapid change in voltage around the endpoint of the
reaction

▪ the endpoint break is the large change in voltage around the endpoint

▪ the endpoint break should be as large as possible to improve accuracy of detection: this is done by
choosing the titrant carefully

▪ the endpoint volume is defined as the volume half-way up the endpoint break

▪ the voltage values before the endpoint are due to the analyte

▪ the voltage values after the end point are due to the titrant
x
x
Applications using Batteries

76
Introduction:
A Battery is an electrochemical cell or often several electrochemical cells connected
in series that can be used as a source of direct electric current at a constant
voltage.
Uses:
➢ Batteries are used in calculators, watches and pacemakers for heart hearing aids,
computers, car engines, stand by power supplies, emergency lightning in
hospitals, electroplating industrial reactions and military and space applications.
➢ Batteries have revolutionized the telecommunication system.
➢ Created a new era of transportation with the possible replacement of petrol
driven automobiles by the electrical powered ones.
➢ In modern days portability of electronic equipment’s in the form of handsets has
been made possible by batteries.
 Battery

Duracell batteries 9v battery 6v dry cell

A cell is a device used to

convert chemical
energy into electrical
energy, a battery being
a combination of two/
more cells.
Battery technology
Note: The size of the batteries ranges from a fraction of a cubic centimeter to several cubic
decimeters.
COMPONENTS OF A BATTERY

Terminals

Seal with
vent

Anode (-ve) Cathode

(+ve)
Anode active material
Cathode active material
Separator Electrolyte
 WORKING OF A BATTERY
Flow of electrons Flow of
electrons DC power supply
Anode Cathode Anode
Cathode
-ve +ve +ve
-ve

Active Active
species species
MCY

(a) (b)

Electroactive material:
▪ When anode and cathode are connected by a metallic wire through load,
spontaneous the reaction occurs at anode and cathode.
▪ Material which take part in the spontaneous reactions are called electroactive
materials.
 Classification of Batteries
Primary Batteries:
Electroinactive materials cannot be converted in to electroactive materials, Irreversible
batteries.
Ex: Dry cell, Alkaline Battery

Secondary Batteries:
Electroinactive materials can be converted in to electroactive materials, reversible batteries
by passing current in opposite direction.
Ex: Lead-acid battery, Ni-Cd Battery, Ni-MH Battery

Reserve Batteries :
These are inactive when not in use and may be activated in several ways prior to the
application. In principle batteries without vital component.
Ex: Silver Chloride Cell, Mg/water/AgCl/Ag
Magnesium Battery, Mg/water/ Cu2 Cl2, Cu

→ Electrolyte activated batteries

→ Heat activated batteries
→ Gas activated batteries
 PRIMARY BATTERY

• CANNOT BE RECHARGED

• CHEMICAL PROCESS NOT REVERSABLE

• ZINC CARBON (1.5V)

• ALKALINE (1.5V)
 SECONDARY CELLS
• CAN BE RECHARGED

• CHEMICAL REACTION REVERSABLE

• LEAD ACID (2.0V)

• NICKEL - CADMIUM (1.2V)
• NICKEL - METAL HYDRIDE (1.2V)
• LITHIUM – ION (3.3V)
During discharge, oxidation takes place at the anode and
reduction takes place at the cathode. The reaction is a spontaneous
reaction. Chemical energy is converted into electrical energy.
Example: Lead-acid battery,
During charging, reverse reactions take place. The revers reactions
are non-spontaneous reactions. The battery is connected to an
external d.c power supply.
Electrical energy is converted in to chemical energy.
Example: The reverse of the above reactions occur during charging.
At anode: electrons are released to the external circuit.
At cathode: electrons from the external circuit are consumed.
 Discharging
At anode
Ma Ma+n + ne-
At Cathode
McY + ne- Mc + Y-n

➢ During the reactions (Oxidation/Reduction), the electroactive

materials are converted in to products called electroinactive
materials.

➢ The process in which electroactive materials are converted in

to electroinactive materials is called discharging.

➢ During discharging the emf of a cell decreases.

 Recharging (Charging)
At Cathode
Mc + Y-n McY + ne-
At Anode
Ma+n + ne- M
➢ In some cases the electroinactive materials can be converted
back to electroactive materials by passing electricity in
opposite direction.
➢ This process is called charging of a battery.
➢ During charging the emf of a cell gradually increases and
reaches its initial value.
 Lithium Batteries
➢ Lithium is the lightest of metals and it can float on
water.

➢ The electrochemical properties of lithium are excellent

and it is also a highly reactive material.

➢ These properties gives Lithium the potential to achieve

very high energy and power densities in high-density
battery applications such as automotive and standby
power.

➢ Lithium batteries are primary batteries in which

lithium metal (or) lithium compound acts as a Anode. A
lithium cell can produce voltage from 1.5 V to about 3
V based on the types of materials used.
Types of Lithium Batteries:
Lithium
Batteries

Lithium
metal Lithium ion
batteries batteries

➢ pure lithium metallic ➢ lithium compounds are

element is used as anode. used as anode.
➢ Primary batteries ➢ Secondary batteries.
➢ Not rechargeable ➢ Rechargeable batteries
Characteristics

• High Energy Density

• High Voltage
• No memory effect
• Flat discharge voltage( stable power)
• Low self discharge 1/10 compared with
Ni-MH/ Ni-Cd battery
• Li ion battery uses LiCoO2 as Cathode
• Specialty carbon as negative electrode

In Li batteries there is merely a migration of Li ions between +ve and –Ve electrodes.
No chemical changes are observed in two electrodes or in the electrolytes.
Lithium Ion Battery
Construction:
➢ Anode: Lithium metal dissolved into a carbon.

➢ Cathode: The cathode material is made up from Lithium

liberating compounds, typically the three electro-active oxide
materials,
Lithium Cobalt-oxide (LiCoO2 )
Lithium Manganese-oxide (LiMn2 O4 )
Lithium Nickel-oxide (LiNiO2)

➢ Electrolyte: Lithium salts like LiPF6, LiBF4, LiAsF6 dissolved

in organic solvents, ( mixed in propylene
carbonate, ethylene carbonate solvent)
Electrolyte should help in effective conduction of Li-ions to cathode
during discharge (ionic conductivity rather than electronic conductivity)
➢ Seperator: A fine porous polymer film
 Li- ion Electrolyte
Cathode Anode

Li-Ion battery Principle

Li doping is charging reaction 93

Undoping is discharging
Working :

The chemical reaction that takes place inside the battery is as

follows, during charge and discharge operation:

During discharge:

At Anode: Li ions present in graphite layer will be oxidized. Electrons

will flow through external circuit to cathode and lithium ions flow
through the organic electrolyte towards cathode.
Li-C6 x Li+ + 6C +x e-

At Cathode: Li-ions are reduced to Li and are inserted in to the

layered structure of metal oxide.
x Li+ + xe- + Li(1-x)CoO2 LiCoO2

Overall reaction: LiC+ Li(1-x)CoO2 LixCoO2 + 6C

94
Working Cont…

During charging:

At Cathode:
Li ions present in layered structure of LiCoO2 will be oxidized.
Electrons will flow through external circuit to cathode and lithium
ions flow through the organic electrolyte towards cathode.
LiCoO2 x Li+ + xe- + Li(1-x)CoO2

At anode:
Li-ions are reduced to Li and are inserted in to the layered structure
of graphite.
xLi+ + 6C + xe- Li-C6

Overall reaction: LixCoO2 + 6C LiC6 + Li(1-x)CoO2

95
Lithium-Ion Battery Charge

Electrolyte

Cu Current AL Current
Collector Collector

Graphite LiMO2

SEI SEI
❑ Charging and discharging reactions
Lithium-Ion Battery Discharge

Electrolyte

Cu Current AL Current

Collector Collector

Graphite LiMO2

SEI SEI
 Advantages and disadvantages
Advantages

➢ They have high energy density than other rechargeable batteries

➢ They are less weight
➢ They produce high voltage out about 4 V as compared with other
batteries.
➢ They have improved safety, i.e. more resistance to overcharge
➢ Fast charge and discharge rate.
Disadvantage

➢ They are expensive

 Applications
➢ The Li-ion batteries are used in cameras, calculators

➢ They are used in cardiac pacemakers and other implantable

device

➢ They are used in telecommunication equipment,

instruments, portable radios and TVs, pagers

➢ They are used to operate laptop computers and mobile

phones and aerospace application
FUEL CELLS
 ➢ Fossil fuels are conventional energy sources.
➢ The chemical energy of a fuel is converted into electrical
energy as follows.
Chemical
Energy

Thermal
energy
Combustion process,
Through redox
Loss of energy in every step,
reactions efficiency Mechanical Energy effeciency-35-40%
would be as high as Energy
70-75%
Electrical
Energy
Combustion “Fuel cells are the galvanic cells
reactions are in which chemical energy of a
replaced by fuel is directly converted in to
Redox Possible in
FUEL CELLS electrical energy by means of
reactions
redox reactions involving fuels
and oxidants.”
 Representation of Fuel Cells
Fuel/ Electrode/ Electrolyte/ Electrode/ Oxidant

Cell Reactions:
At Anode: Fuel Oxidised Product + ne
At Cathode: Oxidant + ne Reduced Product

Over all cell reaction: Fuel + Oxidant Oxidised product + Reduced Product
Special Features of Fuel cells

➢Fuel cells consists of two catalytically active electrodes,

oxidant and a reductant.
➢The fuel and oxidants are not stored in the cell.
➢The thickness of the cell may be less than one cm.
➢In a fuel cell, redox reaction occurs involving fuel and
oxidant.
➢Fuel cells are energy conversion devices.
➢Eco friendly devices.
➢Fuel undergoes oxidation where as oxidants undergo
reduction.
DIFFERENCES BETWEEN CONVENTIONAL CELL AND FUEL CELL

Batteries Fuel cells

They are energy storage device They are energy conversion devices
Battery electrodes doesn’t contain any The porous electrodes are impregnated with
catalysts catalyst
The active materials are complex Active materials are fuel and oxidant
chemical compounds
The active materials are placed along The active material such as fuel and oxidants
with the electrodes are continuously pumped from outside.
The battery components may be By-products of fuel cells are environmentally
environmental pollutants green
Recharging of battery is required Recharging is not required
Electrode materials are very cheep Electrode materials are very costly
 Classification of fuel cells
➢ Classification
Sl No Type based on electrolyte.
Electrolyte Anode Cathode Temp.
range
1 Alkaline fuel cells KOH Porous C/Pt Porous C/Ag 80°C

2 Phosphoric acid fuel Phosphoric acid Pt Pt 160-

cells (PAFC) 220°C

3 Molten carbonate Molten metal Ni/Cr(2-10%) Ni/Li(2-10%) 650°C

fuel cells (MCFC) carbonates

4 Solid oxide fuel cells Solid metal Porous NiZnO2 Porous 650-
(SOFC) oxides LaMnO3 1000°C

5 Solid Polymer Polymer Pt Pt 80°C

electrolyte fuel cells membrane
(SPEFC) containing
Fluorocarbon
with SO3H group
 X
Animation of PEMFC
 X
Contd.....
Why methanol is preferred over hydrogen fuel ?

➢ Energy density: Methanol: 4.8 Wh/cm3

Hydrogen: 2.7 Wh/cm3
➢ Easy transportation and handling
➢ Readily available, relatively lesser cost
➢ Stable at all atmospheric conditions

(Silva et al, 2005)

 Direct Methanol Fuel Cell (DMFC)

➢ Sub-category of PEMFC

➢ Fuel at anode: Methanol ; Oxidant at cathode: Oxygen

➢ Membrane used: Proton exchange membrane (PEM)

➢ Operating temperature: 50-1200C

➢ Power density: 240 mW/cm2

➢ Fuel cell efficiency: ~60%

➢ Power output: 0.1 – 15W

 Methanol-Oxygen Fuel cells:
Construction:
➢ Anode: Porous Ni / Pt-Pd Catalyst. Fuel at anode: Methanol
➢ Cathode: Porous Ni / Ag catalyst. Oxidant at cathode: Oxygen
➢ Electrolyte used: Concentrated KOH
➢ Membrane used: Proton exchange membrane (PEM)
➢Operating temperature: 50-1200C

CH3OH + 6OH - CO2 + 5H2O + 6e- (1/2 O2 + H2O + 2e- 2OH - ) 3

Methanol-Oxygen Fuel cells:
x
Working:
Anodic reaction(Oxidation):
CH3OH + 6OH - CO2 + 5H2O + 6e-

Cathodic reaction (Reduction):

(1/2 O2 + H2O + 2e- 2OH -) X3

Overall reaction:
CH3OH + 3/2 O2 CO2 + 2H2O
EMF:1.186V
➢ The carbon dioxide liberated will react with electrolyte (KOH)
forms corresponding carbonate.

➢ This will reduce the efficiency of the fuel cell.

➢ Hence design of methanol-oxygen fuel cell in presence of acid

electrolyte is attempted
 Methanol-Oxygen Fuel cells: (Alternate Form)
➢ Fuel at anode: Methanol
➢ Oxidant at cathode: Oxygen
➢ Electrolyte used: 3M H2SO4
➢ Membrane used: Proton exchange membrane (PEM)

Reactions:
Anodic reaction(Oxidation):
CH3OH + H2O CO2 + 6H+ + 6e-

Cathodic reaction (Reduction):

(1/2 O2 + 2H+ + 2e H2O)3

Overall reaction:
CH3OH + 3/2 O2 CO2 + 2H2O
 Applications
All kinds of portable, automotive and mobile applications like,
➢ Powering laptop, computers, cellular phones, digital
cameras
➢ Fuel cell vehicles (FCVs)
➢ Spacecraft applications
Fuel-cell cars
➢ Any consumables which require long lasting power compare
to Li-ion batteries.
Experimental set up