UNIT-1: Electrochemical Systems

Introduction:
Electrochemistry is the branch of chemistry which deals with the transformation of
electrical energy to chemical energy and vice versa. In brief it deals with the chemical
applications of electricity.

Electrical Energy Chemical Energy

Electric current is a flow of electrons generated by a battery, when the circuit is completed.
Electrolysis is one process where electrical energy causes chemical changes. It is carried out
in an apparatus called electrolytic cell. The cell contains electrolyte and electrodes. The
electrode connected to the positive pole of the current source is called anode. The electrode
connected to the negative pole of the current source is called cathode. When an electric
current is passed through the electrolytic solution, cations move towards cathode (-ve
electrode and anions move towards anode (+ve electrode)
Ex: Electrolysis of water yields H2 and O2

In other process, certain chemical reactions takes place in a vessel and produce electric
energy. The device is called electrochemical cell. Eg. Galvanic cell, batteries and fuel cells
Broadly we can classify the cells as electrolytic cells and electrochemical cells.

Electrolytic cell: A device which converts electrical energy to chemical energy

Electrochemical cell: A device which converts chemical energy to electrical energy

Types of Conductors:
Electrical Conductors: Substances which allow electric current to pass through them are
known as electrical conductors. Eg. All metals, graphite, fused salts, aqueous solutions of acids
and bases and salts.
Semi conductors: The substances which partially conduct electricity are called semi-
conductors. The conducting properties of semi-conducting properties are increased by
the addition of certain impurities called “dopping”.
Ex: ‘Si’ and Ge on addition of V group elements like P produces n-type semi- conductor.
On addition of III group element like B, Al, produces p-type of semi- conductor.

Non-conductors or Insulators: The substances which do not allow electricity are called non-
conductors. . Eg. Rubber, wood, paper, all non-metals except carbon.

Conductance: The capacity of a conductor to allow the passage of current through it called
conductance. It is a property of conductor which facilitates flow of electricity through it.
1
Conductance (C) =
𝑅

i.e. The reciprocal of resistance is called conductance. Units: Ohm.-1

1
Conductor: The substance which allows the passage of electric current through it is called
conductors. E.g.:- all metals, graphite, aqueous solution of acids and bases.

Band Theory of Electrical Conductivity

Electric conductors are two types

Metallic conductor Electrolytic conductors

Conductance due to the migration of Conductance due to the migration of ions

electrons. in a solution of fused electrolyte.
E.g.: metals, graphite. E.g.: Acids and bases
Passage of current due to electron flow. No Passage of current due to movement of
chemical reaction takes place. ions. Some chemical reaction takes place.
Free electrons are responsible for electrical Free ions are responsible for electrical
conduction. conduction.
Mass is not transferred Mass is transferred.
With increase of temp resistance increases With increase of temperature resistance
and conductance decreases decreases and conductance increases.

Electrolytes are classified into two types:

Strong electrolytes: The electrolytes which completely dissociates in solution at all
concentrations. Their conductance is very high. Eg. NaCl, HCl, NaOH.

Weak Electrolytes: The electrolyte which partially dissociates at moderate concentration.

Their conductance is low as they dissociate only to a small extent even at very high dilutions.
Eg: CH3COOH, NH4OH, sparingly soluble salts like AgCl, AgBr, AgI, BaSO4, PbSO4 etc

2
STANDARD ELECTRODE POTENTIAL:
 When a metal rod is dipped in its salt solution (electrolyte), the metal atom tends either to
lose electrons (oxidation) or to accept electrons (reduction).
 The process of oxidation or reduction depends on the nature of metal.
 In this process, there develops a potential between the metal atom and its corresponding
ion called the electrode potential.
 It is a measure of tendency of a metallic electrode to lose or gain electrons when it is in
contact with its own ions in solution.
 Reduction potential: The tendency of an electrode to gain electrons and to get reduced is
called reduction potential, its value is +x volts.
 Oxidation potential: Similarly the tendency of an electrode to lose electrons and to get
oxidized is called oxidation potential, its value is –x volts
 The potential develop between electrode and electrolyte by the formation of charges and
these charges are formed Helmholtz electrical double layer, through which potential
develop between electrode and electrolyte.

Anode Cathode
Helmholtz Electrical Double LayeR
Single electrode potential:

Each electrochemical cell is made up of two electrodes, at one electrode electrons are
evolved and at other electrode electrodes used up. Each electrode which is dipped in its salt
solution is called Half Cell. The potential of half-cell i.e. the potential difference between the
metal and its salt solution in which it is dipped is called single electrode potential. It cannot
be measured directly.

The total cell E.M.F is equal to the sum of the single electrode potentials. Each electrode is
affixed with a symbol corresponding to the reaction that takes place near the electrode.

E cell = E (anode) + E (Cathode)

4
The half-cell reactions are as follows; the half-cell reaction which corresponds oxidation is

Zn  Zn2+ + 2e-

The electrode is called oxidation electrode and potential of the electrode is oxidation potential
or the potential of left hand electrode which is represented as EOX or EL . The cell reactionof
the electrode where reduction takes place is given below

Cu2+ + 2e -  Cu

The electrode is called reduction electrode or right hand electrode and the potential of this
electrode is reduction potential and represented as E (Red) or E (R).

The total cell reaction is Zn+ Cu2+ Zn2++ Cu.

E (cell) = E (OX) + E (Red)

E.M.F of the cell is equal to the sum of the oxidation potential and reduction potential, also
expressed as the reduction potential of the right hand electrode minus reduction potential of the
left hand electrode.

GALVANIC CELL: A galvanic cell is a system in which a spontaneous oxidation and

reduction reaction occurs and generates electrical energy. Eg. Daniel cell

Construction of Galvanic Cell

A galvanic cell is made up of two half cells. One is oxidation or anodic half- cell and
other one is reduction or cathodic half cell. Daniel cell is an example of galvanic cell having
zinc and copper electrodes. The first half cell consists of zinc electrode dipped in ZnSO 4
solution and the second half is made of copper electrode dipped in copper sulphate solution.
Both half cells are connected externally by metallic conductor and internally by a bent glass
tube having saturated solution of a strong electrolyte (KCl) called salt bridge. It acts as a bridge
between the two half cells.

Working of Galvanic cell:

When two half cells are connected externally by a wire through a voltmeter, spontaneous redox
reaction takes place at the electrode.

At anode: Oxidation takes place with the liberation of two electrons.

Zn Zn+2 + 2e- (oxidation or de-electronation)

At cathode: Reduction occurs and cuprous ion is reduced to metallic copper.

Cu+2 + 2e- Cu (reduction or electronation)

The overall reaction is Zn + Cu+2 Zn+2 + Cu

5
 As the connection is complete, the flow of electrons will be externally from
anode to cathode and internally from cathode to anode through the salt bridge. The flow of
current is due to the difference in electrode potentials of both the electrodes. The potential
difference in the cell is called the EMF and is measured in volts. It can be measured by the
potentiometer. The flow of current becomes slow after using the electrodes for a long time
because of the polarization of the electrodes.
At this stage, the salt bridge comes to the aid and restores the electrical neutrality of the
solution in the two half cells. When the concentration of Zn2+ ions around the anode increases,
sufficient number of Cl- ions migrate from the salt bridge to the anode half cell. Similarly,
sufficient number of K+ ions migrate from the salt bridge to cathode half cell for neutralizing
excess negative charge due to the additional SO42- ions in the cathodic half-cell. Thus it
maintains the electrical neutrality of the two solutions in the half cells.

Representation of a galvanic cell:

1. The electrode showing oxidation reaction is anode and the other electrode where reduction
occurs is cathode.
2. As per IUPAC convention, the anode is always represented on the left and cathode always
represented on the right side of the cell.
Anode Half-Cell || Cathode Half-Cell

Electrode | Anode Soln || Cathode Soln | Electrode

Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s)

3. The electrode on left (i.e, anode) is written by writing the metal first and then theelectrolyte.
The two are separated by a vertical line or a semicolon. The electrolyte may be represented by
the formula of the whole compound or by ionic species and concentration may also be
mentioned in bracket.

Examples of representing anode half-cell as:

Eg: Zn/Zn2+ or Zn;Zn2+ or Zn/ZnSO4(1M).

4. The cathode of the cell (at which reduction takes place) is written on the right hand side. In
this case, the electrolyte is represented first and then the metal. The two are separated by a
vertical line or a semicolon.

6
Examples of representing cathode half-cell as:

Cu2+/Cu or Cu2+; Cu or CuSO4(1M)/Cu.

5. A salt bridge is indicated by two vertical lines, separating the two half-cells.

Zn;Zn2+(1M) // Cu2+(1M); Cu.

Electromotive Force or Cell Potential (EMF):

The flow of electricity from one electrode to another electrode in a galvanic cell
indicates that the two electrodes have different potentials. The difference of potentials between
the electrodes of a cell which causes flow of current from an electrode at higher potential to
other electrode at lower potential is known as electromotive force or cell potential.

The EMF of the cell depends on (a) temperature (b) nature of reactants and (c) concentration
of solutions in two half cells.
Mathematically:

EMF or Ecell = Ecathode− Eanode or

E(cell) = E(right) – E(left)

Where
E(cell) = e.m.f of cell
E(right) = reduction potential of right hand side electrode (cathode)
E(left) = reduction potential of left hand side electrode (anode)

Ecell = Eox (anode) + ERed (cathode)

Ecell = ER - EL (both are reduction potentials)
Ecell = EL (anode) - E R (cathode) (both are oxidation potentials)

Salt bridge: Salt bridge is a U shaped glass tube containing concentrated solution of an inert
electrolyte such as KCl, KNO3 and K2SO4 or paste of inert electrolyte (whose ions do not take
part in redox reaction and do not react with the electrolyte) in agar–agar medium or gelatin.

Functions of salt bridge:

1. Salt bridge helps to complete the circuit by allowing the ions to flow from one solution to
the other without mixing the two solutions.

7
2. It helps to maintain electrical neutrality of the solution in the half cells.

Applications of EMF
Poterntimetric Titration:
A potentiometiic titration is one in which the end point is detected by measuring changes in the
potential of a suitable electrode (after coupling it with a standard reference electrode) during
the course of reaction. No indicator is used in this titration. The electrode whose potential varies
during the reaction and which depends upon the concentration of ionic species is called the
indicator electrode.
The potentiometric titrations are subdivided in terms of the type of chemical reaction involved
in the titration, e. g. acid-base titration, redox titration, precipitation titration and
complexometric titration.

Acid-Base titration: The acid solution whose strength has to be determined is taken in a beaker
and the hydrogen electrode and calomel electrode were dipped in the solution. The electrodes
were connected to the potentiometer and the e.m.f. is measured.
Reference Electrode: Saturated Calomel Electrode (SRP = 0.242 V) [Anode]
Indicator Electrode: Quinhydrone Electrode [Cathode].

Cell Notation:
(-) Pt / Hg, Hg2Cl2 / KCl (sat) // H+ Test Sol. / Q, QH2 / Pt (+) Cell Reactions:
Anode: 2Hg + 2Cl-→Hg2Cl2 + 2e-
Cathode: Q + 2H+ + 2e-→ QH2
Ecell= Ecathode- Eanode= [0.0990 – 0.0591 pH] – 0.242 i.e. E Cell is a function of pH.
During titration, as base is added to the acid, the H+ ion concentration in the half cell containing
Quinhydrone will decrease. Correspondingly, there will be a decrease in the E QE and E Cell
values also. ECell values are noted, graph is plotted, where equivalence point is located and
concentration of test solution is calculated.
The steepest portion of the curve indicates the equivalent point of the titration. Instead
ΔE/ΔV is plotted against the volume of the base.
Electrode potential

E/ V

t
n
End Point

i
o
P
d
n
E

Volume of titrant
Volume of HCl solution

8
Batteries:
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 constant voltages. A device which converts
chemical energy to electrical energy is called battery cells, connected together electrically in
series. Batteries are commercial electrochemical cells.

ADVANTAGES OF BATTERIES:
(1) Batteries act as a portable source of electrochemical energy.
(2) The portability of electronic equipment in the form of handsets has been made possible by
batteries.
(3) A variety of electronic gadgets have been made more useful and popular with the
introduction of rechargeable storage batteries having reliability, better shelf life and
tolerance to service.
(4) For all commercial applications, batteries are constructed for their service. For example
batteries for automotives and aircrafts, stand by batteries etc.

Requirements of Battery:
A useful battery should fulfill the following requirements

1. It should be light and compact for easy transport.

2. It should have long life both when it is being used and when it is not used.

3. The voltage of the battery should not vary appreciably during its use.

11
 Differences between Primary, Secondary and Fuel cells:
Primary cell Secondary cells Fuel Cell
It acts as a simple It acts as a galvanic cell while It acts as a simple galvanic
galvanic cell. discharging and electrolytic cell cell.
while charging.
Cell reaction is not Cell reaction can be reversed. Cell reaction is not
reversible. reversible
Cannot be recharged. Can be recharged Do not store energy
Can be used as long as Can be used again and again by Energy can be withdrawn
the materials are active in recharging the cell indefinitely as long as
their composition. outside supply of fuel is
maintained
E.g: E.g: E.g:
Leclanche or dry cell. 1. Lead storage cell 2. Nicol or H2-O2, CH3OH-O2
Zn/NH4Cl (20%), ZnCl2/ Nickel cadmium battery emf
MnO2/C. emf =1.5V. =1.4 Applications:
Applications: Applications: Electronic Space vehicles due to their
Radios, torches, calculators, electronic flash light weight and the bi
transistors, hearing aids. units & cordless electronic product H2O produced is a
shavers etc. valuable source of fresh
water for astronauts.

PRIMARY CELLS:

Lithium cells:
Lithium cells are primary cells in which lithium acts as anode and the cathode may
differ. Lithium metal is used as anode because of its light weight, high standard oxidation
potential (≥3V) and good conductivity. As the reactivity of lithium in aqueous solution is more,
lithium cells use non-aqueous solvents as electrolyte.
Lithium cells are classified into two categories:

(a) Lithium cells with solid cathode:

The electrolyte in this system is a solid electrolyte. The most widely used cell is lithium
– manganese dioxide cell (3V). MnO2 should be heated to over 3000C to removewater
before keeping it in the cathode, thereby increasing the efficiency of the cell.

12
Anode: Lithium Metal,

Cathode: MnO2 as an active material.

Electrolyte: LiBF4 salt in a solution of propylene carbonate and dimethoxy ethane.

Reactions:

At anode: Li⟶ Li + + e-

At cathode: e- + MnO2 ⟶ MnO2-

Net reaction: Li + MnO2⟶ LiMnO2

Applications:
1. The coin type cells are used in watches and calculators.
2. Cylindrical cells are used in fully automatic cameras.

(b) Lithium cells with liquid cathode: Lithium–sulphur dioxide cell is an example of liquid
cathode. The co-solvents used are acrylonitrile or propylene carbonate (or) mixture of the
two with SO2 in 50% by volume.

Cell reaction: 2Li + 2SO2⟶ Li2S2O4.

Lithium thionyl chloride cell is another example of liquid cathode. It consists of high surface
area carbon cathode, a non – woven glass separator. Thionyl chloride acts as an electrolyte and
as a cathode.

Cell reaction:

At anode: Li ⟶ Li+ + e-

At cathode: 4Li+ 4e-+ 2SOCl2⟶ 4LiCl + SO2 + S

Net reaction: 4Li + 2SOCl2⟶ 4LiCl + SO2 + S

In this cell no co-solvent is required as SOCl2 is a liquid with moderate vapor pressure. The
discharging voltage is 3.3 -3.5V.

13
USES:
1. They are used for military and space applications.
2. In medicinal devices such as neuro-stimulators, drugdelivery system, lithium batteries are
widely used.
3. They are also used in electric circuit boards for supplying fixed voltage for memory
protection and standby functions.

Advantages:
1. The energy output of a lithium cell is 2-4 times better than that of conventional zinc
anode batteries.
2. Lithium batteries can work over temperature range of 40-700C.
3. They have higher voltages of about 4V when compared to other primary cells with 1.5 V
only.

Secondary cell: E.g.: Lead – Acid cell:

If a number of cells are connected in series, the arrangement is called a battery. The lead storage
battery is one of the most common batteries that are used in the automobiles. A 12 V lead
storage battery is generally used, which consists of six cells, each providing 2V. Each cell
consists of a lead anode and a grid of lead packed with lead oxide as the cathode. These
electrodes are arranged alternately, separated by a thin wooden piece and suspended in dil.
H2SO4 (38%), which acts as an electrolyte. Hence, it is called lead acid battery.

Anode: Pb

Cathode: PbO2

Electrolyte: H2SO4 (20-22%)

EMF = 2 V

14
Lead storage cells: To increase the current output of each cell, the cathode and the anode
plates are joined together, keeping them in alternate positions. The cells are connectedparallel
to each other.

The cell is represented as

Pb/PbSO4(s), H2SO4/PbSO4(s),Pb

In the process of discharging, i.e., when the battery produces current, the reactions at the
electrodes are as follows:

Discharging reactions:
At anode: Pb → Pb2+ + 2e-
Pb2+ + SO42- → PbSO4

At cathode: PbO2(s) + 4H+ + 2e-→ Pb2++2H2O

Pb2+ + SO42- → PbSO4

Therefore, the overall reaction is:

Pb(s) +PbO2+4H2SO4(aq) → 2PbSO4(s) + 2H2O + Energy

During discharging the battery, H2SO4 is consumed, and as a result, the density of H2SO4 falls.
When it falls below 1.20 g/cm3, the battery needs recharging. In discharging, the cell acts as a
voltaic cell where oxidation of lead occurs.

Recharging:
During recharging, the cell is operated like an electrolytic cell, i.e. electrical energy is
supplied to it from an external source. The electrode reactions are the reverse of those that
occur during discharge.
PbSO4 + 2e- → Pb + SO42- (Reaction at cathode)
PbSO4 + 2H2O → PbO2 + 2H2SO4 + 2e- (Reaction at anode)

2PbSO4 + 2H2O + Energy → Pb + PbO2 + 2H2SO4

During this process, lead is deposited at the cathode, PbO2 is formed at the anode and
H2SO4 is regenerated in the cell.

Advantages:
Lead-acid batteries are used for supplying current to railways, mines, laboratories,
hospitals, automobiles, power stations, telephone exchange, gas engine ignition, UPS. Other
advantages are its recharge ability, portability, and relatively constant potential and low cost.
Disadvantages: Use of conc. H2SO4 is dangerous. Use of lead battery is fragile.
 Lithium-ion batteries (or) Lithium-ion cells:

Lithium-ion battery is a secondary battery. As in lithium cell, it does not contain metallic
lithium as anode. As the name suggests, the movement of lithium ions are responsible for
charging '& discharging. Lithium-ion cell has the following three components.

1. A positive electrode (Layers of lithium-metal oxide) (cathode).

2. A negative electrode (Layers of porous carbon) (anode).
3. An electrolyte (Polymer gel) (separator)

Construction: The positive electrode is typically made from a layers of chemical compound
called lithium-cobalt oxide (LiCoO2).
The negative electrode is made from layers of porous carbon (C) (graphite).
Both the electrodes are dipped in a polymer gel electrolyte (organic solvent) and separated
by a separator, which is a perforated plastic and allows the Li+ ions to pass through.

Working
Charging Reaction:
During charging, Li+ ions flow from the positive electrode (LiCoO2) to the negative electrode
(graphite) through the electrolyte. Electrons also flow from the positive electrode to the
negative electrode. The electrons and Li+ ions combine at the negative electrode and deposit
there as Li.
LiCoO2 + C→ Li1-xCoO2 + CLix
Discharging Mechanism
Charging Mechanism
load
charger
electrons

seperator electrons
Anode Cathode
Anode seperator
Cathode
LiCoO2
C
graphite
Li+

Li+ Li+ Li+ Li+

Li+
C
graphite
+ + +
Li Li Li
Li+

Li+
Li+ Li+

Electrolyte (gel polymer electrolyte)

Electrolyte (gel polymer electrolyte)
Discharging Reaction:
During discharging, the Li+ ions flow back through the electrolyte form negative electrode to
the positive electrode. Electrons flow from the negative electrode to the positive electrode.
The Li+ ions and electrons combine at the positive electrode and deposit there as Li.
Li1-xCoO2 + CLix → LiCoO2 + C

Advantages (or) Characteristics:

1. Lithium-ion batteries are high voltage and light weight batteries.
2. It is smaller in size.
3. It produces three time the voltage of Ni-Cd batteries.
4. It has none of the memory effect seen in Ni-Cd batteries.
Uses:
It is used in cell phone, note PC, portable LCD TV, semiconductor driven audio, etc.
 UNIT – 2
FUEL CELLS

Definition: A fuel cell is an electrochemical which converts chemical energy contained in

readily available fuel oxidant system into electrical energy.

Principle: The basic principle of fuel cell is as same as that of an electrochemical cell. The fuel
cell operates like a galvanic cell. The only difference is that the fuel and the oxidant are stored
outside the cell. Fuel and oxidant are supplied continuously and separately to the electrodes at
which they undergo redox reaction. Fuel cells are capable of supplying currentas long as
reactants are replenished.

Fuel + Oxidant → Oxidation products + Electric Energy

Examples: 1. H2-O2 fuel cell

2. CH3OH-O2 fuel cell

Hydrogen oxygen fuel cell:

This cell is a common type of fuel cell. Similar to a galvanic cell, fuel cell also have
two half cells. Both half cells have porous graphite electrode with a catalyst (platinum, silver
or a metal oxide). The electrodes are placed in the aqueous solution of NaOH or KOH which
acts as an electrolyte. Hydrogen and oxygen are supplied at anode and cathode respectively at
about 50 atmospheric pressure, the gases diffuse at respective electrodes. The two half-cell
reactions are as follows;

At anode: 2H2 (g) + 4OH- (aq)  4H2O (l) + 4e-

At cathode: O2 (g) + 2H2O (l) + 4e-  4OH- (aq)

The net reaction: 2H2 (g) + O2 (g)  2H2O (l)

The EMF of this cell is measured to be 1.23V. A number of such fuel cell are stacked together
in series to make a battery.
Advantages:
1. The energy conversion is very high (75-82%).
2. Fuel cell minimizes expensive transmission lines and transmission losses.
3. It has high reliability in electricity generation.
4. The byproducts are environmentally acceptable.
5. Maintenance cost is low for these fuels.
6. They save fossil fuels.
7. Noise and thermal pollution are very low.
8. They have low maintenance cost.
9. They have quick start system.

Disadvantages:
1. The major disadvantage of the fuel cell is the high cost and the problems of durability and
storage of large amount of hydrogen.
2. The accurate life time is also not known.

APPLICATIONS:
1. The most important application of a fuel cell is its use in space vehicles, submarine or
military vehicles.
2. The product H2O is valuable source of fresh water by the astronauts.
3. It is hoped that fuel cell technology will bring a revolution in the area of energy
production.
4. Fuel cell batteries for automotive will be a great boom for the future.

Limitations:
1. The life time of fuel cells is not accurately known
2. It cannot store electricity
3. Electrodes are expensive ad short lived.
4. Storage and handling of H2 gas is dangerous because it is inflammable.