Chemistry

CYL1010

Instructor: Dr. Suresh Sarkar

Email: [email protected]
Office: Chemistry Department, #319

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Contents

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 Contents

• Surface Chemistry[3 Lectures]: Surfaces and interfaces, surface modification, surface

energy, contact angle and surface tension.

• Solid State Chemistry [6 Lectures]: Lattice and Unit Cells, X-Ray Diffraction, Bands in solids,
semiconductors, Introduction to nanomaterials based on dimensionality and properties.

• Electrochemical Systems [5 Lectures]: Electrochemical cells and EMF, Applications of EMF

measurements: Steady state approximation, Chain reactions, photochemical kinetics, Fuel Cells
and Batteries, OER and HER reactions, Corrosion

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 INTRODUCTION:

Electro chemistry is the branch of chemistry which deals

with transformation of electrical energy into chemical
energy vice versa.
• Electrochemistry serves as an interface between chemistry and everyday life.
When we switch on calculator, a computer, a radio,start a car, use mobile
phone , use a digital watch, and so on we are depending upon the
electrochemical reactions occurring in the cells or batteries.
A number of Electro chemical industries have been established on the concept
of electrochemistry:
• Electro refining(Cu), Electro plating(Ni, Cr, Au,Ag) ,Fused electrolysis(Al,
Mg,Na), Electro thermal(CaC2,Graphite,SiC) , Electrolytic furnacing (Alloy
steels) , Chemical to electrical Conversion (batteries, fuel cells), Gas phase
electric discharge(O3)
In addition to the above industries, the chemical Engineer uses Electro
chemical principle in dealing with corrosion phenomena.
 Electric power conversion in
electrochemistry
Electrolysis / Power consumption

Electric Chemical
Power Reactions

Electrochemical battery / Power generation

 Electrochemistry

Electrochemistry
•Cell Potentials and Standard cell potentials, EMF
•Galvanic cells/Voltaic Cell
• Electrolytic cells
• Faraday’s Law of Electrolysis
•Applications
 Electrochemistry
• Much of the early work on cell physics & chemistry came
from Michael Faraday - 1791 to 1867
• He was responsible for uncovering ONs, terminology
(anode, cathode, etc), benzene, electromagnetism, Faraday’s
Laws & Faraday’s constant.
• 1 Faraday = Charge on 1 mole of electrons = 96,500 c.
 Electrochemistry
 Redox reaction are those involving the oxidation and reduction
of species.
LEO says GER…
Losing electrons  Oxidation
Gaining Electrons  Reduction

NOTE: Oxidation and reduction must occur together.

They cannot exist alone.

Oxidation
Half-Reaction:
Zn(s)  Zn2+(aq) + 2 e–.
Reduction:
Half-Reaction:
Cu2+(aq) + 2 e–  Cu(s)
 Oxidation and Reduction

 A species is oxidized when it loses electrons.

– Here, zinc loses two electrons to go from neutral zinc metal to the
Zn2+ ion.
 A species is reduced when it gains electrons.
– Here, each of the H+ gains an electron and they combine to form H2.
 What is reduced is the oxidizing agent.
– H+ oxidizes Zn by taking electrons from it.
 What is oxidized is the reducing agent.
– Zn reduces H+ by giving it electrons.
 Electrochemistry

 The study of chemical reactions that produce electricity, and

chemical reactions that occur due to electricity.

 There are many processes that take place because of

electrochemical rxns:

 Electroplating

 Electrolysis of water

 Production of aluminum metal

 Storage of electricity in batteries

 Electrochemical Cells

• Any electrochemical cell must consist of two electrodes.

• The current can flow only between two electrodes with different potentials.
• Every electrode is immersed in an electrolytic solution.
• The two electrolytic solutions are separated by porous separator.
• The electrodes ends, which not exposed to the electrolyte, are connected with each
other by a metallic conductor.
• The current will be carried by electrons in the external conductors, whereas, ions carry
it in the electrolytic solution.
 Electrochemical Cells

There are two main types of electrochemical cells according the direction of the
electric current.

 One of these cells is used in production of electric current by chemical reactions.

Galvanic cell.
 The other type of cells can produce chemical reaction using an electric current.

Electrolytic cell.
 Difference between Electrolytic cell and
Electrochemical cell:
• Electrolytic cell – anode is positive
• Electrochemical cell (galvanic)- anode is negative
• Oxidation always happens at the anode ,reduction always happens at the cathode,
that is independent if cell is Electrolytic cell or Electrochemical cell. The
electrons are always going to be moving from the anode to the cathode. If the cell
is spontaneous, as galvanic is, it makes sense that the electrons will be moving
towards positive electrode, the cathode is positive while for electrolytic, which is
not spontaneous, an electron is actually being forced to move towards a negative
pole ,hence the cathode is negative.
• In the voltaic cell, the current flows from positive electrode (+) to the negative
electrode (-) outside the cell .
• In the electrolytic cell the currents flows from positive electrode to the negative
electrode inside the cell.
• Voltaic cell can become an electrolytic cell by use of an external voltage greater
than the voltaic cell voltage and imposed in opposite direction.
ELECTROCHEMICAL CELLS/GALAVANIC CELL:

• An Electrochemical cell is a device in which a redox

reaction is utilized to get electrical energy

Ex: Daniel cell

Daniel cell consists of zinc and copper electrodes. Zn

electrode is dipped in ZnSO4 solution & Cu is dipped
in CuSO4 solution.
Zn --> Zn2+ + 2e- Cu2+ + 2e- --> Cu
wire
wire
eeleleccttro Reduction
rons
ns Cathode
Oxidation
Anode Zn
Zn salt
salt
bridge
bridge
Cu
Cu Positive

Negative

<--Anions
2+ Cations--> 2+
Zn
Zn2+ions
ions Cu
Cu2+ions
ions

•Electrons travel thru external wire.

Salt bridge allows anions and
cations to move between electrode
compartments.
 Galvanic cells (also called Voltaic cells)

anode cathode
oxidation reduction

spontaneous
redox reaction

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 Galvanic Cells
The difference in electrical
potential between the anode and
cathode is called:
• cell voltage
• electromotive force (emf)
• cell potential
Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)
[Cu2+] = 1 M and [Zn2+] = 1 M
Cell Diagram

phase boundary
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode salt bridge cathode
Electromotive Force (emf): Cell Potentials
• Water only spontaneously flows
one way in a waterfall.
• Likewise, electrons only
spontaneously flow one way in a
redox reaction—from higher to
lower potential energy.

E = +1.10 V
 Cell reaction:
At Anode
Oxidation takes place: Zn  Zn2+ + 2e-
At Cathode
Reduction takes place: Cu2+ + 2e-  Cu
The over all reaction is:
Zn + CuSO4  ZnSO4 + Cu
The two solutions separated by a porous
membrane, a current is seen to be flow on
connecting the two wires externally.
The cell function due to dissolution of zinc and
the simultaneous deposition of copper.

The over all reaction is:

Zn + CuSO4  ZnSO4 + Cu
The cell may be represented as:
Zn/ZnSO4 // CuSO4/Cu
 Uses of salt bridge:
• If you have no salt bridge, eventually all of
the electrons from anode are going to move
into the cathode and have zero electrons flow.
• It completes the circuit by connecting the
electrodes at the electrode side.
• It maintains electrical change neutrality in both
the compartments during cell operation by
selectively providing anions to anode and
cations to cathode.
 Cell Potentials
Calculation of the cell potential
Any one the following two ways could be used to calculate the emf of a galvanic cell:
 The general way: emf equals to the algebraic sum of the anodic and cathodic electrode
potentials.
emf = e (anode) + e (cathode)
In this equation, the oxidation potential must be used for anodic half-reaction and the reduction potential
must be used for the cathodic half-reaction.
 The European way: emf is the difference between the cathodic and anodic electrode potentials.
emf = e (cathode) – e (anode)
In this case, the reduction potential must be used for both the cathodic and anodic half-reactions.
• Or the American way: emf is the difference between the anodic and cathodic electrode

potentials.
emf = e (cathode) – e (anode)
In this case, the oxidation potential must be used for both the anodic and cathodic half-reactions.
 EMF:
• In an electrochemical cell the potential difference across the
electrodes operates as a driving force for the flow of electrons
in one direction and there by making current to flow in
opposite direction and is known as cell potential/electromotive
force(emf). It can be expressed in terms of both reduction
potential and oxidation potential. In terms of tendency to gain
electron, i.e., reduction potential of the cathode remains at
higher potential. On the other hand , with respect to tendency
to lose electron i.e., oxidation potential of the anode remains at
higher potential
• In terms of reduction potential Commonly
represented
• E o Cell = E ocathode –E o anode or E oRight – E oLeft

In terms of oxidation potential

• E o Cell = E o anode - E o cathode
 Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)

Anode: Zn(s)  Zn 2+
+ 2e - Cathode: Cu2+(aq) + 2e-  Cu(s)
(aq)

Ean = +0.76 V Ecat = +0.34 V

The shorthand notation for this cell is:

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

Cell potentials
 The cell potential, E, is a measure of how well a cell reaction can push and
pull electrons through a circuit
 The electrical energy generated by the spontaneous reaction is
proportional to the cell potential.

 The standard cell potential (the cell potential measured when all the species
are in their standard states) is given by:
E°cell = E°cathode - E°anode
• EMF of the total cell is equal to the sum of oxidation
potential and reduction potential of the right-hand
electrode minus left hand electrode.
• Ecell = ER –EL
• Generally, electrode potential refers to the reduction potential.
for example: ER of Cu+2 / Cu = 0.337V
EL of Zn / Zn+2 = -0.763V
Ecell = ER –EL
=0.337-(-0.763)
=0.337+0.763
=1.1V
• Generally, reduction potential can be expressed in terms of oxidation potential
With negative symbol before it. For ex the oxidation potential of Cu +2 / Cu = -0.337V
But when it is substituted in the place of reduction it must be substituted with out negative
symbol.
for example: ER of Cu+2 / Cu = -0.337V
EL of Zn / Zn+2 = +0.763V
Ecell = ER +EL
= 0.763-(-0.337)
= 0.763+0.337
=1.1V
According to IUPAC convention the standard reduction potentials alone are the standard
potentials.
Direction of spontaneous reaction:
If Ecell > 0 , the cell reaction has a tendency to go from left to right. If the E cell < 0 the cell
reaction will have a tendency to go from right to left. The reaction is spontaneous or feasible
only when Ecell is positive.
Standard Cell Potentials (Eo )

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 Standard Cell Potentials (Eo )
 The cell potential at standard conditions can be found by
looking up the reduction potentials for each half reaction on a
table.

 The standard cell potentials (net E0) of all galvanic cells have
positive values and happen spontaneously.

 The oxidation half reaction will be reversed from how it appears on

the table, and the value of it’s voltage will have a reversed sign too.

Eo is a quantitative measure of the tendency of reactants to proceed to products when

all are in their standard states at 25 °C.
 Standard Reduction Potentials
 Standard reduction potential (E0) is the voltage associated with a
reduction reaction at an electrode when all solutes are 1 M and all
gases are at 1 atm.

Reduction Reaction
2e- + 2H+ (1 M) H2 (1 atm)
E0 = 0 V

• Can’t measure half- reaction Eo directly.

Therefore, measure it relative to a standard HALF
CELL: the Standard Hydrogen Electrode (SHE).

Standard hydrogen electrode (SHE)

 Standard Reduction Potentials of Zn (s) | Zn2+ (1 M)

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Anode (oxidation): Zn (s) Zn2+ (1 M) + 2e-
Cathode (reduction): 2e- + 2H+ (1 M) H2 (1 atm)
Zn (s) + 2H+ (1 M) Zn2+ (1 M) + H2 (1 atm)
 Standard Reduction Potentials
Ecell
0
= 0.76 V

Standard emf (Ecell

0
)
Ecell
0
= E0cathode - Eanode
0

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Ecell
0
= E0H+/H2 - EZn
0 2+
/Zn

0.76 V = 0 - E0Zn2+/Zn
E0Zn2+/Zn = -0.76 V
Zn2+ (1 M) + 2e- Zn E0 = -0.76 V
 Standard Reduction Potentials of Cu2+ (1 M) | Cu (s)

Ecell
0
= 0.34 V
Ecell
0
= E0cathode - Eanode
0

E0cell = E0Cu2+/Cu – EH0 +/H 2

0.34 = E0Cu2+ /Cu - 0

E0Cu2+/Cu = 0.34 V

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

Anode (oxidation): H2 (1 atm) 2H+ (1 M) + 2e-
Cathode (reduction): 2e- + Cu2+ (1 M) Cu (s)
H2 (1 atm) + Cu2+ (1 M) Cu (s) + 2H+ (1 M)
 Standard Reduction Potentials

The species
with the more
positive (V)
will be
reduced.

The species
lowest on the
table, and the
more negative
(V) will be
oxidized.
 Standard Reduction Potentials

 The more positive E0 the greater the tendency for the substance to
be reduced
 The half-cell reactions are reversible.
 The sign of E0 changes when the reaction is reversed
 Changing the stoichiometric coefficients of a half-cell reaction
does not change the value of E0
 Relation of Eo and DGo

Eo is related to DGo, the free

energy change for the reaction.
DGo = - n F Eo
• F = Faraday constant
= 9.6485 x 104 J/V•mol
Michael Faraday
• n = the number of moles of 1791-1867
electrons transferred. Discoverer of
• electrolysis
• magnetic props. of matter
• electromagnetic induction
Zn / Zn2+ // Cu2+ / Cu • benzene and other
n for Zn/Cu cell ? n=2 organic chemicals
 Have relationship between Gibbs Free Energy and Equilibrium constant:
ΔG° = - RT lnK
 ΔG for a reaction depends on the concentration by:

ΔG = ΔG° + RT ln Q where Q is the reaction quotient = [product]

[reactant]
 Nernst Equation
ΔG = -n F Ecell and ΔG° = - n F E°cell

-nFEcell = -nFE°cell + RT ln Q

Dividing across by nF gives: Ecell = E°cell – RT ln Q

nF
i.e. the cell potential at any conditions depends on the potential under standard
state conditions and a term for the potential at nonstandard-state conditions
Relationships between ∆G◦, K , E ◦ cell

Spontaneity of Redox Reactions

DG0 = -RT ln K= -nFEcell

0
 Electrolytic cells
• Use an applied voltage to carry out a nonspontaneous chemical
reaction  ΔG > 0
• Electric current supplied by an external source

Power
Supply

Cathode Anode
e.g. inert Ti e.g. inert Ti

 Cl- Na+ 

Electrolyte, e.g.
NaCl

• External source must provide a greater potential than that for the
spontaneous reverse reaction
• Electrolysis = process in which electrical energy is used to cause a
non-spontaneous chemical reaction to occur
Molten sodium chloride (NaCl) can be subjected to electrolysis with the help of an electrolytic
cell, as illustrated below.

Here, two inert electrodes are dipped into molten sodium chloride (which contains dissociated
Na+ cations and Cl– anions). When an electric current is passed into the circuit, the cathode
becomes rich in electrons and develops a negative charge. The positively charged sodium
cations are now attracted towards the negatively charged cathode. This results in the
formation of metallic sodium at the cathode.
Simultaneously, the chlorine atoms are attracted to the positively charged cathode. This
results in the formation of chlorine gas (Cl2) at the anode (which is accompanied by the
liberation of 2 electrons, finishing the circuit). The associated chemical equations and the
overall cell reaction are provided below.
Reaction at Cathode: [Na+ + e– → Na] x 2
Reaction at Anode: 2Cl– → Cl2 + 2e–
Cell Reaction: 2NaCl → 2Na + Cl2
Thus, molten sodium chloride can be subjected to electrolysis in an electrolytic cell to 40
generate metallic sodium and chlorine gas as the products.
Applications of Cells

41
 Applications of Cells
• Electrochemistry can be applied as follows:

 Electrolytic cell: Electrolysis, electroplating….etc.

 Batteries: a portable, self-contained
electrochemical power source that consists of one
or more voltaic cells.
 Batteries can be primary cells (cannot be
recharged when “dead”—the reaction is
complete) or secondary cells (can be
recharged).
 Applications of Electrolytic Cells
• The primary application of electrolytic cells is for the production of
oxygen gas and hydrogen gas from water.
• Another notable application of electrolytic cells is in electroplating,
which is the process of forming a thin protective layer of a specific
metal on the surface of another metal.
• They are also used for the extraction of aluminium from bauxite.
• The electrorefining of many non-ferrous metals is done with the help
of electrolytic cells.
• Such electrochemical cells are also used in electrowinning processes.
• It can be noted that the industrial production of high-purity copper,
high-purity zinc, and high-purity aluminium is almost always done
through electrolytic cells.

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Electrolysis of water
• Electrolysis of water is the
decomposition of water into
oxygen and hydrogen gas due to
the passage of an electric current.

• The reaction has a standard

potential of −1.23 V, meaning it
ideally requires a potential
difference of 1.23 volts to
split water.

• In a non-spontaneous reaction the

E0net is always less than zero.
Electroplating

Electroplating is a procedure that

uses electrolysis to apply a thin
layer of a metal over the surface of
another metal.
 Electroplating
• In electroplating, the anode is made up of the metal you want to use to coat the
surface of another metal.

• A salt solution containing the metal that makes up the anode is used. During
electrolysis, the anode metal is oxidized and goes into solution as positive ions.

• These positive ions are then reduced on the surface of the cathode (the metal
you are coating)
Calculating plating
• Have to count charge.
• Measure current I (in amperes)
• 1 amp = 1 coulomb of charge per
second
• q=Ixt
• q/nF = moles of metal
• Mass of plated metal
• Faraday Constant (F)
(96,480 C/mol e-) gives the amount of
charge (in coulombs that exist in 1
mole of electrons passing through a
circuit.
• 1volt = 1joule/coulomb
Faraday’s Law of Electrolysis: the quantity (moles) of product formed by an
electric current is stoichiometrically equivalent to the amount (moles) of
electrons supplied
Faradays
Current + Time Charge Moles of electrons
constant

Using Faradays Law!

y
etr
iom
i ch
st o
Molar mass
Mass product Moles product

Problem: How many grams of copper are deposited on the cathode of an

electrolytic cell if an electric current of 2.00A is run through a solution of
CuSO4 for a period of 20min?
 Calculating plating
1. Current x time = charge How many grams of copper are
deposited on the cathode of an
2. Charge ∕Faraday = mole of electrolytic cell if an electric current of
e- 2.00A is run through a solution of
CuSO4 for a period of 20min?
3. Mol of e- to mole of
element or compound How many hours would it take to
4. Mole to grams of produce 75.0g of
compound metallic chromium by the electrolytic
reduction of Cr3+ with a current of 2.25
A?

or the reverse these steps

if you want to find the
time to plate
How many grams of copper are deposited on the cathode of an electrolytic cell if an
electric current of 2.00A is run through a solution of CuSO 4 for a period of 20min?

Answer:
Cu2+(aq) + 2e- →Cu(s)

2.00A = 2.00C/s and 20min (60s/min) = 1200s

Coulombs of e- = (2.00C/s)(1200s) = 2400C

mol e- = (2400C)(1mol/96,480C) = .025mol

(.025mol e-)(1mol Cu/2mol e-) = .0125mol Cu

g Cu = (.0125mol Cu)(63.55g/mol) = .79g

 Applications of Cells
• Electrochemistry can be applied as follows:

 Electrolytic cell: Electrolysis, electroplating….etc.

 Batteries: a portable, self-contained
electrochemical power source that consists of one
or more voltaic cells.
 Batteries can be primary cells (cannot be
recharged when “dead”—the reaction is
complete) or secondary cells (can be
recharged).
 What is a battery?
• It is something that converts chemical energy into electrical
energy.
• They produce current via redox reactions:
– Red=reduction (gaining electrons)
– Ox=oxidation (losing electrons)
• Batteries are essentially Voltaic Cells connected in series.

a cell or connected group of cells that converts chemical energy into electrical energy by
reversible chemical reactions and that may be recharged by passing a current through it in
the direction opposite to that of its discharge -- called also storage cell.
 What is a voltaic cell?
Major components:
ZINC
• Metals
• Electrolytes ZnSO4(aq

• “Salt Bridge” 1.0 Molar

• Wire
AGAR

Battery lifetime depends

on the mass of metal in CuSO4(aq) WIRE
the electrodes. 1.0 Molar

COPPER
Cells

• Positive electrode
• Negative electrode
• Electrolyte
• Separator
 Galvanic cells (also called Voltaic cells)

anode cathode
oxidation reduction

spontaneous
redox reaction

55
 How much energy can it make?
• You can predict the voltage (direct current) between
any two materials based on reduction potentials.
• A reduction potential, Eocell, is the difference between
the standard reduction potential of the cathode
(Eored(cathode)) and the anode (Eored(anode)).

Eocell= Eored(cathode)-Eored(anode)
 How much energy can it make?
Step 1: Write the reaction. Zn(s)
+Cu2+(aq)→Zn2+(aq)+Cu(s)
Step 2: Look up values.
Eored(cathode)= 0.337V 1.044 Volts

Eored(anode)= -0.763V
Eocell= 0.337V-(-0.763V)

Eocell= 1.10V

Actual voltage=1.044V
 How can you get more energy?
1. Connect several cells in series
(1.044V+1.044V+1.044V…)
2. Work outside of standard conditions (concentration,
temp, etc.)
3. Use different compounds for the electrodes.
The greatest voltages are from a combination
of the compound with the most negative potential
(anode) and the most positive (cathode). These
happen to be Li and F, respectively.
 Electrode Combinations
Below: Magnesium anode and Zinc
cathode
Expected Vocell=1.607V
Observed Vocell=0.63V

Above: Zinc anode and IronIII

cathode
Expected Vocell=1.534V
Observed Vocell=0.70V
 Electrode Combinations
Below: Magnesium anode and
Copper cathode
Expected Vocell=2.707V
Observed Vocell=1.923V

Above: IronIII anode and Copper

cathode
Expected Vocell=0.434V
Observed Vocell=0.432V
 Electrode Combinations

Above: Magnesium anode and IronIII cathode

Expected Vocell=3.141V
Observed Vocell=1.373V
63
 Environmental Impacts
• Some electrodes are made of hazardous materials
– Cadmium in Ni-Cd batteries
– Lead in lead-acid batteries (like a car battery)
– Mercury-electrode batteries (banned in 1996)
– Arsenic and Antimony in lead-acid batteries
• When batteries are not recycled, they ultimately end up
contaminating soil, air, water, and finally end up in the food
chain.
• Using secondary (rechargeable) batteries helps to prevent
pollution.
 Types of Batteries
The primary battery converts chemical energy to
electrical energy directly, using the chemical
materials within the cell to start the action.
The secondary battery must first be charged with
electrical energy before it can convert chemical
energy to electrical energy.
The secondary battery is frequently called a storage
battery, since it stores the energy that is supplied to
it.
66
 Examples of Batteries

• Lead–acid battery: reactants and products are solids, it is made with lead and sulfuric
acid (hazards).
• Alkaline battery: most common primary battery.
• Ni–Cd and Ni–metal hydride batteries: lightweight, rechargeable; Cd is toxic and
heavy, so hydrides are replacing it.
• Lithium-ion batteries: rechargeable, light; produce more voltage than Ni-based
batteries.
Alkaline Battery Lithium-Ion Battery
Lead–Acid Battery
 Primary cells
Primary cells are not rechargeable and are
generally disposed of after the cell's internal
reaction has consumed the reactive starting
chemicals.

•Zinc–carbon cell
•Alkaline cell
•Lithium cell
•Mercury cell
•Silver-oxide cell

•Zinc–carbon cell
 Zinc carbon battery is being popularly used during last 100 years. Generally
Zinc Carbon Battery there are two types of zinc carbon battery generally available – Leclanche
Voltage: 1.5–1.75 V battery and Zinc chloride battery. Both of these are primary battery. This
battery was invented by Goerge Lionel Leclanche in 1866. This was the first
battery in which low corrosive electrolyte like ammonium chloride was used.
Before that only strong mineral acids were used as electrolyte of battery system.
In this battery cell, one glass jar was used as main container. The container was
filled with ammonium chloride solution as electrolyte. An amalgamated zinc
rod was immersed in this electrolyte as negative electrode or anode. In this
Leclanche battery cell, a porous pot was filled with one to one mixture of
manganese dioxide and carbon powder. A carbon rod was inserted into this
mixture. The porous pot along with the mixture and carbon rod served as
positive electrode or cathode and this was placed in the ammonium chloride
solution in the jar.In 1876, Leclanche himself improved his own prototype
design of zinc carbon battery. Here he mixed a resin gum binder with
manganese dioxide and carbon powder to form a compressed solid block of the
mixture by hydraulic pressure. Due to this solid structure of cathode mixture,
there is no further need of porous pot in Leclanche battery cell. In 1888, Dr. Carl
Gassner, further developed the construction of Leclanche cell. Here he used a
paste of plaster of Paris and ammonium chloride as electrolyte, instead of liquid
ammonium chloride. Instead of inserting a zinc rod inside the electrolyte in
glass container, he made the container by zinc itself. Hence this container also
serves as anode of the battery. He minimized local chemical action in his
battery by wrapping zinc chloride – ammonium chloride saturated cloths to the
cylindrical cathode mix block. Later he replaced plaster of Paris by wheat flour,
in electrolyte mixture. This was the first commercial design of dry zinc carbon
battery cell. This was not the end of journey. After 1960, more effort was
directed in development of zinc chloride battery cell. This is also a popular
version of zinc carbon battery. Here, zinc chloride is used as electrolyte instead
of ammonium chloride. This was developed to provide better performance in
the heavy drain application. In other words, zinc chloride battery is improved
69
substitute of Leclanche’ battery in heavy drain applications.
Chemical Reaction in Zinc Carbon Battery
In Leclanche battery cell, zinc is used as anode, manganese dioxide is used as cathode
and ammonium chloride is used as main electrolyte but there is some percentage of zinc
chloride in the electrolyte. In zinc chloride battery cell, zinc is used as anode, manganese
dioxide is used as cathode and zinc chloride is used as electrolyte.
In both of the zinc carbon battery, during discharge, zinc anode involves in oxidation
reaction and each zinc atom involved in this reaction releases two electrons.

These electrons come to the cathode through external load circuit.

In Leclanche battery cell ammonium chloride (NH4Cl) exists in electrolyte mixture as
NH4+ and Cl –. In cathode MnO2 will be reduced to Mn2O3 in reaction with ammonium
ion (NH4+). In addition to Mn2O3 this reaction also produces ammonia (NH3) and water
(H20).

But during this chemical process some of ammonium ions (NH 4+ ) are directly
reduced by electrons and form gaseous ammonia (NH 3) and hydrogen(H2)

In zinc carbon battery this ammonia gas further reacts with zinc chloride (ZnCl 2) to
form solid zinc ammonium chloride and gaseous hydrogen reacts with manganese
dioxide to form solid di-manganese trioxide and water. These two reactions prevent
formation of gas pressure during discharging of battery. 70
71
72
73
secondary battery

74
75
76
 Lead Acid Batteries

Most important application of lead is in lead acid storage batteries for which more
than 85% of the world production of lead is currently used.

Discharge
PbO2 + 2 H2SO4 + Pb PbSO4 + 2 H2O + PbSO4
Charge
Positive Negative Positive Negative
Plate Plate Plate Plate

Active Electrolyte Active Discharge Discharge

Material Material Material Material

Very
PbO2 H2SO4 (aq) Pb PbSO4 Dilute PbSO4
H2SO4

Fully Charged State Fully Discharged State

 Lead Storage
Battery
• Con-proportionation
reaction - same species
Anode (-) Eo = +0.36 V produced at anode and
cathode
- 
Pb(s) + HSO 4
 PbSO4(s) + H+ + 2e- • RECHARGEABLE

Cathode (+) Eo = +1.68 V


PbO2(s) + HSO4- + 3 H+ + 2e- PbSO4(s) + 2 H2O


Overall battery voltage = 6 x (0.36 + 1.68) = 12.24 V

Working of lead acid battery:
•Dilute sulfuric acid used for lead acid battery has
ratio of acid: water = 1:3. This lead acid storage
battery is formed by dipping lead peroxide plate
and sponge lead plate in dilute sulfuric acid. A
load is connected externally between these
plates.
•During Discharging: In diluted sulfuric acid the
molecules of the acid split into positive hydrogen
ions and negative sulfate ions . The hydrogen ions
when reach at PbO2 plate, they receive electrons
from it and become hydrogen atom which again
attack PbO2 and form PbO and H2O (water). This
PbO reacts with H2SO4 and forms PbSO4 and H2O.

• SO4– ions are moving towards Pb plate where

they give their extra electrons and react with Pb
and forms PbSO4
79
 Ventilation Requirements
• The oxygen and hydrogen gases released during the gassing phase of a typical
flooded lead-acid battery recharge can be dangerous if allowed to exceed 0.8 % (by
volume) or 20 percent of the lower explosive range. Concentrations of hydrogen
between 4 % and 74% are considered explosive (40,000 ppm and 740,000 ppm).
• All lead acid power batteries give off gases when recharging and also for a period
after the charge is completed.
– A Concentration of hydrogen in excess of 4% (by volume). It is suggested that
the concentration be controlled to a maximum of 2% (by volume).
• A typical lead acid motive power cell will, evolve approximately .016 cubic feet of
hydrogen gas over A.H. overcharge.
• Since this gas is given off at the maximum rate at the end of the charging period,
the following calculation assumes a charging current of 5% of the 6 hour A.H.
capacity (C6) during this over charge period. (This charging current is excessive but
has been used to take account of the worst case.)
• Gas given off per hour per cell = 0.16 x .05 = .0008 C6 cu / ft. / cell / hr.
 Applications of lead acid battery

• These are used in automobiles for lighting and starting

the vehicles. In some cases, these batteries supply current
to music system etc. fitted into automobiles.
• These are used to deliver power to the lighting system in
steam fed and diesel railway trains.
• These are used at generating stations and sub station to
operate the controlling equipment.
• These are used in telephone exchanges.
• These are used to operate loudspeakers etc.
• These are used to provide emergency lights etc.

82
 Nickle cadmium battery
Nickel-cadmium batteries, generally referred to as NiCad batteries, are in wide use in the
aviation industry. With proper maintenance, they can provide years of trouble-free service.

Positive plate- Nickel hydroxide(Ni(OH)4)

Negative plate- Cadmium(Cd)
Electrolyte- potassium hydroxide(KOH) with a small addition of lithium hydrate.
Discharging : At cathode: Cd+2OH → Cd(OH)2
At anode: Ni(OH)4 +2K → 2KOH+Ni(OH)2

Charging: At anode: Ni(OH)2 +2OH → Ni(OH)4

At cathode: Cd(OH)2+2K → Cd+2KOH

83
 Secondary (rechargeable) Batteries

Nickel-Cadmium

Anode (-)

Cd + 2 OH-  Cd(OH)2 + 2e-
Cathode (+) 

NiO(OH) + H2O + e- Ni(OH)2 + OH-
Nickel--metal hydride batteries
Lithium-ion battery
 Fuel Cells
• When a fuel is burned, the energy created can be converted to electrical energy.
• Usually, this conversion is only 40% efficient, with the remainder lost as heat.
• The direct conversion of chemical to electrical energy is expected to be more
efficient and is the basis for fuel cells.
• Fuel cells are NOT batteries; the source of energy must be continuously provided.

 A fuel cell converts a chemical fuel, such as hydrogen (used for larger power
requirements) or methanol (a convenient fuel for small applications), directly into
electrical power, using O2 or air as the oxidant. As power sources, fuel cells offer
several advantages over rechargeable batteries or combustion engines, and their
use is steadily increasing.

First developed by William Grove In 1839, Grove was experimenting on electrolysis (the
process by which water is split into hydrogen and oxygen by an electric current), when he
observed that combining the same elements could also produce an electric current
Advantages over conventional energy sources They produce zero or very low emissions,
especially Green House Gases (GHGs) depending on the fuel used. Have few moving parts and
thus require minimal maintenance, reducing life cycle costs of energy production. Modular in
design, offering flexibility in size and efficiencies in manufacturing Can be utilized for combined
heat and power purposes, further increasing the efficiency of energy production

Working Principle
A fuel cell is a device that uses hydrogen (or hydrogen-rich fuel) and oxygen to create electricity
by an electrochemical process. A single fuel cell consists of an electrolyte sandwiched between
two thin electrodes (a porous anode and cathode) Hydrogen, or a hydrogen-rich fuel, is fed to the
anode where a catalyst separates hydrogen's negatively charged electrons from positively charged
ions (protons) At the cathode, oxygen combines with electrons and, in some cases, with species
such as protons or water, resulting in water or hydroxide ions, respectively

The electrons from the anode side of the cell cannot pass through the membrane to the
positively charged cathode; they must travel around it via an electrical circuit to reach the other
side of the cell. This movement of electrons is an electrical current. The amount of power
produced by a fuel cell depends upon several factors, such as fuel cell type, cell size, the
temperature at which it operates, and the pressure at which the gases are supplied to the cell
Still, a single fuel cell produces enough electricity for only the smallest applications. Therefore,
individual fuel cells are typically combined in series into a fuel cell stack. A typical fuel cell stack
may consist of hundreds of fuel cells
89
Fuel cells are classified primarily by the kind of electrolyte they employ. This determines the
kind of chemical reactions that take place in the cell, the kind of catalysts required, the
temperature range in which the cell operates, the fuel required, and other factors. There are
several types of fuel cells currently under development, each with its own advantages,
limitations, and potential applications

Classification of Fuel Cells Based on the type of Electrolyte

1. Alkaline Fuel cell (AFC)
2. Phosphoric Acid Fuel cell (PAFC)
3. Polymer Electrolytic Membrane Fuel Cell (PEMFC) Solid Polymer Fuel Cell (SPFC) and Proton
Exchange Membrane Fuel cell (PEMFC)
4. Molten Carbonate Fuel Cell (MCFC)
5. Solid Oxide Fuel Cell (SOFC)

90
 Fuel Cells

Basic energy conversion of a fuel cell can be described as: Chemical energy of fuel =
Electrical energy + Heat energy
 Hydrogen Fuel Cells
• In this cell, hydrogen
and oxygen form water.
• The cells are twice as efficient as
combustion.
• The cells use hydrogen gas as the fuel
and oxygen from the air.
Application of EMF measurement

How? Detail description with picture as per required

93
 Assigning Oxidation Numbers
1. Elements in their elemental form are given a zero.
2. Monatomic ions are the same as their charge.
3. Nonmetals tend to have negative oxidation numbers, although there
are some exceptions:
– Oxygen has an oxidation number of −2, except in peroxide where it
has a −1.
 Hydrogen is −1 when bonded to a metal, +1 when bonded to a
nonmetal
4. In a neutral compound the sum of the ox #s is zero..
5. In a polyatomic ion is the sum of the ox #s is the charge on the ion.
6. Nonmetals tend to have negative oxidation numbers, although some
are positive in certain compounds or ions.
– Fluorine always has an oxidation number of −1.
– Halogens unless bonded to oxygen in a polyatomic ion.
– ClO3 - , the chlorine is a +5
 Galvanic Cells

Electrochemical cell notation

The following line notation must be considered when describing a galvanic cell:
 The line notation for the anode is written before that of the cathode.
 A single vertical line indicates a change in state or phase.
 The reactants are written before the product, in every half-cell.

 The concentrations of aqueous solutions are written in parentheses after the symbol for ion
or molecule.
 A double vertical line indicates a separation between two liquids with the diffusion potential
is completely eliminated.
 A dashed line indicates a separation between two liquids with the presence of liquid junction
potential (diffusion potential).
 Galvanic cells (also called Voltaic cells)
 Use spontaneous chemical reactions to generate electrical energy in the form of an
electrical current  ΔG < 0
e-

Anode Cathode
e.g. Zinc electrode Salt Bridge e.g. Copper electrode

-
+

Electrolyte, e.g. Electrolyte, e.g.

ZnSO4 CuSO4

• Made up of two half cells Most batteries are made from

• Oxidation (loss of electrons) occurs at the negative anode Voltaic cells!
• Reduction (gain of electrons) occurs at the postive cathode
• Salt bridge acts to complete the circuit by joining the two half cells together
 V. Few More Applications of Electrochemistry

 pH electrode: AgCl(s) + H+Inside (---) Ag(s) + H+outside + Cl-

[Cl-] = 1 M n = 1 [H+Inside ] = constant

Ecell = Eo - (0.0592/n) Log Q = Eo - 0.0592 Log {[H+out ]x[Cl-] / [H+Ins ]}
Ecell = K’ - 0.0592 Log [H+out ] = K’ + 0.0592 pH

Ecell = 0.0592 pH + K’ [1) Eqn a pH meter uses; 2) a plot of voltage vs pH will

be a straight line with a slope of 0.0592; 3) when calibrating a pH meter, you are
setting the slope = 0.0592 and the Y intercept = K’ ]

 Other Ion Specific Electrodes - Example: Fluoride Specific Electrode

typical F- ISE (ion-selective electrode)

F- F- LaF3 Crystal - Potential developed across membrane

Et = Constant - 0.0592 Log F- (at 25oC)
F- F- F- F- Note the potential interferences from the F lab.
 Gibbs Free Energy and Equilibrium
They can be used to together to
ΔG° = - RT lnK
find E(V)

The equilibrium constant for the reaction below is 1.8 × 1019 at 298K.
What is the value of the standard cell potential for this reaction?

Ni(s) + Hg2Cl2(s)  2Hg(l) + 2Cl-(aq) + Ni2+(aq)

ΔG = -RT ln K
= - (8.314 J K-1 mol-1) (298 K) ln (1.8 × 1019)
= - 109847.8 J mol-1
= - 1.098 × 105 J mol-1

E= -ΔG°
nF
= -(-1.098 × 105 J mol-1)
(2 mol) (96500 C)
= 0.57 J/C
 Question
Which of the following statements relating to electrochemistry are
correct?
(i) Oxidation involves the loss of electrons
(ii) Reduction involves the gain of electrons
(iii) Galvanic cells use electricity to produce chemicals
(iv) The anode in a Galvanic cell is positive
(v) Oxidation always occurs at the cathode
Answer: (i) and (ii)
Question
The standard potential of the Ag+/Ag electrode is +0.80 V and the
standard potential of the cell Fe (s)|Fe2+(aq)||Ag+(aq)|Ag(s) is +1.24 V. What
is the standard potential of the Fe 2+/Fe electrode?
Half reactions Fe  Fe2+ + 2e- Oxidation reaction - Anode
Ag+ + e-  Ag Reduction reaction - Cathode

E˚cell = Ecathode - Eanode

Eanode = Ecathode - E˚cell
Eanode = 0.80 V – 1.24 V
Eanode = -0.44 V
Question
If the standard cell potential at 298 K is 1.10 V for the following
reaction Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s), then what is the change in
Gibbs Free Energy?

ΔG° = -n F E°cell

Half reactions: Zn  Zn2+ + 2e-

Cu2+ + 2e-  Cu
n = no of moles of electrons = 2

F = Faradays constant = 96,500 C/mol

E°cell = 1.10 V = 1.10 J/C

ΔG° = - (2) (96500 C/mol) (1.10 J/C)

= - 212300 J/mol
= - 212.3 kJ/mol
 Question
The equilibrium constant for the reaction
Ni(s) + Hg2Cl2(s)  2Hg(l) + 2Cl-(aq) + Ni2+(aq)
is 1.8 × 1019 at 298K. What is the value of the standard cell potential
E°cell for this reaction?
ΔG° = -RT ln K
= - (8.314 J K-1 mol-1) (298 K) ln (1.8 × 1019)
= - 109847.8 J mol-1
= - 1.098 × 105 J mol-1

ΔG° = -n F E°cell

E°cell = -ΔG°
nF
= -(-1.098 × 105 J mol-1) = 0.57 J/C = 0.57 V
(2 mol) (96500 C)
How many hours would it take to produce 75.0g of
metallic chromium by the electrolytic reduction of Cr3+ with a current of 2.25 A?

Answer:
75.0g Cr/(52.0g/mol) = 1.44mol Cr

mol e- = (1.44mol Cr)(3mol e-/1mol Cr) = 4.32mol e-

Coulombs = (4.32mol e-)(96,480C/mol) = 416,793.6 C

(4.17x105C)

Seconds = (4.17x105C)/(2.25C/s) = 1.85x105 s

Hours = (1.85x105 s)(1hr/3600 s) = 51.5 hours

Question
If 306C of charge is passed through a solution of Cu(NO 3)2 during an
electrolysis experiment, what is the number of moles of copper metal
deposited at the cathode?
Cu(NO3)2  Cu2+ + 2NO3- Cu  Cu2+ + 2e-

 2 moles of electrons required to reduce 1 mol Cu 2+

charge = 306 C
No of moles e- =
Faradays constant 96500 C/mol

= 0.00317 moles of electrons

From reaction stoichiometry, 2 moles electrons ≡ 1 mole Cu
 0.00158 moles Cu deposited
Question
If 612 C of charge is passed through a solution of Cu(NO 3)2(aq), calculate
the number of moles of copper metal deposited.
Answer = 0.00317 mol
Question
How long will it take to deposit 0.00235 mol of metallic gold by
electrolysis of KAuCl4(aq) using a current of 0.214A?

KAuCl4(aq)  Au(s) Au3+ + 3e-  Au

 For every 1 mol Au produced, 3 mol electrons required

 For 0.00235 mol Au need 0.00705 mol electrons
Charge
No of moles electrons =
Faradays constant
ÞCharge = moles electrons × Faradays constant
= 0.00705 mol × 96500 C/mol
= 680 C
Charge = current × time Time = Charge/Current
= 680 C / 0.214 A 1C = 1As
= 680 As / 0.214 A
= 3179 s
= 53 mins
Quantitative Aspects of Electrolysis

• 1 coulomb = 1 ampere × 1 second

• Q = I t = nF
• Q = charge (C)
• I = current (A)
• t = time (s)
• n = moles of electrons that travel through the wire in the
given time
• F = Faraday’s constant
Note: n is different than that for the Nernst equation!

105
Question
How long will it take to deposit 0.0047 mol of gold by electrolysis of
KAuCl4 using a constant current of 0.214 A?
Answer: 106 minutes

Question
How much Ca will be produced in an electrolytic cell of molten CaCl 2 if
a current of 0.452 A is passed through the cell for 1.5 hours?
Answer: 0.5 g Ca
Question
If the standard cell potential at 298 K is 1.10 V for the following
reaction Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s), then what is the change in
Gibbs Free Energy?

ΔG° = -n F E°cell

Half reactions: Zn  Zn2+ + 2e-

Cu2+ + 2e-  Cu
n = no of moles of electrons = 2

F = Faradays constant = 96,500 C/mol

E°cell = 1.10 V = 1.10 J/C

ΔG° = - (2) (96500 C/mol) (1.10 J/C)

= - 212300 J/mol
= - 212.3 kJ/mol