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CHAP
Concepts of Electrochemistry
3
Module 3
University Prescribed Syllabus

Introduction, concept of electrode potential, Nemst equation, types of electrochemical cells, concept of
standard electrode with examples, electrochemical series, simple numericals.
3.1 INTRODUCTION TO ELECTROCHEMISTRY... *****en*****ennes** ************oaeeaaeeneedd*aeae*ee***********aueaeaaeu**aa*****************aae** Z
3.1.1 Definition of Electrochemistry.. 3-2

***************************************************e********************************s********e******a**aasnee****.
3.1.2 Half Reactions.. . * ************************°**************a*********************** 3
3.2 TYPES OF ELECTROCHEMICAL CELLS .
**ossoessan********e**n*****ennoo****sa******************************************************************* 3-3
3.2.1 Definition of Electrochemical Cell. *******
*******************ao*****ae***o*ean***##a***********ea******a*na***easeanee.3-3
3.2.2 Types of Electrochemical Cells..*************** -4
3.2.2(A) Galvanic or Voltaic Cl .**********a*************************ea******easo****a***************************e*****aae**euae******sae****aaoe*aena*o**
. 3-4
3.2.2(B) Electrolytic Cell. ********************************************ea*****tseseesseer*.
3.2.2(C) Concentration Cel... *noanonesensnosnne***********************************************************e*s*****e***********************.3-7

3.2.2(D) Fuel Cells..
*******an**asesaanann*********************************ssssassessss*sroreesesrnnisnasaassua 3-9
3.3 CONCEPT OF ELECTRODE POTENTIAL..
-******* **rsoutneusosedssessensenns***************************e******************************************
3-11
3.4 cONCEPT OF STANDARD ELECTRODE.
****************e******e******e***********************e*dad** d*a*ane**********e************
3-12
3.4.1 Introduction to Standard Electrode.. *o******************************************************************a*******a********************** 3-12
3.4.2 Electrodes or Half Cells.. .3-13
*******************na****************************************sesueeue*****saseus* ..
3.5 NERNST EQUATION..
****************a***********************a*******eoresesessu aarisssssn ****e*eo************s****a**********************
.3-14
3.5.1 Introduction to the Nemst Equation. **a*******************ee***************a***"ea******** ************ . 3-14
3.6 ELECTROCHEMICAL SERIES. **********************************e*******.**s********nnousteeourdeeanrasssnseme****ane* 3-16
3.6.1 Electrochemical Series and its Applications..

a*******.assusssees**e*nnoo*sssonane**********a**a***********************ea***********3-16
3.6.2
Applications of Electrochemical Series. sv***************se*o*a*e*a***************************** 16
Chapter Ends. 3-22
LEngineering Chemistry-l (MU Sem 2) (3-2) Concepts of Electrochemist
This chapter can be divided into seven sections as
shown in the Fig. C.3.1.l:
Concept of Electrochemistry
(1) (2)
Introduction (3) (4) (5) (6)
Electro Concept of Concept Nemst Electro
7)
chemical electrode Simple
cell of standard equation chemical numericals
potential electrode senes
(2C1)Fig. C.3.1.1 Concept of electrochemistry

Note he sequence of the topics given in the university
prescribed syllabus is slightly modified for convenience
Part:Theory
Syllabus Covered
Lecture-1
Introduction to electrochemistry,
n Types of electrochemical cells.
3.1 INTRODuCTION TO ELECTROCHEMISTRY

a 3.1.1 Definition of Electrochemistry
GO3.1 Define electrochemistry. State its signiticance. (5 Marks):
Ans.
Definition of electrochemistry
Electrochemistry is defined as that branch of chemistry which deals the study of the
generation of electricity from the
energy which is released during spontaneous chemical reactions and the use of the electrical
energy to bring about the non-
spontaneous chemical transformations.
(I1) Significance of electrochemistry

() Electrochemistry is used for the production of metals like Na, Mg, Ca, Al, Cu, Au, Ag, etc.
(i) Electrochemistry is used in the storage batteries, fuels cells used in
automobiles, sub-marines, air-crafts, wire-less
sets, inverters, lap-top battery back up, mobile telephones, wrist watches, calculators, computers etc.
(ii) Electrochemistry is used in the fabrication of clectronic devices, doping etc.
(iv) For electro-plating, galvanizing, tinning, drawing metal wires etc.
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Thus, clectrochemistry finds large scope in all the spheres of our life. Hence the study of electrolysis and
electrochemistry is very mush significant.
a 3.1.2 Half Reactions
Go 3.1.2 Explain the concept of the half reactions with suitable examples Explain Redox reaction
(sMarks)
Ans.
The concept of half reaction is briefly explained as follows:
) Consider the following reaction
2Na+Clh 2Na"+2c
I t occurs by the transfer of electrons from Na to C1, such that Na loses an electrons and is said to be oxidized to 2Na
ion while simultancously CI gains an electron and gets reduced to C1 ion.
) Such a reaction which takes place by the loss of electrons (oxidation) and gain of electrons (reduction) is called an
Oxidation-Reduction reaction or Redox reaction in brief. Module
Note that in the overall redox reaction no free electrons are generated. 3
()The above redox reaction can be considered as made up oftwo reactions.
2Na 2Na +2e (Oxidation)
Clh+2e 2C1 (reduction)
(viy Each of the two reactions shows just its oxidation or just the reduction portion of the overall redox reaction.
(yi) Being half components of the redox reaction, these reactions are called the half-reactions.
(vit) The first half reaction is called as the oxidation half reaction while the second half reaction is called as the reduction
half reaction.
(ix) When the two half reactions are added together, the sum is the net redox reaction.
(x) Redox reactions are a source of electric current in electrochemical cells explained in the next section 3.2.
3.2 TYPES OF ELECTROCHEMICAL CELLS

a 3.2.1 Definition of Electrochemical Cell
a. 3.21 Define and explain a typical electrochemical cell with a neatlabeled diagram ( Marks)
Ans.
() Definition of electrochemical cell
Electrochemical cellis a device that produces electric current from a chemical reaction (redox reaction).
(i) In an electrochemical cell, the themical energy formed during a redox reaction is converted into an electrical
energy
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Engineering Chemistry-l (MU -Sem 2) (34 isty
() Explanation of a typical electrochemical cell
Fig. 3.2.1, represents the schematic construction of a general electrochemical ceu
Electron fiow
Anode Cathode
- Electrode
--
Electrolyte
(conducting ionic
solution)
(2C2Fig. 3.2.1: Construction of typical electrochemical cell

1) An clectrochemical cell comprises of two dissimilar electrodes immersed in a conducting ionic solution.
(t) The electodes are connected by an external metallic conductor and each electrodelelectrolyte system is termed as a halr
cell.
a 3.2.2 Types of Electrochemical Cells

GO. 3.2.2 State the four types of commonly used electrochemical cells with the help of a neat chart
(sMarks)
Ans.
ype of electrochemical cells
(1) (2) (3) (4)

Galvanic ElectrolyticConcentration Fuel cell
or cell cell
voltaic cal
(2c)Fig. 3.2.2: Types of electrochemical cell
a 3.2.2(A) Galvanic or Voltaic Cell
GQ. 3.2.3 Exolain a galvanic (or voltarc ceiy Witn a sultable

cxample and PrOper
proper reactions. (5 Mars
****
Ans.
) Fig. 3.2.3, represents a typical basic galvanic or voltaic cell.
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Electron fow
-0-
Zinc KNO set in the
Copper
a Anode salt bridge Cathode
(+)
2
SO4
1M
1M 2+
CuSO4
ZnSO4 solution
solution
(2cA)Fig. 3.2.3 : A typical basic simple galvanic or voltaie cell

Module
(i) In this, electrical current is generated by a spontaneous redox reaction of zinc metal
with an aqueous solution ofcopper 3
sulphate, according to the following overall cell reaction.
Zn +Cu Zn" + Cu
(ii) A bar of zinc metal (anode) is placed in zinc sulphate solution in the right container.
(iv) The zinc and copper electrodes are joined by a copper wire.
(v) A salt bridge containing a potassium sulphate solution interconnects the solution in the anode compartment and the
cathode compartment.
(vi) The oxidation half-reaction occurs in the anode compartment.
Zn Zn+ 2e
(vii) The reduction half-reaction occurs in the cathode compartment
Cu+2e Cu
(vii) When the cell is set up, electrons flow from zinc electrode through the copper wire to the copper cathode.
(ix) As a result, zinc dissolves in the anode solution to form Zn" ions.
x) The Cu" ions in the cathode half- cell pick up electrons and are converted to Cu atoms on the cathode.
(xi) At the same time, So ion from the cathode half-cell migrate to the anode half-cell through the salt bridge.
(xi) Likewise, Zn ions from the anode half-cell move into the cathode half-cell.
(xii) This flow of ions from one half-cell to the other half cell completes the electrical circuit which ensures continuous
supply of current.
(xiv) The cell will operate till either the zinc metal or copper ions are completely used up.
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3.2.2(B) Electrolytic Cell nstry
Nole2 Before studying an
electrolytic call, It is very much necessany to understand the folowing
(1)
lmpotant points ;
Water-soluble substances are
distinguished electrolytes or non-electrolytes.
as
(2) Electrolytas are electrovalent substances which form lons in solutions which
can conduct an electric curree
(3) NaCI, Cu sO and KN0,.are some
important examples of electrolytes
(4) Nonelectrolytes on the contrary are covalent substances
water-solutions do not conduct an electric which fumish neutral molecules in a solution. The.
current.
(5) Sugar, alcohol and glycerol are some
important examples of non-electrolytes.
(6) An electrolyte invariably undergoes chemical decomposition due
its solution. to the passage of electric current through
() Electrolysis can be defined as the process of
through its solution' decomposition of an electrolyte by passing electric
current
(8 The process of electrolysis is caried in an
apparatus called the electroilytic cell.
Do not write the above
points in your answer. These are only for the
knowledge purpose only.
Go. 324 Explain an electrolytic cell with a
suitable example and proper reactions.
Ans. Marks
)Fig. 3.2.4, represents atypical basic electrolytic cell.
Electron flow
Battery
Anode
Cathode
Cation
ElectrolyteH O
Anion
Neutral atom
(2c5)Fig. 3.2.4: A typical basic electrolytic cell
(i) In an electrolytic cell, the process of electrolysis is carried out.

ii) The cell contains water-solution of an electrolyte in which two metallic electrode rod[ are
dipped.
(iv) These rods are connected to the two terminals of a battery.
(v) The electrode connected to the positive terminal of the battery attracts the negative ions (anions) and is called anode.
(vi) The other electrode connected to the negative terminal of the battery attracts the positive ions (cation) and is called
cathode.
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(vii) The cations migrate to the cathode and form a neutral by acce; ung elect. ns from it.
(vii) The anions migrate to the anode and yield a neutral particle by transfer of electrons to it.
ix) As a resut of the loss of electrons by anions and gain of clectrons by cations at their respective electrodes chemical
reaction takes place.
(x) Let us consider the electrolysis of HCl as an example.
(xi) In solution, HCl is ionised as
HCI H' +Cr

(xii) In the electrolytic çell, Cl ions will move towards the anode and H ions will move toward the cathode.
(xii) At the clectrodes, the following reactions will take place:
(a) At cathode,
H +e H (reduction)
Thus, eachH ion picks up an electron from the cathode to become a hydrogen atom. Pairs of hydrogen atom then
unite to form molecules of hydrogen gas
Hz
Module
b) At anode,
Cr CI+e (oxidation)
3
After the chloride ion loses its electron to the anode, pair of chlorine atoms unite to form chlorine gas Ch
(xiv) The net effect of the process is the decomposition of HCl into hydrogen and chlorine gases.
Thus, the overall reaction is
2HCI H,+Cl2 (decomposition)

a 3.2.2(C) Concentration Cell
Ga 3.2.5 Explain a concentration cell with a suitable example and proper reactions
(5Marks)i
Ans.
G) A concentration cell can be defined as cell in which emf arises as a result of different concentrations of the same
electrolyte in the component half-cels.
i) Thus, concentration cell is constructed by pairing twò half-cells in which identical electrodes are dipped in a solution of
different concentrations of the same electrolyte.
(1i) Fig. 3.2.5, represents a typical basic concentration cell.
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Electron fow
Ag
Ag
Anode I Cathode
0.1M Ag 0.1MAg
0.1M NOg 1M NO3
Porous membrane
(206)Fig. 3.2.5: A typical basic concentration cell
(iv) It consists of two silver electrodes, one immersed in 0.1 M silver nitrate solution and the other in 1 M solution ofthe
same electrolyte.
T h e two solutions are in contact through a membrane (or a saltbridge).

(vi) When the electrodes are connected by a wire, it is found experimentally that electrons flow from the electrode in more
dilute (0.IM) solution to that in the more concentrated (IM) solution.
(vii) The concentration of Ag ions in the left compartment is lower (0.1M) and in the right compartment it is higher (IM).
(vii) There is a natural tendency to equalize the concentration of Ag' ions in the two compartments.
ix) This can be done if the electrons are transferred from the left compartment to the right compartment.
() This electron transfer will produce Ag' ions in the right compartment by the half-cell reactions
Ag-e Ag (left compartment)

Ag+e Ag right compartment)
(xi) Thus to equalise concentration of Ag ions in the two compartments the cell will develop emf (Le Chatelier's Principle)
to cause the transfer of electrons. Eventually, the solutions in the two compartments will have equal Ag' ion
concentration and there will be then no emf produced.
(xii) EMF of concentration cell
(a) If C and C are the concentrations in the left and right compartments at 25° C and further if C, >C.
(b) Then the emf E of the concentration cell will be given by the difference between the two electrode potentials.
(c) According to the Nernst equation,
E (E 1ogC-(E,+ 1og C,)

E = 0.0591
n
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Where, Concepts of Electrochemistry
E Standard electrode
potential of the metal M
n Valence of the ions
=
in contact with
it.
(d) Finally,
(usually taken 1) =
E .0591 IM
1 08 0.IM =0.0591 V here
Note: If the emt of a concentration cell is asked in the question, then
only write the above step (xi
a
otherwise omit
3.2.2(D) Fuel Cells
GO. 3.2.6
Explain a fuel cell with a Surtable
example and proper reactions. Also
disadvantages and applications State its advantages,
Ans. (6Marks)
There are several types of fuel cells. Let us
consider a
Hydrogen-Oxygen fuel cell as an
example.
Definition of the
hydrogen-oxygen fuel cell
'A fuel cell is Module
electro-chemical device which converts the chemical
an
a chemical reaction
of positively energy from a fuel into electrical
energy through
3
charged hydrogen ions with oxygen or another
(U) Principle of the
oxidizing agent.
()The fuel and the oxidant are combined in the
form of ions at constant pressure and
i) The essential temperature.
process in the fuel cell is as
follows:
Fuel+Oxygen Oxidation products +Electricity
CWI) Construction and working of the
) Fig. 3.2.6, represents the construction of a
hydrogen-oxygen fuel cell.
Electric load
W
H2 O2
Exhaust
gas Exhaust
gas
Anode
Cathode
-Ag20
KOH at 200°C at 20-40 atm
(2CT)Fig. 3.2.6: Construction of a hydrogen-oxygen fuel cell
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) Hydrogen is supplied to anode and oxygen is supplied to the cathode.
(ii) Electrodes are
hollow tubes of porous compressed carbon with finely divided platinum impregnated in the anode
and silver oxide
(Ag,O) incorponated in the cathode.
(iv) The electrolyte is a KOH solution maintained at
200° C at 20-40 Atm.
(V) Both platinum and silver oxide act as
catalysts for the cell operation.
() Electrode reactions in the
hydrogen-oxygen (H-0,) fuel cell
(a)atanode
2H 4H +4e
(b) at cathode
(Oxidation)
O +2H,0+4e 4OH
(c)
(reduction)
the overall reaction is
2H, (g)+0, (e)> 2H,0(e)
() Types of fuel cells (Only for knowledge)
Hydrogen - Oxygen fuel cells (discussed above)

Methanol Oxygen fuel cells
y Solid oxide fuel cell
iv) Molten carbonate fuel cell
Phosphoric acid fuel cell
Avi) Polymer electrolyte membrane fuel cell
(VI) Advatage of fuel cells
() Fuel cells do not require recharging.
(i) Lesser maintenance is required.
(ii) Fuel cells are eco-friendly as the products of cell-reactions are non-toxic.
(iv) Fuel cells have high power efficiency and produce direct current for long period.
(VIl) Disadvantages / limitations of fuel cells

) Fuel cells use costly catalysts which are difficult to replace and reuse.
G) Fuels in the form of gases like H, are stored in the high pressure Lanks which are diffcult to handle and tranpo
(ii) Fuel cells need continuous supply of the fuels and oxidants to produce electricity.
(iv) Commercially fuel cells are not readily available because the fuel cell technology is not yet developed.
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Vl) Applicatlons of fuel cells
(1) To supply power to all types of local and portable apparatus.
2) All types of vehicles e.g. trucks, buses, marine transport.
(3) Stationery power stations": by locating fuel cells near the load centres e.g. construction sites, military camps,
air-ports etc.
(4) To provide power in shuttle aircrafts, space vehicles etc.
(5) For back-up power in hospitals, cogeneration.
(6) Electric load balancing during power staggering / megablock/ emergency.
Syllabus Covered
Concept of electrode potential
inConcept of standard electrode
i Nemst equation
3.3 CONCEPT OF ELECTRODE POTENTIAL Module

3
Ga 33.1 Explain the conceptof electrode potential
(S Marks)
Ans.
Electrode potential (E) is defined as 'the potential developed at the interface of an electrode and the solution of its own.
salt'.
(i) It is the measure of tendency of an electrode to

gain or lose electrons when brought in contact with a solution of its own
salt.
(ii) Experimentally, it is not possible to determine the potential of a single electrode and hence, two electrodes with slight
difference in their electrode potentials are taken as, E anodeE catbode
Civ) A single clectrode potential (E°) develops at the interface between the electrode and the
conducting electrolyte solution.
(v)When two dissimilar electrodes brought in contact by immersing in an electrolyte; the electrode
are
with higher
reduction potential (i.e., tendency of gaining electrons) acts as the cathode and the other acts as
the anode.
(vi) The electrons are forced to move from anode to cathode and a dynamic equilibrium is established at both the half cells
at the electrode interfaces.
(vii) There is a constant interaction of opposite charges at both the electrode, resulting in the formation of an electrical
double layer
vii) Hence, there is always a certain potential between the interface of the electrode and its ionic solution at a given
temperature. This is called the 'electrode potential".
(ix) If an electrode tends to lose electrons it is called oxidation

potential, whereas if an electrode tends to gain electrons, it is
called reduction potential'.
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xConsider electrochemical cell with two different electrolytes in contact with
an
each other in this case, an
nemistny
add
potential difference is present across the electrolytic interface, which is called
"liquid junction potential and. adrtional
nd denoted
as E.
(a) For example, in two

differing concentrations of HCI in an electrochemical cell, the highly mobile hydrogen inn
diffuse into the dilute solution .
causing the bulkier chlorine ions until an has reached. equilibrium

(xii) This causes junction potential to set at the interface
giving a potential value of about 2 mV.
(xii) The concept of junction potential is as shown in the
Fig. 3.3.1.
Diaphragm
1 M HCI 0.1 M HCI
Electrolyte Electrolyte (lower
(higher concentration) concentration)
(2caFig. 3.3.1: Concept of the junction potential(E,)

(xiv)Thus, differing mobilities of ions across the electrolyte cause the
junction potential 'E as shown in the Fig. 3.3.1.
(xv) To reduce or eliminate the junction potential a salt bridge is placed across the electrolyte interface.
3.4 cONCEPT OF STANDARD ELECTRODE
a 3.4.1 Introduction to Standard Electrode
Ga. 3.4.1 Explain in brief the term 'standard electrode'

5 Marks)
Ans.:
) A standard electrode can be defined as follows
It is an electrode necessary to know the potential of some other given electrode'. It is taken as the reference node.
(ii) A standard electrode has a
designated potential that is used as a reference point.
(ii) This reference point is used to calculate the potential of the other electrode in the cell.
(iv) A standard electrode in an electro-chemical reaction is the place (connector) where
electrons enter or leave the cell.
(v) Electrons can either enter through the standard electrode
(making it an anode) or
they can exit through the standard
electrode (making it a cathode).
(vi) Thus standard electrode can be either inert or reactive (means anode or
cathode).
(vii) When a standard electrode is reactive, then it takes part in the electrolytic reaction.
(vii) When a standard electrode is inert, it simply aids in the transport of electrons
without being part of the reaction.
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3.4.2 Electrodes or Half Cells
ga.342 Give the

classitication of electrodes depending upon their material and explain any one type
of electrode
- . (5Marks
Ans.
o The classification of electrodes depending on their material is as shown in the Fig. 3.4.1.
Electrode
(1)
Hydrogen
(2)
Calomel
(3)
Quinhydron Glass
electrode electrode electrode electrode
(2c9)Fig. 3.4.1
From Fig.3.4.1, instead studying of all the four electrodes let us

study the commonly used glass electrode. Module
1. Principe 3
() Glass electrode is reversible to hydrogen ions.
(i) The pH of aqueous solution depends on hydrogen ion concentration and is measured
using a glass electrode.
(ii) When glass electrode is
a
immersed in a solution (unknown pH), a potential difference develops across its ion-
selective membrane which is proportional to the hydrogen ion concentration.
(iv) The measured potential is highly accurate since glass electrode
remains unaffected by oxidizing or reducing agents and can be
employed over a wide range of pH.
(v) During pH determination, the glass membrane undergoes an ion- Pt wire or AgCI
coated Ag wire
exchange reaction in which sodium ions of the membrane exchange
with hydrogen ions.
(vi) A potential difference develops across the membrane and can be -0.1m HC
denoted as, according to the following reaction: Thin walled glass bulb
(2C10)Fig. 3.4.2: A typical glass membrane electrode

-
Sio-Na (membrane) +H (solution)> Sio-H (membrane)

+Na" (solution)
(vii) The potential difference can be written as, Eg = n
(vii) Here, C1 is the concentration of acid solution
present in the glass bulb and C2 is the concentration of the test
solution whose pH is to be determined.
2 Construction
i) Fig. 3.4.2, shows a typical glass electrode that consists of a glass tube that ends in a bulb sealed at
the bottom.
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(11) The bulb is also called the glass membrane, which is as thin as-0.05 mm.
chemisty
i ) The composition of glass is 72% Sio, 22% Na,O, and 6% CaO and it possesses higher electrical conducta.
ctance.
Gv Basically, glass is a three-dimensional network of Si-Oand certain cations such as L, Na, K+, and C.
nd has a
overall negative charge.
(V) The movement of these cations inside the Si-O network imparts a very low electrical conductance.
(vi) The bulb contains either (a) buffer solution of pH -4 with platinum wire dipped in it or (b) 0.1 M hydrochlorie
with Ag wire coated with AgCI dipped in it.
(vii) Keeping potentials of the glass electrode, dipped wires, and the glass membrane constant, when such
such anan eelectrode
is dipped in a test solution, only hydrogen ion activity will affect the potential of the glass electrode.
3.5 NERNST EQUATION

a 3.5.1 Iptroduction to the Nernst Equation
State, explain and derive the Nemst equatioA Kplan tts signticance (5 Marks
Ans.
(0 Explanation of the Nernst equation
) In an electrochemical cell, the electrode potential depends on the nature of the electrode, concentration of the
electrode and the temperature.
(ii) Nernst derived a fundamental equation relating the free energy change of any electrode processes to the
potental
developed at the electrode along with the concentration of the ions and its temperature.
(0) Derivation of the Nernst equation
) Let us consider a reduction reaction occurring in an electrochemical cell,
M"+ne M
(i) As electrochemical cell is doing work, there will be decrease in free energy for the reaction. The decrease in fe
energy change (-AG) for the above reaction can be expressed as,
AG AG° +2.303 RT log10

..(3.5.1)
(ii) We already know that under standard condition_, AG° nFE°, where E° denotes standard electrode potential (m
=-
volts), F denotes the quantity of electricity produced (in Coulombs), and n is the total number of electrons liberaied
at the single electrode.
(iv) Hence, Equation (3.5.1) can be written as,

-
nFE =- nFE° + 2.303 RT log1o 3.5.2)
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(v)Dividing Equation (3.5.2) by - nF, we get
E E°_ 2303 RT
nF log (3.5.3)
(vi) On rearranging Equation (3.5.3), we get

E =E°+2303RT
nF log10 M" ...(3.5.4)
(vii) Equation (3.5.3) represents the Nernst equation for single electrode potential
(vii) On solving further, we get
E Bo+.0591
log1o [M" J.. (at cathode) 3.5.5)
E = E°_U0591
log1o [ M*" ] ... (at anode 3.5.6)
(ix) Equations (3.5.5) and (3.5.6) are generally used for practical purposes.
(u) Significance of the Nernst equation
Using the Nernst equation, we can.find the emf of a. half-cell as follows Module
) Let us consider a cell that is represented as, M, IM, (C) M" (C)IM2, where C and C, are the concentration of
3
the two half cells and Fcathode anode
(ü) The reaction can be expressed as, M, + Ma
net
Ma+M;where M denotes oxidized state of metal
M, and M, denotes oxidized state of metal M.
(ii) Hence, emf of the cell will be, Foell= Eel 2.303 RT
nF og810
M ,where
M
Ee E = Feathode Enode
MM2
Where,
E =
Standard respective electrode potential
R = Gas constant
T = Temperature of the electrolyte in K
N = Number of electrons transferred in the half reaction.
F Faraday's constant of clectrode material
chemical equivalent oftheelectrode material (E

Electrochemical equivalent of the electrode material (Z)
K = Equilibrium constant for the half-cell reaction
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nemistry
Syllabus Covered
Electrochemical series
i)Any three examples
3.6 ELECTROCHEMICAL SERIES
a3.6.1 Electrochemical Series and its Applications

25.1 Explain the term electrochemical series. Also state ts ap
(s Mars
Ans.
Explanation of the electrochemical series
.
When the electrodes are arranged in the order of their increasing standard reduction potentials on a
called electrochemical series. hydrogen scale. t
The reason for using the hydrogen scale is that the values of the standard reduction
potentials
standard hydrogen electrode (SHE) as the reference electrode whose potential is considered as zero. measured ith the
are
(ii) Fig. 3.6.1, represents a table which lists some of the

common electrodes and their standard reduction potentials at 298 K
ElectrodeeC
LiL 3.05
Mg, Mg -2.370
AA 1.660
Zn,Zn
FetB
0.763
Ca,Cd -0.403
Ni Ni 0.236
Sn, Sn - 0.136.
2H,H 0.00
Cu,Cu +0.34
Ag Ag+0.80
( P 2F +2.87
Fig. 3.6.1:Standard common electrodes and their standard reduction potentials at

298 K
a 3.6.2 Applications of Electrochemical Series
GO 36 Discuss some important applications of electrochemical series (5Mane
Ans
Three important applications of electrochemical series are discussed briefly as follows:
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Engineering Chemitry-1l(MU-Sem2) (3-17) Concepts oft Electrochemistry
1, Calcuteton of emf of a cell and the feasibilty ofthe redox reaction
)The standard emf of a cell is given by
ell EabodeEodand hence can be found using the standard electrode potential values
from the table.
) fEe is positive hen the reaction is feasible but if E.ell is negative the reaction is not
feasible.
i ) Let us consider the following example
ZAg(s)+Zn" (aq) Ag' (ag) +Zn (solid)

For the above
example, the half-cell reactions are:
Anode: 2Ag(s) 2Ag' (aq) +2e = 0:8 V
anode
Cathode: Zn+2 ahode =-0.763 V
EEioseEode
=-0.763-0.8
=-1.5633V
Module
Since F is negative the reaction is not feasible.
33
2 Reacthvity of metals
The activity of metals can be decided by the electrochemical series.

The tendency of metals to go into the solution cam be predicted from the magnitude of standard
reduction potential.
i) Those metals which are on the top
of the series easily ionize and go into solution
i Hence metals higher up in the electrochemical series are active than those at the lower end of the series.
3. Predicting the displacement reactions
G)We can easily predict the displacement reactions using the electrochemical series.
i) The metal with a negative reduction potential will displace
hydrogen
from an acid solution.
For example zinc can displace
hydrogen as
Zn+H,SO ZnSO4+ H E =-0.76V
(ii) Metals with positive reduction potential will not displace hydrogen from. acid solution for example. silver cannot
displace hydrogen since.
Ag + HSO, no reaction
.E+0.8V
(iv) Metals at the higher end of the series will easily displace the metals which are at the bottom of the series.
Zinc can easily displace copper from a solution.
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Part lI:Solved Problems
Important Formulae
(1) Generally the cell mechanism is given as follows:
Now note the
following points
LHS electrode is anode at
which oxidation occurs here it is Z E =-0.763 V from emf series
R H S electrode is cathode
P from
at which reduction occurs here it is E-0.126 V emfseries
ii) E =ECathode
cell
anode E-E
= - 0.126-(-0.763)
= 0.637 VV
ADS.
(2) Nernst Formula
2.303 RI los.
EelFel-nf M * | where
cell E°.
=Fathode Fanode
IM2 *M2
Where,
E= Standard respective electrode
potential
R = Gas constant
T
Temperature of the electrolyte in K
N =
Number of electrons transferred in the half reaction.
F =
Faraday's constant of electrode material
chemical equaivalent of the electrode material (E)_
Electrochemical equivalent of the electrode material (Z)
K =
Equilibrium constant for the half-cell reaction
Ex. 3.1
Write the cell reaction and calculate the standard emf of the following cell :
Zn lZn(1 M)| |C(1 M)| Cu (a9-)
Soln.:
Given Required
E -
0.763 V and Cell reaction Ecell

E 0.337 V
(1) The half reaction at anode is oxidation and the half reaction at cathode in reduction. The sum of the two half reactions
the overall cell reaction.
2+
() Zn Z n ( 1 M) +2 (oxidation at anode)
Ventu
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6Engineering ChemistryI(MU-Sem 2) (3-19) Concepts of Electrochemistry
() Cu (1 M) +2e Cu (reduction at cathode) .i)
I) Adding Equations (i) and (i), we get
2 +
Zn+Cua(IM) (IM)+Cuo
(overall cell reaction) Ans
Now, the standard emf is given by
F FCathode E anode
aV) cetiFcatho anode
0.337 V- (-0.763 V)
= 0.337V+0.763 V
E = 1.10 V
ell Ans.
Ex. 3.2
Write the cell reaction Module

and calculate the standard emf of the following cell
3
Given:Fc =-0.403 V and E =0.799 v
Soln.
Given Required
Ec-0.403 V and E=0.799 V E cell
The half reaction at anode is oxidation and the half
reaction at cathode is
theoverall cell reaction.
reduction. The sum of the two half reactions is
Cd Cd(1 M) +2e (oxidation at anode)

..)
1)
2x[Ag(1 M) +e-
Ag (reduction at cathode)
...(ü)
Adding Equations (i) and (ii), we get
(1I1) Cd+2 Ag(1 M)- C (IM)+2Agu
(aq.)
(overall cell reaction)

.Ans.
(IV) Cathode
Eanode
= 0.799 V-(-0.403 V)
= 0.799 +0.403 V
Eet 1.202 V ..Ans.

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Concepts of Electrochen
Ex. 3.3
Construct a cell from Ni*INi and reaction and calculate dard

the standa
potential of the
Cu*ICu half ells. Write the cell
Given:E = -0.257 V and E =0.337 V.
ce
Soln.:
Required
Given
E-0.257Vand0.337 V
() As Cu electrode has higher standard reduction potential than Ni, Cu"ICu will be the cathode under
dergoing the redue
and Ni" 1Ni will be anode
undergoing the oxidation.
( Therefore, the coll can be represented as,
Nig INi(M {Cu( M Cu
The clectrode reactions and overall cell reaction can' be given as follows :
(uT) Ni Ni(1M)+2 (oxidation at anode) )

av)(M) +2* Cu (reduction at cathode)
Adding Equations () and (i), we get

(V) Ni+C(IM-
Ni(1M)+ Cu
(overall cell reaction)
The standard emf of the cell is given by
(V)
-F Cathode anode
=
0.337 V-(-0.257 V)
= 0.337 V +0.257 V
0.594 V
Ex. 34
The standard emf of the following cell is 0462 V.
If the standard potential of Cu electrode is 0.337 V, What is the

standard potential of Ag electrode 2
Soln.
Given Required
F 0.337
V EA
LHS is anode which is Cufor which E=0462 V.
() RHS is cathode which is Ag for which E is required.

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Engineering hemistry-l(MU Sem 2) (3-21) Concepts of Electrochemistry
Pl Fathodemode
= E -0.337 V
.0.462 V E -0.337 V
E 0.462 +0.337 VV
= 0.799 .Ans.
Ex 35
The standard emf of the following cell is 1.94 V.
if the standard potential of Cr electrode is 0.740 V, calculate the standard potential of Pt electrode. Also write the cell
reaction.
Soln.
Module
Given Required
3
Eell1.94 V|Cellreaction E
P-0.740
Here, Cr electrode is an anode where oxidation takes place and Pt electrode is a cathode where reduction takes place.
Thus, the half reactions and the overall cell reaction can be given as follows :
2x[C C ( M+3] (Oxidation at anode)
3xP(1M)+2 Pt (reduction at cathode)
Adding Equations (i) and (i), we get

+
2C +3P (IM) 2C(IM)+ 3Pt

(overall cell reaction) Ans.
FallFatodemode
F E, -(-0.740)
1.94 = E+0.74
E = 1.94 V-0.740 V
P
E 1.2V AIs.
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Engineering Chemistry-lI (MU- Sem 2) (3-22) Concepts of Electrocher
Cnemist
Partl : Home Work Problems
Q. 1 Calculate the emf of a Daniell cell at 25°C with standard potential of 1.1V, if concentration of ZnSo,.
0 and CuSso
0.002 M and 0.2 M
Q.2
respectively.
Calculate the emf of the
following concentration oell at 25°C
(Ans.:1.1592
Culcu(0.05M)l Icut(sM)lCu (Ans.:0.0592
Q. 3 Calculate the emf of the following
concentration cell at 25°C
Ni
N (0.01M)l IN°(0.1M)lNi (Ans.:0.0296
Q.4 Calculate the voltage of the cell given below if E =
1.98 V
Mg Mg(C-1M)l |cd°(C=710M)lcd (Ans.: 1.68
Chapter Ends..
CHAPTER
5 Green Chemistry and Synthesis
of Drugs
Module 5

Introduction : Definition, Significance, Twelve principles of green chemistry, Numerical on atom economy
Conventional and green synthesis of adipic acid, Indigo, Carbaryl, Ibuprofen, Benzimidazole, Benzyl
alcohol,% atom economy, and their numerical. Green fuel-Bidiesel.
5-3
5.1 INTRODUCTION
5-3
5.1.1 Definition and Significance ....
UQ. 5.1.1 What is green chemistry ? Give its significance.

Ref.: (MU - Q.4(b), Dec. 18, Q. 4(c), May 18, 3 Marks, Q. 1(e), Dec. 16, 1 Mark,
5-3
Q. 1(e), May 13, 3 Marks).
5-4
5.2 TWELVE PRINCIPLES OF GREEN CHEMISTRY..
UQ. 5.2.1 List the twelve principles of green chemistry. Ref. : (MU - Q.1(e), May 13, 3 Marks). 5-4
UQ. 5.2.2 List any six principles of green chemistry.

5-4
Ref. : (MU - Q. 1(e), May 17, 3 Marks, Q. 1(e), Dec. 16, 3 Marks).
UQ. 5.2.3 Explain prevention of waste principle in green chemistry.
Ref. : (MU - Q. 1(e), Dec.17, Q.4(b)(), May 17, Q. 1(d), Dec. 16, Q. 1(d), Dec. 15,
5-4
Q. 1(d), May 14, Q. 1(d), Dec. 13,3 Marks).
UQ. 5.2.4 Explain the principle inherently safer chemistry of accidental prevention' in green chemistry.
5-5
Ref. : (MU - Q. 1(e), May 19, 3 Marks)
UQ. 5.2.5 Why is it essential to design safer chemicals and products with respect to green
chemistry principles ? Explain with an example. Ref. : (MU - Q. 1(e), May 18, 3 Marks...
5-5
UQ. 5.2.6 Explain 'Design for energy efficiency' principle in green chemistry. 5-5
Ref. : (MU - Q. 1(d), Dec. 14, 3 Marks).
5-6
5.3 CONVENTIONAL / TRADITIONAL AND GREEN SYNTHESIS OR GREEN CHEMISTRY ROUTE..
5-6
5.3.1 Adipic Acid
UQ. 5.3.2 Explain the conventional and green synthesis of adipic acid. Mention the green
chemistry principle involved. 5-6
Ref. : (MU - Q.5(c), May 17, Q. 3 (b), Dec. 16, Q.3(b), May 15, Q. 3(b), Dec. 13, 5 Marks).
Engineering Chemistry-II (MU - Sem 2) (5-2)
Green Chemistry & Synthesis of Drugs
5-7
5.3.2 Indigo Dye
UQ. 5.3.3
Explain the traditional and green route of production of Indigo dye-highlight the green
chemistry principle involved.
Ref. : (MU - Q. 3(b), May 16, Q. 3 (b), Dec. 15, Q. 3(b), May 14, 5-7
Q. 3(b), Dec. 14, Q. 3(b), May 13, 5 Marks).
5-8
5.3.3
Carbaryl.
UQ. 5.3.4
Explain the traditional and green route of production of carbaryl. Highlight the green 5-8
chemistry principle involved. Ref. : (MU - Q.5(C), Dec. 18, Q. 5 (C), Dec. 17, 4 Marks).
UQ. 5.3.5
The Bhopal Gas Tragedy was one of the worst industrial disasters. With reactions explain
the synthesis of the intermediate which caused the tragedy and the final product.
5-8
Also give principle being adhered to. Ref.: (MU - Q.5(c), Dec. 19, 4 Marks)
5.3.4 5-9
Ibuprofen
5.3.5 Benzimidazole 5-10
5-12
5.3.6 Benzyl Alcohol..
5.4 PERCENTAGE ATOM ECONOMY 5-13
5.5 GREEN FUEL-BIODIESEL 5-14
UQ. 5.5.1 What is bio-diesel? Explain the trans-esterification method for the synthesis of bio-diesel.
Mention the advantages of bio-diesel as fuel.
Ref.: (MU - Q. 6(c), May 19, 4 Marks, Q. 2(b), Dec. 16, 3 Marks,
Q. 6(c), Dec. 17, 4 Marks, Q.5(a), May 15, 6 Marks, Q.5(a), Dec. 14, 6 Marks,
Q. 2(b), Dec. 13, 5 Marks, Q.5(a), May 13, 6 Marks, Q. 2(b)(ii), Dec. 18, 2 Marks,
Q. 3(a)(ii), May 18, 2 Marks, Q. 6(c), Dec. 17, 4 Marks) 5-14
Solved University Problems

5-15
UEx. 5.1 (MU - Q. 2(c), May 13, 4 Marks).
UEX. 5.2 (MU - Q. 2c), Dec. 13, Q. 3(c), May 18, Q. 2(C), Dec. 16, 4 Marks). 5-16
5-16
UEX. 5.3 (MU - Q. 2(c), May 14, 4 Marks).
UEx. 5.4 (MU - Q.2(c), Dec. 14, Q.3(c), Dec. 18, Q. 3(c), Dec. 17, Q. 3(c), May 19, 4 Marks) 5-16
UEx. 5.5 (MU - Q. 2(C), May 15, Q. 3(c), May 17, 4 Marks) 5-17
UEx. 5.6 (MU - Q. 2(c), Dec. 15, 4 Marks) 5-17
Chapter Ends 5-18
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Engineering Chemistry-1I (MU - Sem 2) (5-3)
Green Chemistry & Synthesis ofDrugs
Part1: Theory
This chapter can be divided into five sections as per the Fig. C.5.1.1:
Green chemistry
and synthesis of drug
(5)
(2) (3) Green fuel
Introduction % atom
Twelve Conventional Biodiesel
definition and economy
principles
significance of green
Green synthesis
chemistry of
(vi)
(i) (v)
(iii) (iv) Benzyl
Benzim
Adipic Indigo Carbary! Ibuprofen idazole alcohol
acid
(2E1)Fig. C.5.1.1 : Green chemistry and synthesis of drugs
Syllabus Covered
Lecture-1
1) Introduction, definition significance of Green chemistry.
ii) Twelve principles of green chemistry.
5.1 INTRODUCTION
à 5.1.1 Definition and Significance
5.1.1 What is green chemistry ? Give its significance.

UQ. Ref.: (MU - Q. 4(b), Dec. 18, Q. 4(c), May 18, 3 Marks, Q. 1(e), Dec. 16, 1 Mark, Q. 1(e), May 13, 3 Marks)
Module
Ans.:
15
(1) Definition of green chemistry
Green chemistry can be defined as 'the environmentally benign chemical synthesis which reduces the use and
generation of hazardous substances / pollutants’.
(IN) Significance of green chemistry
1. In green chemistry, non-hazardous chemicals are used hence the main product as well as the bye products if any
are also safer,
2. It results into cleaner environment which gives better health and safety to working personnel and surrounding
nature which includes plants flowers, crops animals, fish, birds, water, earth etc.
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Since the green synthesis employs properly designed and selected ingredients, maximum atom economy is
achieved hence the manufacturing cost is reduced, therefore this results into improved economy and efficiency of
the manufacturing plant.
4.
It minimizes accidents, explosions, fumes, etc and therefore public health problems like T.B., cancer, blindness,
toxicity suffocation etc. are reduced.
5.
It reduces the storage and handling of the raw materials thereby saving space, labour etc.
6.
The disposal of ash, pollutants etc. is minimized which reduces the transportation, labour handling and hences the
increases safety
5.2 TWELVE PRINCIPLES OF GREEN CHEMISTRY
UQ. 5.2.1
List the twelve principles of green chemistry. Ref.: (MU - Q. 1(e), May 13, 3 Marks)
Ans. :
The twelve principles of green chemistry are stated as follows:
1. Prevent waste 2. Maximize atom economy
3. Use non-hazardous chemicals 4. Use safer chemicals,
5. Use catalysts 6. Avoid chemical derivatives,
7. Use renewable feedstock,
8. Avoid minimize the use of auxiliary substances (solvents, separation agents etc.),
9. Increase energy efficiency, 10. Design chemicals and products to degrade after use,
11. Apply new analytical methods, 12. Minimize accidents.
UQ. 5.2.2 List any six principles of green chemistry.
► Ref.: (MU - Q. 1(e), May 17, 3 Marks, Q. 1(e), Dec. 16, 3 Marks)
Ans. :
State first six principles from the answer of the above UQ. 5.2.1.
UQ. 5.2.3 Explain prevention of waste principle in green chemistry.
Ref.: (MU - Q. 1(e), Dec.17, Q. 4(b)(i), May 17, Q. 1(d), Dec. 16,
Q. 1(d), Dec. 15, Q. 1(d), May 14, Q. 1(d), Dec. 13,3 Marks)
Ans. :
1. It is better to prevent waste than to treat or clean up after it is formed.
2. It is best to carry out the synthesis by designing such a pathway so that formation of waste or by-products is minimized
or avoided
3. Further, disposal of waste like for example flue gases, Co, effluent water etc. not only causes pollution but also poses
threat to the health of human, fish, birds and other creatures, plants like mangroves etc. It may cause acid-rains, hence
avoid such disposal methods.
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4. Hence we must prevent the waste as far as possible because prevention is better thancure.
UQ. 5.2.4 Explain the principle 'inherently safer chemistry of accidental prevention' in green chemistry.
Ref. :(MU - Q. 1(e), May 19, 3 Marks)
UQ. 5.2.5
Why is it essential to design safer chemicals and products withRef.respect to green chemistry
: (MU - Q. 1(e), May 18, 3 Marks)
principles ? Explain with an example.
Ans. :
Safer chemicals and products with respect to green chemistry are essential because they will provide the following
results:
1. Cleaner environment i.e. air, water and the earth which will give better health and safety to the working personnels, to
the surrounding nature like animals, plants, fish, birds etc.
2.
To minimize accidents like fire, explosions, gas leakages etc.
3. To minimize public health problems like T.B., cancer, blindness, toxicity, suffocations, vomiting, impotancy etc.
4. Use of D.D.T, gamaxane, aldrin etc. is found to be toxic to humans, animals and even to birds. Hence their use must be
avoided or curtailed and instead biological pesticides must be used.
UQ. 5.2.6 Explain Design for energy efficiency' principle in green chemistry.
Ref. : (MU - Q. 1(d), Dec. 14, 3 Marks)
Ans. :
The aim of green chemistry is to increase the energy efficiency of a chemical process by a proper and optimum design
which includes:
1. Use of catalysts and by avoiding the fossil or gaseous fuels which release solid or gaseous pollutants.
2. Carrying out the synthetic methods at the ambient temperature and pressure.
3. Proper heat transfer.
4. Minimum wastage of electrical energy using energy efficient electrical apparatus.
5. Using fermentation process requiring very low energy and also the products are less harmful.
With a suitable example, explain the application of green chemistry in the waste utilization.
GQ. 5.2.7
(3 Marks) Module
51
Ans. :
1. The application of green chemistry in waste utilization can be explained from the conversion of Glycerin (produced
during preparation of biodiesel) to propylene glycol.
2. The glycerene produced in this process is a waste but when it is converted into propylene glycol, the product is useful,
because otherwise propylene glycol has to be produced using ethylene glycol which is toxic in nature. Further the
propylene obtained by this process is cheaper.
3. Thus, there are three advantages as follows:
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ii) Glycerene is used up.
(iii) The cost of propylene obtained by this process is low.

Lecture-2 Syllabus Covered
Conventional / Traditional and Green chemistry route Adipic acid, Indigo

Dye.
5.3
CONVENTIONAL / TRADITIONAL AND GREEN SYNTHESIS OR GREEN
CHEMISTRY ROUTE
5.3.1 Adipic Acid

GQ. 5.3.1
Explain the conventional and green chemistry route of production of adipic acid. Highlight the
green chemistry principle involved.
UQ. 5.3.2
Explain the conventional and green synthesis of adipic acid. Mention the green chemistry
principle involved.
Ref. : (MU - Q.5(c), May 17, Q. 3 (b), Dec. 16, Q.3(b), May 15, Q. 3(b), Dec. 13, 5 Marks)
From the example of adipic acid, the seventh principle of green chemistry is addressed viz. “A raw material or
feedstock should be renewable’.
1. Conventional / traditional route
Cyclohexanone
Ni, Al2O3 CO, O2 Cu, NHAVO3 CO2H

HO2C
370-800 Psi 120-140 Psi HNO3
OH
Adipic acid
Benzene
Cyclohexane
Cyclohexanol
(2E2)Fig. 5.3.1
K Drawback of Conventional / traditional route
In this, the starting material was benzene whose continuous effects the human health. Shown in Fig. 5.3.1 is the
traditional route for manufacture of adipic acid.
2. Green synthesis or Green chemistry route
In this benzene is replaced by glucose which is non-toxic and absolutely safe. Further, by special process, it can be
renewed also.
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OH
CO2H HO2C
-OH
E, coil E, coil
OH
OH
OH OH
COZH
OH
D-glucose 3-dehydroshikimato Cis, cis-muconic acid
CO2H
PLH2
ноос
50Psi
Adipic acid
(2E3)Fig. 5.3.2
à 5.3.2 Indigo Dye
UQ. 5.3.3 Explain the traditional and green route of production of Indigo dye-highlight the green
chemistry principle involved.
Ref.: (MU - Q. 3(b), May 16, Q. 3 (b), Dec. 15, Q. 3(b), May 14, Q. 3(b), Dec. 14, Q. 3(b), May 13,5 Marks)
Ans. :
The example of Indigo Dye explains the third principle of green chemistry according to which the synthesis
must be so designed to generate substances without causing toxity to human health and the environment'.
(1) Conventional / traditional route
NH2 OH
HOOC
CICH2COOH NaNH2
'N N
Aniline H H
Air
Н.
Moa
H
Indigo
(2E4)Fig. 5.3.3
K Drawbacks with the conventional / traditional route

.
Use of highly toxic aniline.
2. Generation of large amount of waste salt causing the disposal problems.

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(W) Green synthesis or Green chemistry route OH
Trypiophanase Napthalene
L-tryptophan OH
Dioxygenase
N
N
H
H
02
Н.
Indigo
(25)Fig. 5.3.4
Here, the Indolo formed can be hydroxylate enzymatically and then oxidized with oxygen to indigo.
Syllabus Covered
Lecture-3
Conventional / Traditional and Green chemistry route - Carbaryl, Ibuprofen.
5.3.3 Carbaryl
UQ. 5.3.4 Explain the traditional and green route of production of carbaryl. Highlight the green
chemistry principle involved. Ref.: (MU - Q.5(c), Dec. 18, Q. 5 (c), Dec. 17, 4 Marks)
UQ. 5.3.5 The Bhopal Gas Tragedy was one of the worst industrial disasters. With reactions explain the
synthesis of the intermediate which caused the tragedy and the final product. Also give
principle being adhered to. ► Ref.: (MU - Q. 5(c), Dec. 19, 4 Marks)
Ans. :
(1) Conventional / traditional route
Here carbaryl (5) is produced by treating Methyl-isocyanate (3) with 1-naphthol (4) as follows:
o
CH, - NHA CC
CI
сн.,
(2) (3)
CH3
OH NH
CH3
(3) (5)
Carbary
(2ES)Fig. 5.3.5
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Engineering Chemistry-HI (MU - Sem 2) (5-9)
Drawback of conventional / traditional route
Methyl-isocyanate is highly hazardous, while phosgene(2) is loxic and reacts with water.
(11) Green synthesis or Green chemistry route

Really speaking, we cannot call this as 'Green synthesis' because it still uses phosgene (which is toxic and reacts with
water as mentioned above) and methyl-amine which is toxic and flammable gas.
Here, 1-naphthal (1) is reacted with phosgene (2) to form its chloroformate (3) which is then treated with methyl-amine
(CH NH2) to get carbaryl (4).
OO CHE
OH
NaOH
(1) (2) (3)
(287)Fig. 5.3.6
* Advantage of Green synthesis or green chemistry route
The preparation of highly hazardous methyl-isocyanate is avoided
a 5.3.4 Ibuprofen
GQ. 5.3.6 Explain the conventional and green synthesis of production of thuprofen Highlight the
limitations of traditional method and advantages of green chemistry method. (5 Marts)
Ans. :
(1) Conventional/ traditional route
Step 1 Step 2
CHCOCH'S
(CH2C0210 CH3 CICH,CO,CS "CH₃

AICI: NaOC
Bu
Step 4
Step 3 CHO CHE NOH Moda
5
H
CH3
HNOM
H20
Bul
|
CEN COOH
Stop
Step 5
CH сн.
Bu Ibuprofen
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Engineering Chemistry-11 (MU - Sem 2) (5-10) Green Chemistry & Synthesis of Drugs
B Drawbacks of conventional / traditional route
1. Atom economy = 40% only.
2.
It uses auxiliary reagent AICI, which generates a large amount of AICI,.3H,0 as a waste product which is 1 and filled.
(1) Green synthesis or Green chemistry route
There are 3 steps :
Step 1
(CH3CO2) CH3
HF
COOH
Step 2 OH
Step 3
H2
CH3
CO, Pd CH3
Catalyst
Ibuprofen
(2E9)Fig. 5.3.8
B Advantages of green synthesis or Green chemistry route

1. Atom economy = 77% is achieved.
2.
It uses following catalysts:
HF in step 1,
(ii) Raney Nickel in step 2,
(iii) Palladium in step 3. These are recovered and re-used repeatedly.
From the examples of Ibuprofen, following two principles of green chemistry are highlighted.
(i) 7th: A raw material should be renewable and
(ii) 9th: Increase energy efficiency / Atom economy.
Syllabus Covered
Lecture-4
Conventional / Traditional and Green chemistry route -· Benzimidazole, Benzil
Alcohol.
a 5.3.5 Benzimidazole
GQ 5.3.7 Explain the conventional and green synthesis of benzimidazole which principle of green
chemistry is used illustrated. (s Marks)
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Conventional / traditional route
(1) containing functions
(i) Preparation of benzimidazoles practically starts with benzene derivatives possessing nitrogen-
ortho to each other, i.e. the starting material o-Phenylenediamines (OPD) react readily with most carboxylic acids
to give 2-substituted benzimidazoles usually in very good yield.
H3C -NO2 H₂C NH2
a
Sn/HCL
NHCOCH3
NHCOCH3
2-nitro-4-methyl acetanilide
1 -H20
N
H2C
CH3
CH? or
N
N
H3C
H
H
2,5-dimethyl benzimidazole 2,6-dimethyl benzimidazole
Fig. 5.3.9 : Synthesis of Benzimidazole from 2-nitro-4-methyl acetanilide by Hoebrecker

(ii) The reaction is carried out usually by heating the reactants together on a steam bath, by heating together under
reflux or at an elevated temperature, or by heating in a sealed tube.
N
-NH2 O Δ
+ R R + 2H20
OH
NH2
H
o-phenylenediamine Carboxylic
(OPD) acid 2-alkyl benzimidazole
Fig. 5.3.10 : General Laboratory method of synthesis of benzimidazole
(U) Green synthesis or Green chemistry route

A lot of solid waste is generated which is difficult to dispose. There are several methods of green synthesis of
benzimidazole as explained below.
(1) Benzimidazole is synthesis by condensation of o-Phenylene diamine(OPD) promoted by acetic acid under Module
15
microwave. It was observed that a mild, manipulatable procedure, eco-friendly and green aspects avoiding
hazardous solvents, shorter reaction times and high yields of the products are the advantages of this method.
-NH2 ACOH/O2(air)
R + R
+ R - CHO
MW(50°cy N -N
NH2 Aldehyde
Reflux (80°C)
R H
)
o-phenylenediamine
(
OPD
Substituted benzimidazole
Fig. 5.3.11 : Microwave assisted benzimidazole synthesis from o-phenylene diamine(OPD)
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(ii) Further, various 2-substituted benzimidazole in moderate to good yields in a one pot reaction by condensation of
O-phenylene diamine (OPD) and an aldehyde in the presence of ammonium chloride as a catalyst at 80 to 90° C
were synthesized and it was concluded that this method was green and economical.
-NH2
ETOH, NHACI R
+ R- CHO
-NH2 80 - 90°c
Aldehyde I
o-phenylenediamine H
(OPD)
2-alkyl benzimidazole
Fig. 5.3.12 : Synthesis of benzimidazole from o-phenylene diamine by using green catalyst
(iii) Benzimidazole can be prepared by condensation reaction of ortho esters with o-phenylene diamine (OPD) in the
presence of KSF clay under reflux toluene or solventless condiction using focused microwave in few minutes.
C2H50
-NH2 KSF Clay
C₂H Go to H +
C2H50 -NH2 MW N
Ortho ester o-phenylenediamine H
(OPD)
Benzimidazole
Fig. 5.3.13
5.3.6 Benzyl Alcohol
GQ. 5.3.8
Explain the conventional and green synthesis of benzyl alcohol which principle of green
chemistry is used illustrated. (5 marks)
Conventional / Traditional route
(i) Benzyl alcohol can be prepared from benzyl chloride or benzyl bromide or benzyl iodide by boiling it under a reflux
condenser with an excess of 10% K2CO3 (potassium carbonate) solution for 12 hours.
(ii) It is purified by distillation.
CH2-C1 CH2-OH
10% K2CO3
H2O, reflux
Benzyl chloride Benzyl alcohol
Fig. 5.3.14
CHO CH2OH
RuHCI(CO) (PPH3)3
+ HCOOH + CO2T
Formic
acid Benzyl alcohol
Benzaldehyde
Fig. 5.3.15
Engineering Chemistry-|I (MU - Sem 2) (5-13)
Drawbacks of Conventional / Traditional route

(1) This conventional method is very costly.
(1) There are some by-products formed which are hazardous and they pollute the environment.
(iu) The conversion of benzyl chloride to benzyl alcohol is not complete.
(IV) The afom oconomy is low.
(In Green synthesis or green chemistry route
(1) The alternative method for the preparation of Benzyl alcohol is termed as catalytic transfer hydrogenation.
(11) In this method, the hydrogenation of benzaldehyde has been carried out with formic acid using RuHCI(CO)
(PPhz), as a catalyst. CO, gas is eliminated with the formation of benzyl alcohol.
(111) The reaction is carried out by constant microwave irradiation. The reaction gets completed in just 7 minutes.
(iv) There are no bye-products except CO, which evaporates.
(1) Under standard reflux method, the time taken is much more and atom economy is low.
Syllabus Covered
Lecture-5
1) Percentage atom economy.
ii) Green fuel-biodiesel.
iii) Any four examples.
5.4 PERCENTAGE ATOM ECONOMY
GQ. 5.4.1 Explain the term % Atom Economy with a suitable example. Also state its significance.
(3 Marks)
Ans. :
(1) Explanation of % atom economy

(1) The term refers to the second principle of green chemistry viz. “Maximize atom economy'.
(11) The design of the synthesis of a product should be such that all the chemicals / materials i.e. reactants used in the
Moc
process of production must be converted into the final product to the maximum extent.
(111) % atom economy can be calculated as follows:

Molecular weight of the product
x 100
% Atom Economy = Totalmolecular weight of the reactants
(U) Example of % atom economy

(1) Consider the following reaction :
CH, + CHOI →CH,CH, + HCI
Reactants Product
78 50.5 92
Molecular weight
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Molecular weight of the product 92
x 100 = 71.59
(iii) :: % Atom Economy = Total molecular weight of the reactants x 100 =
78 + 50.5
(III) Significance of % atom economy

(1) % atom economy is analogous to efficiency of the reaction. Clearly it must be as high as possible, ideally 100%.
(ii) Higher the % atom economy means lesser are the troubles of cleaning, pollution and disposal and lesser cost.
5.5 GREEN FUEL-BIODIESEL
Note: Given below is the general question along with the answers, from which write the required answer.
UQ. 5.5.1
What is bio-diesel? Explain the trans-esterification method for the synthesis of bio-diesel.
Mention the advantages of bio-diesel as fuel.
Ref. : (MU - Q. 6(c), May 19, 4 Marks, Q. 2(b), Dec. 16, 3 Marks, Q. 6(c), Dec. 17,4 Marks, Q.5(a), May 15, 6 Marks,
Q. 5(a), Dec. 14, 6 Marks, Q. 2(b), Dec. 13,5 Marks, Q. 5(a), May 13, 6 Marks,
Q. 2(bXii), Dec. 18, 2 Marks, Q. 3(a)(ii), May 18, 2 Marks, Q. 6(c), Dec. 17, 4 Marks)
Ans.:
(1) Chemically bio-diesel is the methyl esters of long chain carboxylic acid. It is also called as “green fuel'.
(II) Synthesis of bio-diesel
(1) Bio-diesel is obtained by transesterification (means converting on ester into another ester) of vegetable oil or
animal fats mixed with methyl alcohol using sodium metal or sodium methaoxide as catalyst.
(2) A molecule of oil or fat is the trimester of glycerol and three molecules of long chain carboxylic acids. This
trimester is converted into methyl esters of the fatty acids.
(3) Vegetable
oil or fat
CH2 ooc-R R COOCH3 CH2OH
1
Sodium methoxide
CH +00C-R2 R2COOCH3 + CHOH
|
CHZ ONa
|
R3COOCH3 CH2OH
CH2 → OOC-R3 Heat
3H0+ CH3 Methy! (Biodiesel) Glycerol

alcohol
(2E10)Fig. 5.5.1
(4) During the chemical conversion of vegetable oil to biodiesel we get water soluble glycerol and a small amount of
sodium soaps.
The water soluble part can be easily separated from biodiesel by washing the mixture with water.
(5) The alkaline sodium methoxide catalyst, saponifies some small amount of oil to give soap.
(6) Moisture-free oil or fat with less than 5% free acid and dry methanol or ethanol are taken in 1:3:5 molar ratio in a
3-neck round bottom flask with an arrangement of a stirrer and a heater) and the catalyst methaoxide maintained at
2% by weight
(7) The mixture is heated at 60°C and purified by using vacuum distillation.
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(III) Advantages of bio-diesel
Biodiesel can be used as a good fuel for diesel engines but generally it is used as its 20% mixture with diesel.
(1) Biodiesel is cheaper.
(2) It does not give out particulate and CO pollutants.
(3) It has high cetane numbers 46 to 54 and high C.V. of about 40 kJ/gm.
(4) It has certain extent of lubricity.
(5) It is regenerative and environment friendly.
(6) It is clean to use biodiesel in diesel engines.

(7) Its use provides good market to vegetable oils and reduces our dependence for diesel on foreign countries, saving
the foreign currency.
Part II : Solved Problems
Important Formulae
There is only one formula as follows:

Molecular weight of the product x 100
% Atom Economy =
Total molecular weight of the reactants
UEx. 5.1 MU - Q.2(c), May 13, 4 Marks
Calculate the % atom economy for the reactions given in the following problems w.r.t. clorobenzene.
CI
+ Cl2 + HCI
Clorobenzene
soin.:
(1) Given reaction : C.H. + Cl2 —+CH,Cl + HCI

Module
1
(II) Total molecular weight of the reactants on the LHS : 5
[CH] + [Cl2] = [(12) X6 + (1) $6] + [(35.5) 2] = 149
(III) Molecular weight of the product on the RHS :
[CH,CI] = [(12) x6 +(1) * 5 + 35.5) = 112.5
(IV) % Atom Economy = Total molecular weight of the reactants
112.5 ...Ans.
x 100 = 75.5
49
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UEx. 5.2 MU - Q. 2(c), Dec. 13, Q. 3(c), May 18, Q. 2(c), Dec. 16, 4 Marks
Calculate the % atom economy of the following reaction w.r.t. the product acetophenone.
CH,COCH, + HCI
CH + CH, COCI) Acetophenone
Soln. :
AICI:
(1) Given reaction : C.H. +CH,COCI →CH,COCH+ HCI
(II) Total molecular weights of the reactants on the LHS :

[CH] + [CH3COCI] = [(12) 6+ (1)x6] + [12 + (1) x 3 + 12 + 16 + 35.5] = 156.5
(III) Molecular weight of the product on the RHS:

[CH,COCH3] = [(12) * 6+(1) * 5 + 12 + 16 + 12 + (1) X 3] = 120
(IV) % Atom economy Molecular weight of the product X 100

120.5
=
x 100 = 76.677 ...Ans.
156.5
UEx. 5.3 MU - Q.2(c), May 14. 4. Marks

Calculate percentage atom economy for the following reaction with respect to acetanilide.
CHÚNH + (CH,CO)-0*C,H,NHCOCH, +CH,COOH
Aniline Acetanilide
Soln. :
(1) Given reaction :
CH5NH2 + (CH, CO),0 → Co H, NHCO CH, +CH, COOH
(II) Total molecular weights of the reactantants on the LHS
C, H, NH, + (CH, CO), 0 = (12) X6 + (1) x 5 + (14) x1 + (1) x2
+ [(12) x 1 + (1) X 3+(12) × 1+ (16) X1] × 2 + (16) x 1
= 195
(III) Molecular weight of the product on the RHS
C, H, NHCOCH, = (12) X6 + (1) 5 + (14) 1+(1)x1+(12)x1+(16)* 1 + (12)* 1 +(1) 3

133
Molecular weight of the product

x 100
(IV) % Atom economy Total molecular weight of the reactatants
133
x 100 = 68.20
195 ...Ans.
UEx. 5.4 MU - Q. 2(C). Dec. 14.0.3(c). Dec. 18. Q.30). Dec. 17, Q.3(c), May 19, 4 Marks
Calculate the percentage atom economy for the following reaction with respect to allyl chloride
CH,-CH=CH,+C, --C1-CH, -CH=CH2 + HCI
Allylchloride
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Soln.:
*-CH --CH=CH2+ HCI
(1) Given reaction : CH3-CH = CH, +C12 -
Allyl chloride

(CH2-CH=CH.] + [Cl]] = [12 + (1) * 3 + 12 + 1 + 12 + (1) X 2] + [(35.5) 2] = 113
(CH-CH-CH=CH2] = [35.5 + 12 + (1) 2 + 12 + 1 + 12 + (1) * 2) = 76.5
(IV) % Atom economy = Total molecular weight of the reactants
76.5 ...Ans.
x 100 = 67.69
113
UEX 5.5 MU - Q. 20).May 15, Q. 3c), May 17, 4 Marks

Calculate the percentage atom economy for the following reaction.
CHNH + COC, +CH N = C = 0 + 2HCI
Soln.;
Given reaction : CH NH2 + COCI, —+CHN=C=0 +2HC
(Total molecular weights of the reactants on the LHS.
[CH NH4] + [COC ] = [12 + (1) x 3 + 14 + (1) x 2] + [12 + 16 + (35.5) x 2] = 130
(III Molecular weight of the product on the RHS :
[CH, N = C = 0] = [12 + (1) x 3 + 14 + 12 + 16] = 57

(IV) % Atom economy =
57
x 100 = 43.84 ...Ans.
130
VEX 5.6 MU-Q.2c), Dec. 15. 4 Marks

Calculate percentage atom economy for the following reaction w.r.t. cinnamaldehyde.
NaOH
CHỊCHO CH CHO CH.CH = CHCHO + H2O
Module
Benzaldehyde Acetaldehyde Cinnamaldehyde
5
Soin.
NaOH
(1) Given reactionC.H.CHO + CH CHO CHỊCH = CHCHO + H,O

[(12) * 6+ (1) 5+ 12 + 16] + [12 + (1) x 3 + 12 + + 16) = 150
1

OCH CH = CHCHO) = [(12) x 6+ (1)*5 + 12 + 1 + 12 + 1 + 12 + 1 + 16) = 132
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(IV) % Atom economy = Molecular weight of the product x 100
132 ...Ans.
* 100 = 88
150
Part III : Home Work Problems
Calculate % atom economy for following reactions :

Ni
Q. 1 CH3CH = CH2 + H2 CH2CH2CH3
(Ans. : 100)
AICI:
Q. 2 CGHE + CHCI CGH-CH3 + HCI (Ans. : 71.58)
Q. 3 CH3CH,Br + KOH-CH2CH2OH + KB (Ans. : 27.88)
Alcohol
CH2CH2CH2Br + KOH (Ans. : 22.9)
Q. 4 CH, CH = CH + KBr + H2O
Q5 CGHE NHL + CHECOCI C6H5NHCOCHE + HCI
aniline benzonyl chloride benzanilide (MU - Q2, May 16, 4 Marks)

(Assume atomic weight of Bromium = 80)
Chapter Ends...
‫םסס‬
CHAPTER
6 Fuels and Combustion
Module 6
Definition, classification, characteristics of a good fuel, units of heat (no conversions). Calorific value :
Definition, Gross or higher calorific value and net or lower calorific value, Dulong's formula and numerical for
calculations of Gross and Net calorific values. Solid fuels : analysis of coal : proximate and ultimate
analysis-numerical problems and significance. Liquid fuels : Petrol-knocking, octane number, cetane
number, antiknocking agents, unleaded petrol, oxygenates (MTBE), catalytic converter.
Combustion - calculations for requirement of only oxygen and air (by weight and by volume only) for given
solid and gaseous fuels.
6.1 INTRODUCTION TO FUELS 6-4
6.1.1 Definition of Fuel. 6-4
6-4
UQ. 6.1.1 Define fuel. Ref.: (MU - Q. 1(a), Dec. 18, 3 Marks).
Classification of Fuels. 6-4

6.1.2
6.1.3 Characteristics of Fuels 6-5
UQ. 6.1.3 State and discuss important characteristics of fuels. Ref.: (MU - Dec. 12, 5 Marks). 6-5
6-6
6.1.4 Unit of Heat (only for knowledge)
6-7
6.2 CALORIFIC VALUE.
6-8
6.2.1 Types or Classification of the Calorific Value
6-8
6.2.2 High Calorific Value
6-8
6.2.3 Low Calorific Value
6-9
6.2.4 Dulong's Formula.
6-10
6.3 SOLID FUELS..
6-10
6.3.1 Analysis of Coal...
6-11
6.3.1(A) Proximate Analysis
6-12
6.3.1(B) Ultimate Analysis
UQ. 6.3.4 Why a good fuel must have low ash content ? Ref.: (MU - Q. 1(a), Dec. 18, 3 Marks). 6-16
6-16
6.4 LIQUID FUELS
6-16
6.4.1 Crude Petroleum Oil
6-18
6.4.2 Mining of Crude Petroleum
Engineering Chemistry-1I (MU - Sem 2) (6-2) Fuels and Combustion
6.4.3 Refining of Petroleum. 6-19
UQ. 6.4.3 With a suitable diagram, explain the process of refining of petroleum.
Ref. : (MU - Q.5(a), Dec. 15, 4 Marks, Q. 2(b), May 14, 5 Marks, Q. 2(b), May 13, 5 Marks). 6-19
6.4.3(A) Products of Fractional Distillation of the Crude Oil .... .6-21
UQ. 6.4.5 Name any two fractions obtained during distillation of the crude oil.
Ref.: (MU - Q.5(a), Dec. 15, 2 Marks). .6-21
6.4.4 Cracking of Heavy Oil...... 6-22
UQ. 6.4.6 What is cracking of heavy oil?

Ref. : (MU - Q. 3(a)(1), May 19, Q.5(aXi), Dec. 16, 1 Mark, Q. 1(c), Dec. 15, 1 Mark,
Q.2(a), May 15, 1 Mark, Q. 3(a)(i), Dec. 18, 1 Mark, Q. 3(a), Dec..17, 1 Mark,
Q. 1(c), Dec. 14, 1 Mark, Q.5(a)(i), Dec. 13, 1 Mark) 6-22
6.4.5
Types of Cracking. 6-22
6.4.5(A) Thermal Cracking 6-22
6.4.5(B) Comparison between Liquid phase and Vapour Phase Thermal Cracking. 6-23
6.4.6
Catalytic Cracking. 6-23
6.4.6(A) Fixed Bed Catalytic Cracking. 6-24
UQ. 6.4.11 Explain in details fixed bed catalytic cracking.

Ref.: (MU - Q.3(a)(ii), May 19, 5 Marks, Q. 3(a)(ii), Dec. 18, 5 Marks,
Q. 3(a)(ii), Dec. 17,5 Marks, Q. 3(a), May 17, 6 Marks, Q.5(a)(ii), Dec. 16, 4 Marks,
Q. 2(b), May 15, 4 Marks, Q. 5(a), May 14, 4 Marks)... 6-24
6.4.6(B) Moving Bed Catalytic Cracking.... 6-25
6.4.7
Advantages of Catalytic Cracking over Thermal Cracking 6-26
UQ. 6.4.13 State the advantages of catalytic cracking over thermal cracking.
Ref. : (MU - Q.5(a)(ii), May 16, 4 Marks, Q. 1(c), Dec. 15, 2 Marks,
Q. 5(a)(ii), May 14, 2 Marks)
6-26
6.4.8
Comparison between Fixed Bed and Moving Bed Catalytic Cracking 6-27
6.4.9 Comparison between Thermal Cracking and Catalytic Cracking 6-27

6.4.10 Introduction to knocking.
6-27
UQ. 6.4.16 What is meant by knocking in an internal combustion engine ?
Ref.: (MU - Q. 2(b), Dec. 15, 1 Mark, Q.2(b), Dec. 14, 2 Marks). 6-27
6.4.10(A) Effects of Knocking.
6-28
6.4.10(B) Effect of Chemical Structure on Knocking 6-28
UQ. 6.4.18 HowRef.is knocking tendency of gasoline related to chemical structure of hydrocarbons present ?
: (MU - Q. 1(a)( ii), May 14, 2 Marks).
6-28
6.4.10(C) Reduction of Knocking...
6-29
UQ. 6.4.20 Name any two antiknocking agents.
Ref.: (MU - Q. 2(b), Dec. 15, 2 Marks, Q. 2(b)(iii), Dec. 14, 2 Marks,
Q. 1(a)(ii), Dec. 13, 19, 2 Marks).
6-29
6.4.11 Octane Number and Its Significance
6-29
UQ. 6.4.21 Define octane number and write its significance.....
6-29
Ref.: (MU - Q. 1(a), May 19, 3 Marks, Q. 1(c), May 17, 142 Marks,
Q. 1(b)(i), May 16, 1/2 Marks, Q. 2(b), Dec. 15, 2 Marks, Q. 2(b)(i), Dec. 14, 1 Mark,
Q. 1(a), May 14, 1 Mark, Q. 1(a), Dec. 13, 1 Mark, Q. 1(b), May 13,1 % Marks). 6-29
6.4.12 Cetane Number and Its Significance.
6-30
UQ. 6.4.22 Define the cetane number. state its significance.
Ref.: (MU - Q. 1(c)(i), May 17,1% Marks, Q. 1(b)(ii), May 16,1% Marks,
Q. 2(b), Dec. 14, 1 Mark, Q. 1(b), May 13, 1/2 Mark)
6-30
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Fuels and Combustion
6-30
6.4.13 Comparison between Octane Number and Cetane Number
6.4.14 Unleaded Petrol. 6-31
UQ. 6.4.24 Explain briefly about unleaded petrol. Also state its advantages.
. Ref.: (MU - May 12, 5 Marks). 6-31
6.4.15 Methyl Tertiary Butyl Ether (MTBE). 6-32
6.4.16 Power Alcohol... 6-33
Solved University Problems

UEx. 6.2 (MU - Q. 6(b), Dec. 13, 5 Marks). 6-35
UEX. 6.3 (MU - Q. 6(b), May 14, 5 Marks). 6-35
UEX. 6.4
(MU - Q. 1(g), Dec. 14, 3 Marks). 6-35
UEx. 6.5 (MU - Q. 6(b), Dec. 15, 5 Marks). 6-36

UEx. 6.6 (MU - Q. 1(c), May 19, 3 Marks). 6-36
UEX. 6.7 (MU - Q. 1(c), Dec. 18, 3 Marks) ... 6-36
UEx. 6.8 (MU - Q. 1(c), May 18, 3 Marks). 6-37
UEX. 6.9 (MU - Q. 1(c), Dec. 17, 3 Marks) .. 6-37
UEx. 6.10 (MU - Q. 6(b), May 10, 5 Marks). 6-37

UEx. 6.14 (MU - Dec. 09, 5 Marks). 6-40
UEX. 6.15 (MU - May 11, Dec. 13, 5 Marks) 6-41
UEX. 6.16 (MU - May 12, 5 Marks) 6-41
UEX. 6.17 (MU - Dec. 12, 5 Marks). 6-42
UEX. 6.18 (MU - May 13, 5 Marks). 6-43
UEx. 6.19 (MU - Q. 1(g), May 13, 3 Marks). 6-44
UEX. 6.20 (MU - Q. 6(b), Dec. 14, 5 Marks). 6-44
UEX. 6.21 (MU - Q. 1(g), Dec. 15, 3 Marks). 6-44
UEx. 6.23 (MU - Q. 3(a), May 13, 6 Marks). 6-47
UEX. 6.24 (MU - Q. 3(a), Dec. 13, 6 Marks).. 6-47

Chapter Ends. 6-51
Моа
TO
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Engineering Chemistry-11 (MU - Sem 2) (6-4) Fuels and Combustion
This chapter can be divided into five sections as shown in Fig. C. 6.1.1.
(2) (4) (5)

Introduction Calorific Combustion
Solid Liquid
to
values fuels fuels of fuels
fuels only numerical
and Dulong's
formula Problem's
(2F1)Fig. C. 6.1.1 : Details of fuels and combustion
Part - 1: Theory
Syllabus Covered
Lecture-1
Introduction to Fuels.
» 6.1
INTRODUCTION TO FUELS
a 6.1.1 Definition of Fuel
UQ. 6.1.11 Define fuel.

Ref.: (MU - Q. 1(a), Dec. 18, 3 Martos)
7 Ans. :
(i) A fuel can be defined as a combustible substance, which on proper burning gives a large amount of heat that can be
used economically for domestic and industrial purposes. !
(ii) Wood, charcoal, coal, kerosene, petrol, diesel, oil gas are some of the important fuels.
6.1.2 Classification of Fuels
GQ. 6.1.2
Represent the types of fuels with the help ofa suitable chart.
(3 Marks)
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J Ans. :
Fuels
Primary Secondary
or or
Natural Derived
0
Solid
Liquid Gaseous Solid Liquid e.g.
e.g e.g. e.g. e.g. e.g. Water gas,
wood, Crude oil, Natural Charcoal, Alcohol, LPG
coal, vegetable gas coke, Petrol, diesel, Biogas
dung oil
Pulverized kerosene
coel
(2F2)Fig. 6.1.1 : Classification of fuels
6.1.3 Characteristics of Fuels
UQ. 6.1.3
State and discuss important characteristics of fuels. Ref. : (WU-Dec 12,5
Marta)
Ans. :
Discussed below are some important desirable characteristics of fuel :

1. Low moisture content
The moisture content of the fuel reduces the heating value and involves loss of money. Hence, fuel should have low
moisture content.
2. Moderate ignition temperature
(i) Ignition temperature is the lowest temperature to which the fuel must be pre-heated so that it starts burning
smoothly.
(ii) Low ignition temperature is dangerous for storage and transport of fuel, since it can cause fire hazards.
(iii) On the other hand, high ignition temperature causes difficulty in kindling (or igniting) the fuel, but the fuel is safe
during storage, handling and transport.
(iv) Hence, an ideal fuel should have “moderate” ignition temperature.
3. High calorific value
A fuel should have a colorific value since the amount of heat liberated and the correspond attained temperature depends
upon the calorific value of the fuel.
4. Low cost
Moa..
A good fuel should be readily available in bulk at a cheap rate.
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5. Low non-combustible matter content
(i) After combustion, the non-combustible matter remains in the form of ash.
(ii) The non-combustible matter also reduces the heating value, besides additional cost of storage, handling and
disposal of the waste products.
(iii) Each percent of non-combustible matter in fuel means a heat loss of about 1.5%. Hence, a fuel should have low
content of non-combustible matter.
6. Products of combustion should not be harmful
(i) Fuel, on burning, should not give out objectionable and harmful gases.
(ii) The gaseous products of a combustion should not pollute the atmosphere. CO, SO2, H2S, PH3, etc. are some of the
harmful gases which must be reduced.
7.
A fuel should not undergo spontaneous combustion
Spontaneous ignition can cause fire hazards.
8.
A fuel should burn in air with efficiency, without much smoke.
9.
Moderate velocity of combustion
(i) If the rate of combustion is low, then the required high temperature may not be possible, because a part of the heat
liberated may get radiated instead of raising the temperature.
(ii) On the other hand, too high combustion rates are also not required.
(iii) Hence, a fuel should have moderate combustion rate.
10. Storage cost in bulk should be low to reduce the overall cost.
11. Easy to transport
(i) Fuel must be easy to handle, store and transport at a low cost.
(ii) Solid and liquid fuels can easily be transported from one place to another.
(iii) On the other hand, transportation of gaseous fuels is costly and can even cause fire hazards.
12. Combustion should be easily controllable, i.e. combustion of the fuel should be easy to start or stop, when required.
13. The size of solid fuel, should be uniform so that combustion is regular.
a 6.1.4 Unit of Heat (only for knowledge)
GQ. 6.1.4 State and explain the units of heat.

*** (3 Marks)
7 Ans. :
The units of heat are mainly four which are discussed in brief as follows:
(1) Calorie (cal) or gram calorie (g. cal)
For all practical purposes, the calorie or gram calorie may be defined as the amount of heat required to raise the
temperature of one gram of water through one degree centigrade. (i.e. from 15°C to 16°C) 1 calorie = 4.185 joules.
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(2) Kilocalorie or kilogram calorie or kilogram centigrade unit (kcal or kg cal or K.C.U.)
This is equal to 1000 calories and thus is the amount of heat required to raise the temperature of one kilogram of water
through 1°C (from 15°C to 16°C).
1 kcal = 1000 cal
(3) British thermal unit

A British thermal unit is the amount of heat required to raise the temperature of 1 lb of water through 1 F (more
precisely from 60°F to 61°F).
1B.Th.U = 1,054.6 Joules = 1,054.6 x 10'ergs.
1B.Th.U = 252 cals = 0.252 kcals
1 Kcal = 3.968 B.Th. U
(4) Centigrade heat unit (C.H.U.)
The centigrade heat unit is the amount of heat required to raise the temperature of 1 lb of water through 1°C.
1kcal = 3.968 B.Th.U. = 2.2 C.H.U.
This unit can be interconverted as follows:

1kcal/kg = 1.8 B.Th.U./b
1kcal/m = 0.1077 B.Th.U./ft?

1B.Th.U./ft? = 9.3 kcal/m?
Syllabus Covered
Lecture-2
Calorific Value.
6.2 CALORIFIC VALUE
GQ. 6.2.1 Define calorific value. State its significance. (3 Marks
Ans. :
(1) Definition of calorific value
It is defined as the total quantity of heat liberated after the complete combustion of a unit mass or a unit volume of the
fuel.
(U) Units of calorific value

Modult
The calorific values of solid and liquid. Fuels are expressed in kilocal/kg while calorific value of the gaseous fuels is
expressed in kilocal/m”.

Engineering Chemistry-|| (MU - Sem 2) (6-8) Fuels and Combustion
(III) Significance of calorific value
The heat evolved by the complete combination of a fuel is directly proportional to its calorific value. Therefore a good
fuel should have a high calorific value.
a 6.2.1 Types or Classification of the Calorific Value

GQ. 6.2.2
State the two values of the calorific values with the help of a suitable chart. (2. Marks)
Calorific value
(2)
High Calorific Value Low Calorific Value
(HCV) (LCV)
or or
Gross Calorific Value Net Calorific Value

(GCV) (NCV)
(2F3)Fig. 6.2.1 : Calorific values
6.2.2 High Calorific Value
GQ. 6.2.3
Define thehigh calorific value. Also state its significance. (2 Marks)
Ans. :
(1) Definition of high calorific value
High calorific value (HCV) also called as gross calorific value (GCV) is defined as 'the total amount of the heat
produced when a unit mass (in the case of a solid fuel) or a unit volume (in the case of a liquid or gaseous fuel) is burnt
completely and the products of combustion are cooled to the room temperature.'
(11) Significance of high calorific value
(i) The total heat produced by the complete combustion of a fuel is directly proportional to its calorific value.
(ii) Therefore a good fuel should have a high value of HCV.
6.2.3 Low Calorific Value
GQ. 6.2.4
Define the low calorific value. Also state its significance.
(2 Marks)
✓ Ans. :
(1) Definition of low calorific value
Low calorific value (LCV) also called as net calorific value (NCV) is defined as the net quantity of the heat produced
when a unit mass (in the case of a solid fuel) or a unit volume (in the case of a liquid or gaseous fuel) is burnt completely and
the products of combustion are permitted to escape into the atmosphere'.

Engineering Chemistry-II (MU - Sem 2) (6-9) Fuels and Combustion
(6) Mathematical expression of the low calorific value and its explanation
(i) Low calorific value = Gross calorific value (GCV) – the latent heat of condensation of the water vapour produced
= GCV - (mass of the hydrogen/unit weight of the fuel burnt x g latent heat of steam)
Note:
10 1 part of weight of hydrogen gives 9 parts of weight of water as per the following reaction
Hz+ 0 +H2O
: (2x1) gm + (1 x 16) gm → (2x1 + 16)gm
Dividing bythecommon factor = 2 through out
Weget, 1 gm of hydrogen + 16 gm of oxygen
1 gm of hydrogen+ 8 gm of oxygen = 9 gmof water
@) The latent heat of steam = 587calgm
н
· LCV = GCV-9x X 587
100 Or LCV = GCV - 0.09 x H x 587 kcal/kg
(III) Significance of low calorific value
(i) The net heat produced by the complete combustion of a fuel is directly proportional to its low calorific value.
(ü) Therefore a good fuel should have a high value of LCV.
a 6.2.4 Dulong's Formula
GQ. 6.2.5
State and explain the mathematical expression for the Dulong's formula. Also state its
significance.
(5 Marks)
Ans. :
(1) Explanation and mathematical expression of the Dulong's formula
(1) A formula giving the gross heating value of coal in terms of the weight fractions of carbon, hydrogen, oxygen and
sulphur from the ultimate analysis is called as Dulong's formula. According to Dulong, the calorific value of a fuel
is the sum of the calorific values of its constituent elements.
The calorific value of different elements is given as follows:

Calorific value of carbon = 8080 cal/g
Calorific value of hydrogen 34500 cal/g

Calorific value of sulphur 2240 cal/g
(2) Thus, the Dulong's formula for calculating the high calorific value from the chemical composition of fuel is,
1
HCV =
100
8080 C + 34500 (H
240]Kc
+ 2240 S Kcal/kg
Where, Mon -
C = % carbon
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H =
% Hydrogen
0 = % Oxygen
S = % Sulphur
Oxygen is assumed to be present in combination with hydrogen as water.

LCV = [HCV-0.09 H x 587] Kcal/kg
(II) Significance of Dulong's formula
(1) It helps in theoretically calculating the values of HCV and LCV of the given fuel.
(2) Thus it simplifies the calculation of HCV and LCV and saves the time. (Otherwise we can find C.V. of the solid
and liquid fuels by a time-consuming experiment using a Bomb calorimeter).
Syllabus Covered
Lecture-3
Solid Fuels.
MY 6.3 SOLID FUELS
a 6.3.1 Analysis of Coal
GQ. 6.3.1
With the help of a suitable chart, represent the two types of analyzing the, given coal sample
fordetermining its quality with the relevant tests. (3 Marks)
Ans. :
Two types of analyzing coal sample are as shown in Fig. 6.3.1.
Analysis of coal
Proximate (2)
Ultimate
analysis
analysis
(1) (iii) (0)

% moisture % Ash %Carbon
% Sulphur % Ash
& % Hydrogen
(ii)
(ii)
% volatile % Fixed
matter
% Nitrogen % Oxygen
carbon
(2F4)Fig. 6.3.1 : Analysis of Coal
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IT E T
6.3.1(A) Proximate Analysis

GQ. 6.3.2 Explain briefly the four tests performed under theproximate analysis of the given coal sample
along with the significance of eachtest. (6 Marks)
Ans. :
The four tests performed under the proximate analysis of the given coal sample are explained below along with the
significance of each test.
(1) % Moisture content test
(1) Procedure of the % moisture content test
(i) A known weight of coal taken in a pre-weighted silica crucible and is maintained at 105-110° C for about an
hour in an oven.
(i) It is then taken out, cooled and weighted.
(iii) The process of heating, cooling and weighting is repeated many times till a constant weight of crucible is obtained.
(iv) Knowing the loss in weight of the coal, percentage of moisture can be calculated as,
% Moisture content =
Loss in the weight of the sample X 100
Weight of the air dried sample
(II) Significance of the % moisture content test
(i) Presence of moisture in coal reduces its calorific value and a considerable amount of heat is wasted in evaporating
the moisture during combustion.
(ü) Hence, high percentage of moisture is undesirable.
(2) % Volatile matter test
(1) Procedure of the % volatile matter test
(i) A known weight of coal is taken in a weighted crucible covered with lid and is kept in a muffle furnace at
925 + 20° C for about 7 minutes.
(ii) The hot crucible is taken out, cooled and weighted.
(iii) Loss in weight is reported as volatile matter and is calculated as,

Loss of weight of the sample
% Volatile matter content = x 100
Weight of the air-dried sample
Note: This formula is the same asthat for the % moisture contenttest.
(II) Significance of the % moisture test

(1) Volatile matter evolved consists of combustible gases like CO, H2, CH, and N, which do not have any heating
value and are therefore undesirable. Module
(ii) Coals with high volatile matter burn with long, smoky flame while coals with low volatile matter burn with shorter 6
non-smoky flame.
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(iii) Thus, presence of moisture in coal reduces its calorific value and a considerable amount of heat is wasted in
evaporating the moisture during combustion.
(iv) Hence presence of moisture is undesirable.
(v) This test helps in designing a furnace since combustion space required upon the nature of the flame.
(3) % Ash content test
(1) Procedure of the % ash content test
(i) A known weight of dry coal sample contained in the above process is taken in a weighted silica crucible.
(ii) The crucible is heated in a muffle furnace at 700-750°C for about half an hour.
(iii) The crucible is taken out, cooled and weighted.
(iv) Heating, cooling and weighted is repeated till a constant weight is obtained.
(v) The % of ash is calculated as,
% Ash content = Weight of the residual ash

Weight of the air-dried sample x 100
(II) Significance of the % ash content test

(i) Ash is a non-combustible matter and it reduces the calorific value of coal.
(ii) It also causes obstruction to the flow of heat.
(iii) It lowers the temperature and gives rise to the clinker formation.
(iv) Disposal of ash is also a big problem.
(4) % Fixed carbon
(1) Procedure of the % fixed carbon test
(i) All the above three tests are carried out in succession in the laboratory.
(ii) The % fixed carbon can be easily calculated as
% Fixed carbon content = 100-(% moisture content + % volatile matter content + % ash content)
(II) Significance of the % carbon content test
(i) Fixed carbon varies inversely with the volatile matter which in turn, depends inversely, with the carbon, i.e. the
calorific value a
1
carbon content
(ii) Therefore, more is the % of fixed carbon, higher is the calorific value.
a 6.3.1(B) Ultimate Analysis
GQ. 6.3.3
Explain briefly the five tests formed under the ultimate analysis of the given coal sample
along with the significance of each test.
(8 Marks)
Ans. :
The five tests performed under the ultimate analysis of the given coal sample are explained below along with the
significance of each test.
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(1) % Carbon and % hydrogen contents test
(1) Procedure of the % carbon and % hydrogen contents test

(1) A known weight of coal is taken in a combustion tube and is burnt in excess supply of oxygen.
(ü) The CO2 and H,0 formed are passed through two pre-weighted bulbs containing anhydrous calcium chloride and
second bulb containing potassium hydroxide.
(ii) The increase in the weight of calcium chloride tube represents the weight of water formed; whereas the increase in
the weight of KOH bulb represent the weight of carbon dioxide formed.
(iv) The Fig. 6.3.2 shows the process.
Substance Coarse
in boat Сао
Air or
Cuo Cuo
Oxygen
Spiral guage Guard
tube
UR U
Soda
Lime
Air or Oxygen Supply

H2SO4
Combustion Tube
CaCl2 tube
Potash
Bulbs
(KOH solution)
Absorption Unit
(2F5)Fig. 6.3.2 : Arrangement for finding % carbon and % hydrogen contents

(II) Calculations of the % carbon and % hydrogen contents are done as follows
(i) Let the weight of the coal sample taken = wi'g
'
(ü) Increase in weight of CaCl, bulb (weight of H2O) = W2

(iii) Increase in weight of KOH bulb (weight of CO2) = W3
(iv) Percentage of carbon is calculated as,
C + O2 + CO2
12 44
44 g of CO2 contains carbon = 12 g
12 W3
:: W38 of CO2contain carbon = 44 Х
w
-22 increase in the weight of the water absorption unit

W3
ex
12 22
% of carbon = x 100 =
44 w 44
weight of the coal sample
(v) Percentage of hydrogen is calculated as,
H, +{ 0, +4,0
+
Mc.
2 18
18 g of H2O contains hydrogen = 2 g
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2 W2
:: Wig of H2O contains hydrogen = 18 х
W
2 W2
X x 100 =
2 increase in the weight of the water absorption unit
% of hydrogen 18 18
Х
w weight of the coal sample
(III) Significance of the % carbon and % hydrogen contents test
(i) Carbon is the major combustible constituent.
(ii) Its percentage depends on the ranking of coal and percentage increases from lignite to anthracite.
(iii) Greater the percentage of carbon and hydrogen better the quality of coal and calorific value increases.
(iv) The hydrogen present in the fuel is associated with the volatile matter. It affects the uses for which coal is utilized.
(2) % Nitrogen content test
(1) Procedure of the % nitrogen content test
(i) % nitrogen content in the given coal sample is determined by Kjeldahl's method.
(ii) Fig. 6.3.3 represents the arrangement of Kjeldahl's method for determining % nitrogen contents.
Splash Head
(Kjeldahl Tap)
Kjeldahl
Substance +
NH3 Steam
Flask
Conc H2SO4
+ CuSO4
+ K2SO4
1 litre
RB Water
Flask out
Kjeldahl
Liquid
+ Water
NaOH in
Conical flask
Known volume
of standard
H2SO4 Acid
(2F6)Fig. 6.3.3 : Determination of % nitrogen contents by Kjeldahl's method
(iii) 1 g of powdered coal is taken and heated with concentrated HụSO, along with K,SO, and CuSO, in a Kjeldahl's
flask.
(iv) The heating is continued till a clear solution is obtained.
(v) In this stage nitrogen present in the sample gets converted to (NH4)2 SO, which is then treated with excess of
NaOH to liberate NHz.
(vi) The ammonia produced distills over and is absorbed in a known volume of standard H,SO4.
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(II) Calculations of the % nitrogen content are done as follows

(i) Let the volume of the standard H,SO, acid taken for absorption of NH3 = V, ml of N normality.
(ii) Let the volume of the alkali used for titration of excess H2SO, acid V2 ml of N normality.
(iii) The volume of the unused H2SO4 = (V, -V2) of N normality.
(iv) (a) N2 + H2SO4 ->(NH4) SO4 + 2 NaOH —+2 Na2SO4 + 2NH3 + 2 H20
(b) 2NH3 + H2SO4 >(NH4), SO
(v) (a)
The volume of unused H2SO4 can be determined by titrating against standard NaOH. V ml of 0.1 N NaOH is
required to neutralize the excess acid. The amount of acid neutralized by liberated NH, is determined.
(b)
Standard acid taken for absorption of NH3 = V, ml of N normality
Volume of alkali used for titration of excess acid = V2 ml of N normality
(d)
Volume of H2SO4left unused = (V-V2) ml of N normality
(e) (Vi-V2) ml of N H2SO4 = (V,-V2) ml of N NHz
Volume of NH; evolved = (V,-V2) ml of N normality
N
:. amount of nitrogen = 14 ® (V,-V2) * 1000 g
[1000 ml 1 N NHz = 14 g nitrogen]

1000 ml 0.1 NHz= 1.4 g nitrogen
N
(i)
% N = 1.4 x (V,-V2) * 1000
X 100
%N =
1.4 x Normality of acid Volume of acid used
Weight of coal
(III) Significance of % nitrogen contents
Nitrogen is undesirable in a sample. A good quality coal must have very low nitrogen content.
(3) % Sulphur content test
(1) Procedure of the % sulphur content test
(i) A known amount of coal is burnt completely in a Bomb's calorimeter in a current of oxygen and the sulphur
present is oxidized to sulphate.
(ii) The ash is extracted with diluted HCl and the acid extract is treated with BaCl2 solution to precipitate SO, as
BaSO4
(iii) The precipitate is filtered, washed, dried and heated to a constant weight.
(II) Calculations of the % sulphur content are done as follows
2
Modus
(i) S+02 SO,—-50%
2
so + BaCl2 →BaSO4

(ii) 233 g of BaSO, contains 32 g of sulphur.
W
(iii) :: W g of BaSO, will contain 32 x 233 g of sulphur.
(When W is the weight of the precipitate obtained)

100
(iv) :: % S = 32 x Weight of precipitate x 233 * Weight of coal sample taken
(III) Significance of % sulphur contents
Sulphur increases the calorific value, but on oxidation produces harmful and corrosion causing SO, and SO, gases,
which pollutes the atmosphere. Sulphur is undesirable for making coke for iron industry because it affects the properties
of steel.
(4) % Ash content test
(I) Procedure
(II) Significance Same as that in the given proximate analysis
(5) % Oxygen contents
Note : () following
No test isformula.
required to be performed in the laboratory and % oxygen contentis directly calculated using the
% Oxygen contained = 100– 1% carbon + %Hydrogen + % Nitrogen + % Sulphur + % Ash)
UQ. 6.3.4
Why a good fuel must havelow ash content ? Ref. :(MU - Q. 1(a), Dec. 18, 3 Markus)
Ans. :
(i) Ash is a non-combustible matter and it reduces the calorific value of coal.
(ii) It also causes obstruction to the flow of heat.
(iii) It lowers the temperature and gives rise to the clinker formation.
(iv) Disposal of ash is also a big problem.
Syllabus Covered
Lecture-4
Liquid Fuels.
A
6.4 LIQUID FUELS
6.4.1 Crude Petroleum Oil
GQ. 6.4.1
Explain about crude petroleum oil. Give its composition, classification and briefly discuss its
types.
(6 Marks)

Ans. :
() Explanation of crude petroleum
(i) Crude petroleum is oil also known as crude oil, mineral oil or petroleum oil.
(ii) Petroleum is a natural product generated from organic materials by physical or chemical process inside the earth.
(iii) The term petroleum means oil obtained from the rock because petra = rock and oleum oil.
(iv) Crude petroleum is formed from buried vegetables and marine life due to the action of heat, pressure and microbial
activity over millions of years.
(11) Composition of petroleum
Stated below is the average composition

(i) C = 79.5 to 87.1% (ii) H = 11.5 to 14.8%
(iii) 0 = 0.1 to 0.9% (iv) S=0.1 to 3.5% and
(v) N= 0.4 to 0.9%
(III) Types of compounds in petroleum
(i) Open chain alkanes : Both straight chain and branched chain alkanes are present in crude oil. In some crude oils,
such alkanes make major part.
(ü) Cycloalkanes : Crude oil contains cycloalkanes like cyclopentane, cyclohexane and their alkyl substituted
products. Some crude oils contain dominating amount of cycloalkanes.
(iii) Aromatics : In all the crude oils benzene and alkyl substituted benzenes are upto 2%.
(iv) Asphaltenes: All the crude oils contain the small amount of polycondensed aromatic solids as colloidal dispersion
in crude oil. The asphaltenes also contain N, S, O atoms.
(v) Resins : These are the polymeric substances. They are gummy and are lower molecular weight polymers. They
also contain N, S, O atoms.
All the crude oils contain little amount of emulsified water and the water is rich with dissolved salts. The number of
carbon atoms in the hydrocarbon molecules range from C, to C70, in the crude oil.
(IV) Classification of Petroleum
Petroleum can be mainly grouped into three classes as discussed below :
(i) Paraffinic base crude oil
They contain normal and isoalkanes and less than 1% S. The asphaltene and resin content is below 10%. Percentage of Moduł
aromatic hydrocarbars is low. They yield gasoline of low octane number and gas oil of high cetane number. They give
high grade lubricating oils on distillation and leave behind paraffin wax as residue.
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(11) Naphthenic base crude oil
They contain cycloalkanes (naphthenes). Asphaltic matter is present in quite large proportion. Paraffinic wax is very
little or absent. These crude oils yield good quality gasolines and asphalts and or bitumens.
(iii) Paraffinic-Naphthenic base crude oils/mixed base crude oils
They have both paraffinic and naphthenic hydrocarbons together with a certain proportion of aromatic hydrocarbons.
On distillation, the yield residue containing both paraffin waxes and asphatic matter their density viscosity is more than
the paraffinic class.
a 6.4.2 Mining of Crude Petroleum

GQ. 6.4.2
Explain mining of crude petroleum with the help of a suitable diagram. (6 Marks)
✓ Ans. :
The process of mining of the crude petroleum is discussed briefly as follows:

(i) Petroleum deposits occur deep in the Earth's crust.
(ii) The following three conditions must be satisfied for the accumulation of workable quantities of petroleum :
(1) A porous rock which acts as a reservoir,
(2) A cap rock overlying the reservoir rock. The cap rock is impermeable to the oil and hence prevents the escape of
the oil upwards through the strata above,
(3) A closure to restrict or prevent lateral migration.
(iii) Important reservoir rocks are sandstones and limestones.
(iv)
Shales and clays usually constitute the cap rocks.
(V)
The largest accumulations of petroleum are generally found in the anticline dome structure.
(vi) Generally, accumulation of natural gas occurs above the oil and brine underneath the oil.
(vii) In order to bring the oil
bearing rocks.
the surface, holes are drilled into the Earth's crust and pipes are sunk right upto the oil
(viii) Oil usually rushes out to the surface by itself because of the hydrostatic pressure of the natural gas.
Sometimes, the well dug may miss the oil and strike the water layer in which case oil cannot be brought to the surface
(ix)
by that particular well.
Sometimes, the well may strike gas, in which case it is called the gas well.
(xi) The gas pressure itself may be sufficient to force out some of the crude oil to the surface initially, but later when the
pressure becomes too low, it may have to be mechanically pumped up with the help of lift pumps.
(xii) Then air-lift pumps comprise of two coaxial pipes which are sunk into the oil bed and compressed air is forced
through the outer pipe when oil comes out through the inner pipe.
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(xiii) Fig. 6.4.1 represents the arrangement of mining of the crude oil.
Compressed
air
Natural
Oil
gas
Earth's crust
Sand
Shale
Imparious Rock
Gas
Petroleum
Brine
Porous rock
(2F7)Fig. 6.4.1: Mining of crude oil
(xiv) The productivity of a well can sometime be increased by water flooding.

(xv) Generally two wells are bored near each other, one for gas and the other for oil.
(xvi) When the mixture of gas and oil is forced out due to the pressure of the gas, the method of pumping is called
pressure drive.
(xvii) Later as the gas and oil are withdrawn from the reservoir, the pressure falls progressively and the productivity of the
oil decreases.
(xviii) Then the oil is forced out by pumping water into the well, when a mixture of oil and water comes out of the well. This
method is called water drive.
à 6.4.3 Refining of Petroleum
UQ. 6.4.3
with a suitable diagram, explain the process of refiningof petroleum.
7 Ans. :
Ref.: (MU - Q.5(a), Dec.15, 4 Marks, Q.2(b), May 14, 5 Marks,Q. 2(b), May 13,5 Marks)
(1) The crude oil is separated into various useful fractions by fractional distillation and finally converted into desired
specific products.
(ii) This process is called Refining of crude oil and the plants set up for the purpose are called the oil refineries.
(iii) The process of refining involves the following three steps:
Step 1: Separation of water (De-emulsification)
(a) The crude oil from the oil well is an extremely stable emulsion of oil and salt water. The process of freeing oil
from water consists in allowing the crude to flow between two highly charged electrodes.
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(b) The colloidal water droplets coalesce to form large drops which separate out from the oil.
Step 2: Removal of harmful Sulphur compounds (De-sulphurization)
(a) This involves in treating oil with copper oxide.
(b) A chemical reaction occurs with sulphur compounds which results in the formation of copper sulphide, a solid
precipitate, which is then removed by filtration.
Step 3: Fractional distillation Gases
(a) The crude oil is then heated to

about 400°C in an iron retort,
whereby all volatile
consitituents, except the residue Tray
Petroleum ether
of alphalt ог coke are
evaporated. Gasoline
Chimney
(b) The hot vapours are then passed Down spot Naphtha
up “fractionating column",
Kerosene
which is a tall cylindrical tower Loose cap
containing a
number of
Diesel oil
horizontal stainless steel trays at
short distances.
Lubricating oil
(c) This is shown in Fig. 6.4.2.
Crude Steam
oil
Furnace
at 400°C
Heavy oil
(2F8)Fig. 6.4.2: Fractionation of crude oil

(d) There are 50-60 horizontal stainless steel trays at about half
meter distances in the tower as shown in the Fig. 6.4.2. Each Bubble
tray is provided with 4-5 bubble cups with loose caps so that plate
the rising vapours through the cups bubble in the liquid Draw off plate
deposited on tray. Bubble
cup
Fractions are taken out from some bubble trays only and not Condensate
from all.
Vapours
(e) The temperature of the tower is 400°C near the bottom and Down spout
it decreases gradually to 40°C at the top.

(2F9)Fig. 6.4.3 : Details of the trays
(f) The tower gets cooled by open air
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a 6.4.3(A) Products of Fractional Distillation of the Crude Oil

GQ. 6.4.4 Represent the several products of fractional distillation of the crude oil in the tabularform.
(4 Marks)
UQ. 6.4.51
Name any two fractions obtained during distillationof the crude oil.
Ret.:(MU - Q. 5(a), Dec. 15,2 Marks)
Ans. :
The several products of the fractional distillation of the crude oil are as shown in the Table 6.4.1.
Table 6.4.1: Products of fractional distillation of the crude oil
Sr. Name of the
Boiling range Composition of Uses
No. fraction
hydrocarbon
1.
Uncondensed gases Below 40°C
C, to C4 Domestic and industrial fuel under 'LPG'
name.
2. Aviation fuel or 40-70°C

Cs to C Fuel
for aeroplane, helicopters, as
petroleum ether
solvent.
3.
Petrol or gasoline 60°C - 120°C
Cgto C, Fuel for petrol engines, dry cleaning, as
solvent.
4.
Naphtha or solvent 120°C - 180°C
C toCo
spirit
As solvent and for dry cleaning, for
chemicals.
5. Kerosene
180°C - 250°C
Coto C16 For illumination, domestic fuel, for oil
gas and fuel of jet engines.
6. Diesel
250°C - 320°C isto C,8 Diesel engine fuel.
7.
Heavy oil 320°C - 400°C
Cız to C30
For making petrol by cracking.
(a) Lubricating oil Cig toCo
Lubricating purposes
(b) Vaseline
C20 toC₂2 Cosmetics, medicines, ointments,
lubricant
(c) Grease C22 to C26 Lubrication

(d) Wax C26 toC30
Candles, boot polish, tarpaulin cloth, wax
paper, etc.
8. Residue > 400°C Above C30

Road making, water proofing of roofs.
(a) asphalt Moa.
As fuel, for arc light rods.
6
(b) petroleum coke

a 6.4.4 Cracking of Heavy Oil
UQ. 6.4.6 What is crackingof heavy oil?

Ref. :(MU - Q. 3(axo), May 19, Q. 5(aXI), Dec.16, 1 Mark, Q. 1(c), Dec. 15, 1 Mark, Q.2(a), May15, 1 Marks,
Q. 3(aXI),Dec. 18, 1 Mark, Q. 3(a), Dec. 17, 1Mark, Q. 1(c),Dec. 14, 1Mark, Q.5(@XO), Dec. 13, 1 Mark)
Ans. :
(1) Cracking is a process of braking higher molecular weight high boiling fraction into lower molecular weight low boiling
fraction.
(ii) For example,

a) C10H22 Cracking C5H12 +
C5H10
(Decane) n-pentane pentane
b) C16H34 Cracking CgH18 CgH16

+
octane octene
(2F14)Fig. 6.4.4
à 6.4.5 Types of Cracking
Represent the method of cracking with the help of a suitable chart.

GQ. 6.4.7
(3 Marks)
Ans.:
The graphical representation of the method of cracking is shown in Fig. 6.4.5.
Methods of cracking
(1) (2)
Thermal cracking Catalytic cracking
()
Liquid Vapour Fixed Moving
phase phase bed bed
(2F10)Fig. 6.4.5: Methods of cracking
à 6.4.5(A) Thermal Cracking
GQ. 6.4.8 Discuss briefly the process of thermal cracking. (3 Marks)

Ans.
(1) Liquid phase thermal cracking
(i) By this method, any type of oil can be cracked.
(ii) In this method, the oil is pumped into the coil kept at 420°C to 550°C under a pressure of 15 to 100 kg/cm².
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(iii) As the temperature increases, a better quantity of gasoline is produced.

(iv) The octane value of this gasoline is low, i.e. 65 to 70.
(2) Vapour phase thermal cracking
(i) In this method, the heavy oil is heated in the heater at 400°C to convert it into the vapours and then these vapours
are passed to the reaction chamber which is maintained at 600°C to 650°C and under a pressure of 10 to 20 kg/cm²
(ii) At this stage, the higher hydrocarbons are converted into lower hydrocarbons easily andthe octane value of petrol
is usually 75 to 80.
a 6.4.5(B) Comparison between Liquid phase and Vapour Phase Thermal Cracking
GQ. 6.4.9
Compare between the liquid phase and the vapour phase thermal cracking. (3 Marks)
Ans. :
A tabular comparison between the liquid phase and the vapour phase thermal cracking is as given below:
Sr.No.
Parameter
Liquid phase thermal cracking | Vapour phase thermal cracking
1.
Cracking temperature Moderate i.e. 420°C - 550°C 600°C - 650°C
2. Pressure
High = 15 to 100 kg/cm² Low = 15 – 20 kg/cm?
3.
Yield percentages 50-60%
4.
Octane rating 65-70
> 70 (75 – 80)
5.
Pre-requirement for process Any type of heavy oil can be used. Oil has to be vaporized readily.
6.
Time required Comparatively more Comparatively less
a 6.4.6 Catalytic Cracking

GQ. 6.4.10
Discuss briefly the process of catalytic cracking. Also the two types of catalytic cracking.
(3 Marks)
Ans. :
(i) Catalytic cracking is a process in which heavy-oil is heated in the presence of a catalyst.
(ii) Generally used catalysts are crystalline substances. e.g. bauxite, zeolite, crystalline alumino silicate, bentonite etc.
(iii) The temperature is so adjusted that the heavy oil just starts vapourising.
(iv) During the processcracking
heavy oil gets cracked and forms lower hydrocarbons-one saturated and other unsaturated.
e.g. n-hexadecane octane + octene
(v) There are two types of catalytic cracking as :

(a) Fixed bed catalytic cracking
(b) Moving/fluidised bed catalytic cracking

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a 6.4.6(A) Fixed Bed Catalytic Cracking
UQ. 6.4.11 Explain in details fixed bed catalytic cracking.

Ref.: (MU - Q. 3(@XII), May 19, 5 Marks, Q. 3(aXII), Dec, 18, 5 Marka, Q. 3(a)(11), Dec. 17, 6 Marka, Q. 3(a),May 17, 6 Marks,
Q.5(a)(ii), Dec.16, 4 Marks, Q. 2(b), May 15, 4 Marks, Q. 5(a),May 14,4Marks)
Ans.:
(i) Fig. 6.4.6 represents the schematic arrangement of fixed bed catalytic cracking.
Cracked gases
Cooler Gases
Stabilizer
ILI
Vapours
Heavy Gasoline
Heavy
oil oil
charge
Fractional
Heater
Preheater column
Catalyst
(425°C - 450°C) chamber
(2F11)Fig. 6.4.6 : Schematic arrangement of fixed bed catalytic cracking
(i) In this method, vapours of the heavy oil are heated in the presence of catalyst due to which a better yield of petrol is
obtained
(ii) The heavy oil is vaporized by heating in an electrical heater and then the vapours are passed over a series of trays
containing catalyst.
(iv) Generally, the catalyst used are crystalline alumino-silicate, bentonite, bauxite and zeolites.
(v) The reaction chamber is maintained at 425°C to 540°C and under a pressure of 1.5 kg/cm².
(vi) The cracked gases are taken out from the top of the reaction chamber (cracker) and allowed to pass into fractionating
tower, where gasoline fraction is collected. The octane value of this gasoline is about 80-85.
(vii) During the cracking, free carbon is also formed which deposits on catalyst, then the flow of vapours of heavy oil is
passed over the second set of reaction chamber and the catalyst in earlier chamberis regenerated by burning the carbon
deposits with the help of air and reused.
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a 6.4.6(B) Moving Bed Catalytic Cracking

(s Marks)
GA. 6.4.12 Explain in detailsmoving bed catalytic cracking,
7 Ans. :
(i) Fig. 6.4.7 represents the schematic arrangement of moving bed catalytic cracking.
Fluidised by
Cracked cracking
Fuel gases Cooler
vapour
Cyclones
Gases
Gases
500°C
550°C
Catalyst
regenerators
Stabilizer
Regenerated
catalyst
Gasoline
Spent Heavy
Feed oil catalyst oil
+ catalyst
Fractionating
columns
Matching
columns Gasoline
Air
(85 to 90
octane)
(2F12) Fig. 6.4.7 : Schematic arrangement of moving bed catalytic cracking
(ii) Inheavy
fluidized bed catalytic cracking, a fine powder of catalyst is circulated through the cracker along with the vapours of
oil (Higher hydrocarbon).
(iii) The catalyst accelerates and directs the cracking efficiently to form gasoline and other .
lower hydrocarbons
For example C18H38 Cracking C10H22 +
CgH16
n-octadecane n-decane Octene
C16H34 Cracking C6H14 C10H20

+
n-hexadecane n-hexane Decene
C16H34 Cracking C3H18 CgH16

+
n-hexadecane
Octane Octene
(2F15)Fig. 6.4.8
(iv) In the modern refineries, mostly fluidized bed catalytic cracking is used.
(v) The major part of the process involves crackers and regenerators, which are kept side by side.
(vi) A mixture of heavy oil and catalyst is heated in the still to convert the heavy oil into vapours. Module
(vii) These vapours along with hot catalyst are brought to the cracker. The cracker is maintained at a temperature of 550°C to
570°C and atmospheric pressure.
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(viii) In the cracker, the vapours of the heavy oil and hot catalyst come in intimate contact with each other and the breaking
of higher molecular weight hydrocarbons into lower hydrocarbon (Gasoline) takes place.
(ix) The low boiling hydrocarbons move upto the top of the cracker which are passed through the cyclone separator while
the catalyst remains in the cracker.
(x) These cracked gases are further passed through the fractionating column to have three major fractions
(a) Gasoline (b) Middle oil (c) Heavy oil
(xi) The gasoline is further cooled and purified to remove the impurities of sulphur, unsaturated hydrocarbons and colouring
matter; if present. The catalyst performs two function.
(1) To get a better quality gasoline during cracking process.

(2) To carry heat during process.
(xii) Catalyst gets deactivated due to the deposition of free carbon on catalyst.
(xiii) The deactivated catalyst is taken from the bottom of the cracker and brought into regenerator where it is heated to
about 500°C in the presence of hot air to burn carbon dioxide which is taken out from the top of the regenerator.
(xiv) The regenerated catalyst in hot condition is taken down to the vapours of heavy oil and recirculated in the cracker.
Note : about fixed bed and moving bed catalytic cracking
(1) Outof these two methods, fixed bedmethod is simple and short.
(2) In May16 and Dec. 13question papers, itwas asked toexplainany one method.Clearly we should write the fixed bed
catalytic method.
6.4.7 Advantages of Catalytic Cracking over Thermal Cracking

UQ. 6.4.13
State the advantagesof catalytic cracking over thermal cracking.
Ref. : (MU- Q.5(a)(11), May 16, 4Marks, Q. 1(c), Dec. 15,2 Marks, Q.5(aX(I), May 14, 2 Marks)
Ans.:
(1) Temperatures and pressures used in catalytic cracking (425 – 570°C and 1.5 kg/cm²) are lower as compared to thermal
cracking (475 - 650°C and 15 – 100 kg/cm²).
(2) Octane values of gasoline are higher by catalytic cracking (85 – 90) than those by thermal cracking (65 – 70).
(3) Yield of gasoline is more by catalytic cracking (30 – 40 %) than that by thermal cracking (7 - 25 %).
(4) External fuel is not required in catalytic cracking but it is necessary in thermal cracking.
(5) Cracking can be easily controlled by catalytic process as compared to thermal process.
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6.4.8 Comparison between Fixed Bed and Moving Bed Catalytic Cracking
GQ.6.4.14 Compare between the fixed bed and themoving bed catalytic cracking. (2Marks)
Ans. :
Sr. No. Parameter Fixed bad Moving bed

1.
Chamber reaction temperature 425 – 540°C 550 - 570°C
2. Pressure
About 1.5 kg/cm² About 1 kg/cm²
3. Octane value 80-85 85-90
a 6.4.9 Comparison between Thermal Cracking and Catalytic Cracking

GQ. 6.4.15 Compare between the thermal cracking and catalytic cracking. (5 Marks)
Ans.:
Sr. Parameter
Thermalcracking Catalyst cracking
No.
1.
Catal
Method of cracking Heavy oils are subjected to high Heavy oils are cracked in the presence of
temperature and pressure when bigger catalyst like Alz (SiO), or AIO at
hydrocarbon breakdown to given smaller comparatively low temperature and

molecules.
pressure.
2.
Requirement of High temperature of 475-650°C and High temperature of 425-570°C and low
3.
temperature and pressure pressure of 15-100 kg/cm² are required. pressure of 1.5 kg/cm² are required.
Types
Two types (a) Liquid phase and Two types (a) Fixed bed and (b) Moving
(b) Vapour phase. bed.
4. Octane value Octane value = 65 - 70
Octane value = 85 - 90
5. Yield of gasoline Yield of gasoline is less. Yield of gasoline is more = 30 to 40%
6.
Necessity of external External fuel is necessary. No external fuel is required.
fuel
7.
Control over cracking Cracking cannot be easily controlled. Cracking can be easily controlled.
8. % of gum forming Percentage of gum or gum forming It is less.
compounds compounds is more.
9. Amount
product
of sulphur in the The product contains more amount of The product contains little amount of
sulphur.
sulphur.
10. | Antiknocking properties Product possess less antiknocking Product
of the product properties.
possess better antiknocking
properties.
a 6.4.10 Introduction to knocking
UQ. 6.4.16
What is meant by knocking in an internal combustion engine ?
Mo..
Ref.: (MU- Q. 2(b),Dec.15, 1 Mark, Q. 2(b),Dec. 14, 2Marks)

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Ans. :
(1) The process of knocking is always associated with I.C. engines working on petrol, in which a mixture of gasoline
vapours and air is used as a fuel.
(ii) Its combustion is initiated by a spark in the cylinder using an induction coil and a spark plug.
(iii) The gases formed due to combustion move the piston down the cylinder.
(iv) The piston movement will be uniform without any vibrations when the normal combustion of the fuel say C, H, takes
place in which following reaction takes place.
C, H, + 350,
2- →2002 + 3H20
(v) However, sometimes the combustion of the fuel becomes so high when the chain reactions take place at a very fast rate
due to the sudden increase in the gas volume causing uneven movement of the piston with a rattling noise.
(vi) This phenomenon is called “knocking', and the corresponding explosive combustion reaction can be represented as
follows:
CH. + O2 CH, CO-OCHZ

CH, CO-OCH, CH, CHO + H2O
a 6.4.10(A) Effects of knocking

GQ. 6.4.17
State the major effects of the knocking process. (3 Marks)
Ans. :
Knocking cause the following effects :
(1) Damage to the piston and cylinder, and hence increased maintenance cost.
(2) Loss of large amount of the input energy due to the sound therefore the efficiency of the engine is reduced.
(3) The rattling noise due to knocking causes noise pollution and uneasiness to the surrounding personnel.
(4) The shocks and the vibrations due to the knocking may prove dangerous to the patients travelling by the vehicle having
knocking engine.
6.4.10(B) Effect of chemical structure on knocking
How is knocking tendency of gasoline related to chemical structure of hydrocarbons present?

UQ. 6.4.18
Ref.: (MU- Q. 1(axl), May 14, 2 Marks)

7 Ans.:
(1) The knocking tendency decreases with the increase in the compactness of the hydrocarbon molecules, double bond and
the cyclic structure of the fuel.
(2) The knocking tendency increases with the increase in the length of the hydrocarbon chain, with the number of branches
and their positions.
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(3) The rate of oxidation of a hydrocarbon molecule depends upon the number of carbon atoms in the molecule, on the
structure and on the temperature, such that lesser is the knocking tendency with
(a) More atoms/molecule,
(b) More cyclic structure,
(c) Higher temperature
(4) The tendency of the fuel constituents to knock is in the following order :
Straight-chain paraffins>branched-chain paraffins (iso-paraffins) > 'olefins > cycloparaffins (i.e. naphthalenes) >
aromatics.
a 6.4.10(C) Reduction of knocking
State the methods of reducing the knocking process in the l.C. engines.
GQ. 6.4.19
(2 Marks)
UQ. 6.4.20
Name any two antiknocking agents.
Ref. : (MU -Q. 2(b), Dec.15, 2Marks,Q. 2(bXll), Dec. 14, 2 Marks, Q. 1(a)(II), Dec. 13, 2Marks)
Ans. :
The knocking process in the internal combustion engines can be reduced by using,
(1) Antiknocking agents like
(i) Tetraethyl lead (TEL): (CH3)Pb

(ii) Tetramethyl lead (TML): (CH3)4 Pb
(iii) A mixture of TEL and TML.
(2) Unleaded petrol
Two popularly used antiknocking agent are as follows:

(i) Tetraethyl lead (TEL): (CH3)4 Pb and
(ii) Tetramethyl lead (TML): (CH3), Pb
a 6.4.11 Octane Number and Its Significance

UO. 6.4.21
Define octane number and write its significance.
Ref. : (MU- Q. 1(a),May 19, 3Marks, Q.1(c), May 17, 1% Marks, Q.1(bXO), May 16, 1% Marks,
Q. 2(b),Dec. 15,2Marks,Q. 2(bXU),Dec.14, 1 Mark, Q. 1(a), May 14, 1 Mark,
Ans. :
Q. 1(a), Dec.13, 1 Mark, Q. 1(b),May 13, 1 % Marks)
(1) Definition of the octane number
The octane number ofa petrol sample is defined as the percentage of isooctane in a mixture of isooctane and n-heptane Mode
which matches the fuel under test in knocking characteristics.

(II) Significance of the octane number
(i) The octane number represents the knocking characteristics of a petrol sample, such that higher the octane number,
lower is the tendency to knock and better is the quality of the petrol.
(ü) For example, Ico-octane (2,2,4 trimethylpentane) has the least knocking tendency and its octane number is
arbitrarily fixed as 100.
6.4.12 Cetane Number and Its Significance
UQ. 6.4.22 Define the cetane number. state its significance.

Ref. : (MU - Q. 1(c)(), May 17, 1% Marks, Q. 1(bXII),May 16, 1% Marka,
Q. 2(b),Dec. 14, 1 Mark, Q. 1(b), May 13, 142 Mark)
7 Ans. :
(1) Definition of the cetane number
Cetane number is defined as the percentage of hexadecane (n-cetane) present in a mixture of hexadecane and 2-methyl
naphthalene, which has the same ignition characteristic of diesel fuel in test.
(1) Significance of the cetane number
(i) The knocking tendency of a diesel fuel is expressed in terms of the cetane number such that lower is the cetane
number higher is its quality.
(ü) Cetane number of hexadecane [CH3 - (CH) 14 - CH3] is a saturated hydrocarbon and its cetane number is
arbitrarily fixed as 100, while the cetane number of 2-methyl naphthalene is arbitrarily fixed as zero.
(iii) Note that an oil having low cetane number has a high octane number.
a 6.4.13 Comparison between Octane Number and Cetane Number
GQ. 6.4.23
Compare between octane number and cetane number.
(5 Marks)
7 Ans. :
A tabular comparison between the octane number and the cetane number is given in Table 6.4.2.
Table 6.4.2: Comparison between octane number and cetane number
Sr. Parameter Octane number

Cetane number
No.
1. the
Definition Octane number is defined as
Cetane number is defined as the percentage
percentage by volume of iso-octane in a by volume of cetane in a mixture of cetane
mixture of iso-octane and n-heptane which and a-methyl naphthalene which just matches
just matches the knocking characteristics the knocking characteristics of diesel oil
of gasoline under test. under test.
2.
Representing quality Octane number is an arbitrary scale which The ignition quality of a diesel oil is
expresses the knocking characteristics of a measured in terms of cetane number.
petrol.
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Parameter Octane number

Cetane number
Sr.
No.
3. Increasing technique The octane number of petrol can be The cetane number can be increased by
increased by addition of tetraethyl lead or addition of certain additives like ethyl nitrite,
diethyl telluride. ethyl nitrate etc. which are known as
accelerators.
4. Effect of contents
Petrol containing aromatics have highest | Diesel oils containing n-paraffins have
octane number. highest cetane number.
5. Ignition delay
Oils having least ignition delay are poor Oils having least ignition delay are good
gasoline fuels i.e. possesses low octane diesel fuels i.e. possesses high octane number.
number.
6. Effectiveness
on Anti-knocking agents are effective in Anti-knock agents are not effective in petrol
antiknocking petrol fuels having low octane number. fuels having low cetane number.
7. Relationship Oils having high octane number has a low Oils having high cetane number has a low
between octane and cetane number.
octane number.
cetane number
6.4.14 Unleaded Petrol
UQ. 6.4.24
Explain briefly about unleaded petrol.Also state its advantages. Ref. : (MU -May 12, 5 Marks)
Ans.:
(1) Explanation of unleaded petrol
(i) Unleaded petrol is practically zero lead quantity gasoline supplied for motor fuels.
(ii) In car exhaust, if catalytic converter is connected, leaded petrol cannot be used; because, lead destroys the active
sites of catalyst.
(iii) In catalytic converter, two types of catalysts are used as,
(a) Reduction catalyst
(b) Oxidation catalyst
(iv) Catalyst helps to reduce emissions of harmful gases by following reactions.

(v) Reduction catalyst contains Pt or Rh, which can reduce NO, as,
2 NO, + N2 + xO2
(vi) Oxidation catalyst helps treating unburnt hydrocarbons oxidation catalyst unburnt hydrocarbons and carbon
monoxide, due to presence of Pd or Pt,
Μα
xco +Ž0, + CO2

Engineering Chemistry-1!(MU - Som 2) (6-32) Fuels and son
x HC +x02 +ŽH40+co,
(vii) Engine is connected with computerised oxygen sensos, and signals are indicated to adjust the requirement of
oxygen which is adjusted.
(ll) Advantages of Unleaded Petrol

(i) It is fuel without lead (which is a heavy metal and very harmful).
(ü) Octane rating can be further improved by adding small amount of MTBE which supports combustion also.
(iii) The use of ULP helps in controlling knocking in engines as it supports the use catalytic converters machki so
exhaust in automobiles.
(iv) ULP also allows use of catalyst like rhodium which converts exhaust gases like CO and NO LO CO, and NZ
Rhodium also converts unburnt hydrocarbons to CO2 and H2O.
6.4.15 Methyl Tertiary Butyl Ether (MTBE)
GQ. 6.4.25
Explain briefly about MTBE. Also state its advantages and disadvantages. (5 Maris)
Ans. :
(1) Explanation about MTBE
(i) For gasoline, octane number was increased by adding benzeneltoluenelxylene etc.
(i) But use of these hydrocarbons is restricted due to following reasons,

(1) Benzene is carcinogenic
(2) Toluene xylene show photochemical reactions.
(iii) Recently, due to above problems, the aromatic hydrocarbons are avoided, and are replaced by “oxygenates”.
(iv) Generally following oxygenates are used to greater extent.
(1) Alcohols : E.g. CH, OH or CH3OH
(2) Ethers : MTBE or ETBE
(v) These oxygenates possess octane ratings higher than 100.
(vi) CH,OH is preferred over MTBE, in countries where corn/molasses are available in large quantity.
(vii) MTBE (Methyl Tertiary Butyl Ether) is widely accepted as oxygenate by oil refineries because,
(viii) It can be produced by simple reaction of iso-butylene with methanol.
(ix) It helps to avoid disadvantages of methanol, rather provides alternative with safety and efficiency.
() Advantages of MTBE
(1) It contains 0, in the form of ether group. It has low petrochemical with hydroxyl radical.
(2) This O, supports combustion of petrol in I.C. engine.

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(3) Due to O2, Octane value is enhanced.

(4) Environmental protection is achieved.
(5) Use of lead is avoided.
(III) Disadvantages of MTBE

(1) It must be blended with gasoline during refining only and can't be added later.
(2) It is poisonous.
6.4.16 Power Alcohol
GQ.6.4.26 Define power alcohol, explain the method of its synthesis, write advantages and
disadvantages. (5 Marks)
Ans. :
(1) Definition
When ethyl alcohol is used as fuel in I.C. engine, it is defined as power alcohol. It is used as 5-25% mixture with petrol.
(11) Synthesis or Manufacture
(i) Molasses is converted into ethyl alcohol using yeast containing enzymes invertase and zymase causing
fermentation as per the following reactions :
C12H22011 Invertase CH1206, CH,206
Surcose in Molasses H2O Glucose Fructose
CH,206 zymase
Glucose/Fructose →
2C,H,OH + 2CO2
(ii) The starch or sucrose in molasses is converted into ethyl alcohol obtained contains 95.5% alcohol and 4.5% water.
Water is separated by distilling it with benzene.
(III) Advantages
(1) Octane number of ethyl alcohol is @ 90% while that of petrol is 60-70%. Therefore alcohol blended petrol has
increased octane number therefore it has better antinocking properties.
(2) Power alcohol absorbs traces of moisture which may otherwise enter the petrol system.
(3) It reduces starting troubles.
(IV) Disadvantages
(1) Calorific value of petrol is reduced due to alcohol.
(2) It may cause corrosion of engine parts due to high 02.

Module
(3) Its atomisation at low temperature is troublesome.
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Part II : Solved Problems
The types of problems on fuels are four as shown in the Fig. 6.4.9.
Types of fuel problems
(2) (3) (4)

H.C.V.& L.C.V. Proximate Ultimate Combustion
by analysis analysis of solid and
Dulong's formula gaseous fuels
(2F13)Fig. 6.4.9 : Types of fuel problems
Syllabus Covered
Lecture-5
UEX. 6.2, UEx. 6.3, VEx. 6.6, UEX. 6.7, UEX. 6.8,UEX. 6.9
Type 1 Problems : HCV and LCV Dulong's Formula
Important Formulae
(1) According to the dulong's formula,

1
HCV = 100 8080 C + 34500 H
s]K calke
+ 2240 S Kcal/kg
Where,
HCV = High calorific value

C = % Carbon
H =
% Hydrogen,
O =
% Oxygen
S =
% Sulphur
(2) LCV = HCV - 0.09 H x 587 kcal/kg
Where, LCV = Low calorific value
Ex. 6.1
A sample of coal has the following composition by mass : C = 85%, H = 6%, O = 8%, S = 0.5%, and Ash = 0.5%
Soln. :
Given
Required
C = 85%, H = 6%, 0 = 8%, S =
HCV, LCV
Ash = 0.5%

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1
(1) HCV = 8080
100 C + 34500 (H- ) + 2240 ]
1
100 0.5] -
8080 x 85 + 34500 (6 + 2240 x 0.5 = 8604.2 K Cal/kg
(II) LCV = HCV – 0.09 H x 587 = 8604.2 - 0.09 x6 x 587 = 8287.22 KCalkg
UEx. 6.2 MU - Q. 6(b). Dec. 13. 5 Marks
A sample of coal hasthe following composition by weight :
C = 82%, H = 6%, 0 = 8%, S = 0.5%, N= 3% and Ash = 0.5%. Calculate the Gross and Net Calorific value using Dulong's
formula.
Soln. :
Given Required
C = 82%, H = 6%, 0 = 8 %, S = 0.05%, N = 3%, Ash = 0.5% GCV, NCV
(1) GCV =
100
4500(4-3)+2240
8080 C + 34500 (H-9 ]
100
8080 x 82 +34500 (6-) ++ 2240 x 0.5 = 8361.8 KCal/kg
(II) NCV = [HCV – (0.09 H x 587)] = 8044.82 KCal/kg
UEx. 6.3 MU - Q. 6(b), May 14.5 Marks
1.5
of a coal sample was analysed for nitrogen content by Kjeldahl's method. Theliberated ammonia required 14 ml of
0.1 NH2SO, solution for neutralization. In a separate experimentusing Bomb calorimeter, 1.5 g ofthe same sample gave
0.3 gof BaSO4. Calculate percentage nitrogen andsulphurinthe sample.
Soln. :
Given
Required
C = 80%, H = 4%, 0 = 6%, S = 3, N = 2%, Ash = 5%
GCV, NCV
1 O
(1) GCV =
100
8080 C + 34500 (H | + 2240 S KCal/kg
1
| + 2240 x3]:
8080 x 80+ 34500 (4
100 3) = 7652.45 KCal/kg
(II) NCV = [GCV -(0.09 H x 587)] = 7652.45 – (0.09 x 4 x 587) = 7441.13 KCal/kg
UEX. 6.4 MU - Q. 119). Dec. 14,3 Marks
ACalculate
sampleGross
of coalCalorific
has thevalue
following
ofthecomposition by mass formula.
fuel using Dulong's : C =75%, H = 7%, O = 8%, S = 4%, N = 2% and Ash = 4%.
✓ Soln.:
Given
Required
C = 75%, H = 7%, O = 8%
GCV
S = 4%, N = 2%, Ash = 4% Module
GCV = Ido8080
[s C + 34500(H-) + 2240 s]Kcalke
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100
8080 X 75 + 34500 7 - + 2240 x 4 = 8219.6 KCal/kg
UEX. 6.5 MU - Q.6b), Dec. 15, 5 Marks

A sample of coal has the following composition by mass : C = 70%, H = 10%, 0 = 4%, S = 2%, N = 2% and Ash = 12%
Calculate Gross and Net calorific value using Dulong's formula.
Soln. :
Given Required
C = 70%, H = 10%, O = 4% GCV, NCV
S = 2%, N = 2%, Ash = 12%
(1) GCV =
100[8080 C + 34500 (9-3) +2240 s] kcalkg
1
100 8080 x 70 + 34500 (10 9 «2];

+ 2240 x 2 = 8978.3 KCal/kg
(II) NCV =
GCV - (0.09 H x 587) = 8978.3 - (0.09 x 10 x 587) = 8450 Kcal/kg
UEx. 6.6 MU - Q. 1(c),May 19, 3 Marks
Calculate higher calorific value of a coal sample containing C= 85%, H = 10%, N = 1.5%, 0 = 5%, S = 0.4% and remaining
being ash.
Soln.:
Given
Required
C = 85%, H = 1%, 0 = 5%, HCV
S = 0.4%, N= 1.5%,
1
(I) HCV =
100 8080 C + 34500 (H - 9) + 2240 ]
1
100 8080 x 85 + 34500 (1-3) + 2240 x 0,4]

=
7006.975 KCal/kg
UEX. 6.7 MU - Q. 1(c), Dec. 18, 3 Marks
A sample of coal contains C = 66%, 0 = 28%, H = 4%, S = 1,5%, N=0.8% and ash = 0.2%. Calculate the G.C.Y and N.CY
of the coal.
soln. :
Given
Required
C = 66%, H = 4%, O = 28% GCV, NCV
S = 1.5%, N = 0.8%, ash = 0.2%
(1) GCV =
100( 8080 C + 34500 (H - ) +2240 ]
28
8080 x 66 + 34500 (4 + 2240 x 1.5
100 8
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5538.9 KCal/kg
(II NCV = HCV - (0.09 H X 587)
5538.9 - (0.09 x 4 x 587)

...Ans.
5327.58 KCal/kg
VEX. 6.8 MU - Q.1(c), May 18, 3 Marks

Athesample of coalhas the following composition : C=70%, () + 23%, 11.5%, S - 15%, N * 0,4%, Ash = 0).1%.Calculate
G.C.V. of this fuel.
Soln. :
Given
Required
GCV
C = 70%, H = 5%, 0 = 23%
S = 1.5%, N = 0.4%, ash = 0.1%
9) +2240 ]
1
(1) GCV = 100

8080 C + 34500 H -
100 8080 x 70 + 34500 (5 ->) + 2240 x 1.5]

...Ans.
- 6422.725 KCal/kg
UEx. 6.9 MU - Q. 1(c), Dec. 17, 3 Marks

Calculate the higher and lower calorific values of coal sample containing 84% carbon, 1.5% sulphur, 0.6 Nitrogen, 5.5%
hydrogen and 8.4% oxygen.
Soln. :
Given Required
HCV, LCV
C = 84%, H = 5.5 %,0) = 8.4%
S = 1.5%, N = 0.6%, ash = 0.1%
HCV = to 8080 C + 34500 (H -3) + 2240 ]

1
100
8080x84 + 34500(5.5.-8.9+ + (15]
2240 x 1.5
8356.05 KCal/kg
(II) LCV = HCV - (0.09 x H x 587)

...Ans.
8356.05 - (0.09 x 5.5 x 587) = 8065.48 Kcal/kg
VEX. 6.10 MU - Q.6(b), May 10, 5 Marks 85%, H = 7%, O = 3.5%, S = 3.5%, N = 2.1% and
A sample of coal has the following composition by mass, C =
Ash = 4.4%. Calculate HCV and LCV using Dulong formula.
Modus.
Soln. : Required
Given 6
HCV, LCV
C = 85%, H = 7 %,0) = 3.5%
S = 3.5%, N = 2.1%, ash = 4.4%
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6 Engineering Chemistry-tl (MU - Sem 2) (6-38)
1
8080 C + 34500 (H + 2240 S
(1) HCV = 100
1
100 [8080 x 85 + 34500 (7 – +2240 x 3.5]
= 9232.025 K Cal/kg
(II) LCV = [HCV-0.09 x H x 587]

= [9232.025 - (0.09 x 7 x 587)
= 8062.215 Kcal/kg
Syllabus Covered
Lecture-6
UEX. 6.11, UEx. 6.15, UEX. 6.18, UEX. 6.21, UEX. 6.22, UEX. 6.23
Type 2 Problems : Proximate Analysis
Important Formulae
loss in the weight of the sample

(1) % Moisture content = x 100
loss of weight of the sample
(2) % Volatile matter content = X 100
weight of the air-dried sample
Weight of the residual ash
(3) % Ash content = x 100
(4) % Fixed carbon content = 100 - (% moisture content + % Volatile matter content + % Ash content)
UEx. 6.11 MU - Q. 6(b), May 15, 5 Marks
2.5 gm of air dried coal sample was taken in a silica crucible, after heating it in an electric oven at 110° C for 1 hr the residue
was weighed 2.41 gm. The residue was heated in silica crucible covered with vented lid at a temperature 925 25° C for
exactly 7 minutes. After cooling the weight of residue was found to contain 1.98 gm. The residue was then ignited to a
constant weight of 0.246 gm. Report the results of above analysis.
7 Soln. :
Given Required
Weight of dried coal-sample = 2.5 g Results of the analysis i.e. % moisture, % volatile
matter, % ash, % C.
After 1" heating, residue = 2.41g
After cooling, residue = 1.98g
after 2nd heating, residue = 0.246g.

mass of the moisture after 1" heating X 100
% Moisture =
mass of the coal-sample

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(6-39)
(2.5 -2.41)
-x 100 = 3.6
2.5
mass of the volatile matter at 2nd heating x 100

% Volatile matter =
(II) mass of the coal-sample
(2.41 – 1.98)
x 100 = 17.2
2.5
mass of the residue after 2nd heating

% ash = x 100
(III) mass of the coal-sample
0.246
x 100 = 9.84
2.5
(IV) % C = 100-(% moisture + % volatile matter + % ash)

=
100 - (3.6 + 17.2 +9.84)
= 69.36
Ex. 6.12
2.5 g of coal sample was taken in a silica crucible and heated in an oven at 100 °C for 1 hour. Weight after heating was
2.368 g, same sample was analysed for volatile matter and weight obtained was 1.75 g. The sample was further heated to get
fixed weight of 0.95 gms. Calculate % moisture, % volatile Matter, % ash & % fixed carbon.
7 Soln. :
2.5 -2.368
% moisture = x 100 = 5.28
2.5
2.368 - 1.75
(II) % volatile matter = x 100 = 24.72

2.5
Weightof ash 0.95

x 100 = x 100 = 38
(III) % ash = 2.5
Weight of the sample
(IV) % fixed carbon = 100 - (% moisture + % volatile matter + % ash)

= 100 - (5.28 + 24.72 + 38) = 32
Ex. 6.13
One gram of air dried sample of coal on heating at 110° C for 1 hour produced a residue 0.850 g and this residue on heating
at 950° C for 7 minute in absence of air left 0.72 g mass which on combustion left 0.1 g of non-combustible matter.
Calculate the result of proximate analysis.
✓ Soln. :
(I) (i) Weight of coal taken = 1 g

(ii) Mass of moisture in coal sample = 1.0 - 0.850
= 0.150 g
Mc
Loss in weight of coal x 100
(iii) % S= Weight of coal taken
0.150 x 100
= 15
1

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(6-40) Fuels and Combustion
(II) (i) Mass of volatile matter = 0.850 - 0.720
= 0.13 g
Loss in weight due to volatile matter

x 100
% volatile matter =
Weight of coal
0.13 x 100
= 13
1
(III) (i) Mass of residue = 0.1 g
Weight of ash left

(ii) % ash =
x 100
Weight of coal taken
0.1 x 100
= 10
1
(iii) % of fixed carbon = 100 - (% Moisture + % Volatile matter + % Ash)
100 - (15 + 13 + 10)
100 - 38 = 62
UEx. 6.14 MU - Dec. 09, 5 Marks
A sample of coal was analyzed for content of moisture, volatile matter and ash. From the following data, calculate the
percentage of the above quantities.
(1) Weight of coal taken = 2.5 g
(ü) Weight of coal after heating at 100° C = 2.368 g
(ii) Weight of coal after heating covered crucible at 950 + 20° C = 1.75 g
(iv) Constant weight obtained at the end of the experiment = 0.95 g
Soln.:
(1) (i) Weight of coal taken = 2.5 g
Mass of moisture in coal sample = 2.5 - 2.368 = 0.132 g

Loss in weight of coal
% moisture = x 100
(iii)
0.132 x 100
= 5.28 %
2.5
(II) (i) Mass of volatile matter = 2.368 - 1.75 = 0.618 g

x 100
(ii) % volatile matter = Weight of coal
0.618 x 100
= 24.72 %
2.5
Mass of ash 0.95 g

(III) (i)
Weight of ash left
x 100
% ash =
0.92 x 100
= 38 %
2.5

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(6-41)
Engineering Chemistry-|| (MU - Sem 2)
% fixed carbon = 100 - (% moisture + % Volatile matter + % Ash)
100 - (5.28 + 24.72 + 38) = 32
JEX. 6.15 MU - May 11 Dec. 135

, Marks
25g of air dried coal sample was taken in a silica crucible, after heating it in an electric oven at 105-110°C for 1 hour, the
residue was weighed 2.410g. The residue was heated in a silica crucible covered with vented lid at a temperature 950 + 20°C
for exactly 7 minutes. After cooling the weight of residue was found to be 1.78 g. The residue was then ignited at
200- 750°C to a constant weight of 0.246 g. Calculate the percentage of fixed carbon in a coal sample.
Soin.
Weight of coal taken = 2.5 g
Mass of moisture in coal sample = 2.5 - 2.410 = 0.09 g

% moisture = x 100
0.09 x 100
= 3.6
2.5
Mass of volatile matter = 2.410 - 1.78 = 0.63 g

x 100
(u) Percentage of volatile matter =
Weight of coal
0.63 x 100
= 25.2
2.5
(m) Mass of residue after ignition at 700-750° C = 0.246 g

Weight of ash left
. % ash = x 100
0.246 X 100
= 9.84
2.5
% carbon = 100 - (% Moisture + Volatile matter + Ash)
100 - (3.6 +25.2 +9.84)
100 - 38.64
61.36
UEL 6.16 MU -May 12 5 Marks

As air dried sample of coal weighing 2.9 g was taken for volatile matter determination. After losing volatile matter the coal
sample weighed 1.96 g. If it contains 4.5 % moisture, find the percentage of volatile matter in it.
soin :
Weight of coal taken = 2.9g

4.5%
% of moisture = Mod.
Loss in weight of coal 16
x 100
% moisture Weight of coal taken
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Engineering Chemistry-|I (MU - Sem 2) (6-42) Fuels and Combustion
4.5 x 2.9
(II) (i) Loss in weight of coal = 100
0.1305 g
(ii) :: Weight of coal after removal of moisture = 2.9 -0.1305 = 2.7695 g
(iii) Mass of volatile matter = 2.7695 - 1.96
0.8095 g
(iv) % Volatile matter = x 100
Weight of coal
0.8095 x 100
2.9
= 27.91 %
UEX. 6.17 MU - Dec. 12, 5 Marks

2.499
gms of coal sample was taken in silica crucible and heated in oven maintained at 110°C for one hour. The weight after
heating was 2.368 gms. The same sample was analysed for volatile matter and weight obtained was 1.75 g. the sample was
further treated to get fixed weight of 0.95 gms. Calculate the percentage of moisture, volatile matter, ash and fixed carbon for
this sample.
Soln.:
(1) (i)
Weight of coal taken = 2.499 gms
Mass ofmoisture in coal sample = 2.499 -2.368
= 0.131 g

:: Percentage of moisture = x 100
0.131
x 100 = 5.24 %
2.499
(II) (i) Mass of volatile matter = 2.368 - 1.75
= 0.618 gms
(ii) :: Percentage of volatile matter =

x 100
Weight of coal
0.618
=
x 100 = 24.73
2.499
(III) (i) Mass of residue =

0.95 gms
Weight of ash left
(ii) :: Percentage of ash x 100
0.95
x 100 = 38.02
2.499
(IV) % fixed carbon = 100 - (% Moisture + Volatile matter + Ash)
100 - (5.24 + 24.73 + 38.02)
100 - 67.99 = 32.01
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UEx. 6.18 MU - May 13, 5 Marks

A coal sample as analyzed as follows:
Exactly 2.5
g was weighed into silica crucible. After heating for 1 hour at 110°C the residue weighed 2.415 g, the crucible
next covered with a vented lid and strongly heated for exactly seven minutes at 950 + 20° C. The residue weighed 1.528 g.
The crucible was then heated without cover at 700º C until a constant weight was obtained. The last residue was found to
weight 0.245 g. Calculate the percentage results of above analysis.
Soln. :
(1) (i) Weight of coal taken = 2.5 g
(ii) Mass of moisture in coal sample = 2.5 - 2.415 = 0.085 g
(iii) % moisture = Loss in weight of coal
X 100
0.085 x 100
= 3.4
2.5
(II) (i)
Mass of volatile matter = 2.415 - 1.52 = 0.887 g.
(ii) :: % volatile matter = x 100
Weight of coal
0.887 x 100
2.5 = 35.48
(III) (i) Mass of ash = 0.245 g

Weight of ash left
(ii) % ash = X 100
0.245 x 100
= 9.8
2.5
(I) % fixed carbon =

100-(% Moisture + % volatile matter + % Ash)
V
=
100-(3.4 + 34.48 +9.8) 53.32
Type 3 Problems : Ultimate Analysis
Important Formulae
2 increase in weight of water absorbing unit

(1) % Hz = 18
х
Weight of coal sample
x 100
12 increase in weight of CO2 absorbing unit

(2) %C= X x 100
44 Weight of coal sample
(V, -V2) > Normality of NaOH 1.4

(3) %N =
Weight of coal sample (W)
(4) % O2 = 100 (% C + % H + % N + % S + % ash)

Module
Weight of BaSO4 32
(5) % S = Х x 100
Weight of coal 233
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UEX. 6.19 MU - Q. 119).May 13. 3 Marks
A coal sample was subjected to ultimate analysis, 0.6 gm of coal on combustion in a bomb calorimeter, produces 0.05 gm
BaSO. Calculate the percentage of 'S' in coal sample.
Soln.:
Given Required
% S
Weight of coal = 0.6 gm
Weight of BaSO, = 0.05 gm
Weight of BaSO4 32
% S = Х x 100
Weight of coal 233
0.05 32
236 x 100 = 1.144
Х
0.6
VEX. 6.20 MU - Q.6(b).Dec. 14. 5 Marks

2.5 g of a coal sample was analysed for nitrogen content by Kjeldahl's method. The liberated ammonia required 12.7ml of
0.SN H,SO, solution for neutralization. In a separate experiment, using Bomb calorimeter, 1.5 g ofcoal sample gave 0.28g
of BaSO.. Calculate percentage of Nitrogen and Sulphur in the sample.
Soln.:
Given
Required
Weight of coal = 2.5 gm % N and % S
Volatile of H2SO4 = 12.7 ml

Normality of H2SO, = 0.5 gm
Weight of coal = 1.5 gm
Weight of BaSO, = 0.28 gm
%N =
Volatile of H2SO. * Normality * 1.4 12.7 x 0.5 x 1.4
X
Weight of coal 2.5 = 3.556
Weight of BaSO 32
% S = Х x 100
Weight of coal 238
0.28 32
= х x 100 = 2.563
1.5 238
VEX.6.21 MU-0.19). Dec. 15. 3 Marks

1.5 g of a sample was burnt in acombustion apparatus and products of combustion were collected in previously weighed
KOH bulb and CaCl, tube. The increase in weights of KOH bulb and CaCl, tube were found to be 3.92 g and 1.25 &
respectively. Calculate percentage carbon and hydrogen in the sample.
soin :
Given
Required
Mass of coal-sample = 1.5 g
% C and %H
Increase in weight of KOH bulb = Weight of Co, formed = 3.92 g
Increase in weight of cacl, tube = Weight of water formed = 1.25 g
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Engineering Chemistry I(MU. Som 2) (0-45)
(1) To calculate % C
(1) Reaction : C+02 +CO, (absorbed in KOH)

12 32
:: 44 gms of Co, 12 gms of C

3.92 x 12
:: 3.92 gms ofCO, 44 = 1.069 gms of C
Weight of C
(iii) %C =
Weight of coal-sample X 100
1.069
x 100
1.5
71.266
(II) To calculate % H
() Reaction : H+0+4,0
2 16 18
(ii) : 18 gms of H20 = 2 gms of H

1.25 x 2
:: 1.25 gms of H2O =18 = 0.138 gms of H
Weight of H 0.138
(iii) % H =
Weight of coal-sample * 100 = 1.5
x 100 = 9.2
Type 4 Problems : Combustion of Solld and Gaseous Fuols
Most commonly involved combustion reactions :
(Remember by heart)
(1) C + O2 + CO2
(2) H,+0, +4,0

(3) S+02 → SOZ
(4) co+į02+00
(5) CH. + 202 + CO2 + 2H,0
(6) C,H, ,
+30 + 2CO + HẠO
(7) CH. + 302 2002 + 2H20
(8) CH, +20,- 200, + 34,0

Module
(9) CH. +20,– 300, + 34,0 16
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(10) CH, +502 + 3CO2 + 4H20

(11) CH, +602 4CO2 + 4H20
13
(12) CH10+ 2-02 + 4CO2 + 5H,0
UEx. 6.22 MU - Q. 6(b). May 13, 5 Marks

A gaseous fuel has following composition by volume :
H2 = 10% CH4 = 30% C, H, = 20% CO = 20% CO2 = 15 %, N = 5%
Calculate the volume of air required for complete combustion of I m' of this gas. 3
✓ Soln. :
Given
Required
Gaseous fuel, component by volume Volume of air required for complete combustions of im' of the gas
H2 = 10%, CH. = 30%, CzHg = 20 %
CO = 20%, CO2 = 15%, N2 = 5%
Note: CO2, Ny and Ash being incombustible, do not take oxygen therefore do not consider CO2, N. and Ash at all
Explanation to understand how to calculate volume of oxygen say at the step (III) i.e. for CHa proceed in the following
sub-steps :
(i) Write the combustion reaction as shown above.

(ii) Assign ‘l' to C,H, and '5' to O, according to Volatile. (: air volume required).
(iii) Note volume of C,H, given in the data it is 20% convert into a fraction = 0.2 m
(iv) Finally ;
calculate volume of O2 required of CzH* volume of C,Hy = 0.2 x 5 = im.
Step No. Constituent Volume Reaction
Volume of oxygen required (m)
3
Hz 10
0.1 H, +20, = H90 0.1 0.2 = 0.05
1 0.5
(II) CH,
300.3 CH. + 20, = CO2 + 2H2O 0.3 x 2 = 0.6
1 2.
(III) C,H, 20
0.2 CH3 + 50, = 3C0, +4H.00.2x5=1
1 S
(IV) CO
20 +
0.2 co +10:-CO 0.2 x 0.5-0.1
0.5
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1.MCHIVU
engineering Chemistry I (MU. Som 2) (641 Fuels and non
( Toul volume of oxygen required = 1005 +0,641 +0.1) - 175 tn
(vi) Since air contains 21% oxygen by volume
Therefore the volume of air required 175 100
21
VEX. 6.23 MU 0.30. May 13, G Marks

A conl sample has the following composition by weights: C 82%, H -3%, 0 = 8%, 2%, N = 2% and Ash = 3%.
Calculate the minimum amount of air required both by weight and volume for complete combustion of 2 kg of coal.
(Molecular weight of air 28,94 gm),
Soin.
Given
Required
Coal sample, composition by weight Weight and volume of air for complete combustion of 2 kg of cosal.
C-82%, H = 3%, O-8, S2%,
N = 2%, Ash = 3%
Molecular weight of air = 28.949
Step No. Constituent Welght Reaction

Weight of O, required /kg of coal kg
% kg
C
82 0.82 C + 02 = CO2 32
12 32
82x32 =
0.82 x
12
= 2.186
H 3 0.03
03xha
H2+1 02= H,0 0.03 16
- 0.24
2
2 16
(III) 0 8 0.08 -0.08
(IV) S 2
0.02 S + O2 = SO2 32
32 32
2x32== 0.02
0.2 x
32
(v) Weight of oxygen required/kg of coal = (2.186 +0.24 - 0,08 +0.02) = 2.366 kg
(vi) Since air contains 23% oxygen by weight
100
:: amount of air required = x
21 2.336 = 11.266 kg/kg of coal
.. for 2kg of coal total amount of air = 11.266 x 2 = 22.532 kg

(viii) : 28.949 kg of air occupies 22.4 m' of air
22.532
:: 20.572 kg air will occupy 28.949
x 22.4= 17.434 m?
VEx. 6.24 MU -0.3(a), Dec. 13. 6 Marks

A gascous fuel has the following composition by volume : Module
H, - 50%, CO = 10%.CH, -30%, CH = 5%, N, = 1%, 0,= 2% and CO2 = 2% 6
Calculate volume and weight of air required for complete combustion of 1 m' of fuel (Molecular weight of air = 28.949)
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Soln.:
Given
Required
Gaseous fuel, component by volume Volume and weight of air for complete combustion of lm of fuel.
H = 50%, CO = 10%, CH, = 30%, CH = 5 %,
N2 = 1%, O2 = 2%, CO2 = 2%
Molecular weight of air = 28.949
Step No. Constituent Volume Reaction Volume of oxygen required mº

% m?
(I) H2 50 0.5
H2 + Ź 02 == H20
0.5 x 0.5 = 0.25
1 0.5
100.1 co+0,=CO;
CO
0.1 x 0.5 = 0.05
1 0.5
(III) CH, 30 0.3 CH4 + 202 = CO2 + H2O 0.3 x 2 = 0.6
1 2
(IV) CH4 5
0.05 CH4 + 302 = 2CO2 + 2H20 0.05 x 3 = 0.15
1 3
(V) 02 2 0.02
-0.02
(VI)
Total volume of O, required = (0.25 +0.05 +0.6 +0.15 – 0.02) = 1.03 m²
100
(VII) :: Volume of air required = 1.03 x = 4.904 m?
21
(VIII) : 22.4 m’ of air weights 28.949 kg

4.904
:: 4.904 m? of air will weigh 22.4 x 28.949 = 6.337 kg
Part III : Home Work Problems
Type 1 Problems : (HCV and LCV by Dulong's formula)

Q. 1
Calculate HCV and LCV of the following two coal samples with :
(A) C = 85 %, H = 7%, O = 3%, S = 3.5%, N = 2.1 % and Ash = 4.4 %
(B) C = 80 %, H = 7%, O = 2.8%, S = 3.4%, N = 9% and Ash = 3.5 %
(Ans. : HCV = 9232.03 kcal/kg, LCV = 8862.02 kcal/kg)

Q. 2
A sample of coal has the following composition by mass :
C = 70%, H = 9%, O = 4%, S = 2%, N = 1% and Ash = 14%
Calculate gross calorific values of the fuel using Dulong's formula.

(MU - Q. 1(g), May 16, 3 Marks) Ans. : HCV = 8808 kcal/kg, LCV = 8438.2 kcal/kg)
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Q3 A coal sample contains C = 70%, O = 23%, H = 5%, N = 0.4% Ash = 0.1 %. Calculate GCV and NCV of the fuel.
(MU - Q. 1(9), May 17, 3 Marks)
Type 2 : Problems (Proximate analysis)

Q.4
2 gm of dried coal on heating at 110°C for 1 hour, left a residue of 1.75 gm. This residue on heating of at 950 + 20°C
for 7 minutes in the absence of air produced a residue 1.45 gm. This residue on further composition left 0.3 gm of
noncombustible - matter. Calculate the results of the proximate analysis.
(Ans. : % moisture = 12.5% volatile matter = 15,% ash = 15% fixed carbon = 58.5)
Q.5
From the following data, calculate % of
(a)
moisture, (b) volatile matter, (c) ash and (d) fixed carbon.
(0)
Weight of coal taken = 2.5 gm
Weight of coal after heating at 100°C = 2.37 gm
(iii)
Weight of coal after heating in a covered crucible at 950 + 20°C = 1.75 gm
(iv)
Constant weight obtained at the end of the test = 0.95 gm (Ans. : 5.28, 24.72, 38, 32 respectively)
Type 3 : Problems (Ultimate Analysis)

Q. 6
By kjeldahle's method, 2.3 g of coal sample was analysed for nitrogen content, The liberated ammonia was
neutralized by 12.5 ml of 0.5 N H2SO, solution. The same weight of sample gave 0.64 g of Baso, precipitate.
Calculate % N and % S respectively.
(Ans. : 3.8 and 3.82 respectively)
Q.7
3.2 g of coal evolved NH, which was absorbed in 40 ml of 0.5 N H2SO4. After absorption the excess acid required 16
ml of 0.5 N KOH for complete neutralisation. 2.5 g of coal required sample gave 0.42 gm of BaSO4. Calculate % N
and % S.
(Ans. : 5.25 and 2.31 respectively)
Q. 8
1.5 g of a coal sample was analysed for nitrogen content by Kjeldahl's method. The liberated armonia required 14
ml of 0.1 N H SO, solution for neutralization. In a separate experiment using Bomb Calorimeter, 1.5 g of the same
sample gave 0.3 g of BaSO4. Calculate percentage nitrogen and sulphur in the sample.
(MU - Q. 6(b), May 16, 5 Marks)
Q. 9
A coal sample was subjected to ultimate analysis. 2.45 g of coal on combustion in a Bomb-Calorimeter gave 0.67 g
of BaSO4. Calculate percentage of sulphur. (MU - Q. 1(f), Dec. 16, 3 Marks)
Q. 10
0.5 gm of coal sample was burnt in Bomb. Calorimeter experiment produced 0.06 gm of BaSO.. Calculate
percentage of sulphur. (MU - Q. 2(b)(i), May 17, 3 Marks)
Q. 11
1.95 gm of a coal sample was taken for nitrogen estimation by Kjeldahis's method.
The ammonia liberated required 9.5ml of 0.4N H,SO, for neutralization. Calculate the percentage of Nitrogen in coal
sample. Required sample gave 0.42 gm of BaSO4. Calculate % N and % S.
(MU - Q. 2(b)(1), May 18, 3 Marks) (Ans. : 5.25 and 2.31 respectively)
Module
6
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Type 4 Problems : (Combustion of solid and gaseous fuel)
Q. 12 A coal sample contain C = 0.1 %,0 = 8 %, S = 1%, H = 5 %, N=1 % Ash = 4%
Calculate minimum amount of air required for complete combustion of 2 kg of coal. (Ans. : 28.85 kg)
Q. 13
A coal sample contains C = 85 %, O = 5%, S = 2%, ash = 3%
Calculate minimum amount air by volume and weight for complete combustion of 2 kg of the fuel.
(Ans. : 22.96 kg and 17.77 m)

Q. 14
A fuel contains O2 = 1%, SO2 = 5%, CO2 = 6.5, CaHg = 1%, C2H6 = 6%, CH4 = 4.5%, CH4 = 35%, H2 = 22% and
remaining nitrogen. Find weight of oxygen and air required for complete combustion of 1 kg fuel.
(Ans. : Oxygen = 3.59 kg, weight = 15.61 kg)
Q. 15
A fuel gas has following constituents by volume :
CO = 15%, CH4 = 5 %., CH4= 35%, N = 1%, H2 = 40 m, Water vapour = 4% calculate volume of air required for
complete combustion of 1 m of the fuel.
(Ans. : 5.33 m)
Q. 16
A gaseous fuel has the following composition by volume.
CO = 40%
He = 42% CHg == 4%
CH, = 4% Ny = 4% and
O2 = 6%
Calculate volume and weight of air required for complete combustion of 1 mⓇ of fuel
(Molecular weight of air = 28.949) (MU - Q. 3(a), May 16, 6 Marks)
Q. 17
A gaseous fuel has the following composition by Volume :
H = 25%, CO = 20%, CH, = 30%
C.Hg == 20%, O2 = 2%, N2 = 1%, CO, = 2%
Calculate volume and weight of air required for complete combustion of 1 m of fuel.
(Molecular weight of air = 28.949) (MU - Q. 3(a), Dec. 16, 6 Marks)
Q. 18
Calculate the weight and volume of air needed for complete combustion of 2 kg of coal containing:
C = 54%, H = 6.5,
% O = 3%, W = 1.8%
(Molecular Weight of air = 28.949) (MU - Q. 6(b), Dec. 16, 5 Marks)

Q. 19
Calculate weight of air needed for complete combustion of 2 kg of coal containing.
C = 70%, O = 10%, H = 10%, N = 5% and remaining ash. (MU - Q. 5(a), May 17, 6 Marks)
Q. 20
A sample of coal was found to contain the following constituents.
C = 81%, O = 8%, S = 1%, H = 5%, N = 1% and Ash = 4%.
Calculate the minimum weight and volume of an required for the complete combustion of 1kg of coal.
(MU - Q. 5(a), Dec. 17, 6 Marks)
Q. 21
A gaseous fuel contains Hy = 50%, Cha = 30%, N2 = 2%, CO = 7%, C2 Hy = 3%, C2Hg = 5%, and water vapour = 3%,
Calculate weight and volume of air required for 2mº of the gas.
(Given : molecular weight of an air = 28.949 kg). (MU - Q.5(a), May 18, 6 Marks)
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Q. 22 A gaseous fuel has the following composition by volume.

H2 = 55%, CHA = 30%, CaHa = 5%, CO = 5%, N2 = 1%, CO2 = 2% and O2 = 2%. Calculate volume and weight of air
required for complete combustion of 1m of fuel. (Molecular weight of air = 28.949)
(MU - Q. 3(a), May 14, 6 Marks) (Ans.: V = 4.904 m, W = 6.337 kg)
Q. 23
A gaseous fuel has the following composition by volume :
H2
= 40%, CH, = 30%, CO = 10%, CzHg = 12%, N2 = 3%, O2 = 2% and CO2 = 3%. Calculate volume and weight of air
required for complete combustion of 1m of fuel. (Molecular weight of air = 28.949)
(MU - Q. 3(a), Dec. 14, 6 Marks) (Ans. : V = 6.809 mº, w = 8.8 kg)
Q. 24
A gaseous fuel has the following composition by volume.
CHA
= 35%, CyHa = 5%, CO = 15%, Hy = 40% N, = 1 water vapour = 4%. Calculate volume and weight of air required
for complete combustion of 1 mø of fuel [Molecular weight of air = 28.94]
(MU - Q. 3(a), May 15, 6 Marks) (Ans.: V = 5.357 mº, w = 6.921 kg)
Q. 25
A gaseous fuel has the following composition by volume : H2 = 30%, CH4 = 10%, CO = 46%, C2H4 04%, N2 = 1%,
O2 = 7% and CO2 = 02%. Calculate volume and weight of air required for complete combustion of 1m of fuel.
(Molecular Weight of air = 28.949). (MU - Q. 3(a), Dec. 15, 6 Marks) (Ans. : V = 3mº, w = 3.877 kg)
Chapter Ends...
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University Prescribed Syllabus

3.1 INTRODUCTION TO ELECTROCHEMISTRY... *****en*****ennes** ************oaeeaaeeneedd*aeae*ee***********aueaeaaeu**aa*****************aae** Z

3.1.1 Definition of Electrochemistry.. 3-2

3.2.2(C) Concentration Cel... *noanonesensnosnne***********************************************************e*s*****e***********************.3-7

3.6.1 Electrochemical Series and its Applications..

(2C1)Fig. C.3.1.1 Concept of electrochemistry

3.1 INTRODuCTION TO ELECTROCHEMISTRY

(I1) Significance of electrochemistry

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electrochemistry is very mush significant.

a 3.1.2 Half Reactions

) Consider the following reaction

3.2 TYPES OF ELECTROCHEMICAL CELLS

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(2C2Fig. 3.2.1: Construction of typical electrochemical cell

a 3.2.2 Types of Electrochemical Cells

(1) (2) (3) (4)

(2c)Fig. 3.2.2: Types of electrochemical cell

a 3.2.2(A) Galvanic or Voltaic Cell

GQ. 3.2.3 Exolain a galvanic (or voltarc ceiy Witn a sultable

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(2cA)Fig. 3.2.3 : A typical basic simple galvanic or voltaie cell

(vi) The oxidation half-reaction occurs in the anode compartment.

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(i) In an electrolytic cell, the process of electrolysis is carried out.

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(x) Let us consider the electrolysis of HCl as an example.

(xi) In solution, HCl is ionised as

HCI H' +Cr

(xii) At the clectrodes, the following reactions will take place:

Thus, the overall reaction is

2HCI H,+Cl2 (decomposition)

(1i) Fig. 3.2.5, represents a typical basic concentration cell.

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0.1M NOg 1M NO3

T h e two solutions are in contact through a membrane (or a saltbridge).

Ag-e Ag (left compartment)

(xii) EMF of concentration cell

(c) According to the Nernst equation,

E (E 1ogC-(E,+ 1og C,)

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KOH at 200°C at 20-40 atm

(2CT)Fig. 3.2.6: Construction of a hydrogen-oxygen fuel cell

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Hydrogen - Oxygen fuel cells (discussed above)

(VI) Advatage of fuel cells

() Fuel cells do not require recharging.

(i) Lesser maintenance is required.

(VIl) Disadvantages / limitations of fuel cells

(4) To provide power in shuttle aircrafts, space vehicles etc.

(5) For back-up power in hospitals, cogeneration.

(6) Electric load balancing during power staggering / megablock/ emergency.

3.3 CONCEPT OF ELECTRODE POTENTIAL Module

(i) It is the measure of tendency of an electrode to

(ix) If an electrode tends to lose electrons it is called oxidation

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(a) For example, in two

3.1 INTRODUCTION TO ELECTROCHEMISTRY... ***en*ennes ************oaeeaaeeneeddaeaeee*aueaeaaeuaa*******aae Z

3.2.2(C) Concentration Cel... *noanonesensnosnne***********************************************************ese*******************.3-7