Gate Flix Process-Calculation
Uploaded by
ca23m008Gate Flix Process-Calculation
Uploaded by
ca23m008PROCESS CALCULATIONS
For
CHEMICAL ENGINEERING
PROCESS
CALCULATIONS
SYLLABUS
Steady and unsteady state mass and energy balances including multiphase, multi-
component, reacting and non-reacting systems. Use of tie components; recycle, bypass
and purge calculations; Gibb’s phase rule and degree of freedom analysis.
ANALYSIS OF GATE PAPERS
Exam Year Total
2001 4
2002 4
2003 8
2004 6
2005 4
2006 2
2007 5
2008 9
2009 8
2010 4
2011 4
2012 4
2013 4
2014 0
2015 2
2016 4
2017 2
2018 1
2019 6
CONTENTS
Topics Page No
1. UNIT AND DIMENSIONS 7-35
1.1 Introduction
1.2 Physical Quantity
1.3 Fundamental and Derived Quantities
1.4 Fundamental and Derived Units
1.5 Standards of Length, Mass and Time
1.6 Dimensions of a Physical Quantity
1.7 Applications of Dimensional Analysis
1.8 Limitations of Dimensional Analysis
1.9 Significant Figures
1.10 Order of Magnitude
1.11 Errors of Measurement
2. CHEMICAL CALCULATIONS AND GAS LAWS 36-69
2.1 Introduction
2.2 Structure of Atom
2.3 Basics of Concentration
2.4 Gas Laws and Its Applications
3. PHASE RULE 70-92
3.1 Introduction
3.2 Phase
3.3 Component
3.4 Degree of Freedom
3.5 Derivation of Phase Rule
3.6 Phase Reaction for Chemical Equation Equilibrium
3.7 Phase Diagram
3.8 Phase Diagram & Features of One-Component System
3.9 Phase Diagram & Features of Two-Component System
3.10 Phase Diagram & Features of Three-Component System
3.11 Applications of Phase Rule
4. FUELS 93-126
4.1 Introduction
4.2 Classification of Fuel
4.3 Some Important Types of Fuel
4.4 Solid Fuels
4.5 Liquid Fuels
4.6 Gaseous Fuels
5. COMBUSTION 127-140
5.1 Introduction
5.2 Factors Affecting Rate of Combustion
5.3 Calorific Value
5.4 Flue-Gas Analysis – Orsat’s Method
6. MASS BALANCE 141-167
6.1 Introduction
6.2 System
6.3 Process
6.4 Material Balance Without Chemical Reaction or Non-Reactive
System
6.5 Material Balance With Chemical Reaction or Reactive
System
6.6 Material Balance on Single Unit Without Chemical Reaction
6.7 Material Balance on Multiple Unit Without Chemical Reaction
6.8 Material Balnce With Chemical Reaction
7. ENERGY BALANCE 168-179
7.1 Introduction
7.2 Different forms of Energy
7.3 Enthalpy
7.4 The General Energy Balance
7.5 Heat capacities
7.6 Kopp’s rule
7.7 Enthalpy change of phase changes
7.8 Heating curve
7.9 Hess’s law
8. GATE QUESTIONS 180-208
1 UNIT AND DIMENSIONS
Introduction
Dimensional analysis offers a method for reducing complex physical problems to the
simplest (that is, most economical) form prior to obtaining a quantitative answer.
Bridgman (1969) explains it thus: "The principal use of dimensional analysis is to
deduce from a study of the dimensions of the variables in any physical system certain
limitations on the form of any possible relationship between those variables. The
method is of great generality and mathematical simplicity"
Physical Quantity
A quantity which can be measured and by which various physical happenings can be
explained and expressed in form of laws is called a physical quantity. For example
length, mass, time, force etc.
On the other hand various happenings in life e.g., happiness, sorrow etc. are not
physical quantities because these can not be measured.
Measurement is necessary to determine magnitude of a physical quantity, to compare
two similar physical quantities and to prove physical laws or equations.
A physical quantity is represented completely by its magnitude and unit. For example,
10 meter means a length, which is ten times the unit of length 1 kg. Here 10 represents
the numerical value of the given quantity and meter represents the unit of quantity
under consideration. Thus in expressing a physical quantity we choose a unit and then
find that how many times that unit is contained in the given physical quantity, i.e.
Physical quantity (Q) = Magnitude × Unit = n × u
Where, n represents the numerical value and u represents the unit. Thus, while
expressing definite amount of physical quantity, it is clear that as the unit (u) changes,
the magnitude (n) will also change but product ‘nu’ will remain same.
1
i.e. n u = constant, or n1u1 = n 2 u 2 = constant; n
u
i.e. magnitude of a physical quantity and units are inversely proportional to each other
. Larger the unit, smaller will be the magnitude.
Types of Physical Quantity
(1) Ratio (numerical value only): When a physical quantity is a ratio of two
similar quantities, it has no unit.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
e.g. Relative density = Density of object/Density of water at 4o C
Refractive index = Velocity of light in air/Velocity of light in medium
Strain = Change in dimension/Original dimension
Note: Angle is exceptional physical quantity, which though is a ratio of two similar
physical quantities (angle = arc / radius) but still requires a unit (degrees or radians)
to specify it along with its numerical value.
(2) Scalar (Magnitude only): These quantities do not have any direction e.g.
Length, time, work, energy etc. Magnitude of a physical quantity can be negative. In
that case, negative sign indicates that the numerical value of the quantity under
consideration is negative. It does not specify the direction.
Scalar quantities can be added or subtracted with the help of ordinary laws of addition
or subtraction.
(3) Vector (Followed by Vector Law of Addition): A physical quantity that
follows vector law of addition is called a Vector. e.g. displacement, velocity,
acceleration, force etc.
Note: Vector Law of addition: There are 3-Laws of vector addition: Triangle law,
Parallelogram law and Polygon law. All these three laws states the same hypothesis.
Triangle Law: It states that if two vectors acting simultaneously at a point are
represented in magnitude and direction by the two sides of a triangle taken in same
order then their resultant is represented in magnitude and direction by the third side
of the triangle taken in opposite order.
Parallelogram law: If two vectors are considered to be adjacent sides of a
parallelogram, then the resultant of two vectors is given by the vector that is a diagonal
passing through the point of contact of two vectors.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
Polygon Law: If a number of vectors can be represented in magnitude and direction
by the sides of a polygon taken in the same order, then their resultant is represented
in magnitude and direction by the closing side of the polygon taken in the opposite
order.
Why Zero Vector is a Vector Quantity?
Zero Vector do not have any magnitude. Its direction is undefined. However, it is a
vector quantity as it satisfies Vector law of addition.
A0 A
(4) Tensor (Magnitude and Direction not followed by Vector Law of
Addition): A physical quantity that have magnitude and direction both but do not
follows vector law of addition is called as Tensor. e.g. Moment of inertia, Electric
Current etc
Moment of inertia is not a vector as by changing the sense of rotation its value is not
changed. It is also not a scalar as it has different values in different directions (i.e.
about different axes).
Fundamental and Derived Quantities
(1) Fundamental quantities: Out of large number of physical quantities, which
exist in nature, there are only few quantities, which are independent of all other
quantities, and do not require the help of any other physical quantity for their
definition, therefore these are called absolute quantities. These quantities are also
called fundamental or base quantities, as all other quantities are based upon and can
be expressed in terms of these quantities.
(2) Derived quantities: All other physical quantities can be derived by suitable
multiplication or division of different powers of fundamental quantities. These are
therefore called derived quantities.
If length is defined as a fundamental quantity then area and volume are derived from
length and are expressed in term of length with power 2 and 3 over the term of length.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
In mechanics Length, Mass and time are arbitrarily chosen as fundamental quantities.
However this set of fundamental quantities is not a unique choice. In fact any three
quantities in mechanics can be termed as fundamental as all other quantities in
mechanics can be expressed in terms of these. e.g. if speed and time are taken as
fundamental quantities, length will become a derived quantity because then length will
be expressed as Speed / Time and if force and acceleration are taken as fundamental
quantities, then mass will be defined as Force / acceleration and will be termed as a
derived quantity.
Fundamental and Derived Units
Normally each physical quantity requires a unit or standard for its specification so it
appears that there must be as many units as there are physical quantities. However, it
is not so. It has been found that if in mechanics we choose arbitrarily units of any three
physical quantities we can express the units of all other physical quantities in
mechanics in terms of these. Arbitrarily the physical quantities mass, length and time
are chosen for this purpose. So any unit of mass, length and time in mechanics is called
a fundamental, absolute or base unit. Other units which can be expressed in terms of
fundamental units, are called derived units. For example light year or km is a
fundamental units as it is a unit of length while s 1 , m 2 or kg / m are derived units as
these are derived from units of time, mass and length respectively.
System of units: A complete set of units, both fundamental and derived for all
kinds of physical quantities is called system of units. The common systems are given
below –
(1) CGS system: The system is also called Gaussian system of units. In it length, mass
and time have been chosen as the fundamental quantities and corresponding
fundamental units are centimeter (cm), gram (g) and second (s) respectively.
CGS System
Physical Quantity Unit of Physical Quantity Symbol
Length Centimeter cm
Mass Gram gm
Time Second s
(2) MKS system: The system is also called Giorgi system. In this system also length,
mass and time have been taken as fundamental quantities, and the corresponding
fundamental units are meter, kilogram and second.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
MKS System
Physical Quantity Unit of Physical Quantity Symbol
Length Meter m
Mass Kilogram kg
Time Second s
(3) FPS system: In this system foot, pound and second are used respectively for
measurements of length, mass and time. In this system force is a derived quantity with
unit poundal.
FPS System
Physical Quantity Unit of Physical Quantity Symbol
Length Foot ft
Mass Pound lb
Time Second s
(4) S. I. system: It is known as International system of units, and is in fact extended
system of units applied to whole physics. There are seven fundamental quantities in
this system. These quantities and their units are given in the following table
S.I. System
Physical Quantity Unit of Physical Quantity Symbol
Length Meter m
Mass kilogram Kilogram kg
Time Second s
Electric Current Ampere A
Temperature Kelvin K
Amount of Substance Mole mol
Luminous Intensity Candela cd
Besides the above seven fundamental units two supplementary units are also defined
Radian (rad) for plane angle
Steradian (sr) for solid angle.
Note: Apart from fundamental and derived units, we also use very frequently practical
units.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
These may be fundamental or derived units e.g., light-year is a practical unit
(fundamental unit) of distance.
Horsepower is a practical unit (derived unit) of power.
Practical units may or may not belong to a system but can be expressed in any system
of units. e.g. 1 mile 1.609 km = 1.609 × 103 m.
S.I. Prefixes
In physics we have to deal from very small (micro) to very large (macro) magnitudes
as one side we talk about the atom while on the other side of universe, e.g., the mass
of an electron is 9.110 –31 kg while that of the sun is 2 1030 kg . To express such large or
small magnitudes simultaneously we use the following prefixes:
Power of Prefix Symbol
10
1018 exa E
1015 peta P
1012 tera T
109 giga G
106 mega M
103 kilo k
10 2 hecto h
101 deca da
10 1 deci d
10 2 centi c
10 3 milli m
106 micro
10 9 nano n
1012 pico p
10 15 femto f
10 18 atto a
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
Standards of Length, Mass and Time
(1) Length: Standard meter is defined in terms of wavelength of light and is called
atomic standard of length.
The meter is the distance containing 1650763.73 wavelength in vacuum of the
radiation corresponding to orange red light emitted by an atom of krypton-86.
Now a days meter is defined as length of the path travelled by light in vacuum in 1/299,
7792, 458 part of a second.
(2) Mass: The mass of a cylinder made of platinum-iridium alloy kept at International
Bureau of Weights and Measures is defined as 1 kg.
On atomic scale, 1 kilogram is equivalent to the mass of 5.0188 1025 atoms of 6
C12
(an isotope of carbon).
(3) Time: 1 second is defined as the time interval of 9192631770 vibrations of
radiation in Cs-133 atom. This radiation corresponds to the transition between two
hyperfine levels of the ground state of Cs-133.
Practical Units.
(1) Length:
(i) 1 fermi = 1 fm = 1015 m
(ii) 1 X-ray unit = 1XU = 1013 m
(iii) 1 angstrom = 1A = 1010 m = 10 8 cm = 107 mm = 0.1 m
(iv) 1 micron = m = 106 m
(v) 1 astronomical unit = 1 A.U. = 1. 49 1011 m
(vi) 1 Light year = 1 ly = 9.46 1015 m
(vii) 1 Parsec = 1pc = 3.26 light year
(2) Mass:
(i) Chandra Shekhar unit : 1 CSU = 1.4 times the mass of sun = 2.8 10 30 kg
(ii) Metric tonne : 1 Metric tonne = 1000 kg
(iii) Quintal : 1 Quintal = 100 kg
(iv) Atomic mass unit (amu) : amu = 1.67 10 27 kg mass of proton or neutron is of the order of 1 amu
(3) Time:
(i) Year : It is the time taken by earth to complete 1 revolution around the sun in its orbit.
(ii) Lunar month : It is the time taken by moon to complete 1 revolution around the earth in its orbit.
1 L.M. = 27.3 days
(iii) Solar day : It is the time taken by earth to complete one rotation about its axis with respect to sun.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
Since this time varies from day to day, average solar day is calculated by takin g average of the duration of all
the days in a year and this is called Average Solar day.
1 Solar year = 365.25 average solar day
1
or average solar day = part of solar year
365 .25
(iv) Sedrial day : It is the time taken by earth to complete one rotation about its axis with respect to a
distant star.
1 Solar year = 366.25 Sedrial day = 365.25 average solar day
(v) Shake : It is an obsolete and practical unit of time.
1 Shake = 108 sec
Dimensions of a Physical Quantity
When a derived quantity is expressed in terms of fundamental quantities, it is written
as a product of different powers of the fundamental quantities. The powers to which
fundamental quantities must be raised in order to express the given physical quantity
are called its dimensions.
Dimensions of some standard physical quantities
Sr. Physical Quantity Unit Dimension
No.
1 Length m L
2 Mass kilogram kg M
3 Time s T
4 Electric Current A A
5 Temperature K
6 Amount of Substance mole mol
7 Luminous Intensity cd cd or J
Dimensions of derived physical quantities
Engineering Mechanics
Sr. Physical Quantity Unit Dimension
No.
1 Velocity or speed (v) m/s [M 0 L1T 1 ]
2 Acceleration (a) m/s 2 M 0 LT 2
3 Momentum (P) kg m / s M1L1T 1
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
4 Impulse (I) Newton-sec or kg m / s M1L1T 1
5 Force (F) Newton M1L1T 2
6 Pressure (P) Pascal M1L1T 2
7 Kinetic energy E K Joule M1L2 T 2
8 Power (P) Watt or Joule/s M1L2 T 3
9 Density (d) kg/m 3 M1L3T 0
10 Angular displacement (𝜃) Radian(rad.) M 0 L0 T 0
11 Angular velocity (𝜔) Radian/sec M 0 L0 T 1
12 Angular acceleration () Radian / sec 2 M 0 L0 T 2
13 Moment of inertia (I) kg m 2 M1L2 T 0
14 Torque ( ) Newton-meter M1L2 T 2
15 Angular momentum (L) Joule-sec M1L2 T 1
16 Force constant or spring Newton/m M1L0 T 2
constant (k)
17 Gravitational constant (G) N m 2 / kg 2 M 1L3T 2
18 Intensity of gravitational N/kg M1L2 T 2
field (E g )
19 Gravitational potential Joule/kg M 0 L2 T 2
(Vg)
20 Surface tension (T) N/ m or Joule/ m2 M 1L0 T 2
21 Velocity gradient (Vv) Second 1 M 0 L0 T 1
22 Coefficient of viscosity kg/m-s M1L1T 1
23 Stress N / m2 M1L1T 2
24 Strain No unit M0 L0T0
25 Modulus of elasticity (E) N / m2 M1L1T 2
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
26 Poisson Ratio ( ) No unit M0 L0T0
27 Time period (T) Second M 0 L0 T1
28 Frequency (n) Hz M 0 L0 T 1
Heat Transfer
Sr. Physical Quantity Unit Dimension
No.
1 Temperature (T) Kelvin M 0 L0 T 0 1
2 Heat (Q) Joule ML2T 2
3 Specific Heat (c) Joule/kg-K M 0 L2 T 2 1
4 Thermal capacity Joule/K M 1L2 T 2 1
5 Latent heat (L) Joule/kg M 0 L2 T 2
6 Gas constant (R) Joule/mol-K M 0 L2 T 2 1
7 Boltzmann constant (k) Joule/K M 0 L2 T 2 1
8 Coefficient of thermal Joule/m-s-K M 0 L2 T 3 1
conductivity (K)
9 Stefan's constant ( ) W att/m 2 -K 4 M 1L0 T 3 4
10 Wien's constant (b) Meter-K M0 L1T 01
11 Planck's constant (h) Joule-s M 1L2 T 1
12 Coefficient of Linear Kelvin 1 M 0 L0 T 01
Expansion ( )
13 Mechanical eq. of Heat (J) Joule/Calorie M0 L0T0
14 Vander wall’s constant (a) Newton m 4 ML5T 2
15 Vander wall’s constant (b) m3 M0 L3T 0
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
Electricity
Sr. Physical Quantity Unit Dimension
No.
1 Electric charge (q) Coulomb M 0 L0 T1A1
2 Electric current (I) Ampere M 0 L0 T 0 A1
3 Capacitance (C) Coulomb/volt or Farad M 1L2 T 4 A 2
4 Electric potential (V) Joule/coulomb M1L2 T 3 A 1
5 Permittivity of free Coulomb2 M 1L3T 4 A 2
space ( 0) Newton meter 2
6 Dielectric constant (K) Unit less M0 L0T0
7 Resistance (R) Volt/Ampere or ohm M1L2 T 3 A 2
8 Resistivity or Specific Ohm-meter M1L3T 3 A 2
resistance ( )
9 Coefficient of Self- Volt second M1L2 T 2 A 2
or Heneryor ohm sec
induction (L) ampere
10 Magnetic flux ( ) Volt-second or weber M1L2 T 2 A 1
newton Joule
or
ampere meter ampere meter 2
M1L0 T 2 A 1
volt second
11 Magnetic induction (B) or or Tesla
meter 2
12 Magnetic Intensity (H) Ampere/meter M0 L1T0 A1
13 Magnetic Dipole Ampere/meter2 M 0 L2 T 0 A1
Moment (M)
Newton Joule
or or
ampere 2
ampere 2 meter
Permeability of Free Volt second Ohm second
or
ampere meter meter
14 Space M1L1T 2 A 2
henery
or
(0) meter
15 Surface charge density Coulomb meter-2 M0 L2T1A1
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
()
16 Electric dipole moment C oulom b m eter M 0 L1T1A 1
(p)
17 Conductance ohm 1 M 1L2 T 3A 2
(G) = (1/R)
18 Conductivity ohm 1meter 1 M 1L3T 3A 2
( )= (1/ )
19 Current density (J) Ampere/ m2 M 0 L2 T 0 A 1
20 Intensity of electric field Volt/meter, Newton/coulomb M1L1T 3 A 1
(E)
21 Rydberg constant (R) m 1 M 0 L1T 0
Quantities having same Physical Dimensions.
Sr. No. Physical Quantity Dimension
1 Frequency, angular frequency, angular velocity, velocity M 0 L0 T 1
gradient and decay constant
2 Work, internal energy, potential energy, kinetic energy, M 1L2 T 2
torque, moment of force
3 Pressure, stress, Young’s modulus, bulk modulus, M1L1T 2
modulus of rigidity, energy density
4 Momentum, impulse M 1 L1T 1
5 Acceleration due to gravity, gravitational field intensity M 0 L1T 2
6 Thrust, force, weight, energy gradient M 1 L1T 2
7 Angular momentum and Planck’s constant M 1L2 T 1
8 Surface tension, Surface energy (energy per unit area) M 1L0 T 2
Strain, refractive index, relative density, angle, solid
9 angle, distance gradient, relative M0 L0T0
permittivity (dielectric constant), relative permeability
etc.
10 Latent heat and gravitational potential M 0 L2 T 2
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
11 Thermal capacity, gas constant, Boltzmann constant and M 0 L2 T 2 1
entropy
l / g, m/ k, R / g where l = length M 0 L0 T1
12
g = acceleration due to gravity, m = mass, k = spring
constant
LC , RC where L = inductance, R = resistance, C = M 0 L0 T1
L/R,
13
capacitance
V2 q2
I2Rt, t, VIt, qV, LI2 , , CV2
R C ML2T 2
14 where I = current, t = time, q = charge,
L = inductance, C = capacitance, R = resistance
Application of Dimensional Analysis
To find the unit of a physical quantity in a given system of units:
Writing the definition or formula for the physical quantity we find its dimensions. Now
in the dimensional formula replacing M, L and T by the fundamental units of the
required system we get the unit of physical quantity. However, sometimes to this unit
we further assign a specific name, e.g. Work = Force Displacement
W MLT 2 L ML2 T 2
Therefore, its units in C.G.S. system is gcm2 /s2 . It is also called as “erg”, while in M.K.S.
system its unit is kgm2 / s2 , called as “joule”.
Examples
a
Q.1 The equation P V b constant. The units of a is
V2
(a) Dynecm5 (b) Dynecm4 (c) Dynecm3 (d) Dynecm2
a
Sol: According to the principle of dimensional homogeneity P
V
2
a P V 2 ML1T 2 L6 ML5 T 2
orunitof a gmcm2 sec2 Dynecm4
Ans: b
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
Q.2 If x at bt 2 where x is the distance travelled by the body in kilometer while t
is the time in seconds, then the units of b are
(a) km/s (b) km-s (c) km / s 2 (d) km s 2
Sol: From the principle of dimensional homogeneity
x bt 2 b
x
2
Unit of b km / s2 .
t
Ans: c
To find dimension of physical constant or coefficient:
As dimensions of a physical quantity are unique, we write any formula or equation
incorporating the given constant and then by substituting the dimensional formulae
of all other quantities, we can find the dimensions of the required constant or
coefficient.
(i) Gravitational constant: According to Newton’s law of gravitation
m1m 2 Fr 2
FG or G
r2 m1m 2
Substituting the dimensions of all physical quantities
MLT2 L2
G M1L3T2
M M
E
(ii) Planck constant: According to Planck E hV or h
v
ML2T2
Substituting the dimensions of all physical quantities h ML2T1
T
1
(iii) Coefficient of viscosity: According to Poiseuille’s formula
dV p r 4 p r4
or
dt 8l 8l dV / dt
Substituting the dimensions of all physical quantities
ML1T 2 L4
ML1T 1
L L / T
3
Examples
Q.1 If X 3YZ , find the dimension of Y in (MKSA) system, Where X and Z are the
2
dimension of capacity and Magnetic field respectively
(a) M 3 L2 T 4 A 1 (b) ML2 (c) M 3 L2 T 4 A 4 (d) M 3L2T8 A 4
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
Sol: X 3YZ 2
Y 2
X
M 1L2 T 4 A 2
M 3 L2 T 8 A 4
Z 2 1 2
MT A
Ans: d
1
Q.2 Dimensions of where symbols have their usual meaning, are
0 0
(a) LT1 (b) L1T (c) L2 T 2 (d) L2 T 2
1 1
Sol: We know that velocity of light C C2
0 0 0 0
1 1 2
LT L T
2 2
0 0
Ans: d
To convert a physical quantity from one system to the other:
The measure of a physical Quantity is nu = constant
If a physical quantity X has dimensional formula Ma LbTc and if (derived) units of that
physical quantity in two systems are M1a Lb1T1c and M a2 Lb2 T2c respectively and n1 and n 2
be the numerical values in the two systems respectively, then
n1 u1 n 2 u 2
n1 M1a Lb1T1c n 2 M a2 Lb2T2c
a b c
M L T
n2 n1 1 1 1
M2 L2 T2
Where M1,L1 andT1 are fundamental units of mass, length and time in the first (known)
system and M2,L2 andT3 are fundamental units of mass, length and time in the second
(unknown) system. Thus knowing the values of fundamental units in two systems and
numerical value in one system, the numerical value in other system may be evaluated.
Example:
(1) Conversion of Newton into Dyne
The Newton is the S.I. unit of force and has dimensional formula MLT 2
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
So1N 1kg m / sec2
a b c 1 1 2 1 1 2
M L T kg m sec 103 gm 102 cm sec
By using n 2 n1 1 1 1 1 1 cm sec 10
5
M L T
2 2 2 gm
cm sec gm
1N 10 Dyne
5
(2) Conversion of gravitational constant (G) from C.G.S. to M.K.S. system
The value of G in C.G.S. system is 6.67 10 8 units while its dimensional formula is
M 1L3T 2
So,G 6.67 108 cm3 / g s 2
a b c 1 3 2
M L T gm cm sec
By using n 2 n1 1 1 1 6.67 108
M 2 L2 T2 kg m sec
1 3 2
gm cm sec
6.67 108 3 2 6.67 1011
10 gm 10 cm sec
G 6.67 1011 M.K.Sunits
Examples
Q.1 A physical quantity is measured and its value is found to be nu where
n=numerical value and u =unit. Which of the following relations is true?
1
(a) n u2 (b) n u (c) n u (d) n
u
1
Sol: We know P nu constant n 1 u 1 n 2 u 2 or n .
u
Ans: d
Q.2 In C.G.S. system, the magnitude of the force is 100 dynes. In another system
where the fundamental physical quantities are kilogram, meter and minute, the
magnitude of the force is
(a) 0.036 (b) 0.36 (c) 3.6 (d) 36
Sol:
n 1 100, M 1 g, L1 cm, T1 sec and M 2 kg, L 2 meter, T2 minute,
x = 1, y = 1, z = 2
By substituting these values in the following conversion formula
x y z
M L T
n 2 n1 1 1 1
M2 L2 T2
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
1 1 2
gm cm sec
n 2 100 meter minute
kg
1 1 2
gm cm sec
n 2 100 3 2 3.6
10 kg 10 meter 60 minute
Ans: c
To check the dimensional correctness of a given physical relation:
This is based on the ‘principle of homogeneity’. According to this principle, the
dimensions of each term on both sides of an equation must be the same.
If X A BC DEF,
2
Then according to principle of homogeneity
X A BC2 DEF
If the dimensions of each term on both sides are same, the equation is dimensionally
correct, otherwise not. A dimensionally correct equation may or may not be physically
correct.
Example:
mv 2
(1) F
r2
By substituting dimension of the physical quantities in the above relation –
MLT2 M LT1 / L
2 2
i.e. MLT2 MT2
As in the above equation, dimensions of both sides are not same; this formula is not
correct dimensionally, so can never be physically.
(2) S ut 1 at 2
2
By substituting dimension of the physical quantities in the above relation –
L LT1 T LT2 T2
i.e. L L L
As in the above equation, dimensions of each term on both sides are same, so this
equation is dimensionally correct.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
Examples
Q.1 From the dimensional consideration, which of the following equation is
correct?
R3 GM GM R2
(a) T 2 (b) T 2 (c) T 2 (d) T 2
GM R3 R2 GM
Sol:
R3 R3 R
T 2 2 2 As GM gR 2
GM gR 2 g
Now, by substituting the dimension of each quantity in both sides.
1/ 2
T 2
L
T
LT
L.H.S. = R.H.S. i.e., the above formula is Correct.
Ans: a
Q.2 A highly rigid cubical block A of small mass M and side L is fixed rigidly onto
another cubical block B of the same dimensions and of low modulus of rigidity
such that the lower face of A completely covers the upper face of B. The lower
face of B is rigidly held on a horizontal surface. A small force F is applied
perpendicular to one of the side faces of A. After the force is withdrawn block,
A executes small oscillations. The time period of which is given by
M L ML M
(a) 2 (b) 2 (c) 2 (d) 2
L M L
Sol: Given m mass M , coefficient of rigidity ML1T 2 , L length L
By substituting the dimension of these quantities, we can check the accuracy
of the given formulas
M
1/2 1/2
M
T 2 1 2 T
L ML T L
L.H.S. = R.H.S. i.e., the above formula is Correct.
Ans: d
As a research tool to derive new relations:
If one knows the dependency of a physical quantity on other quantities and if the
dependency is of the product type, then using the method of dimensional analysis,
relation between the quantities can be derived.
Example:
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
(i) Time period of a simple pendulum:
Let time period of a simple pendulum is a function of mass of the bob (m), effective
length (l), acceleration due to gravity (g) then assuming the function to be product of
x
power function of m, l and g i.e., T K m y g z ; where K = dimensionless constant
If the above relation is dimensionally, correct then by substituting the dimensions of
quantities
T M L
x y z
LT 2
or M 0 L0T1 M x Lyz T 2z
Equating the exponents of similar quantities x 0, y 1 and z – 1
2 2
1
So the required physical relation becomes T K
g
The value of dimensionless constant is found ( 2π ) through experiments. Therefore,
1
T 2
g
(ii) Stoke’s law: When a small sphere moves at low speed through a fluid, the viscous
force F, opposing the motion, is found experimentally to depend on the radius r, the
velocity of the sphere and the viscosity of the fluid. So, F f ,r,
If the function is product of power functions of , r and ,
F Kxryvz; Where K is dimensionless constant.
If the above relation is dimensionally correct
L
x y z
M LT 2 M L 1T 1 LT 1
Or MLT 2 M x L x y z T x z
Equating the exponents of similar quantities
x 1; – x y z 1 and – x – z –2
Solving these for x, y and z, we get x y z 1
Therefore, F = K r
On experimental grounds, K = 6π ;
So, F = 6π r
This is the famous Stoke’s law.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
Examples
Q.1 If the velocity of light (c), gravitational constant (G) and Planck's constant (h)
are chosen as fundamental units, then the dimensions of mass in new system is
(a) c1/ 2 G1/ 2 h1/2 (b) c1/2 G1/ 2 h 1/2 (c) c1/2 G 1/ 2 h1/2 (d) c 1/2 G1/ 2 h1/2
Sol: Let m cxGyhz or m KcxGyhz
By substituting the dimension of each quantity in both sides
x y z
M 1L0 T 0 K LT 1 M 1 L3 T 2 ML2 T 1 M y z Lx 3 y 2 z T x 2 y z
By equating the power of M, L and T in both sides:
y z 1, x 3y 2z 0, x 2y z 0
1 1 1
By solving above three equations x , y and z .
2 2 2
m c 1/ 2 G 1/ 2 h 1/ 2
Ans: c
Q.2 If the time period (T) of vibration of a liquid drop depends on surface tension
(S), radius (r) of the drop and density () of the liquid, then the expression of
T is
(a) T K r 3 / S (b) T K 1/ 2 r 3 / S
(c) T K r 3 / s1/2 (d) None of these
Sol:
LetT Sxryz orT LSxryz
By substituting the dimension of each quantity in both sides
L
x y z
M 0 L0 T 1 K MT 2 M L3 M x z Ly 3z T 2 x
By equating the power of M, L and T in both sides x z 0, y 3z 0, 2x 1
By solving above three equations x 1 / 2, y 3 / 2, z 1 / 2
r 3
Therefore, the time period can be given as, T KS1/2 r 3/21/2 K .
S
Ans: a
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
Limitations of Dimensional Analysis
Although dimensional analysis is very useful it cannot lead us too far as,
(1) If dimensions are given, physical quantity may not be unique as many physical
quantities have same dimensions. For example, if the dimensional formula of a
physical quantity is ML2T 2 it may be work, energy or torque.
1
(2) Numerical constant having no dimensions [K] such as ,1 or π etc. cannot
2
be deduced by the methods of dimensions.
(3) The method of dimensions can not be used to derive relations other than
product of power functions. For example, s ut 1/ 2 at or y asin t can not
2
be derived by using this theory (try if you can). However, the dimensional
correctness of these can be checked.
(4) The method of dimensions cannot be applied to derive formula if in mechanics
a physical quantity depends on more than 3 physical quantities as then there
will be less number (= 3) of equations than the unknowns (>3). However still
we can check correctness of the given equation dimensionally. For example
T 2 1/ mgl can not be derived by theory of dimensions but its dimensional
correctness can be checked.
(5) Even if a physical quantity depends on 3 physical quantities, out of which two
have same dimensions, the formula cannot be derived by theory of dimensions,
e.g., formula for the frequency of a tuning fork f d / L2 v cannot be derived
by theory of dimensions but can be checked.
Significant Figures
Significant figures in the measured value of a physical quantity tell the number of
digits in which we have confidence. Larger the number of significant figures obtained
in a measurement, greater is the accuracy of the measurement. The reverse is also true.
The following rules are observed in counting the number of significant figures in a
given measured quantity.
(1) All non-zero digits are significant.
Example: 42.3 has three significant figures.
243.4 has four significant figures.
24.123 has five significant figures.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
(2) A zero becomes significant figure if it appears between to non-zero digits.
Example: 5.03 has three significant figures.
5.604 has four significant figures.
4.004 has four significant figures.
(3) Leading zeros or the zeros placed to the left of the number are never significant.
Example: 0.543 has three significant figures.
0.045 has two significant figures.
0.006 has one significant figures.
(4) Trailing zeros or the zeros placed to the right of the number are significant.
Example: 4.330 has four significant figures.
433.00 has five significant figures.
343.000 has six significant figures.
(5) In exponential notation, the numerical portion gives the number of significant
figures.
Example: 1.32 10 2 has three significant figures.
1.3 2 10 4 has three significant figures.
Rounding Off
While rounding off measurements, we use the following rules by convention:
(1) If the digit to be dropped is less than 5, then the preceding digit is “left
unchanged”.
Example: x = 7.82 is rounded off to 7.8, again x = 3.94 is rounded off to 3.9
(2) If the digit to be dropped is more than 5, then the preceding digit is “raised by
one”.
Example: x = 6.87 is rounded off to 6.9, again x = 12.78 is rounded off to 12.8
(3) If the digit to be dropped is 5 followed by digits other than zero, then the
preceding digit is raised by one.
Example: x = 16.351 is rounded off to 16.4, again x = 6.758 is rounded off to 6.8
(4) If digit to be dropped is 5 or 5 followed by zeros, then preceding digit is left
unchanged, if it is even.
Example: x = 3.250 becomes 3.2 on rounding off, again x = 12.650 becomes 12.6
on rounding off.
(5) If digit to be dropped is 5 or 5 followed by zeros, then the preceding digit is
raised by one, if it is odd.
Example: x = 3.750 is rounded off to 3.8, again x = 16.150 is rounded off to 16.2.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
Significant Figures in Calculation
In most of the experiments, the observations of various measurements are to be
combined mathematically, i.e., added, subtracted, multiplied or divided as to achieve
the result. Since, not all the observations in measurements have the same precision, it
is natural that the final result cannot be more precise than the least precise
measurement. The following two rules should be followed to obtain the proper number
of significant figures in any calculation.
(1) The result of an addition or subtraction in the number having different
precisions should be reported to the same number of decimal places as are
present in the number having the least number of decimal places. The rule is
illustrated by the following
Examples:
i 33.3 has only one decimal place
3.11
0.313
36.723 answer should be reported to one decimal place
Ans : 36.7
ii 3.1421
0.214
0.09 has 2 decimal places
3.4731 answer should be reported to 2 decimal places
Ans: 3.47
iii 62.831 has 3 decimal places
24.5492
answer should be reported to 3 decimal
38.2818
places after rounding off
Ans: 38.282
(2) The answer to a multiplication or division is rounded off to the same number of
significant figures as is possessed by the least precise term used in the
calculation. The rule is illustrated by the following examples:
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
i 142.06
0.23 (two significant figures)
32.6738 (answer should have two significant figures)
Ans : 33
ii 51.028
1.31 three significant figures
66.84668
Ans : 66.8
0.90
iii 0.2112676
4.26
Ans : 0.21
Order of Magnitude
In scientific notation the numbers are expressed as, Number Where M is a number lies
between 1 and 10 and x is integer. Order of magnitude of quantity is the power of 10
required to represent the quantity. For determining this power, the value of the
quantity has to be rounded off. While rounding off, we ignore the last digit which is
less than 5. If the last digit is 5 or more than five, the preceding digit is increased by
one. For example
(1) Speed of light in vacuum
(2) Mass of electron
Examples
Q.1 Each side a cube is measured to be 7.203 m. The volume of the cube (in m3 ) up
to appropriate significant figures is
(a) 373.714 (b) 373.71 (c) 373.7 (d) 373
Volume a 3 7.023 373.715m 3
3
Sol:
In significant figures, volume of cube will be 373.7 m3 because its side has four
significant figures.
Ans: c
Q.2 The number of significant figures in 0.007 m2 is
(a) 1 (b) 2 (c) 3 (d) 4
Ans: a
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
Q.3 The length, breadth and thickness of a block are measured as 125.5 cm, 5.0 cm
and 0.32 cm respectively. Which one of the following measurements is most
accurate?
(a) Length (b) Breadth (c) Thickness (d) Height
Sol: Relative error in measurement is minimum, if quantity is minimum. Therefore,
measurement of thickness is most accurate.
Ans: c
Q.4 The mass of a box is 2.3 kg. Two marbles of masses 2.15 g and 12.39 g are added
to it. The total mass of the box to the correct number of significant figures is
(a) 2.340 kg (b) 2.3145 kg (c) 2.3 kg (d) 2.31 kg
Sol: Total mass = 2.3 + 0.00215 + 0.01239 = 2.31 kg
Total mass in appropriate significant figures be 2.3 kg.
Ans: c
Q.5 The length of a rectangular sheet is 1.5 cm and breadth is 1.203 cm. The area of
the face of rectangular sheet to the correct no. of significant figures is:
(a) 1.8045cm2 (b) 1.804cm2 (c) 1.805cm
2
(d) 1.8cm2
Sol: Area 1.5 1.203 1.8045cm2 1.8cm2 Upto correct number of significant figure .
Ans: d
Q.6 Each side of a cube is measured to be 5.402 cm. The total surface area and the
volume of the cube in appropriate significant figures are:
(a) 175.1cm2 ,157cm2 (b) 175.1cm2 ,157.6cm3
2
(c) 175cm ,157cm2 (d) 175.08cm2 ,157.639cm2
Sol: Upto correct number of significant figure
Total surface area 6 5.402 175.09 cm 2 175.1cm 2
2
Total volume 5.402 175.64 cm 3 175.6 cm 3
3
Q.7 Taking into account the significant figures, what is the value of 9.99 m + 0.0099
m?
(a) 10.00 m (b) 10 m (c) 9.9999 m (d) 10.0 m
Sol:
9.99 m + 0.0099 m = 9.9999 m = 10.00 m (In proper significant figures)
Ans: a
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
Q.8 The value of the multiplication 3.124 4.576 correct to three significant
figures is
(a) 14.295 (b) 14.3 (c) 14.295424 (d) 14.305
Sol:
3.124 4.576 14.295 14.3 (Correct to three significant figures).
Ans: b
6
Q.9 The number of the significant figures in 11.118 10 V is
(a) 3 (b) 4 (c) 5 (d) 6
6
Sol: The number of significant figure is 5 as 10 does not affect this number.
Ans: c
Q.10 If the value of resistance is 10.845 ohms and the value of current is 3.23
amperes, the potential difference is 35.02935 volts. Its value in significant
number would be
(a) 35 V (b) 35.0 V (c) 35.03 V (d) 35.025 V
Sol: Value of current (3.23 A) has minimum significant figure (3) so the value of
potential difference V (=IR) have only 3 significant figure. Hence, its value be
35.0 V.
Ans: c
Errors of Measurement
The measuring process is essentially a process of comparison. In spite of our best
efforts, the measured value of a quantity is always somewhat different from its actual
value, or true value. This difference in the true value of a quantity is called error of
measurement.
(1) Absolute error:
Absolute error in the measurement of a physical quantity is the magnitude of
the difference between the true value and the measured value of the quantity.
Let a physical quantity be measured n times. Let the measured value be a1 , a 2 , a 3 ,......a n .
a 1 a 2 ....a n
The arithmetic mean of these values is a m
n
Usually, a m is taken as the true value of the quantity, if the same is unknown otherwise.
By definition, absolute errors in the measured values of the quantity are
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
a 1 a m a 1
a 2 a m a 2
............
a n a m a n
The absolute errors may be positive in certain cases and negative in certain other cases.
(2) Mean absolute error:
It is the arithmetic mean of the magnitudes of absolute errors in all the
measurements of the quantity. It is represented by a .
Thus;
a1 a 2 .... a n
a
n
Hence, the result of measurement may be written as a a m a
This implies that any measurement of the quantity is likely to lie between
a m
a and a m a
(3) Relative error or Fractional error:
The relative error or fractional error of measurement is defined as the ratio of
mean absolute error to the mean value of the quantity measured.
Thus,
mean absolute error a
Relative error or Fractional error =
mean value am
(4) Percentage error:
When the relative/fractional error is expressed in percentage, we call it
percentage error.
Thus;
a
Percentageerror 100%
am
Propagation of Errors
(1) Error in sum of the quantities: Suppose x = a + b
Let a = absolute error in measurement of a
b = absolute error in measurement of b
x = absolute error in calculation of x i.e. sum of a and b.
The maximum absolute error in x is x = ±( a + b)
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
a b 100%
Percentage error in the value of x
a b
(2) Error in difference of the quantities: Suppose x = a – b
Let a = absolute error in measurement of a,
b = absolute error in measurement of b
x = absolute error in calculation of x i.e. difference of a and b.
The maximum absolute error in x is x = ±( a + b)
a b 100%
Percentage error in the value of x
a b
(3) Error in product of quantities: Suppose x a b
Let a = absolute error in measurement of a,
b = absolute error in measurement of b
x = absolute error in calculation of x i.e. product of a and b.
x a b
The maximum fractional error in x is
x a b
Percentage error in the value of x
= (Percentage error in value of a) + (Percentage error in value of b)
a
(4) Error in division of quantities: Suppose x
b
Let a = absolute error in measurement of a,
b = absolute error in measurement of b
x = absolute error in calculation of x i.e. division of a and b.
x a b
The maximum fractional error in x is
x a b
Percentage error in the value of x = (Percentage error in value of a) +
(Percentage error in value of b)
am
(5) Error in quantity raised to some power: Suppose x
bn
Let a = absolute error in measurement of a,
b = absolute error in measurement of b
x = absolute error in calculation of x
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Unit and Dimensions
x a b
The maximum fractional error in x is m n
x a b
Percentage error in the value of x
= m (Percentage error in value of a) + n (Percentage error in value of b)
Note: The quantity that have maximum power must be measured carefully because
its contribution to error is maximum
Examples
Q.1 A physical parameter a can be determined by measuring the parameters b, c, d
and e using the relation a b c / d e . If the maximum errors in the
measurement of b, c, d and e are b1%, c1%, d1% and e1%, then the maximum
error in the value of a determined by the experiment is
(a) b1 c1 d1 e1 % (b) b1 c1 d1 e1 %
(c) b1 c1 d1 e1 % (d) b1 c1 d1 e1 %
Sol: a b c / d e
So, maximum error in a is given by
a b c d e
100 100 100 100 100
a max b c d e
b1 c1 d1 e1 %
Ans: d
Q.2 The pressure on a square plate is measured by measuring the force on the plate
and the length of the sides of the plate. If the maximum error in the
measurement of force and length are respectively 4% and 2%, the
maximum error in the measurement of pressure is
(a) 1% (b) 2% (c) 6% (d) 8%
F F
Sol: P , so maximum error in pressure (P)
A l2
P F l
100 100 2 100 4% 2 2% 8%
P max F l
Ans: d
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
2 CHEMICAL CALCULATIONS AND GAS LAWS
Introduction
All matter is made of particles. At one time, it was thought that the tiniest particle was
the atom; the word comes from the Greek word meaning ‘indivisible’.
We now know that atoms can be split and that there are smaller particles than atoms,
the so-called sub-atomic particles, electrons, protons and neutrons. You will need to
know something about these particles, which make up the different kinds of atoms.
However, you must understand that chemistry is all about rearrangements of atoms
that do not themselves change.
Atoms are very small. The hydrogen atom, the smallest and lightest of all atoms, has a
diameter of about 120 pm. 1 g of hydrogen contains about 6.02 1023 atoms. It is
very difficult to ‘see’ an individual atom and to find its mass.
An atom is the smallest, electrically neutral, particle of an element that
can take part in a chemical change.
A molecule is the smallest, electrically neutral, particle of an element or
compound that can exist on its own.
An ion is an atom, or group of atoms, which carries an electric charge.
You need to know these definitions by heart, but you also need to be able to recognize
the formulae of atoms and molecules when you see them. Li, O, Cl, C are all formulae
which represent atoms. Some of these can exist on their own, but not all of them.
Oxygen, for example, always exists as oxygen molecules, O2, which contain two atoms,
unless it is combined with something else. Water contains only one atom of oxygen but
here it is combined with two hydrogen atoms.
Make sure that you really understand these ideas:
• A single oxygen atom, O, cannot exist on its own
• A single oxygen atom can exist when it is combined with something else, but then it
is part of a molecule
• An oxygen molecule O2 has two oxygen atoms
• A few elements exist as single atoms: for these elements, an atom is the same as a
molecule.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Structure of the atom
The atom is composed of electrons, neutrons and protons. You have to remember the
relative mass of, and the electric charge on, each.
The atom is mostly empty space. It has a solid core or nucleus, the center that contains
the protons and neutrons. The electrons circulate round the nucleus in specific orbits
or shells.
We can picture the hydrogen atom - the simplest of all atoms with one electron, and
one proton in the nucleus - by considering a pea placed in the center of a football pitch,
to represent the nucleus with its proton. On this scale the electron will revolve in a
circular orbit round the goal posts. Between the electron and the nucleus is empty
space.
Atoms are the particles whose symbols are found in the periodic table given on next
page
You can see there are only about 100 of them. The middle part of the atom, the nucleus,
contains one or more protons. It is the number of protons that make the atom what it
is. An atom with one proton is always a hydrogen atom; one with two protons is a
helium atom and so on.
There are more substances in the world than the 100 or so different kinds of atom. The
other substances are made by combining atoms in various ways to make molecules.
When a chemical reaction takes place the atoms are rearranged to make different
molecules but no atoms can be made or destroyed. To show this you have to be able to
find a method of counting the atoms that take part in a reaction and its products.
The mass of an individual atom is very small and it is much more convenient to
measure atomic masses as relative masses.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
The mole
When chemists measure how much of a particular chemical reacts, they measure the
amount in grams; or they measure the volume of a gas. However, chemists find it
convenient to use a unit called a mole. You need to know several definitions of a mole
and be able to use them.
• The mole is the amount of substance, which contains the same number of particles
(atoms, ions, molecules, formulae or electrons) as there are carbon atoms in 12 g of
carbon -12
• This number is known as the Avogadro constant, L, and is equal to
6.02 10 23 mol –1 .
• The molar mass of a substance is the mass (in grams) of one mole of that substance.
• The molar volume of a gas is the volume occupied by one mole at room
temperature and atmospheric pressure (r.t.p). It is equal to 24 dm 3 at room
temperature and atmospheric pressure (r.t.p).
Avogadro’s Law
It states that equal volumes of all gases, under the same conditions of temperature and
pressure contain the same number of moles or molecules.
When you talk about moles, you must always state whether you are dealing with atoms,
molecules, ions, formulae etc.
Relative atomic mass A r :
The mass of a single atom on a scale on which the mass of an atom of carbon-12 has a
mass of 12 atomic mass units. The relative atomic mass does not have units.
The Difference between Atomic Weight and Atomic Mass
Atomic mass (ma) is the mass of an atom. A single atom has a set number of protons
and neutrons, so the mass is unequivocal (won't change) and is the sum of the number
of protons and neutrons in the atom. Electrons contribute so little mass that they
aren't counted.
Atomic weight is a weighted average of the atomic mass of all natural isotopes of an
element.
Both atomic mass and atomic weight rely on the atomic mass unit (a.m.u), which is
1/12th the mass of an atom of carbon-12 in its ground state.
Atomic Mass of Carbon is 12 a.m.u
Atomic Weight of Carbon is 12.0107 a.m.u
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Molecular weight of a compound is the sum of the atomic weights of atoms that
constitutes a molecule of the compound.
Molecular weight of CO2 112 2 16 44 a.m.u
Equivalent weight is defined as the ratio of atomic weight or molecular weight to its
valence. The valence of an element or a compound depends on the hydroxyl ions
OH donated
or the hydrogen ions H
accepted for each atomic weight or
molecular weight.
Gram Atom: It is used to specify the amounts of chemical elements. It is defined as
the mass in grams of an element which is numerically equal to its atomic weight.
Gram Mole: It is used to specify the amounts of chemical compounds. It is defined
as the mass in gram of a substance which is numerically equal to its molecular weight.
Relative Molecular Mass or Molar Mass M r :
The mass of a single molecule on a scale on which the mass of an atom of carbon-12
has a mass of 12 atomic mass units.
Relative Molecular Mass or Molar Mass of a molecule is calculated by adding together
the relative atomic masses of the atoms in the chemical formulae.
• The molar mass of a substance is the mass (in grams) of one mole of that substance.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Relative formula mass:
In many ways this is more accurate than Relative Molecular Mass. Many salts, even in
the solid state, exist as ions rather than molecules. Although the formula of sodium
chloride is normally given as NaCl, it is not a simple molecule but a giant lattice and it
is more accurately written as Na C l – . Since this compound does not have
n
molecules, it cannot have relative ‘molecular’ mass. However, the principle is the
same: add the relative atomic masses of sodium (23) and chlorine (35.5) to give 58.5,
the relative formula mass of NaCl.
Note: Relative atomic mass, Molar Mass and relative formula mass have
no units
Calculations involving the use of moles:
(1) Calculation of the number of moles of material in a given mass of
that material:
Examples
Q.1 Calculate the number of moles of oxygen atoms in 64 g of oxygen atoms.
(a) 2 (b) 4 (c) 8 (d) 16
Sol:
You need the mass of one mole of oxygen atoms. This is the Relative Atomic
–1
Mass in grams; in this case it is 16 g mol .
Ans: d
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Q.2 Calculate the number of moles of chlorine molecules in 142 g of chlorine gas.
(a) 2 (b) 4 (c) 8 (d) 16
Sol:
The first stage of this calculation is to calculate the molar mass of Chlorine
Molar mass of Cl2 235.5 71 g mol
–1
molecules.
Ans: a
Q.3 Calculate the number of moles of CuSO4 5H2O in 100 g of the solid.
(a) 2.008 (b) 4.008 (c) 8.008 (d) 16.0008
Sol:
The Relative Molecular Mass of CuSO4 5H2O
63.5 32 4 16 5{ 2 1 16} 249.5 g mol –1
Ans: b
(2) Calculation of the mass of material in a given number of moles of
that material:
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Examples
Q.1 Calculate the mass of 3 moles of Sulphur dioxide SO2
(a) 190 g (b) 46 g (c) 192 g (d) 146 g
Sol:
1 mole of Sulphur dioxide has a mass 32 2 16 64 g mol
–1
3 moles of SO2 364 192 g
Ans: c
Q.2 What is the mass of 0.05 moles of Na2S2O3 5H2O ?
(a) 2.4 g (b) 4.8 g (c) 12.4 g (d) 16.8 g
Sol:
1 mole of
Na 2S2O3 5H 2O = 23 2 32 2 16 3 5 2 1 16 248 g mol –1
0.05 moles of Na2S2O3 5H2O 0.05248 12.4 g
Ans: c
(3) Calculation of the volume of a given number of moles of a gas:
1 mole of any gas has a volume of 24 dm 3 24000 cm 3 at room temperature and
pressure.
Examples
Q.1 What is the volume of 2 mol of carbon dioxide?
(a) 12 dm 3 (b) 24 dm 3 (c) 36 dm 3 (d) 48 dm 3
Sol:
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Remember you do not need to work out the molar mass to do this calculation,
as it does not matter what gas it is.
2 moles of CO2 2 24000 cm3 48000 cm3 48 dm3
Ans: d
Q.2 What is the volume of 0.0056 moles of chlorine molecules?
(a) 134.4 cm 3 (b) 13.4 cm 3 (c) 34.4 cm 3 (d) 13.4 cm 3
Sol:
Volum e of 0.0056 moles of chlorine 0.0056 24000 cm 3 134.4 cm 3
Ans: a
(4) Calculation of the number of moles of gas in a given volume of that
gas:
Examples
Q.1 Calculate the number of moles of hydrogen molecules in 240 cm 3 of the gas.
(a) 0.010 (b) 0.012 (c) 0.101 (d) 1.010
Sol:
Ans: a
Q.2 How many moles of a gas are there in 10 00 cm 3 of the gas?
(a) 0.0142 (b) 0.0154 (c) 0.0147 (d) 0.0247
Sol:
Ans: c
(5) Calculation of the volume of a given mass of gas:
This calculation require you to apply the skills covered in the previous examples
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Example
3
Q.1 Calculate the volume (in dm ) of 10 g of hydrogen gas.
(a) 12 (b) 120 (c) 1200 (d) 1.2
Sol:
This is a two-stage calculation
a) You need to calculate how many moles of hydrogen gas are present, and
b) You need to convert this to a volume.
Ans: b
(6) Calculation of the mass of a given volume of gas:
This calculation require you to apply the skills covered in the previous examples
Example
Q.1 Calculate the mass (in gram) of 1000 cm 3 of carbon dioxide.
(a) 1.288 (b) 2.83 (c) 3.283 (d) 1.833
Sol:
Again this is a two-stage calculation
a) You need to calculate the number of moles of carbon dioxide and then
b) Convert this to a mass.
Ans: d
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
(7) Calculation of the molar mass of a gas from mass and volume data
for the gas:
Calculations of this type require you to find the mass of 1 mole of the gas, i.e.
24000 cm 3 . This is the molar mass of the gas.
Example
Q.1 Calculate the Relative Molecular Mass of a gas for which 10 0 cm 3 of the gas at
room temperature and pressure, have a mass of 0.0667 g.
(a) 16 g mol1 (b) 8 g mol1 (c) 4 g mol1 (d) 2 g mol1
Sol:
Ans: a
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Basics of Concentration
Concentration Units
The concentration of a chemical substance expresses the amount of a substance
present in a mixture. There are many different ways to express concentration.
Chemists use the term solute to describe the substance of interest and the
term solvent to describe the material in which the solute is dissolved. For example,
in a can of soda pop (a solution of sugar in carbonated water), there are approximately
twelve tablespoons of sugar (the solute) dissolved in the carbonated water (the
solvent). In general, the component that is present in the greatest amount is termed
the solvent.
There are many ways to express concentrations. Some of the more common
concentration units are:
Mass per unit volume: Mass per unit volume is handy when discussing how soluble
a material is in water or a particular solvent. For example, "the solubility of substance
X is 3 grams per liter".
Commonly used Mass per unit volume units are milligrams per milliliter (mg/mL) or
milligrams per cubic centimeter mg/cm3 . Note that 1 mL 1 cm 3 and that cm 3 is
sometimes denoted as a "cc”.
Percent by mass: It is also called as weight percent or percent by weight, this is
simply the mass of the solute divided by the total mass of the solution and multiplied
by 100%
Example: A solution consisting of 30 grams of sodium chloride and 70 grams of
water would be 30% sodium chloride by mass:
To avoid confusion whether a solution is percent by weight or percent by volume, the
symbol "w/w" (for weight to weight) is often used after the concentration such as "10%
potassium iodide solution in water (w/w)".
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Percent by volume: It is also called volume percent or percent by volume, this is
typically only used for mixtures of liquids. Percent by volume is simply the volume of
the solute divided by the sum of the volumes of the other components multiplied by
100%.
If we mix 30 mL of ethanol and 70 mL of water, the percent ethanol by volume will be
30% BUT the total volume of the solution will NOT be 100 mL (although it will be
close). That's because ethanol and water molecules interact differently with each other
than they do with themselves.
To avoid confusion whether we have a percent by weight or percent by volume
solution, we could label this as "30% ethanol in water (v/v)" where v/v stands for
"volume to volume".
Molarity: Molarity is the number of moles of solute dissolved in one liter of solution.
Examples
Q.1 What is the molarity of a solution if 1.47 moles of sugar is dissolved into 2.31 L
of solution?
moles moles moles moles
(a) 0.636 (b) 0.236 (c) 0.436 (d) 0.836
L L L L
Sol:
1.47 moles of sugar moles
Molarity M 0.636
2.31 litres of solution L
Ans: a
Q.2 How many grams of NaCl will be needed to make 1.50 Liters of an aqueous
0.500 M solution?
(a) 43.8g (b) 23.4 g (c) 0 .4 38 g (d) 0 .3 8 6 g
Sol:
The equation for Molarity must be rearranged to solve for the moles of solute
(NaCl). The moles of solute can then be converted into grams.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
moles
moles of solute Molarity L of solution
L
0.500 1.5 0.750 moles
Now, convert the moles of solute into grams by using the molar mass of NaCl.
gram
grams of NaCl 0.750 moles 22.99 35.45 43.8 gram
mole
Ans: a
Molality: Molality is the number of moles of solute dissolved in one kilogram of
solvent.
Note: Notice the two key differences between molarity and molality. Molality uses
mass rather than volume and uses solvent instead of solution.
Example
Q.1 Determine the molality of a solution prepared by dissolving 28.60 g of glucose
C6 H12 O 6 into 250 g of water.
(a) 0.35 m (b) 0.23 m (c) 0.463 m (d) 0.635 m
Sol:
mass of solute 28.60 g C 6 H12 O 6
molar mass of C 6 H12 O 6 180.18 g / mol
28.60
Number of moles of C 6 H12 O 6 in 28.60 g mole 0.1587 mole
180.18
0.1587
Molality m 0.635m
0.250
Ans: d
Normality: It is the number of mole equivalents per liter of solution. The units are
given as eq/L or an italicized capital “N".
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Normality is generally only used when a substance has more than one sub-species that
can participate in a specified reaction such as a proton for acid/base reactions, an
electron for oxidation/reduction reactions, or in precipitation reactions.
For example, sulfuric acid has two ionizable protons H which can participate in the
neutralization of a base such as sodium hydroxide, NaOH:
H2SO4 (aq) 2 NaOH 2 Na (aq) 2 H2O SO42 (aq)
So if the concentration of our sulfuric acid solution is 1 M (mol/l) expressed as a
molarity then it is 2 N expressed as normality. We call these solutions 1 molar and 1
normal, respectively.
Example
Q.1 Find the normality of 0.1MH2SO4 (sulfuric acid) for the reaction:
H2SO4 2 NaOH Na2SO4 2 H2O
(a) 0.35 m (b) 0.23 m (c) 0.463 m (d) 0.635 m
Sol:
According to the equation, 2 moles of H ions (2 equivalents) from sulfuric acid
react with sodium hydroxide (NaOH) to form sodium sulfate (Na2SO4 ) and water.
Using the equation:
Normality M olarity Equivalents 0.1 2 0.2 N
Ans: d
Mass Percent: The mass percent is used to express the concentration of a solution
when the mass of a solute and the mass of a solution is given:
Volume Percent: The volume percent is used to express the concentration of a
solution when the volume of a solute and the volume of a solution is given:
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Mole Percent: The mole percent is used to express the concentration of a solution
when the mole of a solute and the mole of a solution is given:
Mole Fraction: The mole fraction, X, of a component in a solution is the ratio of
the number of moles of that component to the total number of moles of all
components in the solution.
To calculate mole fraction, we need to know the number of moles of each component
present in the solution.
The mole fraction of A, XA, in a solution consisting of A, B, C, ... is calculated using
the equation:
Parts per million (ppm): Parts per million works like percent by mass, but is more
convenient when there is only a small amount of solute present. PPM is defined as the
mass of the component in solution divided by the total mass of the solution multiplied
by 1 0 6 (one million).
Specific Gravity: It is the ratio of the density (mass of a unit volume) of a substance
to the density of a given reference material at a given temperature and pressure. For
liquid, reference material is taken as water and for gases reference material is taken as
Air. It is also known as Relative density.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Gas laws and its applications
The first substances to be produced and studied in high purity were gases. Gases are
more difficult to handle and manipulate than solids and liquids, since any minor
mistakes generally results in the gas escaping to the atmosphere. However, the ability
to produce gases in very high purity made the additional difficulty acceptable. The
most common way of producing a gas was by some sort of chemical reaction, and the
gas was collected by liquid displacement (either water or mercury).
Generally, gases have properties substantially different from solids or liquids. Gases
do not have fixed volumes; instead, their volume depends directly upon pressure and
temperature. Gases do not have a fixed shape, but are said to “take the shape of their
container”. Gases do have a fixed mass, although measuring the mass may be difficult
sometimes.
The properties of any gas generally, depends on Pressure, Volume, Temperature,
amount of gas etc.
What is Pressure?
Pressure is force per unit area, calculated by dividing the force by the area on which
F
the force acts. P=
A
The earth's gravity acts on air molecules to create a
force, that of the air pushing on the earth. This is
called atmospheric pressure.
The units of pressure that are used are Pascal (Pa),
standard atmosphere (atm), and torr. 1 atm is the
average pressure at sea level. It is normally used as a
standard unit of pressure. The SI unit though, is the
Pascal.
= 1 atm =
101.325 kPa =
760 torr 760 mm Hg
How do Gasses Exert Pressure?
Gas molecules are constantly moving in a random
pattern. The molecules are continuously collides with
each other and with the walls of the container. When
a molecule collides with the wall, they exert small
force on the wall. The pressure exerted by the gas is
due to the sum of all these collision forces. The more
particles that hit the walls, the higher the pressure.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Ideal Gas
An "ideal gas" is a gas in which
All collisions are totally elastic (particles always bounce off each other)
There are no intermolecular attractions (a particle can only change direction
when it collides with another particle)
The molecule is infinitely small (particles will come all the way together before
they collide)
What does this mean?
An ideal gas is a collection of super-small bouncy-balls that never stop bouncing.
There are three gas laws that can be used to determine how the pressure, volume, and
temperature of an ideal gas are related to each other.
Note: The Kelvin scale must be used for the gas laws.
Boyle's Law
Boyle's Law from 1662. Robert Boyle (1627-1691) was an Irish-born gentleman
philosopher who did research and investigation in physics, chemistry, alchemy, and
theology. Boyle was one of the original Fellows of the Royal Society. His opus magnum
is The Sceptical Chymist, 1661. Boyle concentrated intently on the quiet study of
science, rather than the wealth or praise he could have attained from his studies. Boyle
is known as the founder of modern chemistry because he believed in the intrinsic value
of chemistry, developed the rigorous experimental scientific method, and defined the
element. Boyle worked at Oxford University, along with Robert Hooke, who stated
Hooke's Law, relating the force of elasticity. Boyle, in his study of gas, conceptualized
the gas particle as a spring. He also expanded on the assumptions of René Descartes,
who said pressure is due to the "restless agitation" of the air particles. Boyle proved his
law for both great and small pressures, using the now-famous Mercury U-Tube
experiment. Boyle's study of gases also helped lead to the development of atomic
theory. He, along with others in his time, discussed the role of distinct "corpuscles" in
the application of his Law. He published what is now known as Boyle's Law in 1662.
“Boyle's law states that the volume of a given amount of gas held at
constant temperature varies inversely with the applied pressure when
the temperature and mass are constant.”
1
Mathematically; P or PV = C or P1V1 = P2 V2
V
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Graphical Representation of Boyle’s Law
Real World Applications
A car (combustion) engine works when the sudden increase in pressure from the
combustion of the fuel expands the cylinder and pushes on the piston, causing the
crankshaft to turn.
Boyle’s Law operates syringes and turkey basters: pulling back on the plunger
increases the volume inside the syringe, which decreases the pressure, which then
corrects when liquid is drawn into the syringe, thereby shrinking the volume again.
Spray cans, like spray paint and air freshener, are governed by Boyle's Law: intense
pressure inside the can pushes outward on the liquid inside the can, trying to
escape, and forces the liquid out when the cap makes an opening.
You breathe because of Boyle's Law.
Balloons work because of Boyle's Law.
Charles' Law
Charles' Law from 1787. Jacques Charles (1746-1823) was a French-born balloonist
who flew the first hydrogen balloon in 1783. Charles did an experiment filling five
different balloons with the same volume of five different gases and heating them each
uniformly. He noted the balloons each grew uniformly. This observation was not
published until 1802, by Gay-Lussac, but was named for the original observer, Charles.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
“Charles' Law states that the volume of a given mass of gas varies
directly with the absolute temperature of the gas when pressure is kept
constant.”
The absolute temperature is temperature measured with the Kelvin scale. The Kelvin
scale must be used because zero on the Kelvin scale corresponds to a complete
stoppage of molecular motion.
V V1 V2
Mathematically; V T or =C or =
T T1 T2
Graphical Representation of Charles' Law
Real World Applications
Car (combustion) engines work by this principle; the heat from the combustion of
the fuel causes the cylinder to expand, which pushes the piston and turns the
crankshaft.
Humans' lung capacity is reduced in colder weather; runners and other athletes
may find it harder to perform in cold weather for this reason.
A balloon blown up inside a warm building will shrink when it is carried to a colder
area, like the outdoors.
Charles' Law, along with a couple other gas laws, is responsible for the rising of
bread and other baked goods in the oven; tiny pockets of air from yeast or other
ingredients are heated and expand, causing the dough to inflate, which ultimately
results in a lighter finished baked good.
Gay-Lussac's Law
Gay-Lussac's Law from 1802. Joseph Louis Gay-Lussac (1778-1850) was a French
professor who, in 1802, published the law of expansion of gases by heat. He worked
closely with other scientists to publish other significant conclusions about gases and
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
other facets of chemistry. He improved various chemical tools, such as the
thermometer and the barometer. Gay-Lussac was among those at the center of
scientific investigation in France, and France was the world leader in the scientific
disciplines at the time. Gay-Lussac also made discoveries in the reactivity of gases,
specifically in the formation of water and carbon dioxide, among others.
“Gay-Lussac's Law states that the pressure of a given amount of gas held
at constant volume is directly proportional to the Kelvin temperature.”
If you heat a gas, you give the molecules more energy so they move faster. This means
more impacts on the walls of the container and an increase in the pressure. Conversely,
if you cool the molecules down they will slow and the pressure will decreased.
P P1 P
Mathematically; P T or =C or = 2
T T1 T2
Graphical Representation of Gay-Lussac's Law
Real World Applications
Bullets and cannons are based on these principles: gas super-heated by the burning
of gunpowder is trapped behind the bullet and expands until the bullet leaves the
barrel.
Someone opening an oven may feel a quick flow of hot air; the air inside the oven
is heated, therefore pressurized.
The same is true when heating food in closed containers; often, a container will
open to release the pressure. If it does not, opening the container will quickly
release all the pent-up pressure, which can be very dangerous because the gases
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
inside the hot container may be super-heated. This is why it is always best to open
hot containers away from your body and face.
Avogadro's Law
Avogadro's Law from 1811. Amedeo Avogadro (1776-1856) was an Italian physicist
and lawyer. He taught physics in Turin, Italy. Avogadro published two memoirs, once
in 1811, and the second in 1814. Both were published in French. Ampere stated
Avogadro’s Law separately in 1814, and the two are generally interchangeable,
historically speaking.
It is seen that Gay-Lussac's work directly influenced the research of Amedeo Avogadro
in the formation of Avogadro's Law.
Avogadro's Law is widely regarded as a significant contributor to the determination of
atomic and molecular weights. Gaudin and Cannizzaro used Avogadro's law to
determine atomic weights. Avogadro suggested the diatomic nature of many
"elementary" gases, as did Dumas using Avogadro's Law. The Law also contributed to
the determination of molecular formulae by demonstrating the ratios of combinations
of gases, such as in the gases of water, hydrogen chloride, ammonia, and nitric oxide.
Cannizzaro also used Avogadro's Law to "simplify the teaching of chemistry" and
present a unified system consistent for chemical and physical observations.
Avogadro's Law contributed to the development of the kinetic theory of matter.
Avogadro's Law can also be applied to osmosis, which, in turn, allows the
determination of molecular weights by osmotic pressure.
“Avogadro's Law states that the volume of a gas is directly proportional
to the number of moles (or number of particles) of gas when the
temperature and pressure are held constant.”
V V1 V2
Mathematically; V n or =C or =
n n1 n2
Graphical Representation of Gay-Lussac's Law
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Real World Applications
A balloon inflates because of Avogadro's Law; the person blowing into the balloon
is inputting many gas particles, so the balloon increases in volume.
We breathe because of Avogadro's Law, among others; the lungs expand, so more
gas particles can enter the lungs from the outside air (inhaling). Then the lungs
contract, so the waste gas particles are expelled (exhaling).
Avogadro's Law explains projectiles, like cannons and guns; the rapid reaction of
the gunpowder very suddenly creates a large amount of gas particle, mostly carbon
dioxide and nitrogen gases, which increase the volume of the space behind the
cannon, or bullet until the projectile has enough speed to leave the barrel.
Combined Gas Law
Pressure, volume, and temperature are all related. This is a combination of Boyle's
Law, Charles' Law, and Gay-Lussac's Law.
“Combined Gas Law states that the ratio between the pressure-volume
product and the temperature of a system remains constant”
PV P1V1 P2 V2
Mathematically; C or =
T T1 T2
Any units will work here for pressure and volume but the temperature must be
absolute (Kelvin).
Real World Applications
Car (combustion) engines
Breathing
Projectiles (guns, cannons)
Cooking
Balloons
The Ideal Gas Law
Émile Clapeyron (1799–1864) is able to combine the laws of Boyle, Charles and
Avogadro into a form known as the ideal gas equation.
“The Ideal Gas Law states that the ratio between the pressure-volume
product and the number of mole(s)-temperature product of a system
remains constant”
PV P1V1 P2 V2
Mathematically; R or PV nRT or =
nT n1T1 n 2T2
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Where n is the number of moles of gas and R the universal gas constant.
Universal gas constant
The value of the universal gas constant 'R' depends on the units used for
pressure, volume and temperature.
Most frequent used value of universal gas constant is
R 8.3145 J / mol·K 8.3145 kJ / kmol·K
R 0.0821 liter·atm / mol·K
Specific Gas Constant
A related factor is the specific gas constant or individual gas constant. This may be
indicated by R gas . It is the universal gas constant divided by the molar mass (M) of a
pure gas or mixture. This constant is specific to the particular gas or mixture (hence
its name), while the universal gas constant is the same for an ideal gas.
universal gas constant R
Specific gas constant R gas
Molar Mass M
Example
Q.1 Suppose that an “empty” aerosol spray-paint can has a volume of 0.406 L and
contains 0.025 mol of a propellant gas such as CO 2 . What is the pressure in
atm of the gas at 27°C?
(a) 1.21 (b) 1.62 (c) 2.51 (d) 1.51
Sol: Using Ideal gas equation;
nRT 0.025 0.08206 300
PV nRT P 1.51 atm
V 0.406
Ans: d
Q.2 Which is lighter than dry air?
(a) Moist air (b) SO 2 (c) Cl2 (d) O2
Sol: Air contains N 2 , O2 and H 2 O etc. Drying the air reduces the composition of
H 2 O . Therefore, Moist air is lighter than dry air.
Ans: a
Q.3 Air at sea level is dense. This is a practical application of
(a) Boyle’s law (b) Charles’ law (c) Avogadro’s law (d) Dalton’s law
Sol: Boyle’s law
Ans: a
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Raoult's Law
In the 1880s, French chemist François-Marie Raoult discovered that when a substance
is dissolved in a solution, the vapor pressure of the solution will generally decrease.
This observation depends on two variables:
1. the mole fraction of the amount of dissolved solute present and
2. the original vapor pressure (pure solvent).
At any given temperature for a particular solid or liquid, there is a pressure at which
the vapor formed above the substance is in dynamic equilibrium with its liquid or solid
form. This is the vapor pressure of the substance at that temperature. At equilibrium,
the rate at which the solid or liquid evaporates is equal to the rate that the gas is
condensing back to its original form. All solids and liquids have a vapor pressure, and
this pressure is constant regardless of how much of the substance is present.
Raoult's law states that the vapor pressure of a solvent above a solution is equal to
the vapor pressure of the pure solvent at the same temperature scaled by the mole
fraction of the solvent present:
Psolution χ solvent Psolvent
o
o
Psolvent is the vapour pressure of the pure solvent at a particular temperature.
χ solvent is the mole fraction of the solvent. That is exactly what it says it is - the
fraction of the total number of moles present, which is solvent.
moles of solvent
χ solvent
total number of solvent
Limitations on Raoult's Law
Raoult's Law only works for ideal solutions. An ideal solution is defined as one which
obeys Raoult's Law.
In practice, there's no ideal solution. However, very dilute solutions obey Raoult's Law
to a reasonable approximation.
In an ideal solution, it takes exactly the same amount of energy for a solvent molecule
to break away from the surface of the solution as it did in the pure solvent. The forces
of attraction between solvent and solute are exactly the same as between the original
solvent molecules - not a very likely event!
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Example
Q.1 1.5 moles of cherry Kool-Aid are added to a pitcher containing 2 liters of water
on a nice day at 25o C . The vapor pressure of water alone is 23.8 mm Hg at
25o C . What is the new vapor pressure of Kool-Aid?
(a) 23.3 mm Hg (b) 23.8 mm Hg (c) 25.24 mm Hg (d) 18.4 mm Hg
Sol: PH 2O 23.8 mm Hg
To solve for the mole fraction, you must first convert the 2 L of water into moles:
1 L = 1000 mL = 1000 g
Knowing this, you can convert the mass of water (2000 g) into moles:
2000 g / 18.02 g (molar mass of water) = 110.9 moles H 2 O
Solve for the mole fraction,
moles H 2O 110.9 moles
H O 0.979
2
total moles 110.9 1.5 moles
Finally, apply Raoult's Law
PKool Aid H 2O PH 2O 0.979 23.8 mm Hg 23.3 mm Hg
Ans: a
Henry’s Law
Henry’s Law states that the solubility of a gas in a liquid is directly proportional to
the partial pressure of the gas above the liquid. Henry’s law can be written as
follows:
S1 S2
P1 P2
S1 and P1 are the solubility and the pressure at an initial set of conditions; S2 and
P2 are the solubility and pressure at another changed set of conditions.
“The pressure above a liquid affects the solubility of a gas in the liquid and hence the
solubility of a gas in a liquid is directly proportional to the partial pressure of the gas
above the liquid.”
PA k H X A
PA is the partial pressure of the solute A above the solution
X A is the concentration of the solute A in the solution (in one of its many units)
k H is the Henry's law constant, which has units such as L·atm/mol, atm/mole fraction
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Comparison between Raoult's law and Henry's Law
In the mathematical expressions of the two laws, both state that the partial pressure
of a component in a solution is proportional to the concentration of that component
in the solution. Using mole fractions, x, as the expression of concentration, Henry's
law can be written as:
This can be compared with Raoult's law:
p p* x
Where p * is the vapor pressure of the pure component.
Thus, Raoult's law appears to be a special case of Henry's law where kH is equal to
p * . This is true for pairs of closely related substances, such as benzene and toluene,
which obey Raoult's law over the entire composition range (such mixtures are called
ideal mixtures). The general case is that both laws are limit laws, and they apply at
opposite ends of the composition range. The vapor pressure of the component with
largest concentration by far, such as the solvent for a dilute solution, is proportional
to the mole fraction, and the proportionality constant is the vapor pressure of the pure
substance (Raoult's law). The vapor pressure of component with the smallest
concentration by far, such as the solute in a dilute solution, is also proportional to the
mole fraction, but the proportionality constant is the Henry's law constant which must
be determined experimentally (Henry's law).
In mathematical terms:
p p
Raoult 's law : lim p Henry 's law : lim k H
x 1
x x 0
x
Example
Q.1 The solubility of a certain gas in water is 0.745 g/L at standard pressure. What
is its solubility when the pressure above the solution is raised to 4.50 atm?
The temperature is constant at 20°C.
(a) 3.35 g/L (b) 2.25 g/L (c) 5.25 g/L (d) 1.35 g/L
Sol: Applying Henry’s law
S1 × P2 0.745 g/L 4.50 atm
S2 3.35 g/L
P1 1.00 atm
Ans: a
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Dalton's Law
Dalton's Law of Partial Pressures from 1801. John Dalton (1766-1844) was born in
Eaglesfield, England, in Cumberland. His father was a weaver; his mother came from
landowners. Raised as a Quaker, Dalton had the opportunity to work for a Quaker of
scientific persuasion, Elihu Robinson, at the age of ten. Robinson introduced Dalton
to mathematics. At age twelve, Dalton taught in a village school, and, in 1793, attained
a professorship at New College in Manchester, where he taught math and natural
philosophy. After the college moved to York, Dalton stayed in Manchester and worked
as a private tutor. John Dalton was directly influenced by Newtonian physics and
highly fascinated by meteorological sciences. Dalton initiated the chemical atomic
theory that still holds ground in modern science, created a new system of chemical
symbology, and determined a composition of the atmosphere close to the
atmosphere's true composition. Dalton was a member of the Literary and
Philosophical Society and theorized on colorblindness, a condition by which he was
afflicted. He determined the Law of Partial Pressures by adding water vapor to dry air
and observing the effect on pressure.
“Dalton’s Law, or the Law of Partial Pressures, states that the total
pressure exerted by a mixture of “Non-reacting gases” is equal to the sum
of the partial pressures of the gases in the mixture.”
Mathematically; PTotal P1 P2 + P3
From the molar composition of gases we can write
n Total n1 n 2 + n 3
Therefore from Ideal Gas equation; PTotal V n Total RT
Real World Applications
Dalton's Law is especially important in atmospheric studies. The atmosphere is
made up principally of nitrogen, oxygen, carbon dioxide, and water vapors; the
total atmospheric pressure is the sum of the partial pressures of each gas. The
different partial pressures account for a lot of the weather we experience.
Dalton's Law plays a large role in medicine and other breathing areas. Different
proportions of gas have different therapeutic effects, so it is important to know the
partial pressures of each gas.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Example
Q.1 Which one of the following mixtures of gases at room temperature does not
obey Dalton’s law of partial pressure?
(a) He and O 2 (b) NH 3 and HCl (c) H 2 and He (d) N 2 and He
Sol: Dalton’s law of partial pressure apply for the mixture of non-reacting gases.
Ans: b
Q.2 A sample of air contains only N 2 , O2 and H 2 O . It is saturated with water
vapours and the total pressure is 640 torr. The vapour pressure of water is 40
torr and the molar ratio of N 2 : O 2 is 3:1. The partial pressure of N 2 in the air is
(a) He and O 2 (b) NH 3 and HCl (c) H 2 and He (d) N 2 and He
Sol: As per Dalton’s law of partial pressure
Pair PN2 + PH 2O + PO 2
PN2 n N2 3 1
PO2 PN2
PO2 n O2 1 3
Therefore,
1
Pair PN 2 + PH2O + PO2 640 PN2 40 PN 2
3
4
PN 600 PN 2 450 torr
3 2
Ans: b
Q.3 The partial pressure of dry gas is ________ that of wet gas.
(a) less than (b) greater than (c) equal to (d) None
Sol: As per Dalton’s law of partial pressure
Pwet gas Pdry gas + Pvapour
Ans: a
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Real Gases
The ideal gas equation PV nRT provides a valuable model of the relations between
volume, pressure, temperature and number of particles in a gas. As an ideal model it
serves as a reference for the behavior of real gases. The ideal gas equation makes some
simplifying assumptions, which are obviously not quite true. Real molecules do have
volume and do attract each other. All gases depart from ideal behavior under
conditions of low temperature (when liquefaction begins) and high pressure
(molecules are more crowed so the volume of the molecule becomes important).
Critical temperature of a gas
Gases can be converted to liquids by compressing the gas at a suitable temperature.
Gases become more difficult to liquefy as the temperature increases because the
kinetic energies of the particles that make up the gas also increase. The critical
temperature of a substance is the temperature at and above which vapor of the
substance cannot be liquefied, no matter how much pressure is applied.
Every substance has a critical temperature. Some examples are shown below
Critical pressure of a gas
The critical pressure of a substance is the vapor pressure at the critical temperature.
The point at which the critical temperature and critical pressure is met is called
the critical point.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Pressure – Temperature Diagram
Reduced Temperature and Pressure
P T
The reduced temperature and pressure is given by Pr = and Tr = . Where Pc and Tc
Pc Tc
are critical pressure and temperature of any pure gas respectively.
Compressibility factor
The compressibility factor (Z), also known as the compression factor, is a useful
thermodynamic property for modifying the ideal gas law to account for the real gas
behavior. In general, deviation from ideal behavior becomes more significant the
closer a gas is to a phase change, the lower the temperature or the larger the pressure.
The compressibility factor is defined as
Vm PVm
Z
m idealgas RT
V
RT
Vm : is the molar volume, Vm idealgas : is the molar volume of the corresponding
P
ideal gas, P is the pressure, T is the temperature and R is universal gas constant.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
For ideal gas, the compressibility factor (Z) is equal to 1.
For engineering applications, it is frequently expressed as
P
Z
ρR specificT
R
Where is the density of the gas, R specific , M is the molar mass.
M
In most engineering work, the compressibility factor is used as a correction factor to
ideal behavior. Thus, Vreal Z Vid is used to calculate the actual volume, Vreal , as the
product of the compressibility factor and the ideal gas volume, all at the same pressure
and temperature.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Real Gases - Van der Waals Equation
The idea gas models does not accurately model the behavior of real gases in all
situations. This is because the ideal gas model is that of a gas of completely non-
interacting particles. The particles have no attraction for one another and no
repulsions for one another. Real gas particles do. However, since these attractions and
repulsions typically have a distance dependence that is very short ranged. That means
that when the particles are separated by distances that are on par with their size these
forces are very small. Therefore, for many gases the ideal gas model works well since
under typical conditions the gas particles are separated by distances that are large
compared to the particle size. Nonetheless, we can develop a more complex model for
a gas that includes both attractions and repulsions. This is the van der Waals (VDW)
model for a gas. The van der Waals equation is:
n 2a
P V nb nRT
V2
Where
P is the pressure of the fluid
V is the total volume of the container containing the fluid
a is a measure of the attraction between the particles
b is the volume excluded by a mole of particles
n is the number of moles
for one mole of gas Van der Waals equation is
a
P 2 V b RT
V
The terms a and b are characteristic of each gas and can be obtained by analyzing the
dP d 2P
WEOS at the critical point, i.e., zeroing the first and second derivative, and ,
dV dV 2
at this point where the P−V curve has a flat inflection,
a 8a 3
Pc 2
, Vc 3b , Tc , Zc
27b 27Rb 8
Here, Pc , Vc , Tc and Zc are critical Pressure, Critical Volume, Critical Temperature and
Critical Compressibility factor respectively. Practically, the value of critical
3
compressibility factor Zc is not possible; it is slightly less.
8
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Chemical Calculations and Gas Laws
Example
Q.1 The compressibility factor for a real gas at high pressure is
Pb Pb RT
(a) 1 (b) 1 + (c) 1 (d) 1
RT RT Pb
Sol: at high pressure, the compressibility factor Z is greater than 1.
Ans: b
Q.2 At high temperature, the Vander wall’s equation (for one mole) becomes
a
(a) Z 1 (b) PV = RT + Pb
RTV
a Pb
(c) PV = RT + (d) Z = 1
V RT
Sol: at high temperature, a is negligible
Ans: b
Q.3 At moderate pressure, the Vander wall’s equation becomes
(a) PVm RT (b) P Vm b RT
a RT a
(c) P + 2 Vm RT (d) P = 2
Vm Vm Vm
Sol: at moderate pressure, b is negligible
Ans: c
Q.4 Which one of the following can be most readily liquefied?
Given value of Vander wall’s constant ‘a’ for NH 3 4.17, CO 2 3.59,
SO 2 6.71, Cl 2 6.49
(a) NH3 (b) CO 2 (c) SO 2 (d) Cl2
Sol: The Vander wall’s ‘a’ is a measure of the attraction between the particles. All the
substances given is gas. As ‘a’ increases the attraction between the particles
increases which causes to liquefy the gas.
Ans: c
Q.5 In Vander wall’s equation of state for non-ideal gas, the term accounts for
intermolecular forces is
a 1
(a) V b (b) P + (c) RT (d)
V2 RT
Sol: The Vander wall’s ‘a’ is a measure of the attraction between the particles.
Ans: b
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
3 PHASE RULE
Introduction
The phase rule is a generalization given by Willard Gibbs (1874), which seeks to
explain the equilibria existing in heterogeneous system. It may be stated as: “provided
the equilibrium between any number of phases is not influenced by gravity, or
electrical, or magnetic forces or by surface action and only by temperature, pressure
and concentration, then the number of degrees of freedom (F) of the system is related
to number of components (C) and of phases (P) by the phase rule equation for any
system at equilibrium at a definite temperature and pressure.
Phase (P)
A phase is defined as “ an homogeneous, physically distinct and mechanically
separable portion of system, which is separated from other such parts of the system
by definite boundary surfaces”
Homogeneous system
A system consisting of only one phase is said to be homogeneous. Air constitutes a
single phase only as it contains a mixture of nitrogen, oxygen, carbon dioxide, water
vapour etc.
Heterogeneous system
A system consisting of more than one phase is said to be heterogeneous. When various
phases are in equilibrium with one another in a heterogeneous system, there can be
no transfer of energy or mass from one phase to another. This means that at
equilibrium, the various phases must have the same temperature and pressure and
their respective compositions must remain constant all along.
Liquid phase
The number of liquid phase depends on the number of liquids present and their
miscibility.
If two liquids are immiscible, they will form two separate liquid phases.
Example : benzene and water
If two liquids are miscible, they will form one liquid phase only. Example : alcohol
and water
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
Solid phase
Each solid forms a separate phase. The number of solid phase depends on the number
of solids present in it.
Example: Many forms of Sulphur can exist together, but these are all separate phases.
Gaseous phase
Since a gaseous mixture are thoroughly miscible in all proportions, it will form one
phase only.
Example: a mixture of N 2 and H 2 forms one phase only.
Component (C)
Component is defined as “the smallest number of independently variable constituents,
by means of which the composition of each phase can be expressed in the form of a
chemical equation”
Example:
Water system
The chemical component of all the three phases is H 2 O and therefore it is one
component system
Sulphur
Sulphur exists in four phases namely rhombic, monoclinic, liquid and vapour, but the
chemical composition of all phases is S. Thus, it is one component system.
A system of saturated solution of NaCl
A system of saturated solution of NaCl consists of solid salt, salt solution and water
vapour. The chemical composition of all the three phases can be expressed in terms
of NaCl and H 2 O . Therefore, it is a two-component system.
Degree of freedom
Degree of freedom is defined as the minimum number of independent variable factors
such as temperature, pressure and concentration of the phases, which must be fixed
in order to define the condition of a system completely. It is also known as Variance.
A system having 1, 2, 3 or 0 degrees of freedom is called univariant, bivariant,
trivariant and invariant respectively.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
Example:
Water system
The three phases can be in equilibrium only at particular temperature and pressure.
Therefore, when all the three phases are present in equilibrium, then no condition
need to be specified. The system is therefore zero variant or invariant or has no degree
of freedom.
In this system if pressure or temperature is altered , three phases will not remain in
equilibrium and one of the phases disappears.
Consider a system consisting of water in contact with its vapour,
To define this system completely, we must state either the temperature or pressure
Thus degree of freedom is one and the system is univariant.
Consider a system consisting of water vapour only,
For a system consisting of water vapour phase only, we must state the values of both
the temperature and pressure in order to define the system completely. Hence, the
system is bivariant or has two degrees of freedom.
DERIVATION OF PHASE RULE
Consider a heterogeneous system having P phases and C components. Now according
to definition the degree of freedom (F) of the system is minimum of independent
variables, which must be fixed arbitrarily to define the system completely. However,
the number of these variables is equal to the total number of variable minus the
number of relations between them at equilibrium, since each relation diminishes the
number of independent variables by one.
Now let us calculate the total number of independent variables:
Temperature: At equilibrium, temperature of every phase is same, so there is only
one temperature variable for the entire system.
Pressure: At equilibrium, each phase has the same pressure, so there is only one
pressure variable for the entire system.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
Concentration: Concentration of each components is generally expressed in terms
of mole fractions. As a rule, the number of composition variables required for each
phase are C 1 , since the composition of all components may be expressed by stating
the mole fraction of all except one of the components. For example, it there are two
components A and B in one phase and if we know the concentration (or mole fraction)
of one (say A), the concentration of other (i.e. B) can be automatically found, because
the sum is always unity. Thus, if mole fraction of A is 0.4, that of B is known to be 0.6.
Similarly, if we have three components and if the composition of two is known that of
the third can be found out. Thus, if we have C components, we must know the
concentration of C 1 component. Therefore, for P phases the total composition
variable are P C 1 .
Hence,
Total number of variables
= 1(for temperature) + 1(for pressure) + P C –1 (for composition)
Total number of variables P C –1 2
Now let us calculate the number of relations at equilibrium. We know that for a system
in a thermodynamic equilibrium, the chemical potential μ , which is related to
concentration of component in the entire particular component i , we have at
equilibrium: [ µi ] [ µi ] [ µi ] .
Consequently, there are two equilibrium relationships for each component if there are
3 phases , and .
Hence, for P phases, the number of such relationships for each component are P 1 ,
Consequently, for C components, such relationships will be C P 1 .
Hence, Degree of freedom (F) = Total number of independent variables No. of
relationships between these variables
Mathematically; F = C P 2
The above is also called as Gibb’s Phase Rule.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
Merits of the Phase rule:
It is applicable to both physical and chemical equilibria.
It requires no information regarding molecular/micro-structure, since it is
applicable to macroscopic systems.
It is a convenient method of classifying equilibrium states in terms of phases,
components and degrees of freedom.
It helps us to predict the behaviour of a system, under different sets of variables.
It indicates that different systems with same degree of freedom behave similarly.
It helps in deciding whether under a given set of conditions, various substances
would exist together in equilibrium or some of the substances present would
be interconverted or some of the substances present would be eliminated.
Limitations of Phase rule:
It can be applied only for system in equilibrium. Consequently, it is of little value
in case of very slow equilibrium state attaining system.
It applies only to a single equilibrium system; and provide no information
regarding any other possible equilibria in the system.
It requires at most care in deciding the number of phases existing in an equilibrium
state, since it considers only the number of phases, rather than their amounts.
Thus even if a trace of phase is present, it accounts towards the total number of
phases.
It conditions that all phases of the system must be present simultaneously under
the identical conditions of temperature and pressure.
It conditions that solid and liquid phases must not be in finely divided state;
otherwise, deviations occur.
PHASE RULE FOR CHEMICAL REACTION EQUILIBRIUM
In a chemical reaction, various reactant with one another forming products.
Consequently, the phase equilibrium become rather complicated due to simultaneous
presence of reactants and products. Let N e be the total number of chemical substances
present in the overall system at equilibrium and r be the number of reactants, then the
component term C of the phase rule equation is replaced by N e r .
i.e. C N e – r
Hence, phase rule equation becomes:
F Ne r P 2
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
Example: Let us consider the reaction of oxygen with carbon producing a mixture of
carbon dioxide.
Thus;
C s O2 g CO2 g
1
C s O 2 g CO g
2
No. of phases at equilibrium (P) = (Solid phase due to carbon + Gaseous phase due to
CO 2 CO O 2 ) 1 1 2
No. of reactants (r) = (Carbon + oxygen) 1 1 2
No. of chemical substances present at equilibrium N e = Carbon CO2 CO O 2
1111 4
Degree of freedom (F) Ne – r – p 2 4 – 2 – 2 2 2
Phase Diagram
Phase diagram is a graph obtained by plotting one degree of freedom against another.
If the phase diagram is plotted between temperature against pressure, the diagram
is called P-T diagram. “P-T diagram is used for one component system”.
If the phase diagram is drawn between temperature against composition, the
diagram is called T-C diagram. “T-C diagram is used for two component system”.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
Uses of Phase diagram
From the phase diagram, it is possible to predict whether an eutectic alloy or a solid
solution is formed on cooling a homogeneous liquid containing mixture of two
metals.
The phase diagrams are useful in understanding the properties of materials in the
heterogeneous equilibrium system.
The study of low melting eutectic alloys, used in soldering, can be carried out using
phase diagrams.
Phase Diagram and features of one component system
A phase diagram lets you work out exactly what phases are present at any given
temperature and pressure. In the cases we'll be looking at on this page, the phases will
simply be the solid, liquid or vapour (gas) states of a pure substance. This is the phase
diagram for a typical pure substance
PT-Diagram of Pure Substances
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
The slope of the sublimation and vapourisation curves for all substances are positive.
The slope of the fusion curve for most substances is positive, but for some of the
substances e.g. water, it is negative.
T-V and P-V Diagram, are also important for the study of Pure substances.
Water system
The water system is a one-component system.
Since water exists in three possible phases such as solid, liquid and vapour, there are
three forms of equilibria:
Each equilibrium involves two phases. The nature of these phases which exist in
equilibrium at any time depends on the conditions of temperature and pressure.
These conditions have been determined and summarized in the pressure-
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
temperature diagram in which pressure is treated as independent variable and is
plotted along y – axis whereas temperature is plotted along x-axis. The phase diagram
for the water system is shown in Fig
PT-Diagram of Water System
The phase diagram consists of
Curves
There are four curves OA, OB, OC and OB’. Along the curves the degree of
freedom of the system is one, i.e., univariant. This is predicted by the phase
rule; F C – P 2 ; F 1 – 2 2 ; F 1
1. Curve OA
The curve OA is called vapourisation curve, it represents the equilibrium
between water and vapour. At any point on the curve, the following equilibrium
will exist.
The degree of freedom of the system is one, i.e., univariant.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
This equilibrium (i.e., line OA) will extend up to the Critical Point (Critical
temperature 374.15C , Critical Pressure 221.2 bar ). Beyond the critical
temperature, the equilibrium will disappear only water vapour will exist.
2. Curve OB
The curve OB is called sublimation curve of ice, it represents the
equilibrium between solid and vapour. At any point on the curve, the following
equilibrium will exist.
The degree of freedom of the system is one, i.e., univariant.
This equilibrium line will extend up to the absolute zero – 273C where no
vapour can be present and only ice will exist.
3. Curve OC
The curve OC is called Fusion curve of ice, it represents the equilibrium
between solid and liquid. At any point on the curve, the following equilibrium
will exist.
The curve OC is slightly inclined towards pressure axis. This shows that
melting point of ice decreases with increase of pressure.
The degree of freedom of the system is one. i.e., univariant.
4. Curve OB’
The curve OB’ is called metastable vapourisation curve, it represents the
equilibrium between liquid and vapour. The degree of freedom of the system is
one. i.e., univariant.
Areas
Three curves OA, OB and OC divide the diagram into three areas AOB, AOC and
BOC. Area AOC, BOC, AOB represent water, ice and vapour respectively. In order
to define the system at any point in the areas, it is essential to specify both
temperature and pressure. The degree of freedom of the system is two. i.e.,
Bivariant. This is predicted by the phase rule F C – P 2; F 1 –1 2 ; F 2
Triple point
The above three curves meet at the point O and is known as triple point. At triple
point all the three phases namely ice, water and vapour coexist. Thus, the value of
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
P is 3. Applying phase rule equation, the degree of freedom at this point is zero. It
means that three phases can coexist in equilibrium only at a definite temperature
and pressure. The values are 0.01C and 4.58 mm of Hg respectively.
At this triple point, neither pressure nor temperature can be altered even slightly
without causing the disappearance of one of the phases. The triple point is not the
same as the ordinary melting point of ice i.e., 0C . It’s value has been increased
due to the fact that 0C is the melting point of ice at 760 mm of mercury
and a decrease of 4.58 mm of mercury will rise the melting point to 0.01C .
Some salient features of the water system
Reduced phase rule or condensed phase rule
In solid-liquid equilibrium of an alloy, practically there is no gaseous phase and the
pressure will not have much influence. In the case of solid-liquid equilibrium, the
experiments are generally carried out at constant pressure.
Thus, the system in which only the solid and liquid phases are considered and the gas
phase is ignored is called a condensed system. This reduces the degree of freedom
of the system by one. The phase rule equation is then written as F ' C – P 1
There are various types of solid-liquid equilibria of which only two of them are taken
here.
Type-I
Those equilibria in which the components are completely miscible with one another in
liquid state. They do not form any compound on solidification. They give rise to merely
an intimate mixture known as Eutectic. Some examples of this system are
1) lead-silver system 2) Lead-Antimony system
3) Zinc-cadmium system 4) Potassium iodide- water system
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
Type-II
Those equilibria in which the components enter into chemical combination. They give
rise to one or more compounds. Some examples of this system are
1) Zinc-magnesium system
2) Calcium chloride – Potassium chloride system
3) Gold-Tellurium system.
Phase Diagram and features of two-component system
The two component systems are classified into the following three types
Simple eutectic formation
A system with two substances which are completely miscible in the liquid state, but
completely immiscible in the solid state is known as eutectic system. In this system,
the substances do not react chemically.
Among the mixtures of different proportions of two substances, the mixture, which
has the lowest melting point, is known as the eutectic mixture.
The temperature and composition corresponding to the point eutectic point is called
eutectic temperature and eutectic composition respectively. Here the pressure does
not have the considerable effect. Hence, the other two variables viz, temperature and
compositions are taken into account.
Characteristics of eutectic mixtures
The eutectic mixture possesses the following properties
It has a definite composition.
It has a definite lowest melting or freezing point.
The eutectic mixture is not regarded as a compound due to the following reasons:
The components of eutectic mixture are not in stoichiometric proportion.
The eutectic mixture reveals the existence of separate crystals under a
microscope.
Eutectic mixture is defined as a liquid mixture of two components, which has the
lowest freezing point, compared to all other liquid mixtures and on cooling
(freezing) such a mixture, both the components separate out as solid phases.
The heat of solution of eutectic mixture is the sum of heats of solution of the
components.
The composition of eutectic mixture changes with pressure.
Eutectic mixture increases the strength of alloy.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
The eutectic mixture can keep its temperature constant for a long period, unless
one of the components completely disappears. That is why eutectic points, the
liquid state will disappear. That is why eutectics are used as 'temperature
standards'.
If the eutectic mixture is cooled below the eutectic point, the liquid state will
disappear and whole mass will solidify as a mixture of pure A and B. If temperature
is raised, the solids will melt.
The general phase diagram for eutectic system is shown in Fig
Simple Eutectic system
In the diagram,
A, B: Two components, completely miscible in liquid state.
Point A: Freezing point of pure component A
Point B: Freezing point of pure component B
Curve AC: The addition of component B to A will lower the freezing point of A.
Hence, AC is known as freezing point curve of A. Along this curve, solid A is in
equilibrium with the solution of B and A. The number of phases along the curve AC
are two. Since, the pressure is maintained constant, therefore according to reduced
phase rule equation, degree of freedom (F) = 1
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
Curve BC: Along the curve BC, solid B is in equilibrium with the solution of A in B.
The number of phases along the curve AC are two. Since, the pressure is maintained
constant, Hence, according to reduced phase rule equation, degree of freedom (F) = 1
Point C: At point C, both the curves AC and BC intersects. The solution is saturated
with both A and B. Hence, at the point C , three phases, namely solid A, solid B and
solution coexists in equilibrium. Hence, according to reduced phase rule equation, at
the point C, degree of freedom (F) = 0, system in invariant.
Area ACB: In this area A and B are present as a homogeneous liquid solution. Hence,
there is only one phase. According to reduced phase rule equation, degree of freedom
(F) = 2, system in this area is bivariant.
Area ACD and BCD: Any point in these areas represents equilibrium between solid
A (Solid B) and liquid. System in this area is bivariant.
Area OO’DD’: As liquid phase can not exists below the eutectic temperature, in this
area only solid phase exists.
Some salient features of the simple eutectic system
Congruent melting point system
In this type of binary alloy system, the two substances form one or more compounds
with definite proportions. Of the compounds, a compound is said to possess congruent
melting point, if it melts exactly at a constant temperature into liquid, having the same
composition as that of the solid. The components of a binary mixture at a certain stage
enter into chemical combination and form one or more compounds (inter-metallic
compounds) in stoichiometric proportions. These compounds melt sharply at a
constant temperature into a liquid having the same composition as that of the solid.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
The temperature at which such a compound melts is called the congruent melting
point.
Some common examples of this type of system are zinc-magnesium system, mercury-
thallium system, gold-tin system and ferric chloride-water system etc.
Zn-Mg system
Zn-Mg System is a two-component system and possess a congruent melting point. The
phase diagram of Zn-Mg system is shown in Fig
Temperature – Component Phase Diagram for Zn-Mg System
In this system, the two components are zinc and magnesium, which melt at 419°C and
650°C respectively which are represented as point B and A in the phase diagram of the
system. Both metals enter into chemical combination and form an intermetallic
compound MgZn2 and melts at 590°C to give a liquid of the same composition. Hence,
590°C is the congruent melting point of the system. In the reduced form, the system
has the following four phases: Solid magnesium, solid zinc, solid MgZn2 and liquid
solution of Zn and Mg.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
Some salient features of Zn-Mg System
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
Incongruent melting point system
A compound is said to possess incongruent melting point, if it decomposes completely
at a temperature below its melting point yielding a new solid phase with a composition
different from that of the original.
Examples of binary system that possess incongruent melting point system are Gold-
antimony system, Sodium-bismuth system, sodium-potassium system, Sodium
sulphate-water system etc.
Na-K System
This is a two-component system having incongruent melting point. The melting points
of sodium and potassium are 97.8°C and 63.8°C respectively, which are shown in the
phase diagram in Fig.
Temperature – Component Phase Diagram for Na-K System
Both elements chemically combine together in the ratio of 2:1 to form a compound
Na 2 K . However, this compound is unstable, decomposes into solid Na, and melt at a
temperature of 70°C. It is the incongruent melting point or peritectic temperature of
this system. This system consists of four phases i.e. Solid K, Solid Na, Solid Na 2 K and
Liquid of Na and K.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
As the pressure does not have any effect on this type of equilibria hence the degree of
freedom for such a system is reduced by one, so, reduced phase rule is applicable on
the Na-K system, F' C P 1
Some salient features of Na-K System
Phase Diagram and features of three-component system
In this type, when two substances, especially metals, are completely miscible in both
the solid and liquid states, they form solid solutions where mixing takes place in the
atomic levels. A solid solution can be formed only when the difference between the
atomic radiuses of two metals is not greater than 15%.
Equilibrium Crystallization, where all 2 Component Systems are Binary
Eutectic Systems
Figure 1 shows a three dimensional representation of the three component (ternary)
system ABC. Note that composition is measured along the sides of the basal triangle
and temperature (or pressure) is measured vertically. The top of the figure shows a
surface with contour's representing lines of constant temperature. These contours are
called isotherms. Note that the eutectic points in each of the binary systems project
into the ternary systems as curves. These curves are called boundary curves, and
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
any composition on one of these curves will crystallize the two phases on either side of
the curve.
Three-dimensional representation of the three-component system
Figure 2 shows the same figure in two dimensions as seen from above. The boundary
curves and isotherms are also shown projected onto the basal triangle. Note how the
temperature decreases toward the center of the diagram
Two-dimensional representation of the three-component system
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
In Figure 3, we trace the crystallization of composition X. Figure 3 is the same as
Figure 2, with the isotherms left off for greater clarity.
Simple two-dimensional representation of the three-component system
Note that the final solid must consist of crystals A + B + C since the initial composition
is in the triangle ABC. Note that the final solid must consist of crystals A + B + C since
the initial composition is in the triangle ABC.
At a temperature of about 980 C , the liquid of composition X would intersect the
liquidus surface. At this point, it would begin to precipitate crystals of C. As
temperature is lowered, crystals of C would continue to precipitate, and the
composition of the liquid would move along a straight line away from C. This is
because C is precipitating and the liquid is becoming impoverished in C and enriched
in the components A + B.
“At a temperature of about 820°C, point L in Figure 3”, we can determine the relative
proportion of crystals and liquid.
a
% crystals 100
a b
b
% liquid 100
a b
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
With further cooling, the path of the liquid composition will intersect the boundary
curve at point 0. At the boundary curve crystals of A will then precipitate. The liquid
path will then follow the boundary curve towards point M. The bulk composition of
the solid phase precipitated during this interval will be a mixture of A + C in the
proportion shown by point P.
At point M, the bulk composition of the solid phases so far precipitated through the
cooling history lies at point N (the extension of the straight line from M through the
initial composition X). At this time the
distance MX
% solid 100
distance MN
distance XN
% liquid 100
distance MN
Note, however, that the solid at this point consists of crystals of A and crystals of C. So,
we must further break down the percentages of the solid. This is done as follows: The
percentage of the solid that is A will be given by the distance from C to N relative to
the distance between A and C; i.e. by the formula:
distance NC
%A in solid 100
distance AC
distance AN
%C in solid 100
distance AC
APPLICATIONS OF THE PHASE RULE
Phase rule has wide applications in electronic industries, pharmaceutical science,
medical science, etc. Some major applications of phase rule are as follows:
Solders
Solder is an alloy, which is homogenous mixture having melting point lower than
that of the corresponding metal pieces, which have to be joined together. Solders
have compositions somewhat different from the eutectics so that the freezing
occurs over a range of temperatures. The quality of solder depends upon the
formation of a surface alloy between the solder and parts of metals being used. The
selection of solder alloy is based upon the melting point desired and the pieces of
metals to be joined. Some essential qualities of the solder are as follows:
(1) Melting point of the solder should be less than the material to be soldered.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
(2) Solder should spread in liquid form and form homogeneous mixture with the
metals.
Some common solders, which are available in the market, are:
(i) 'Soft solder' alloy of Pb and Sn.
(ii) 'Plumber alloy' contains Pb = 67% and Sn = 33%.
(iii) 'Half-half alloy' contains Pb = 50% and Sn = 50%
Half-half alloy is commonly used for soldering the pipes with a bright surface
finishing after soldering but very expensive. Also due to high contents of tin, it is
not widely applicable for several electric appliances. The solder, which contains
about 60% Pb, is used in the electrical wires.
Safety Plug
Safety plugs are also known as the safety fuses. It is an alloy having low melting
point, used to ensure the safe working and avoid accidents. Safety fuses are used in
buildings to protect them against fires. One alloy is woods metal, which is used in
the safety fuses. This alloy melts at 65°C and consists of the composition woods
metal Bi = 50%, Pb = 25%, Sn = 12.5% and Cd = 12.5%.
Examples
Q.1 The system KCl NaCl H 2O and KCl NaBr H 2O should be regarded as ___
and ___ component systems, respectively.
(a) 1, 2 (b) 2, 3 (c) 3, 3 (d) 3, 4
Sol: We know, C N E
Where, C is number of component, N is number of possible species and E is the
number of independent equations relating their concentration, mole fraction
etc. Each independent chemical equilibrium involving the constituents counts
as one equation. The condition that a solution be electrically neutral also counts
as one if ions are considered constituents.
a) KCl NaCl H 2O
Number of possible species N 3 KCl, NaCl and H 2O
Number of independent equations E 0
Number of components C N E 3 0 3
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Phase Rule
b) KCl NaBr H 2O
Number of possible species N 5 KCl, NaBr, NaCl, KBr, H 2O
Number of independent equations E 1 KCl NaBr KBr NaCl
Number of components C N E 5 1 4
Q.2 The number of degree of freedom in liquid water and water vapour equilibrium
is_______.
(a) 0 (b) 1 (c) 2 (d) 3
Sol: From the Gibb’s Phase rule; F C P 2
Number of components (C) 1
Number of phases (P) 2
Hence, Degree of freedom (F) C P 2 1 2 2 1
Q.3 The number of degree of freedom in liquid water and water vapour equilibrium
at a pressure of 1 atm is_______.
(a) 0 (b) 1 (c) 2 (d) 3
Sol: Since, the pressure is held constant; the degree of freedom is reduced by one.
Hence, the phase rule equation becomes F C P 1
Number of components (C) 1
Number of phases (P) 2
Hence, Degree of freedom (F) C P 1 1 2 1 0
Q.4 Which one of the following system do not have Quadruple point in phase-
diagram?
(a) 1-component system (b) 2-components system
(c) 3-components system (d) 4-components system
Sol: For a quadruple point, the number of phases in equilibrium with one another
must be 4. From Gibb’s Phase rule; F C P 2 C 4 2 C 2
Degree of freedom can not be negative, therefore one component system is not
possible.
Q.5 Which one of the following is True for Red and Yellow phosphorus?
(a) 2-Phases, 1-component system (b) 2-Phases, 2-component system
(c) 1-Phases, 1-component system (d) 1-Phases, 2-component system
Sol: 2-Phases due to Red and Yellow Phosphorous
1-component system as Red and Yellow Phosphorous both have same
chemical formula
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
4 FUELS
Introduction
Fuel is a combustible substance, containing carbon as a main constituent, which on
proper burning gives large amount of heat, which can be used economically for domestic
and industrial purpose.
Example:
Wood, charcoal, coal, kerosene, petrol, diesel, producer gas, oil gas etc.
During the process of combustion, carbon, hydrogen, etc., combine with oxygen with a
liberation of heat.
The combustion reaction can be explained as
C + O2 CO2 + 94 kcals
2H 2 + O2 2H 2O + 68.5 kcals
The calorific value of a fuel depends mainly on the amount of Carbon and Hydrogen.
Requirements of a Good Fuel
A good fuel should have the following characteristics:
High calorific value.
Moderate ignition temperature
Low contents of non-combustible matters.
Low moisture content.
Free from objectionable and harmful gases like CO, SOx , H2S.
Moderate velocity of combustion.
Combustion should be controllable.
Easy to transport and readily available at low cost.
Classification of Fuels
Fuels are classified into
(i) Primary or Natural fuels - These are found in nature.
(ii) Secondary or Artificial fuels - These are derived from primary fuels.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Primary and secondary fuels may also be divided into 3 classes namely solid, liquid and
gaseous fuels.
Some Important Types of Fuels
Fossil fuels: Fossil fuels are those, which have been derived from fossil remains of
plant and animal life.
They are found in the earth’s crust. All conventional fossil fuels whether solid, liquid or
gaseous (coal, petroleum or Natural gas) contain carbon and / or hydrogen. The fuels on
combustion in presence of oxygen in the air release heat energy. This heat energy can be
utilized for domestic and industrial purposes.
Solid Fuels: Coal and its varieties are solid fuels.
Advantages of Solid fuels
Handling and transportation of solid fuels are easy.
Solid fuels are cheap and easily available.
They have a moderate ignition temperature
This type of fuel can be stored conveniently without any risk.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Disadvantage of solid fuels
During burning, solid fuels produce a large amount of ash and disposal of ash is a
big problem.
The calorific value of solid fuel is comparatively low.
Since a lot of air is required for complete combustion, its thermal efficiency is not
so high.
A large space is required for storage.
Combustion is a slow process and it cannot be easily controlled.
Coal is an important primary solid fuel that has been formed because of alteration of
vegetable matter under some favorable conditions.
The process of conversion of lignite to anthracite is called coalification (or)
metamorphism of coal.
Coal is classified based on its rank. The rank of coal denotes its degree of maturity.
Vegetable matter, under the action of pressure, heat and anaerobic conditions, is
converted into different stages of coal namely,
With the progress of coal, forming reaction, moisture content and oxygen content reduces
and % of carbon increases. Also calorific value increases from peat to bituminous.
Classification of solid fuels & its calorific values
Peat
Peat is the first stage in the formation of coal.
Its calorific value is about 4000-5400 k cal/kg.
It is an uneconomical fuel due to its high proportion of (80 -90%) moisture and
lower calorific value.
It is a brown fibrous mass.
Lignite
Lignite is an intermediate stage in the process of coal formation.
Its calorific value is about 6500-7100 k cal/kg
Due to the presence of high volatile content, it burns with long smoky flame
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Bituminous coal
Bituminous coal is further sub-classified based on its carbon content into three types
as:
Sub- bituminous coal,
Bituminous coal and
Semi-bituminous coal.
Anthracite
Anthracite is the superior grade of coal.
Its volatile, moisture and ash contents are very less.
Its calorific value is about 8650 k cal/kg.
Here peat is the most immature coal, hence it is lowest in rank whereas anthracite is the
most matured coal, and hence it is highest in rank.
Table: Classification of solid fuels & its calorific values
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Analysis of Coal
In order to assess the quality of coal, the following two types of analysis are made
I. Proximate Analysis
It means finding out weight percentage of moisture, volatile matter, fixed carbon and ash
in coal. This analysis gives the approximate composition of the main constituents of coal.
It is useful in deciding its utilization for a particular industrial use.
Determination of moisture content in coal
About 1 gm of powdered, air-dried coal sample is heated in silica crucible at 100 to 105 °C
for one hour. Percentage of moisture can be calculated from the loss in weight of the coal
sample as
Determination of Volatile Matter (V.M.) in coal
After the analysis of moisture content, the crucible with residual coal sample is covered
with a lid, and it is heated at 950 ± 20 °C for 7.0 minutes in a muffle furnace. Percentage
of volatile matter can be calculated from the loss in weight of the coal sample as
Determination of ash in coal
After the analysis of volatile matter the crucible with residual coal sample is heated
without lid at 700 ± 50 °C for 30 minutes in a muffle furnace.
Percentage of ash content can be calculated from the loss in weight of the coal sample as
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Determination of fixed carbon
It is determined by subtracting the sum of total moisture, volatile and ash contents from
100.
Significance (or) Importance of Proximate Analysis
Moisture: High moisture content in coal is undesirable because it,
Reduces Calorific Value of coal
Increases the consumption of coal for heating purpose
Lengthens the time of heating.
Hence, lesser the moisture content, better is the quality of coal.
Volatile Matter: During burning of coal, certain gases like CO, CO 2 , CH 4 , H 2 , N 2 , O 2 ,
hydrocarbons etc. that come out are called volatile matter of the coal.
The coal with higher volatile content,
Ignites easily (i.e.: it has lower ignition temperature)
Burns with long yellow smoky flame
Has lower Calorific Value
Will give more quantity of coal gas when it is heated in absence of air.
Ash: Ash is the combustion product of mineral matters present in the coal. It consists
mainly of SiO2, Al2O3 and Fe2O3 with varying amounts of other oxides such as
Na2O, CaO, MgO etc.
Ash containing oxides of Na, Ca and Mg melt early. (Low melting ash). During coke
manufacture, the low melting ash forms a fused lumpy - expanded mass which block the
interspaces of the ‘grate’ and thereby obstructing the supply of air leading to irregular
burning of coal and loss of fuel.
High ash content in coal is undesirable because it (a) increases transporting, handling,
storage costs, (b) is harder and stronger, (c) has lower Calorific Value.
Fixed Carbon: It is the pure carbon present in coal. Higher the fixed carbon content of
the coal, higher will be its Calorific Value.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
II. Ultimate Analysis
It means finding out the weight percentage of carbon, hydrogen, nitrogen, oxygen and
Sulphur of the pure coal free from moisture and inorganic constituents. This analysis
gives the elementary constituents of coal. It is useful to the designer of coal burning
equipment and auxiliaries.
Determination of carbon and hydrogen in coal
A known amount of coal is burnt in presence of oxygen there by converting carbon and
1
hydrogen of coal into CO2 : C O2 CO2 and H2O : H2 O2 H2O respectively.
2
The products of combustion CO2 and H2O are made to pass over weighed tubes of
anhydrous CaCl2 and KOH , which absorb H2O and CO2 respectively.
The increase in the weight of CaCl2 tube represents the weight of water formed while
increase in the weight of KOH tube represents the weight of CO2 formed. % of carbon and
hydrogen in coal can be calculated as follows.
Let X - The weight of coal sample taken
Y - The increase in the weight of KOH tube
Z - The increase in the weight of CaCl2 tube
a) Carbon
C + O 2 CO 2
12 32 44
44 gms of CO 2 contains 12 gms of carbon
12
1 gm of CO 2 contains gms of carbon
44
12
Y gms of CO 2 contains Y gms of carbon
44
12 Y
% of C in coal 100 %
44 X
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
b) Hydrogen
1
H2 O 2 H 2O
2
2 16 18
18 gms of Water contains 2 gms of Hydrogen
2
1 gm of water contains gms of Hydrogen
18
2
Z gms of water contains Z gms of Hydrogen
18
2 Z
% of hydrogen in Coal = 100 %
18 X
Determination of Nitrogen in coal
Nitrogen estimation is done by Kjeldahl’s method. A known amount of powdered coal is
heated with con H2SO4 and K2SO4 in a long necked flask (called Kjeldahl’s flask), there by
converting nitrogen of coal to ammonium sulphate.
When the clear solution is obtained (i.e. the whole nitrogen is converted into ammonium
sulphate), it is heated with 50% NaOH solution.
The ammonia thus formed is distilled over and is absorbed in a known quantity of
standard 0.1N HCl solution. The volume of unused 0.1 N HCl is then determined by
titrating against standard NaOH solution.
Thus, the amount of acid neutralized by liberated ammonia from coal is determined.
Let,
Volume of 0.1 N HCL = A ml
Volume of unused HCL = B ml
Acid neutralized by ammonia = (A - B) ml
We know that 1000 ml of 1 N HCl = 1 mole of HCL = 1 mole of NH 3 = 14 gms of N 2
14 A B 0.1
(A B) ml of 0.1N HCl = gms of N 2
1000 1N
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
14 A B 0.1
X gms of coal sample contains = gms of N 2
1000 1N
1.4 Volume of Acid consumed Normality
% of Nitrogen %
Weight of coal sample(X)
Determination of Sulphur in coal
A known amount of coal is burnt completely in bomb calorimeter in presence of oxygen.
Ash thus obtained contains Sulphur of coal as sulphate, which is extracted with dil HCl.
The acid extract is then treated with BaCl2 solution to precipitate sulphate as BaSO4 .
The precipitate is filtered, washed, dried, and weighed, from which the Sulphur in coal
can be computed as follows.
Let,
X = weight of coal sample taken
M = weight of BaSO 4 precipitate formed
S 2O 2 SO 4 BaSO 4
32 233
233 gms of BaSO 4 contains 32 gms of Sulphur
32
1 gm of BaSO 4 contains gms of Sulphur
233
32
M gms of BaSO4 contains M gms of sulphur
233
Significance of Ultimate Analysis
Carbon and Hydrogen
Higher the % of carbon and hydrogen, better the quality of coal and higher is its
calorific value.
The % of carbon is helpful in the classification of coal.
Higher the % of carbon in coal reduces the size of combustion chamber required.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Nitrogen
Nitrogen does not have any calorific value, and its presence in coal is undesirable.
Good quality coal should have very little nitrogen content.
Sulphur
Though Sulphur increases the calorific value, its presence in coal is undesirable
because
The combustion products of Sulphur, i.e., SO 2 and SO3 are harmful and have
corrosion effects on equipment.
The coal containing Sulphur is not suitable for the preparation of metallurgical
coke as it affects the properties of the metal.
Oxygen
Lower the % of oxygen higher is its calorific value.
As the oxygen content increases its moisture holding capacity increases and the
calorific value of the fuel is required.
Carbonization of coal
Heating of coal in absence of air at high temperature to produce a residue coke, tar and
coal gas is called as carbonization.
Caking of coal
When coal is heated strongly, the mass becomes soft and coherent, and then it is called
caking of coal.
Coking of coal
Otherwise, if the mass produced is hard, porous and strong then it is called coking of coal.
Not all the caking coals form strong, hard and coherent residue coke. Hence, all the caking
coals are not necessarily coking coal but all the coking coals have to be necessarily caking
in nature.
Metallurgical Coke
When bituminous coal is heated strongly in absence of air, the volatile matter escapes out
and a lustrous, dense, strong, porous and coherent mass is left, which is called
metallurgical coke.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Properties or Characteristics of Metallurgical Coke
The most important industrial use of coke is in the metallurgical industry, especially in
the blast furnace. Good coke for metallurgy should possess the following requirements.
Purity: Low moisture and ash content are desirable in metallurgical coke. It must
contain minimum % of P and S.
Porosity: High porosity is desirable in furnace cokes to obtain high rates of combustion.
Strength: The coke should be hard and strong to withstand pressure of ore, flux etc. in
the furnace.
Size: Metallurgical coke must be uniform and medium size.
Calorific value: The Calorific Value of coke should be high.
Combustibility: It should burn easily.
Reactivity: It refers to its ability to react with O 2 , CO 2 , steam and air. The metallurgical
coke must have low reactivity.
Cost: It must be cheap and readily available.
Why is Coke superior as a Metallurgical fuel?
Coke is stronger and more porous than coal.
Coke contains lesser amount of Sulphur than coal.
Coke does not contain much volatile matter.
Manufacturing of Metallurgical Coke
Mainly two types of ovens are used for metallurgical coke production. They are
Beehive Coke Oven Process
Otto Hoffman’s by-product method
Beehive Coke Oven Process
The oven is a dome shaped structure and made up of firebricks. There are two openings,
one at the top and the other at the side. Coal is charged through the top circular opening
whereas coke is removed through the side door after carbonization. The side door also
acts as air inlet.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Beehive Coke Oven
Its typical dimensions are, height = 2 m; base diameter = 3.5 m and capacity = 5 tons of
coal.
First, some air is supplied in to the oven to ignite the coal. The volatile matter present in
coal escapes and burns inside. Therefore, heat for carbonization is supplied by burning of
volatile matter and partly by coal itself.
Carbonization proceeds, from top to bottom. It takes about 3 to 4 days to complete. The
hot coke is then removed through the side door and quenched with water.
Demerits of Beehive Coke Oven: Since volatile matter present in coal escapes into
atmosphere as waste, we cannot recover any byproduct. Large coking time and coke yield
of only 60% are other demerits.
Otto Hoffman’s by-product method
In order to increase the thermal efficiency of the carbonization process and recover the
valuable by products (like coal gas, ammonia, benzene, etc.) Otto Hoffman developed
modern by-product coke oven.
The oven consists of a number of silica chambers. Each chamber is about 10 - 12 m long,
3 - 4 m height and 0.4 - 0.45 m wide. Each chamber is provided with a charging hole at
the top, it is also provided with a gas off take valve and iron door at each end for
discharging coke.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Otto Hoffman’s by-product coke oven
Coal is introduced in to the silica chamber and the chambers are closed. The chambers
are heated up to 1200°C by burning pre heated air and the producer gas mixture in the
interspaces between the chambers.
The air and gas are preheated by sending them through 2nd and 3rd hot regenerators.
Hot flue gases produced during carbonization are allowed to pass through 1st and 4th
regenerators are heated by hot flue gases, the 2nd and 3rd regenerators are used for
heating the incoming air and gas mixture.
For economical heating, the direction of inlet and flue gases are changed frequently. The
above system of recycling the flue gases to produce heat energy is known as the
regenerative system of heat economy. When the process is complete, the coke is
removed and quenched with water.
Time taken for complete carbonization is about 12 - 20 hours. The yield of coke is about
70 %.
The valuable by products like coal gas, tar, ammonia, H2S and benzene, etc. are removed
from the flue gas.
Recovery of by products:
Tar: The coke oven gas is first passed through a tower in which liquor ammonia is
sprayed. Tar and dust get collected in a tank below, which is heated by a steam coil to
recover back the ammonia sprayed.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Ammonia: The gas is then passed through the other tower where water is sprayed.
Ammonia gets converted to NH4OH .
Benzene and other aromatic compounds: The gas is then passed through the next
tower in which creosote oil is sprayed. Benzene and other aromatic compounds are
dissolved in the oil and recovered.
Hydrogen sulphate: The gas then enters into a purifying chamber packed with Fe2O3,
which removes any Sulphur compound present in coal gas.
Advantages of Otto Hoffman’s process:
High thermal efficiency and carbonization time is less.
Valuable by products (like coal gas, ammonia, benzene, etc. are recovered as by
products. Heating done externally by producer gas.
Liquid Fuels: Petroleum and its varieties are Liquid fuels.
Petroleum or crude oil is a naturally occurring brown to black colored viscous oil formed
under the crust of earth, on shore or off shore. Chemically it is a mixture of various
hydrocarbons with small amounts of N, O, S compounds.
The approximate composition of petroleum is
C = 80 - 84%, H = 10 - 14 %, S = 0.1 - 0.5 %, N + O = Negligible
Advantages of Liquid fuels
Liquid fuels do not yield any ash after burning.
They require comparatively less storage space.
Calorific value of liquid fuel is higher than that of solid fuels.
Their combustion is uniform and easily controllable.
Disadvantages of liquid fuels
Liquid fuels are comparatively costlier than the solid fuels.
They give unpleasant odour during incomplete combustion.
Some amount of liquid fuels will escape due to evaporation during storage.
Special type of burners are for effective combustion.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Classification of Liquid Fuels: Petroleum is classified based on various types of
hydrocarbons.
Paraffin based oil: Contains mainly n - alkanes (e.g. Pennsylvanian and gulf coast oil)
Asphalt base oil: Contains aromatic and alicyclic hydrocarbons. (e.g. Californian oil)
Mixed base oil: Contains higher proportion of aromatics and naphthenic (cyclo
alkanes). (e.g. Mexican oil)
Refining of Petroleum (or) Crude Oil
The process of removing impurities and separating out the oil into various fractions
having different boiling points is known as refining of petroleum.
Fractional distillation of crude oil
Removal of Impurities
The impurities present in the oil are the fine water droplets, NaCl, MgCl 2 , Sulphur etc.
The crude oil is an extremely stable emulsion of oil and salt water. Water is separated
from the oil by Cottrell’s process using ring electrodes. In this method, the crude oil is
allowed to flow between two highly charged electrodes. The colloidal water droplets
combine to form large drops, which are then separated from oil.
Modern techniques like electrical desalting are used to remove NaCl and MgCl 2 from oil.
Sulphur is removed by treating the oil with copper oxide and separated by filtration.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Fractional Distillation
The purified crude oil is heated in a furnace called oil heater where the temperature will
be around 400o C . Here the oil gets vaporized. The hot vapors are then sent to the
fractionating column.
It is a tall cylindrical tower consisting of a number of horizontal stainless steel tray at short
distances. Each tray is provided with a small chimney, which is covered with a loose cap.
The tower will be hot at the lower end and comparatively cooler at the upper end.
When the oil vapors go up in the tower, they become cool and condense. The heavier
compounds having higher boiling points get cooled first and condensed in the trays
whereas the fractions having lower boiling points condense near the top of the tower.
Lower fractions are used after purification while the high boiling point fractions are
subjected to cracking operation to get more useful lower fractions.
The gasoline obtained by this fractional distillation is called straight-run gasoline. Various
fractions obtained at different trays are given in Table below
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Heavy oils on refraction gives
Some important fractions of petroleum
Petrol (or) Gasoline C5 C9 :
It is a low boiling fraction of petroleum obtained between 40 - 120o C.
It is a mixture of hydrocarbons pentane to nonane (in terms of carbon atoms
C5 C9 ).
Its calorific value is about 11,250 kcals/kg.
It is used as fuel in ICE of automobiles and aero planes.
Its antiknock value can be improved by the addition of Tetra Ethyl Lead (TEL).
Uses: It is used as a fuel in IC engine and also used in dry cleaning and as a solvent.
Naphtha C9 C10 :
It is a colorless, light fraction obtained between 1200C to 1800C during fractional
distillation of petroleum.
It is a mixture of hydrocarbons such as nonane and decane.
Uses: Naphtha is also called as white spirit, which is generally used in dry cleaning and
as thinner for varnish, floor and furniture polishes etc. The lightest portion of the distillate
is used as solvent for fats and rubbers, whereas the heaviest portion of the same is
used as a fuel.
Kerosene C10 C16 :
It is relatively a high boiling fraction obtained between 180 250 o C during fractional
distillation of petroleum. It is a mixture of hydrocarbons such as decane to hexadecane
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
approximate composition is C = 84%, H = 16%, > 0.1% S. Its calorific value is about 11,100
kcal/kg.
Uses: It is mainly used as a domestic fuel in stoves and lamps. It is also used as jet engine
fuel and for making oil gas.
Diesel C15 C18 :
It is also a high boiling fraction obtained between 250 320 o C during fractional
distillation of petroleum. It is a mixture of hydrocarbons such as C15H32 to C18H38 . Its
calorific value is about 11,000 kcal/kg.
Uses: It is used as a very good diesel engine fuel.
Heavy oil or Residual fuel oil C17 – C30 :
The left over portion of petroleum after distilling off all the lighter fractions are called
Fuel Oil. The approximate composition of fuel oil is C = 86%, H = 12%, S = 1%, H 2 O =
0.6%, sediments = 0.4%. Its calorific value is about 9200 kcal/kg.
The following fractions are obtained on further vacuum distillation of the fuel oil.
1. Light fuel oil = 350 420 o C
2. Heavy neutral oil = 420 500o C
Uses: It is used as fuel for ships and also used in metallurgical furnaces. Gasoline is also
obtained from oil by cracking process.
Asphalt:
Asphalts are obtained by
1. The oxidation of residual heavy oil in presence of air at higher temperature.
2. The deep vacuum distillation of residual heavy oil.
Asphalts are available in the market in liquid, semi-solid and solid forms.
Uses: It is used for road making and making water-proofing roofs. It is also used for the
manufacture of water proofing concrete and water proofing paints.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Cracking
Cracking is defined as “the decomposition of high boiling hydrocarbons of high molecular
weight into smaller, low boiling hydrocarbons of low molecular weight”
The crude oil on fractional distillation yields only about 15 - 20 % gasoline. This is known
as Straight Run Gasoline.
The quality of straight run gasoline is not so good. It contains mainly straight chain
paraffin’s, which ignite readily and more rapidly than any other hydrocarbons and hence
it produces knocking (unwanted sound) in IC engines.
In order to overcome these difficulties and also to improve the quality of gasoline, high
boiling fractions are cracked into more valuable low boiling fractions suitable for SI
engines. The gasoline obtained by cracking is called Cracked Gasoline.
During cracking
Straight chain alkanes are converted into branched chain hydrocarbons.
Saturated hydrocarbons are converted into mixture of Saturated and Unsaturated
hydrocarbons.
Aliphatic alkanes are converted into cyclic alkanes.
All hydrocarbons obtained by cracking have lower boiling point than the parent
hydrocarbons.
Types of cracking
There are two kinds of cracking
1. Thermal cracking
2. Catalytic cracking
1. Thermal Cracking:
When cracking is carried out a higher temperature and pressure without any catalyst, it
is called Thermal cracking. There are two types of thermal cracking:
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
i) Liquid phase Thermal cracking
In this method, the heavy oil is cracked at a temperature of 475 530 0 C under high
2
pressure of 100 kg / cm to keep the reaction product in liquid state. The cracked products
are then separated into various fractions in a fractionating column. The yield of gasoline
is about 50-60% and the octane number is 65-70.
ii) Vapour phase thermal cracking
In this method, the heavy oil is first vapourised and then cracked at a temperature of
600 650 0 C under a lower pressure of 10 20 kg/ cm . The yield of gasoline is about 70%.
2
This process is suitable only for those oils which are readily vapourised.
2. Catalytic Cracking:
When cracking is carried out at lower temperature and pressure in the presence of
suitable catalyst, it is called Catalytic Cracking. The Catalyst used are aluminium silicate
or alumina. There are two types of catalytic cracking.
i) Fixed bed catalytic cracking
The heavy oil vapour is heated to 420 450 o C in a preheated chamber. The hot vapours
are then passed through a catalytic chamber, maintained at 425 450 o C and 1.5 kg/ cm2
pressure, where catalyst (artificial clay mixed with zirconium oxide), are kept in fixed
beds. During this passage through the catalytic chamber about 40% of the heavy oil is
converted into gasoline and about 2-4% carbon is formed.
Fixed bed catalytic cracking
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
The carbon gets adsorbed on the catalyst bed. The cracked vapours are then passed
through the fractionating column, where heavy oil gets condensed at the bottom. The
vapours of gasoline are then sent through the cooler where gasoline gets condensed along
with some gases. The gasoline containing some dissolved gases is then sent to a stabilizer,
where the dissolved gases are removed and pure gasoline is recovered.
After 8-10 hours, the catalyst loses its activity due to the deposition of carbon. It is
reactivated by burning off the deposited carbon.
ii) Moving bed or Fluid bed catalytic cracking
In this process, the solid catalyst is finely powdered, so that it behaves as a fluid, which
can be circulated in oil vapour (as shown in figure below)
Moving bed catalytic cracking
The heavy oil vapour is heated to 420 450o C in a preheater and it is mixed with the
catalyst powder. Then this mixture is forced into the reactor, which is maintained at a
temperature of 500 o C and a pressure of 5 kg / cm 2 , where cracking takes place. Near the
top of the reactor, there is a centrifugal separator (called cyclone), which allows only the
cracked oil vapours to pass on to the fractionating column leaving behind the catalyst
powder in the reactor itself.
The catalyst powder gradually becomes heavier, due to coating of carbon and it settles
down at the bottom of the reactor. Then it is forced into the regenerator maintained at
600 o C , where carbon is burnt and the regenerated catalyst is again recirculated along the
heavy oil vapour.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
From the reactor, the cracked oil vapours are passed into the fractionating column, where
heavy oil settles down and the vapours are then passed through the cooler where gasoline
condenses along with some gases. The dissolved gases are separated from gasoline by
passing it through a stabilizer.
Manufacture of Synthetic Petrol
Any one of the following methods can synthesize petrol
1. Polymerization:
The gases produced in cracking contain C3 and C4 olefins (iso propylene, iso butylene etc)
and alkanes (methane, ethane, propane, butane). These gases undergo Polymerization in
presence of catalyst, H3PO4 at suitable temperature and pressure to give gasoline
(Polymer petrol), rich in branched chain hydrocarbons.
Hence, Polymerization is mainly for the production of superior gasoline and is
complementary to catalytic cracking.
Polymerization is of two types
Thermal Polymerization
Polymerization of cracked gases is carried out at 500 600C and 70 350 kg/ cm2
pressure. The product is the gasoline and gas oil mixture, from which gasoline is separated
by fractionation.
Catalytic Polymerization
This process is carried out in presence of catalyst like H3PO4 . By this method isobutylene
can be polymerized to give higher olefin’s which is hydrogenated to gasoline
hydrocarbons.
2. Hydrogenation of Coal
Coal contains 4.5 % of Hydrogen, whereas petroleum contains 18 % of hydrogen. So coal
is a hydrogen deficient compound, if coal is heated with hydrogen at high temperature
and high pressure, it is converted in to gasoline. The preparation of liquid fuels from solid
coal is called Hydrogenation of coal.
Petrol can be synthesized by destructive hydrogenation of coal (Bergius process) and
liquification of coal (Fischer - Tropsch process).
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Bergius Process or Direct Process
The raw materials used in this process are coal dust, heavy oil and nickel oleate or tin
oleate.
A coal paste is prepared by mixing coal dust with heavy oil and catalyst. It is then pumped
into the converter where the paste is heated to 450 500C under 200 - 250 atm in
presence of hydrogen.
Bergius Process
The reaction products mainly contain mixture of hydrocarbons.
Since the reaction is exothermic, the vapours leaving the converter are condensed in the
condenser to give synthetic petroleum or crude oil.
The oil is then fractionally distilled to give
(i) Petrol (ii) Middle oil (iii) Heavy oil.
Middle oil is again hydrogenated in presence of solid catalysts to produce more amount
of gasoline. Heavy oil is used for making paste with fresh coal dust. Yield is about 60 %.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Fisher Tropsch Process or Indirect Process
The raw materials used in this process are hard coke, steam to produce water gas i.e.,
water gas is obtained, by passing steam over red hot coke.
The first step in this process is purification of gas. To remove HS
2 , the gas is passed
through Fe2O3 and to remove organic Sulphur compounds, the gas is again passed through
a mixture of Fe2O3and Na2CO3.(as shown in the figure).
Fisher Tropsch Process
The purified gas is compressed to 5 - 25 atm. and passed over a catalyst bed containing
oxides of Th, Co and Mg at 200 300 o C . While passing the purified gas through this
catalyst bed, it is converted to straight chain paraffin and olefins.
Since the reactions are exothermic, the vapours leaving the vessel are condensed in the
condenser to give petroleum. It is fractionally distilled to yield petrol and heavy oil.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
3. Alkylation:
Replacement of hydrogen atom from a hydrocarbon by an alkyl group is known as
Alkylation.
Example: The reaction of isobutane and isobutene in the presence of anhydrous HF at
room temperature gives isooctane. This process is highly useful for the production of high
quality petrol.
Purification of Petrol (or) Gasoline:
Gasoline or petrol obtained either from crude oil or synthetic process may contain some
undesirable impurities. They are mainly unsaturated olefins, colouring matters, Sulphur
compounds etc.
The unsaturated olefins get oxidised and polymerised there by causing gum and sludge
formation on storing.
On the other hand, Sulphur compounds lead to corrosion of ICE and also affect tetra ethyl
lead (TEL) which is added to gasoline to obtain good petrol. So these undesirable contents
must be removed from gasoline. Unsaturated olefins and colouring matter are removed
by using adsorbent like Kieselguhr, fuller’s earth.
Sulphur containing petrol is known as sour spirit.
The process of de-sulphurisation of petrol is called sweetening of petrol.
Desulphurisation:
It can be done by Doctor’s treatment. i.e.; petrol is treated with an alkaline solution of
sodium plumbite (Doctor’s solution) and little of Sulphur.
The resulting disulphide (lead mercaptide) in gasoline are extracted by using suitable
solvent. After refining of gasoline, some inhibitors or antioxidants are added in order to
retard the oxidation of olefins (olefin peroxide) which cause the formation of gum on
storage.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Knocking
Fractions like petrol and diesel oil are used as engine fuels. Piston engines can be divided
into spark ignition (SI) and compression ignition (CI) engines. The former consumes
petrol and the latter operates on diesel oil.
SI Engines
In a four stroke SI engine, petrol vapour is mixed with air in the carburetor. It is sucked
into the cylinder during the suction stroke. The mixture is compressed by the piston in
the compression part of the cycle. Then the compressed mixture is ignited by an electric
spark. The product of combustion increases pressure and pushes the piston out, providing
an output of power.
In the last part of the cycle, the piston ascends and expels the exhaust gases from the
cylinder.
Knocking in SI Engines (Petrol Engines)
Normally the fuel - air mixture should burn smoothly and rapidly by sparking. In some
cases, as a result of compression, the fuel-air mixture may get heated to a temperature
greater than its ignition temperature and spontaneous combustion occurs even before
sparking. This is called pre-ignition.
Further, the spark also is emitted which makes the combustion of the rest of the mixture
faster and explosive. So, we have a sudden, badly controlled burning and explosion results
a characteristic metallic or rattling sound from the engine. This is called knocking or
detonation or pinking. Knocking lowers the efficiency of engine which results in loss of
energy.
Chemical Structure and Knocking
The knocking tendency decreases as follows:
n-alkanes have lowest antiknock value. So the presence of maximum quantity of
aromatics and minimum quantity of n-alkanes is desirable in petrol.
Octane number (Measurement of knocking in SI engines)
Octane number expresses the knocking characteristics of petrol. n - heptane (a
constituent of petrol) knocks very badly, so its anti-knock value has been given zero. On
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
the other hand, iso-octane (also a constituent of petrol) gives very little knocking, so its
anti-knock value has been given 100.
Percentage of iso-octane present in iso octane & n-heptane mixture, which matches the
same knocking characteristics of gasoline mixture test sample.
If a petrol, sample behaves like a mixture of 60% iso-octane and 40% n-heptane, its octane
number is taken as 60.
Leaded Petrol (or) Improvement of Anti-knock Value
Adding some additives in it increases octane number of petrol. In motor fuel about 1.0 to
1.5 ml tetra ethyl lead (TEL) is added per litre of petrol. Petrol to which TEL is added is
called leaded petrol.
Disadvantage of using TEL
TEL forms lead oxide, which deposits on spark plug and creates problems. So, to remove
it, ethylene dibromide is added. During burning lead bromide is formed which evaporates
away in the heat engines and goes out together with exhaust gases. This creates
atmospheric pollution for human beings. Hence, at present aromatic phosphates are used
instead of TEL.
Diesel C15 C18 :
It is also a high boiling fraction obtained between 250 320 o C during fractional
distillation of petroleum. It is a mixture of hydrocarbons such as C15H32 to C18H38 . Its
calorific value is about 11,000 kcal/kg.
Its antiknock value can be improved by doping with isoamyl nitrate.
CI Engines
In a CI engine, air is alone compressed. This raises the cylinder temperature as high as
300o C. Then the oil is injected or sprayed, which must ignite spontaneously. Now
combustion products expand and power stroke begins.
Knocking in CI Engines
Sometimes, even after the compression stroke is over and even after the diesel oil is
sprayed, burning may not start. So, more and more fuel is injected automatically and
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
sudden ignition may occur and burn the whole of the oil. This delayed ignition results an
uncontrolled, excessive combustion produces ‘diesel knock’.
Therefore, in SI - engine, knocking is due to premature or too early ignition, While in CI
- engines, knocking is due to delayed ignition or ignition lag.
Cetane number (or) Cetane Rating
Cetane number expresses the knocking characteristics of diesel. Cetane C16H34 has a very
short ignition delay and hence its cetane number is taken as 100. On the other hand, α
methyl naphthalene has very large ignition delay and hence its cetane number is taken as
zero.
Cetane number is defined as “the percentage of cetane present in a mixture of α methyl
naphthalene and cetane”.
Chemical Structure and Knocking
The knocking tendency in CI - engines increases as follows
Octane numbers decreases in this order. Therefore an oil of high octane number has a low
cetane number and vice-versa. Consequently, petroleum crude gives petrol of high octane
number and diesel of low cetane number.
Diesel Index
The quality of a diesel oil is indicated by diesel index number using the following formula
Diesel index number API Aniline point in o F
Diesel index number
100
Aniline point and specific gravity is noted from API (American Petroleum Institute) Scale.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Comparison between Petrol and Diesel:
Sr. No. PETROL DIESEL
1. Low boiling petroleum C5 – C10 High boiling fraction of petroleum
contains C15 – C18 hydrocarbons
2. Fuel for SI engine Fuel for CI engine
3. Knocks due to premature ignition Knocks due to ignition delay
4. Knocking tendency measured in Knocking tendency measured in
octane rating cetane rating.
5. Anti-knocking is improved through Anti-knocking is improved by doping
addition of TEL with isoamyl nitrate
6. Lower thermal Efficiency Higher thermal efficiency
7. More consumption Less consumption
Improvement of cetane number
Adding additives called dopes can increase cetane number. E.g.: ethyl nitrate, isoamyl
nitrate.
Aviation gasoline:
Low molecular weight petroleum fraction, which is used as a fuel in aero planes is known
as Aviation Gasoline. It condenses at 30 120 o C during fractional distillation of crude oil.
Its octane number is 100 or even more.
Aviation gasoline may also be produced by the Polymerisation, alkylation, isomerisation
and reforming process.
Generally aviation gasoline is made up of higher percentage of isoparaffins and smaller
percentage of naphthalene’s, an aromatics.
Aviation gasoline possesses very good stability, higher volatility and antiknock value than
ordinary gasoline and in some cases; TEL is mixed with aviation gasoline.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Gaseous Fuels:
Natural Gas
Natural gas is always found above the oil in the oil wells. It is also called Marsh gas. It
consists of methane and other saturated hydrocarbons. The average composition of
natural gas is as follows:
Its calorific value varies from 12,000 to 14,000 kcal / m 3 .
Constituents Percentage (%)
Methane 88.5
Ethane 5.5
Propane 4.0
Butane 1.5
Pentane 0.5
If natural gas contains lower hydrocarbons like methane and ethane it is called lean or
dry gas. In the natural gas contains higher hydrocarbons like propane, butane along with
methane it is called rich or wet gas.
Uses:
1. It is used as a domestic and industrial fuel.
2. It is used as a raw material for the manufacture of carbon black and hydrogen.
3. It is also used for the generation of electricity by using it in fuel cells.
Water Gas or Blue Gas
Water gas essentially a mixture of combustible gases like CO, H 2 with a little non-
combustible gases like CO 2 and N 2 .
Calorific Value: Its Calorific Value is 2800 kcals / m 3 .
Composition: The average composition is
H2 = 48 %, CO = 44 %, CO2 , N2 and CH4 = rest
Production: A Water gas generator is a steel cylindrical vessel. At the top, it is provided
with a hopper for adding coke. Water gas outlet is provided near the top. At the bottom,
it is provided with an arrangement of taking out ash formed (as shown in figure)
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Water gas production
In order to avoid the above undesirable reaction, the blow of air replaces the blow of
steam. The following reaction now occurs.
Due to exothermic reactions, the temperature of the bed rises and when the temperature
increases to 1000° C, air entry is stopped and steam is again passed. Thus steam and air
are blown alternatively. Therefore, the manufacture of water gas is intermittent.
Properties: It has high Calorific Value & burns with non- luminous flame. Its flame is
short but very hot.
Uses:
1. It is used for the manufacture of ammonia by Haber’s process.
2. Carbureted water gas (water gas + oil gas) is used for lighting and heating purposes.
3. Water gas is also used for welding purposes.
4. Used for the manufacture of methyl alcohol.
5. Used for the manufacture of synthetic petrol.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Producer Gas
It is prepared by passing air mixed with a little steam over a red hot coal (or) a coke bed
maintained at above 1100° C in a special reactor called ‘‘ Gas Producer’’.
Composition: It is a mixture of CO and N 2 . Its average composition is
N 2 = 50 %, CO = 30 %, H 2 = 10 %, CO 2 and CH 4 = rest.
Calorific Value: Its Calorific value is 1800 kcal/m 3
Manufacture: The furnace used for the manufacture of producer gas is known as
producer. It consists of large airtight mild steel cylindrical tower, lined inside with
refractory bricks. At the bottom, it is provided with pipe for blowing air and an
arrangement for removing ash. Coal is added through a hopper at the top and producer
gas comes out from an exit near the top.
Combustion zone: When a mixture of air and little steam is passed through a bed of
red-hot coal, carbon (of the coal) combines with oxygen (of the air) in the lower part of
the furnace to form CO 2 .
C + O2 CO2 + 97 kcals
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
Reduction zone: CO 2 so formed rises up through the red-hot coal and gets reduce to
CO during its passage
CO2 + C 2CO 39kcals
N 2 of air remain unaffected throughout the process. Thus, a mixture of CO and N 2 with
traces of CO 2 and hydrocarbons comes out through the exit at the upper end of the
producer.
Properties:
1. It is a poisonous gas.
2. Insoluble in water.
3. Heavier than air.
Uses:
1. It is used as fuel for heating open - hearth furnaces (used in steel and glass
manufacture), muffle furnaces (used in coal gas and coke manufacture).
2. It provides reducing atmosphere in certain metallurgical operations.
Liquefied Petroleum Gas (LPG)
It is a mixture of propane and butane. It is obtained as one of the top fractions in the
fractional distillation of petroleum. It is easily liquefied and so can be economically stored
and transported in cylinders.
Composition:
Its approximate composition is
n-Butane = 70 %, Isobutane = 17 %, n-Propane = 11 %, Butylene and Ethane = rest.
Calorific Value: Its Calorific value is 27,000 kcal/m 3
Uses:
1. It is used as a fuel for domestic cooking.
2. Used for heating industrial furnaces.
3. Used as an alternate for Gasoline in automobiles.
Biogas
These gases generally produced by the fermentation of bio wastes, sewage wastes etc., by
anaerobic bacteria. For example: natural gas is a Biogas, which results after a long
periodic decay of animal and vegetable matters buried inside the earth. The cheapest and
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Fuels
easily obtainable biogas is Gobar gas, which is produced by anaerobic fermentation of
cattle dung. The biogas is burnt to raise steam, which can drive turbines to produce
electricity.
Bio Gas Plant
Composition: It is essentially methane. Its average composition is
CH 4 60 %, CO 2 30 %, H 2 10 %
Calorific Value: Its Calorific Value is 5400 kcals / m 3 .
Manufacture: It is obtained by fermentation of Gobar (dung) in absence of air. In a
typical Gobar gas plant, the dung in the form of slurry is introduced into a brick - lined
well-called fermentation well.
An inverted drum is placed air tightly on the well. It acts as gasholder and it can be moved
up and down with the help of pulleys
Formation of gas starts in a week. The optimum temperature for this fermentation is
34 48o C . As the gas starts collecting in the drum, the drum begins to rise and float. The
gas is taken out from the exit provided at the top of the drum.
Uses:
1. It is used as a domestic fuel in villages.
2. It is used for domestic heating and small pump running.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
5 COMBUSTION
Introduction
Combustion is an exothermic chemical reaction, which is accompanied by development
of heat and light at a rapid rate, temperature rises considerably. For example, combustion
of carbon in oxygen:
C(s) +O2(s) CO2(g) + 97 kcal
For proper combustion, the substance must be brought to its kindling (or) ignition
temperature, which may be defined as the minimum temperature at which the substance
ignites and burns without further addition of heat from outside.
Factors affecting the rate of combustion
The rate of combustion depends on the following factors:
1. The concentration of the fuel and air.
2. The nature of the combustible substance
3. The temperature
4. With increase in pressure or surface area of the fuel the rate of combustion can be
increased.
5. It increases with increase in pressure of air.
6. It Increases with preheating of fuel and air.
Calorific Value
It is the most important characteristic property of any fuel.
Calorific value may be defined as “the amount of heat liberated by the complete
combustion of a unit mass of a fuel”.
The following units can measure the quantity of heat: Calorie, Kilocalorie, British thermal
units, Centigrade heat units
Calorie
The amount of the heat required to raise the temperature of 1 gm of water through
1 C (15 to 16 C )
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
Gross Calorific Value (GCV)
The total heat generated when a unit quantity of fuel is completely burnt and the products
of combustion are cooled to room temperature. It is also called as Higher Calorific
Value (HCV)
For example, when a fuel containing hydrogen is burnt, it under goes combustion and will
be converted to steam. If the combustion product is cooled to room temperature, the
steam gets condensed into water and the latent heat is evolved. Therefore, the latent heat
of combustion of condensation of ‘steam’ so liberated is included in gross calorific value.
Dulong’s formula (Theoretical calculation)
Theoretical calculation of Gross calorific value is given by Dulong’s formula
1 O
GCV (or) HCV = 8080 C 34500 H 2240 S kcal / kg
100 8
Where, C, H, O & S represent the % of the corresponding elements in the fuel.
It is based on the assumption that the calorific values of C, H & S are found to be 8080,
34500 and 2240 kcal, when 1 kg of the fuel is burnt completely. However, all the oxygen
in the fuel is assumed to be present in combination with hydrogen in the ratio H : O as 1 :
O
8 by weight. Therefore, the surplus hydrogen available for combustion is H .
8
Net Calorific Value (NCV)
The net heat produced when a unit quantity of fuel is completely burnt and the products
of combustion are allowed to escape. It is also called as Lower Calorific Value (LCV)
NCV = GCV 0.09H × 587 kcal/kg
where , H = % of H 2 in the fuel.
Determination of Calorific value using Bomb Calorimeter
The calorific value of a solid or liquid fuel can be determined by using bomb calorimeter.
The bomb calorimeter consists of a strong stainless steel bomb inside of which the fuel
sample in burnt. The bomb is provided with an oxygen inlet valve and two stainless steel
electrodes. To one of the electrodes, a small ring is attached. In this ring, a nickel or
stainless steel crucible is placed.
The bomb is placed in a copper calorimeter containing a known weight of water. The
copper calorimeter containing a known weight of water. The copper calorimeter is
provided with a Beckmann thermometer and a stirrer for stirring water. The copper
calorimeter is surrounded by an air jacket and water jacket.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
Procedure: A known weight of the fuel sample is taken in the crusible. A fine magnesium
wire, touching the fuel sample, is then stretched across the electrodes. The bomb lid is
tightly screwed. The bomb is filled with oxygen at 25 atmospheric pressure. The bomb is
kept in a copper calorimeter containing a known weight of water. Initial temperature of
the water in the calorimeter is noted after thorough stirring. The electrodes are then
connected to 6-volt battery. The current is switched on and the fuel sample in the crucible
burns with the evolution of heat. The heat liberated raises the temperature of water in the
calorimeter. The final maximum temperature of the water is noted. The calorific value of
the fuel can now be calculated as follows
Calculations of Gross Calorific Value:
Weight of the fuel taken in the crucible x gms
Weight of the water in the calorimeter W gms
Water equivalent of the calorimeter and stirrer w gms
Initial temperature of water in the calorimeter t1C
Final temperature of water in the calorimeter t2C
Higher calorific value of the fuel (to be determined) = G.C.V.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
Heat absorbed by water W t 2 t1 cal
Heat absorbed by calorimeter w t 2 t1 cal
Heat absorbed by water and calorimeter W t 2 t1 + w t 2 t1 cal = W w t 2 t1 cal
Heat liberated by the fuel x G.C.V.
Since,
Heat liberated by the fuel = Heat absorbed by the water and calorimeter
x G.C.V. = W w t 2 t1
G.C.V.
W w t 2 t1 cal/gm
x
Calculations of Net Calorific Value:
The percentage of Hydrogen in the fuel = H
Weight of water produced from 1 gm of the fuel = 0.09 H gms
Heat liberated during condensation of steam is called as Latent Heat of the water
Latent Heat of the water 0.09 H 587 cal/gm
N.C.V. G.C.V. 0.09 H 587 cal/gm
Corrections:
To get more accurate results, the following corrections are made
1. Fuse wire correction:
The burning fuse wire in the bomb contributes additional heat to the bomb combustion.
Since the amount of fuse wire consumed in each test may vary, the energy contributed
by the fuse must be determined for each test and a correction applied to compensate for
this variance.
2. Acid Correction:
During ignition, S and N 2 present in the fuel get oxidized to the corresponding acids.
S 2H 2O2 H2SO4 Heat
2N 2H 3O2 2HNO3 Heat
Formation of these acids is an exothermic reaction. Hence, these heat values must be
subtracted from G.C.V.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
3. Cooling correction:
When the bomb calorimeter is allowed to cool from maximum temperature to room
temperature, some amount of heat is radiated. From the rate of cooling and actual time
for cooling, cooling correction is made and it is added to the temperature difference.
G.C.V.
W w t 2 t1 cooling correction Acid + Fuse wirecorrection cal/gm
x
Example
Q.1 The Net calorific value in kcal/kg of a coal having the following compositions
C 80 %, H2 8 %, O2 8 %, S 2 % and ash 2 %is_______________.
Latent heat of steam is = 587 cal/gm.
(a) 8501.16 (b) 8923.80 (c) 6325.41 (d) 3256.26
Sol:
1 O
G.C.V. = 8080 C 34500 H 2240 S kcal/kg
100 8
1 8
= 8080 80 34500 8 2240 2 kcal/kg = 8923.80 kcal/kg
100 8
N.C.V. G.C.V. 0.09 H 587 cal/gm
8923.80 0.09 8 587 cal/gm
= 8501.16 cal/g = 8501.16 kcal/kg
Q.2 On analysis, a coal sample has the following composition by weight;
C 75 %, O2 04 %, S 05 %, and ash 3%.
Net calorific value of the fuel is 9797.71 kcal / kg. The percentage of hydrogen in
coal is_________.
(a) 5 (b) 8 (c) 10 (d) 13
1 O
Sol: G.C.V. = 8080 C 34500 H 2240 S kcal/kg
100 8
1 4
= 8080 75 34500 H 2240 5 kcal/kg
100 8
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
= 5999.5 + 345 H kcal / kg
Again;
N.C.V. G.C.V. 0.09 H 587 kcal/kg
9797.71 G.C.V. 0.09 H 587 kcal/kg
G.C.V. 9797.71 0.09 H 587 kcal/kg
Using the above, two results
5999.5 + 345 H 9797.71 0.09 H 587
%of H2 13%
Theoretical Calculation of Minimum Air required for Combustion of Solid and
Liquid Fuel
In order to achieve efficient combustion of fuel, it is essential that the fuel is brought
into intimate contact with sufficient quantity of air to burn all the combustible matter
under appropriate conditions.
The correct conditions are
1. Intimate mixing of air with combustible matter and
2. Sufficient time to allow the combustion process to be completed.
If these factors are inappropriate, inefficient combustion occurs.
The elements usually present in common fuels, which enter into the process of
combustion, are mainly C, H, S and O.
Nitrogen, ash and CO 2 (if any) present in the fuel are incombustible matters and hence
they do not take any oxygen during combustion.
Air contains 21% oxygen by volume and 23% of oxygen by weight.
Hence, from the amount of oxygen required by the fuel, the amount of air can be
calculated.
From the combustion reaction equations, we can calculate the quantity of oxygen by
weight or volume and from this, the weight or volume of air required can be calculated.
For example
Combustion of Carbon:
C + O 2 CO 2
12 32 44 by weight
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
12 parts by weight of carbon require 32 parts by weight of oxygen for complete
combustion.
(or)
1 part by volume of carbon requires 1 part by volume of oxygen for complete combustion.
32 C
C parts by weight of carbon require parts by weight of O 2
12
Combustion of Hydrogen:
Oxygen when present in the fuel is always in combination with hydrogen. Therefore, the
quantity of hydrogen in combination with oxygen, which is present in the fuel, will not
take part in the combustion reaction. Therefore, the quantity of hydrogen in combination
with oxygen is deduced from the total hydrogen in the fuel.
O
Now, the quantity of hydrogen available for combustion reaction will be H , where H
8
is the total quantity of hydrogen and O is the total quantity of oxygen in the fuel. (In water
the quantity of hydrogen in combination with oxygen is one-eighth of the weight of
oxygen).
2H 2 O 2 2H 2 O
4 32 36 by weight
4 parts by weight of hydrogen require 32 parts by weight of oxygen for complete
combustion.
(or)
2 parts by volume of hydrogen require 1 part by volume of oxygen for complete
combustion.
32H
H parts by weight of hydrogen requires = parts by weight of O 2
4
However, some of the hydrogen is present in the combined form with oxygen (i.e, as H2O).
This combined hydrogen does not take part in the combustion reaction. Therefore, the
quantity of combined hydrogen must be deduced from the total hydrogen in the fuel.
O O
H part by weight of hydrogen requires 8 H parts by weight of O2
8 8
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
Combustion of Sulphur:
S + O 2 SO 2
32 32 64 by weight
32 parts by weight of Sulphur requires 32 parts by weight of oxygen for complete
combustion.
(or)
1 part by volume of sulphur requires 1 part by volume of oxygen for complete
combustion.
S parts by weight of sulphur requires = S parts by weight of O 2
Combustion of Nitrogen:
N2 is a noncombustible constituent. They do not burn and do not require any oxygen.
Theoretical amount of oxygen required for the complete combustion of 1kg
of solid or liquid fuel:
32 O
Theoretical minimum O2 C 8 H S kg
12 8
Theoretical amount of Air required for the complete combustion of 1kg of
solid or liquid fuel:
100 32 O
Air (theoretical) = C 8 H S kg
23 12 8
Excess air for combustion:
It is necessary to supply excess air for complete combustion of the fuel. It is found out
from the theoretical amount of air as follows. The amount of air required if excess air is
supplied, is given by
Theoretical amount of air
100 % of excess air
100
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
Example
Q.1 Calculate the minimum theoretical quantity of air needed for the combustion of 10
kg of coal, which is 95 % pure.
(a) 10.25 kg (b) 14.26 kg (c) 25.36 kg (d) 13.65 kg
Sol:
100 32
Air (theoretical) = 0.95 10 kg 110.14 kg
23 12
Q.2 Calculate the minimum amount of air required for the complete combustion of 150
kgs of fuel containing 70 % Carbon, 15 % hydrogen, 5 % Sulphur and the rest
nitrogen by weight.
(a) 2032.68 kg (b) 1058.25 kg (c) 1825.23 kg (d) 1256.36 kg
Sol:
100 32 O
Air (theoretical) = C 8 H S kg
23 12 8
100 32
Air (theoretical) = 0.70 8 0.15 0.05 150 kg 2032.68 kg
23 12
Volume of Air Required for Complete Combustion of Gaseous Combustible
Matters
Combustion of Hydrogen gas:
1
H 2 (gas) + O2 H 2O
2
1 Volume 0.5 Volume
1 volume of H 2 (gas) requires 0.5 vol. of oxygen
Combustion of Methane gas:
CH4 + 2O2 CO2 + 2H2O
1 Volume 2 Volume
1 volume of CH4 requires 2.0 volume of oxygen
Combustion of Carbon mono-oxide gas:
1
CO gas + O2 CO 2
2
1 Volume 0.5 Volume 1 volume of CO requires 0.5 volume of oxygen
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
Combustion of Ethane gas:
C2 H 4 gas + 3O 2 2CO 2 2H 2 O
1 Volume 3 Volume
1 volume of C2 H 4 requires 3.0 volume of oxygen
Amount of O2 required by the fuel will be given by subtracting the amount of O2 already
present in the fuel from the total or theoretical amount of O2 required by the fuel.
Theoretical amount of oxygen required for the complete combustion of 1-
Volume of gaseous fuel:
Theoretical minimum O2 required Total amount of O2 required O2 already present in the fuel
Air contains 21 % of O2 by volume and 23 % of O2 by weight. Hence, from the amount of
O2 required by the fuel, the amount of air required can be calculated.
Theoretical amount of Air required for the complete combustion of 1
Volume of gaseous fuel:
100
Minimum volume of air required Theoretical minimum O2 required
21
Excess air for combustion:
It is necessary to supply excess air for complete combustion of the fuel. It is found out
from the theoretical amount of air as follows. The amount of air required if excess air is
supplied, is given by
Theoretical amount of air
100 % of excess air
100
Example
Q.1 Calculate the volume of air (Volume % of O2 in air = 21) required for complete
combustion of 1 litre of CO
(a) 2.38 litre (b) 4.30 litre (c) 3.25 litre (d) 2.24 litre
Sol:
100 1 100 1
Minimum volume of air required Volumeof CO 2.38 litre
21 2 21 2
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
Q.2 What is the volume of air required in m3 for the complete combustion of 1m 3 of
mixture containing 75 % of CH4 and 25 % of C2H6 ?
(a) 12.56 (b) 11.31 (c) 2.58 (d) 6.25
Sol:
Here, Volume of CH4 0.75m ,
3
CH4 2O2 CO2 2H2O
Volume of C2H6 0.25m
3
7
C2H 6 O 2 2CO 2 3H 2 O
2
100 7
Minimum volume of air required 2 Vol. of CH4 Vol. of C2H6
21 2
100
21
2 0.75 3.5 0.25 11.309 m 3
Some important Parameters
The density of dry air is
1.29 kg/ m at 0C and 760 mm of Hg
3
1.2754 kg / m3 at STP (0 C and 100 kPa )
1.2041 kg / m3 at NTP 20C and 760 mm of Hg
x
x mm of Hg = kpa
7.501
Flue Gas Analysis - Orsat’s Method
The mixture of gases (like CO 2 , O 2 , CO, etc.,) coming out from the combustion chamber is
called flue gases. The analysis of a flue gas would give an idea about the complete or
incomplete combustion process. The analysis of flue gases is carried out using Orsat’s
apparatus.
Description of Orsat’s apparatus
It consists of a horizontal tube. At one end of this tube, a U-tube containing fused CaCl2
is connected through a 3-way stop cock. The other end of the tube is connected with a
graduated burette. A water jacket to keep the temperature of gas as a constant surrounds
the burette. The lower end of the burette is connected to a water reservoir by means of a
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
rubber tube. The level of water in the burette can be raised or lowered by raising or
lowering the reservoir.
The horizontal tube is also connected with three different absorption bulbs I, II and III
for absorbing CO2, O2 and CO.
I - bulb: It consists of ‘potassium hydroxide’ solution and it absorbs only
CO2
II - bulb: It consists of ‘alkaline pyrogallol’ solution and it absorbs only
CO2 and O2
III - bulb: It consists of ‘ammoniacal cuprous chloride’ solution and it
absorbs CO 2 , O 2 and CO.
Orsat’s apparatus
Working:
The 3-way stop cock is opened to the atmosphere and the reservoir is raised, till the
burette is completely filled with water and air is excluded from the burette. The 3-way
stop cock is now connected to the flue gas supply and the flue gas is sucked into the burette
and the volume of flue gas is adjusted to 100 cc by raising and lowering the reservoir.
Then the 3-way stopcock is closed.
Absorption of CO 2 :
The stopper of the absorption bulb-I, containing KOH solution, is opened and all the gases
is passed into the bulb-I by raising the level of water in the burette. The gas enters into
the bulb-I, where CO 2 present in the flue gas is absorbed by KOH.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
The gas is again sent to the burette. This process is repeated several times to ensure
complete absorption of CO 2 . The decrease in volume of the flue gas in the burette
indicates the volume of CO 2 in 100 cc of the flue gas.
Absorption of O 2 :
Stop cock of bulb-I is closed and stop cock of bulb-II is opened. The gas is again sent into
the absorption bulb-II, where O2 present in the flue gas is absorbed by alkaline pyrogallol.
The decrease in volume of the flue gas in the burette indicates the volume of O2 .
Absorption of CO :
Now the stop cock of bulb-II is closed and stop cock of bulb-III is opened. The remaining
gas is sent into the absorption bulb-III, where CO present in the flue gas is absorbed by
ammoniacal cuprous chloride. The decrease in volume of the flue gas in the burette
indicates the volume of CO. The remaining gas in the burette after the absorption of
CO 2 , O 2 and CO
Significance of flue gas analysis:
Flue gas analysis gives an idea about the complete or incomplete combustion process.
If the flue gases contain considerable amount of CO, it indicates that incomplete
combustion is occurring and it also indicates that the short supply of O2 .
If the flue gases contain considerable amount of O2 , it indicates that complete combustion
is occurring and also it indicates that the excess of O2 is supplied.
Ignition Temperature:
It is defined as “the lowest temperature to which the fuel must be heated, so that it starts
burning smoothly”.
The ignition temperature of coal is about 300C . In the case of liquid fuels, the ignition
temperature is called the flash point, which ranges from 200 – 400C . For gaseous fuels,
the ignition temperature is in the order of 800C .
Spontaneous Ignition Temperature (SIT):
It is defined as the minimum temperature at which the fuel catches fire (ignites)
spontaneously without external heating.
If the ignition temperature of a fuel is low it can catch fire very quickly. On the other hand
if the ignition temperature is high it is difficult to ignite the fuel. If the heat evolved in a
system is unable to escape, temperature of the system goes on increasing and when SIT is
reached, the system burns on its own.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Combustion
Explosive Range (or) Limits of Inflammability:
Most of the gaseous fuels have two percentage limits called upper limit and lower limit.
Those limits represent percentage by volume of fuel present in fuel-air mixture. The range
covered by these limits is termed as explosive range of the fuel.
For continuous burning the amount of fuel present in the fuel-air mixture should not go
below the lower limit or above the upper limit.
For example, the explosive range of petrol is 2 – 4.5. This means that when the
concentration of petrol vapour in petrol-air mixture is between 2 and 4.5 by volume, the
mixture will burn on ignition. When the concentration of petrol vapour in petrol-air
mixture is below 2% (lower limit) or above 4.5% (upper limit) by volume, the mixture will
not burn on ignition.
Calorific Intensity (or) Flame Temperature:
It is the minimum temperature reached when the fuel is completely burnt in the
theoretical amount of air.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
6 MASS BALANCE
Introduction
Material balance involves calculations the quantities of all materials that enter and
leave any system or process which are based on the principle of the "law of
conversation of mass". This law states, “Matter is neither created nor destroyed
in the process and the total mass remains unchanged”.
The general principle of material balance calculations is to put and solve a number of
independent equations involve number of unknowns of compositions and mass flow
rates of streams enter and leave the system or process.
System
The system can be defined as any arbitrary portion of a process that you want to
consider for analysis. The system boundary must be fixed in each problem by drawing
an imaginary boundary around it as shown in the following figure
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Based on energy, system is classified as
Open system
An open system is a system that freely exchanges energy and matter with its
surroundings. For example, boiling water without a lid, Heat escape into the air, at the
same time, steam (which is matter) also escapes into the air.
Closed system
A closed system is a system that exchanges only energy with its surroundings, not
matter. For example, Pressure Cooker, It allows heat to be transferred from the stove
to the water, Heat is also transferred to the surroundings
Note: If a system is 100% closed, it is in danger of exploding. Pressure cooker designed
with safety mechanisms to prevent the system from over-pressurizing by allowing
steam to escape when needed.
Isolated Systems
An Isolated system is a system that do not exchanges any energy or matter with its
surroundings. For example, An Insulated gas tank and the Universe, It do not allows
mass or Energy to transferred from the system.
Process
The process can be defined as one or a series of operations in which physical and
chemical treatments are carried out and a desired product is result in the end such as
distillation, drying, absorption, chemical manufacture, … etc.
Types and characteristics of processes based on modes of operation
Batch process
The feed materials are placed into the system (reactor, mixer, filter,….etc) at the
beginning of the process. These materials are held for a period known as "residence
time" or "retention period" during which the required physical and/or chemical
changes are occurred. The products are removed all at once after this time. No masses
crossed the system boundary during this time. Batch process fall into the category of
closed systems.
The basis used in such processes is usually "one batch", and the material balance for
physical batch processes in which there is no chemical reaction, can be written as
Semi-batch process
A semi-batch reactor of stirred type tank as shown in the Figure, often used for its own
particular characteristics. In this type, all quantity of one reactant is initially put in the
reactor,
© Copyright Reserved Gateflix.and
No partthen other
of this material reactants
should are continuously
be copied or reproduced without permission fed. Only flows enter the systems,
Mass Balance
and no leave, hence the system is an unsteady state. This arrangement is useful when
the heat of reaction is large. The heat evolved can be controlled by regulating the rate
of addition of one of the reactants.
Continuous process (Flow process)
The input and output materials are continuously transferred across the system
boundary; i.e. the feed continuously enters the system and the product continuously
leaves the system. The physical and/or chemical changes take place during the flow of
materials through the effective parts of equipment’s (packing, sieve plate, filter
cloth,…etc). A convenient period such as minute, hour, or day must chosen as a basis
over which material balance calculations be made.
This type of processes can be classified as "steady state" and "unsteady state" processes
Steady and unsteady state Process
A process or system is at steady state if all conditions (temperature, pressure,
concentration, flow rates, volume and mass) remain constant and unchanged with
time. This condition is also referred as a system in dynamic equilibrium.
In such process, there is no accumulation in the system, and the equation of material
balance can be written as:
Input = Output
For example, the concentration of nitrogen in a river is in dynamic equilibrium.
For an unsteady state process, not all of the operating conditions in the process
(e.g., temperature, pressure, compositions, flow rate,… etc.) remain constant with
time, and/or the flows in and out of the system can vary with time, hence the
accumulation of materials within can be written as follows:
Accumulation = Input Output
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
This condition is also referred as a system in Transient state.
For example, flow through a pipe of variable diameter under variable pressure due to
an increasing/decreasing water level of the reservoir or opening or closure of a valve
or stopping/starting hydraulic machines connected to the pipe.
Difference between steady state and equilibrium
A system that is in a steady state remains constant over time, but that constant state
requires continual work. This condition is also referred to as a system in dynamic
equilibrium. Were the process maintaining the system to cease, the conditions would
not remain. “A system in a steady state has a higher level of energy than its
surroundings.” Steady state processes can be as complex as interconnected
biochemical reactions or as simple as flow into and out of a system to maintain a
constant volume.
A system at equilibrium is stable over time, but no energy or work is required to
maintain that condition. No free energy will be entering or leaving a system in
equilibrium. “The system is maintained in a low free energy state that is no different
from that of its surroundings.”
General balance equation
To introduce the concept of material balance in a simple way, we may consider the
process (physical or chemical) shown in the diagram as a system. Compound A is fed
to the system at mAin and withdrawn from the system at mAout and the amount of A
in the system is originally mAsys . The process unit has no leakage.
If mAin = mAout , the two possible causes are,
A is consumed in the process unit as a reactant then mA out mAin or
generated as a product then mA out mAin .
A is accumulated in the system, with mAsys increased then mA out mAin or
decreased then mA out mAin .
The general material balance equation for a system is represented by
accumulation Input output generation consumption
Each terms Input, Output, Generation, Consumption and accumulation must have
same unit (mass/time)
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Input: materials added or fed to the system (feed)
Output: materials withdrawn from the system (products)
Generation and consumption: products formed or reactants consumed in the
system by chemical reactions.
Accumulation: The change in the quantity of material (Q) inside the system with
time t, usually represented by a derivative dQ/dt .
Material balances for steady-state systems
Under steady-state conditions, all process variables in the system including the total
quantity of material Q remain constant with time dQ / dt 0 , i.e., there is no
accumulation of material within the system, so that,
Input output generation consumption 0
Basic Process Unit Functions
Splitter
It divides a single input into two or more outputs of the same composition without
any chemical reaction. It is also called as Filter
Overall Material Balance:
Feed Rate (F) = Rate of A + Rate of B
Component Material Balance:
Component C in feed F = Component C in A + Component C is B
xF Feed rateof F xA rateof A xB rateof B
Mixer
It combines two or more inputs (usually of different compositions) into a single
output without any chemical reaction.
Overall Material Balance:
Feed Rate (A) + Feed Rate (B) = Rate of D
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Component Material Balance:
Component C in feed A + Component C is feed B = Component C in output D
xA Feed rateof A xB Feed rateof B xD output rateof D
Separator
It separates a single input into two or more outputs of different composition
without any chemical reaction.
Overall Material Balance:
Feed Rate (F) = Rate of A + Rate of B
Component Material Balance:
Component C in feed F = Component C in A + Component C is B
xF Feed rateof F xA rateof A xB rateof B
Heat exchanger
It transfers heat from one input to a second input without any chemical reaction.
Pump
It changes the pressure of an input to that of the corresponding output without any
chemical reaction.
Reactor
It carries out a chemical reaction that converts atomic or molecular species in the
input to different atomic or molecular species in the output.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Dryer
It separates the moisture from the input to the system.
Distillation Column
It separates the materials on the nature of their volatility.
Evaporator
It vaporized the solvent or a part of solvent to make concentrated solute.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Crystallizer
Crystallization is a method of solid-fluid separation in which pure chemical crystals
are formed. Crystallizer is used to form the crystals, which is a solid material whose
constituents (such as atoms, molecules, or ions) arranged in a highly ordered
microscopic structure.
The crystals have water or formed from water is called Hydrated crystal. If the
water had driven out from the hydrated crystals, it becomes anhydrous
crystal.
molecular weight of anhydrous crystal
Purity of crystals xc
molecular weight of hydrated crystal
For anhydrous crystal, Purity of crystal = 1
Example: The purity of crystals in Na2SO4 10H2O
molecular weight of Na2SO4 142
= 0.441
molecular weight of Na2SO4 10H2O 322
Absorption and Stripping
In absorption (also called gas absorption, gas scrubbing, or gas washing), there is
a transfer of one or more species from the gas phase to a liquid solvent.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
The species transferred to the liquid phase are referred to as solutes or absorbate.
Absorption involves no change in the chemical species present in the system.
Absorption is used to separate gas mixtures, remove impurities, or recover valuable
chemicals. The operation of removing the absorbed solute from the solvent is called
stripping. Absorbers are normally used with strippers to permit regeneration (or
recovery) and recycling of the absorbent. Since stripping is not perfect, absorbent
recycled to the absorber contains species present in the vapor entering the
absorber. When water is used as the absorbent, it is normally separated from the
solute by distillation rather than stripping.
Extraction
This operation is used for the separation of the components from the mixture with
the help of a suitable solvent as shown in the figure
MATERIAL BALANCE WITHOUT CHEMICAL REACTION OR NON-
REACTIVE SYSTEM
Total Mass Balance
As total mass can not be generated or consumed in any system,
Generation = 0 and Consumption = 0
For Steady state system:
Accumulation = 0
Mass Balance equation: Input = Output
For Unsteady state system:
Mass Balance equation: Accumulation = Input – Output
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Component Mass Balance
As there is no chemical reaction involved in the system, there is “No Generation”
and “No Consumption”.
For Steady state system:
Accumulation = 0
Mass Balance equation: Input = Output
For Unsteady state system:
Mass Balance equation: Accumulation = Input – Output
MATERIAL BALANCE WITH CHEMICAL REACTION OR REACTIVE
SYSTEM
Total Mass Balance
As total mass can not be generated or consumed in any system,
Generation = 0 and Consumption = 0
For Steady state system:
Accumulation = 0
Mass Balance equation: Input = Output
For Unsteady state system:
Mass Balance equation: Accumulation = Input – Output
Component Mass Balance
As there is chemical reaction involved in the system, there is “Generation” and
“Consumption” in a component.
For Steady state system:
Accumulation = 0
Mass Balance equation: Input – Output + Generation – Consumption = 0
For Unsteady state system:
Mass Balance equation:
Accumulation = Input – Output + Generation – Consumption
MATERIAL BALANCE ON SINGLE UNIT WITHOUT CHEMICAL
REACTION
If a system have only one process unit like splitter, evaporator, condenser, etc. is
called single unit system.
For Steady state system:
Accumulation = 0
Mass
Gateflix.
© Copyright Reserved No partBalance
of this materialequation:
should be copied orInput =without
reproduced Output permission
Mass Balance
Tie Component
The component which do not take participate in any chemical reaction and enters
and leave the system in a single stream without any like material being added to
or removed from it.
Example:
1) In the process of drying, as shown in the figure, Air is the tie component.
2) In the process of distillation, as shown in the figure, there is No Tie
component.
3) In the process of vapourisation, as shown in the figure, solute is the tie
component.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Examples
Q.1 A wood sample containing 40% moisture is dried up to 5% moisture content.
What mass of water is evaporated per kg of bone-dry wood?
(a) 190 g (b) 646 g (c) 315 g (d) 615 g
Sol:
Let’s take wet wood (F) = 1 kg
Overall Material Balance:
1= W + P ... 1
Component Material Balance:
For Moisture: 0.4 F = W + 0.05 P
0.4 = W + 0.05P ... 2
On solving the equations (1) and (2), P = 0.631 Kg, W =0.369 kg
Hence, 1 kg of wet wood have 0.369 kg of moisture.
As F kg of wet wood have 40% moisture, it have 60% bone-dry wood.
Therefore, 0.6 kg of bone-dry wood have 0.369 kg of moisture.
0.369
1 kg of bone-dry wood have 0.615 kg of moisture.
0.6
Ans: d
Q.1 A weight solid contains 60% moisture is dried up to 15% moisture by weight.
If the water evaporated is 30kg then find the mass of wet solid.
(a) 16.33 kg (b) 30.66 kg (c) 56.66 kg (d) 46.33 kg
Sol:
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Overall Material Balance:
F = 30 + P ...1
Component Material Balance:
For Moisture: 0.6 F = 30 + 0.15 P
0.6F = 30 + 0.15P ... 2
On solving the equations (1) and (2), F = 56.66 Kg, P = 26.66 kg
Hence, mass of wet solid = 56.66 kg
Ans: c
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
MATERIAL BALANCE ON MULTIPLE UNIT WITHOUT CHEMICAL
REACTION
Phase (P)
A phase is defined as “ an homogeneous, physically distinct and mechanically
separable portion of system, which is separated from other such parts of the system
by definite boundary surfaces”
Degree of freedom (F)
Degree of freedom is defined as the minimum number of independent variable factors
such as temperature, pressure and concentration of the phases, which must be fixed
in order to define the condition of a system completely. It is also known as Variance.
A system having 1, 2, 3 or 0 degrees of freedom is called univariant, bivariant,
trivariant and invariant respectively.
Degree of freedom (F) = Total number of independent variables No. of relationships
between these variables.
Based on degree of freedom, a system is classified as
Degree of Freedom Unit or System Solution Priority
Zero Exactly determined system First
Positive Overdetermined system Next
Negative Underdetermined system Next
If a system have multiple units, we have to write the balance equation for zero degree
of freedom first.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Examples
Q.1 A dryer is fed with wet solid to reduce the moisture content from 50% to 15%.
The product leaving the dryer is admitted to an oven, which further brings down
the moisture to 2%. If the dryer can handle 1000 kg wet solid per day, then
percentage of original water which is removed in the dryer and the oven
respectively.
(a) 82.33%, 15.61% (b) 62.33%, 45.61%
(c) 52.33%, 25.61% (d) 42.33%, 85.61%
Sol:
Degree of Freedom analysis;
For Dryer (Unit-1):
Number of independent variable = 2
Number of relationship between the variable = 2
Degree of Freedom = 2 – 2 = 0
For (Oven) Unit-2:
Number of independent variable = 3
Number of relationship between the variable = 2
Degree of Freedom = 3 – 2 = 1
Hence, we have to write the mass balance equation for the unit-1 first.
Mass balance equation for the (Dryer) unit-1:
Overall Material Balance:
1000 = WD + PD ... 1
Component Material Balance:
For Moisture: 0.50 1000 = WD + 0.15 PD
500 = WD + 0.15PD ... 2
OnNosolving
© Copyright Reserved Gateflix. the should
part of this material equations (1) andwithout
be copied or reproduced PD
(2),permission 588.23 Kg, WD 411.77 kg
Mass Balance
Mass balance equation for the (Oven) unit-2:
Overall Material Balance:
588.23 = WO + PO ... 3
Component Material Balance:
For Moisture: 0.15 588.23 = WO + 0.02 PO
88.23 = WO + 0.02PO ... 4
On solving the equations (3) and (4), PO 510.20 Kg, WO 78.03 kg
% of original water removed from the dryer
WD 411.77
= 100 = 100 = 82.35%
WF 0.5 1000
% of original water removed from the oven
WO 78.03
= 100 = 100 = 15.61%
WF 0.5 1000
Ans: a
Q.2 A dryer is fed with wet solid to reduce the moisture content from 50% to 15%.
The product leaving the dryer is admitted to an oven, which further brings down
the moisture to 2%. If the dryer can handle 1000 kg wet solid per day, then
percentage of original water which is removed in the dryer and the oven
respectively.
(a) 82.33%, 15.61% (b) 62.33%, 45.61%
(c) 52.33%, 25.61% (d) 42.33%, 85.61%
Sol:
Degree of Freedom analysis;
For Dryer (Unit-1):
Number of independent variable = 2
Number of relationship between the variable = 2
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Degree of Freedom = 2 – 2 = 0
For (Oven) Unit-2:
Number of independent variable = 3
Number of relationship between the variable = 2
Degree of Freedom = 3 – 2 = 1
Hence, we have to write the mass balance equation for the unit-1 first.
Mass balance equation for the (Dryer) unit-1:
Overall Material Balance:
1000 = WD + PD ... 1
Component Material Balance:
For Moisture: 0.50 1000 = WD + 0.15 PD
500 = WD + 0.15PD ... 2
On solving the equations (1) and (2), PD 588.23 Kg, WD 411.77 kg
Mass balance equation for the (Oven) unit-2:
Overall Material Balance:
588.23 = WO + PO ... 3
Component Material Balance:
For Moisture: 0.15 588.23 = WO + 0.02 PO
88.23 = WO + 0.02PO ... 4
On solving the equations (3) and (4), PO 510.20 Kg, WO 78.03 kg
% of original water removed from the dryer
WD 411.77
= 100 = 100 = 82.35%
WF 0.5 1000
% of original water removed from the oven
WO 78.03
= 100 = 100 = 15.61%
WF 0.5 1000
Ans: a
Q.3 A process flow sheet analysis results in a degree of freedom having a value of
2 . Which one of the following step must be next carried out?
(a) Identify and add two new independent equations from process model
(b) Remove two equations that have been wrongly assumed to be independent
© Copyright Reserved Gateflix.
(c)NoAssign
part of this material
the valueshould be of
copied or reproduced
two without permission
variables in the process
Mass Balance
(d) Assign the value to one variable and remove one equation, which was
wrongly assumed to be independent
Sol:
Degree of freedom (F) = Total number of independent variables No. of
relationships between these variables
Given That Degree of Freedom = 2 . So, n r = 2
To write the mass balance equation, we need degree of freedom to be zero.
a) Add two new independent equations from process model
r' r 2, F' n (r 2) n r 2 2 2 4
b) Remove two equations that have been wrongly assumed to be independent
r' r 2, F' n (r 2) n r 2 2 2 0
c) Assign the value of two variables in the process
n' n 2, F' n 2 r n r 2 2 2 4
d) Assign the value to one variable and remove one equation, which was
wrongly assumed to be independent
n' n 1, r' r 1, F' n 1 r 1 n r 2
Ans: b
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Recycle
Recycle is a term denoting a process that returns material from downstream of a
process unit back to the process unit. We study the system at steady state. Recycling
is done to increase the yield of the product.
Mass balance equation for the Mixer:
Overall Material Balance:
FR M
Component Material Balance:
F XF R X R M X M
Mass balance equation for the Process Unit:
Overall Material Balance:
MG + W
Component Material Balance:
M X M G XG W X W
Mass balance equation for the Separator:
Overall Material Balance:
GR + P
Component Material Balance:
G XG R X R P X P
Mass balance equation for Overall System:
Overall Material Balance:
FP + W
Component Material Balance:
or reproduced
© Copyright Reserved Gateflix. No part of this material should be copied F X Pwithout
X permission
WX
F P W
Mass Balance
Recycle Ratio:
It is the ratio of the quantity of recycle stream to the quantity of fresh feed stream.
R
Recycle Ratio =
F
Combined Feed Ratio:
It is the ratio of the quantity of mixed feed stream to the quantity of fresh feed
stream.
M
Combined Feed Ratio =
F
Bypass
Bypass stream is a stream that skips one or more stages of the process and goes
directly to another downstream stage. Bypass is done to control the composition
and the properties of the final product.
Mass balance equation for the Separator:
Overall Material Balance:
FB + G
Component Material Balance:
F XF B X B G XG
Mass balance equation for the Process Unit:
Overall Material Balance:
GW + Z
Component Material Balance:
G XG W X W Z X Z
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Mass balance equation for the Mixer:
Overall Material Balance:
B Z P
Component Material Balance:
B XB Z X Z P X P
Mass balance equation for Overall System:
Overall Material Balance:
FP + W
Component Material Balance:
F XF P XP W X W
Bypass Ratio:
It is the ratio of the quantity of bypass stream to the quantity of fresh feed stream.
B
Bypass Ratio =
F
Combined Feed Ratio:
It is the ratio of the quantity of mixed feed stream to the quantity of fresh feed
stream.
M
Combined Feed Ratio =
F
PURGE
Purge is a stream bled off to remove an accumulation of inert or unwanted material
that might otherwise build up in the recycle stream.
At steady state, Inert in purge = inert in fresh feed
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Mass balance equation for the Mixer:
Overall Material Balance:
FR M
Component Material Balance:
F XF R X R M X M
Mass balance equation for the Process Unit:
Overall Material Balance:
MG + W
Component Material Balance:
M X M G XG W X W
Mass balance equation for the Separator - 1:
Overall Material Balance:
GR + Z P
Component Material Balance:
G XG R X R Z X Z P X P
Mass balance equation for Overall System:
Overall Material Balance:
FP + Z+ W
Component Material Balance:
F XF P XP Z X Z W X W
Purge Ratio:
It is the ratio of the quantity of purge stream to the quantity of recycle stream.
Quantity of purge stream
Purge Ratio =
Quantity of recycle stream
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Examples
Q.1 A distillation column separates 10,000 kg/hr of a mixture containing equal
mass of benzene and toluene. The product D recovered from the condenser at
the top of the column contains 95% benzene, and the bottom W from the
column contains 96% toluene.
The vapor V entering the condenser from the top of the column is 8000 kg/hr.
A portion of the product from the condenser is returned to the column as reflux
R, and the rest is withdrawn as the final product D. Assume that V, R, and D are
identical in composition since V is condensed completely. Find the ratio of the
amount refluxed R to the product withdrawn D.
(a) 0.25 (b) 0.58 (c) 0.46 (d) 72.45
Sol:
Overall Process
Total Balance: 10000 D W
Benzene Balance: 10000 0.50 D 0.95 W 0.04
Solving simultaneously, D 5050 kg / hr ; W 4950 kg / hr
Total balance around the separator: 8000 R D, R 2950 kg / hr
R 2950
Ratio 0.58
D 5050
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Ans: b
Mass Balance
MATERIAL BALANCE WITH CHEMICAL REACTION
Definitions and Terminology
Chemical reaction equations
Chemical reactions do not create, destroy, or convert atoms. Therefore, the
quantities of each type of atom on the two sides of a chemical reaction equation
MUST be the same.
Stoichiometry
For reactive systems, in addition to input and output of materials, generation and
consumption terms should be considered in the general mole balance equation.
Theory of proportions in which chemical compounds react is called stoichiometry.
Stoichiometric equation
A statement of the relative number of moles or molecules reacting to produce
products is given by a chemical equation known as stoichiometric equation. For
example, 2 moles of SO2 and one mole of O 2 react to produce 2 moles of SO3 . Then
the stoichiometric equation will be 2SO2 O2 2SO3 .
Stoichiometric coefficient of a reacting species
Numbers that precede the molecular formulas are known as stoichiometric
coefficients. For example, in stoichiometric equation 2SO2 O2 2SO3 , the
stoichiometric coefficients of SO2 ,O2 andSO3 are 2, 1 and 2 respectively.
Stoichiometric ratio
Ratio of stoichiometric coefficients of two species is known as stoichiometric ratio.
For example, in stoichiometric equation
2SO2 O2 2SO3 ,
2
Stoichiometric ratio of SO2 to SO3 1
2
Stoichiometric proportion
Two chemical species participating in the same chemical reaction are in
stoichiometric proportion if their actual amounts present are in the same
proportion as their stoichiometric coefficients. In the case that all reactants are
present in stoichiometric proportion, if the reaction proceeds to full conversion
there will be no reactant molecules (of any type) left.
Example, If there are 0.5 gmol CH4 available to react, what quantity of O 2 would
beGateflix.
© Copyright Reserved in Stoichiometric proportion,
No part of this material should in without
be copied or reproduced the reaction
permission CH4 2O2 CO2 2H2O ?
Mass Balance
Amount of CH4 stoichiometric coefficients of CH4 0.5gmol 1
Amount of O2 stoichiometric coefficients of O2 Amount of O2 2
Hence, Amount of O 2 is 1 gmol
Stoichiometric requirement
The amount of an excess reactant that would be needed to completely react with
the limiting reactant.
Example, If there are 11 gmol CH4 available to react in the reaction
CH4 2O2 CO2 2H2O , what is the stoichiometric requirement of O 2 ?
Limiting and excess reactant
Usually reactants are not present in stoichiometric proportion. In that case, if the
reaction proceeds sufficiently far, one of the reactants will be the first to be used
up. That reactant is the limiting reactant. The other reactants are excess reactants.
Fractional and Percentage excess
The fractional excess of a reactant A is defined by
amount A present stoichiometric requirement of A
Fractional excess of A
stoichiometric requirement of A
Percentage excess = (fractional excess) × 100 %
Fractional and percentage conversion
The fraction of reactant that has reacted is said to be Fractional conversion.
moles reactant reacted
Fractional conversion
moles reactant fed in
Percentage conversion: (fractional conversion) × 100 %
Yield
Reactions, in general, do not go to 100% conversion of the reactant into the desired
product. This is because of side reactions taking place as well as thermodynamic
limitations (see below). “Yield” is used to measure how effective a reaction is in
converting reactant to the desired product. It has several possible definitions, so it
is important to always note which one is being used. Often, yield is defined as
moles of desired product formed
Yield
moles of desired product that would have been formed if there were no side
reactions and if complete conversion of the limiting reactant had taken place
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Mass Balance
Selectivity
Selectivity measures how effective a reaction is in producing the desired product
relative to undesired products that result from side reactions.
moles of undesired product formed
Selectivity
moles of desired product formed
Examples
Q.1 Methane and steam are fed to a reactor in molar ratio 1:2. The following
reaction takes place
CH4 2H2O CO2 H2
CH4 H2O CO 3H2
Where CO2 is the desired product, CO is the undesired product and H 2 is the
bi-product. The exit stream has the following composition
Species CH4 H 2O CO2 H2 CO
mole % 10.21 20.56 13.88 53.12 2.23
(1) The selectivity of desired product to the undesired product is
(a) 6.12 (b) 7.25 (c) 6.22 (d) 12.52
(2) The fractional Yield of CO2 is
(a) 0.73 (b) 0.21 (c) 0.53 (d) 0.27
(3) The fractional conversion of methane is
(a) 0.612 (b) 0.725 (c) 0.622 (d) 0.152
Sol:
13.88
(1) The selectivity of desired product to the undesired product 6.22
2.23
(2) The fractional Yield of CO2
moles of CO2
moles of CO2 that would have been formed if there were no side reactions
and if complete conversion of the limiting reactant had taken place
13.88
0.53
No part of
© Copyright Reserved Gateflix.13.88 materialshould
10.21
this 2.23 be copied or reproduced without permission
Mass Balance
(3) The fractional conversion of methane
CH4 Reacted 13.88 2.23
0.612
CH4 fed 13.88 2.23 10.21
Ans: (1) b
(2) c
(3) a
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
7 ENERGY BALANCE
Introduction
As an engineer designing a process, one of your principal jobs would be
To account carefully for the energy that flows into and out of each process unit
and
To determine the overall energy requirement for the process
This can be done by writing energy balances on the process, in much the same way that
you write material balances to account for the mass flows to and from the process and
its units.
In process industries, wasting energy leads to reduced profits
Coal, natural gas and petroleum are the major energy sources being utilized.
Sun, winds, and tides; are sources for renewable energy
Nuclear power generation is feasible, but the need for safe disposal of radioactive
wastes from nuclear reactors is a serious unresolved problem.
The tremendous increase in fuel prices and the environmental problems associated
with the combustion of fossil fuel are the driving force for energy research.
Different forms of Energy
Kinetic energy
Energy due to the translational motion of the system as a whole relative to some
frame of reference (usually the earth's surface) or to rotation of the system about
some axis.
The Kinetic energy, E k J , of an object of mass m kg moving with velocity u m/s
relative to the surface of earth is
1
E k mu 2
2
If a fluid enters a system with a mass flow rate m kg/s and uniform velocity u m/s
E k mu
1 2
2
E k J/s may be thought of as the rate at which kinetic energy is transported into the
system by the fluid.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Energy Balance
Examples
Q.1 Water flows into a process unit through a 2-cm ID pipe at a rate of 2.00 m3 /h .
Calculate E k for this stream in joules/second.
(a) 0.870 (b) 0.259 (c) 0.654 (d) 0.458
Sol: Given that,
Diameter, D = 2 cm = 0.02 m
2
Flow rate, q 2.00 m 3 /h = m 3 /s
3600
Density of water, 1000 kg/m3
2 5
Therefore, mass flow rate, m q 1000 kg/s = kg/s
3600 9
q 1
Velocity, u , A πD 2
A 4
1 1
A πD 2 π 4 104 π 10 4 m 2
4 4
q 2 104 50
u m/s
A 3600 π 9π
2
E k mu
1 2 1 5 50
0.868 J/s
2 2 9 9π
Ans: a
Potential energy
Energy due to the position of the system in a potential field (such as a gravitational or
electromagnetic field).
The gravitational potential energy of an object of mass m is
E p mgz
Where g is the acceleration of gravity and z is the height of the object above a reference
plane at which E p is arbitrarily defined to be zero.
and an elevation z relative to the
If a fluid enters a system with a mass flow rate m
potential energy reference plane,
E p mgz
E p J/s may be thought of as the rate at which gravitational potential energy is
transported into the system by the fluid.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Energy Balance
The change in potential energy when a body or fluid moves from one elevation to
another,
E p 2 E p1 mg
z2 z1
Examples
Q.1 Crude oil is pumped at a rate of 15.0 kg/s from a point 220 meters below the
earth's surface to a point 20 meters above ground level. Calculate the attendant
rate of increase of potential energy in J/s.
(a) 35316 (b) 24614 (c) 12548 (d) 45789
Sol: E p mg
z2 z1 15 9.81 20 220
E p 35316 J/s
Ans: a
Internal energy
Energy due to the motion of molecules relative to the center of mass of the system, to
the rotational, vibrational motion and the electromagnetic interactions of the
molecules, and to the motion and interactions of the atomic and subatomic
constituents of the molecules.
The internal energy of a system depends almost entirely on:
The chemical composition,
State of aggregation (solid liquid or gas) and
Temperature of the system materials.
It is independent of pressure for ideal gases and nearly independent of pressure for
liquids and solids.
The internal energy will be represented by the symbol U.
Enthalpy
The enthalpy H of a system is defined by
H U PV
Change of Enthalpy of the system:
H = U + (PV)
Where P is the pressure and V is volume. Let’s think about the PV term. We know that
PA, where A is the area subjected to a pressure P, is the force acting on that area. If a
fluid inside a system is displaced through a distance d by the force PA, then the
resultant work W done on the system can be calculated as the product of this force
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Energy Balance
times the displacement. In other words, W = PAd. Now note that Ad = V, the volume
swept out by the displacement. Thus, an alternate way to write the displacement work
is W = PV. This type of work, where pressure results in the displacement of a fluid, will
be referred to as flow work. If an amount of fluid of volume V is inserted into a system
against a pressure P, the work required to accomplish this is PV. Enthalpy, therefore,
can be viewed as the sum of the internal energy of this fluid volume added to the
system plus the flow work performed on the system in order to insert the fluid.
Specific Properties and Enthalpy
The properties of a process material are either
Extensive (proportional to the quantity of the material) or
Intensive (independent of the quantity), T, P and ρ
A specific property is an intensive quantity obtained by dividing an extensive property
(or its flow rate) by the total amount (or flow rate) of the process material.
If
χ
χ is an extensive property and m is the mass flow rate, then χ̂ m
Where χ̂ is specific property of χ .
Hence, the equation for the enthalpy H U PV can be written as Hˆ Uˆ PVˆ
Where,
Ĥ is the specific enthalpy, P is the total pressure, Û is the specific internal energy and
Vˆ is the specific volume.
Flow Work and Shaft Work
The work or the rate of energy transferred as work is required to move fluid through a
continuous process system,
The net rate of work done by an open system on its surroundings
W
W W
s fl
is the shaft work, or rate of work done by the process fluid on a moving part within
Ws
the system(e.g., a pump rotor)
is the flow work, or rate of work done by the fluid at the system outlet minus the
Wfl
rate of work done on the fluid at the system inlet
Energy may be transferred between such a system and its surroundings in two ways:
As heat, or energy that flows because of temperature difference between a system
and its surroundings.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Energy Balance
The direction of flow is always from a higher temperature to a lower one.
Heat is defined as positive when it is transferred to the system from the
surroundings
As work, or energy that flows in response to any driving force other than a
temperature difference, such as a force, a torque, or a voltage.
Work is defined as positive when it is done by the system on the
surroundings
For example, if a gas in a cylinder expands and moves a piston against a
restraining force, the gas does work on the piston (energy is transferred as
work from the gas to its the gas does work on the piston (energy is
transferred as work from the gas to its surroundings, which include the
piston)
In chemical processes, work may come from pumps, compressors, moving
piston and moving turbines
“The terms "work" and "heat" refer only to energy that is being transferred”
The General Energy Balance
“Black Box” Analysis: This method of analysis, in the context of process modeling,
does not concern itself with how individual process units work. The input and output
streams are instead analyzed by applying constraints imposed by nature, namely
conservation of mass and conservation of energy. The inner workings of the physical
apparatus are not relevant. This course treats process units as black boxes. Future
courses will go into detail of how different process units work.
The process can be defined as one or a series of operations in which physical and
chemical treatments are carried out and a desired product is result in the end such as
distillation, drying, absorption, chemical manufacture, … etc.
First Law of Thermodynamics
The First Law of Thermodynamics is a statement of energy conservation. Although
energy cannot be created or destroyed, it can be converted from one form to another
(for example, internal energy stored in molecular bonds can be converted into kinetic
energy; potential energy can be converted to kinetic or to internal energy, etc.). Energy
can also be transferred from one point to another or from one body to a second body.
Energy transfer can occur by flow of heat, by transport of mass (transport of mass is
otherwise known as convection), or by performance of work. The general energy
balance for a process can be expressed in words as:
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Energy Balance
Accumulation of Energy in System =
Input of Energy into System – Output of Energy from System
Now the total energy of a system, as considered above, is composed of kinetic,
potential, and internal energies. These energies can be transferred into or out of the
system by flow of mass through process streams that bring the various forms of energy
with them. In addition, they can be transferred by performance of work, or by flow of
heat. after expressing all terms as rates, thus becomes:
Q U f U i E kf E ki E pf E pi W
Q U E k E p W
HEAT CAPACITIES
The heat capacity of a substance is the quantity of heat to be supplied to cause a
temperature rise of one degree. Thus,
dQ = C dT
Where C is known as heat capacity of the substance. The heat capacity of the unit mass
of a substance is also known as specific heat of the substance. Heat capacity depends
on the way in which the heat is supplied. When heat is supplied to a system at constant
volume, the system is unable to do any work and the quantity of heat required is given
by
Q = CV dT (constant volume)
Where C V is known as the heat capacity at constant volume. Thus,
Q
CV
T V
For a constant volume process, dU dQ
Therefore,
U
CV
T V
If heat is supplied to a substance at constant pressure, it is free to expand doing work
against the constant pressure. A part of the heat supplied to the system is utilized for
the work of expansion and more heat will be required to rise the temperature than that
required in a constant volume process for the same temperature change. The amount
of heat required is related to the temperature rise as
Q = CP dT (constant pressure)
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Energy Balance
Where CP is called the heat capacity at constant pressure. Thus,
Q
CP
T P
For a constant pressure process,
dU = δQ PdV
δQ = dU + PdV = dH (constant pressure)
Therefore,
H
CP
T P
Since for a given temperature change, the heat required is more in a constant pressure
process than that in a constant volume process, generally CP > CV . However, the
difference between CP and C V for solids and liquids are very small compared to that
for gases, as the change in volume of solids and liquids during heating is not very
significant.
dU = C V dT (constant volume)
dH = C P dT (constant pressure)
Relationship between C P and CV
For 1 mole of an ideal gas;
CP CV R
Mean Heat Capacity
For calculating the heat interaction and enthalpy changes in processes involving gases,
it is sometimes convenient to use a mean or average heat capacity in the temperature
range of interest. The mean heat capacity is given by
T2
Q
C dt
T1
Cm
T2 T1 T2 T1
Heat Capacity of Mixtures of Gases
The heat capacity of an ideal gas mixture can be evaluated as the sum of the heat
capacities of the individual constituents each weighted according to the mole fraction
in the mixture. Thus
n
Cmixture yi Ci
i 1
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Energy Balance
Where yi represents the mole fraction of component i in the mixture of n components
and Ci is its specific heat in the pure state.
Kopp’s rule
When experimental data are lacking, Kopp’s rule may be used for making a rough
estimation of the heat capacity of solids. Kopp’s rule predicts that the heat capacity of
a solid compound at room temperature is approximately equal to the sum of the heat
capacities of the individual elements.
Examples
Q.1 Determine the heat capacity (J/g-atom K) of Na 2SO 4 10H 2O at room
temperature using Kopp’s rule. The atomic heat capacities of elements (J/g-
atom K) are 26.04 for Na, 22.6 for S, 16.8 for O, and 9.6 for H.
(a) 568.25 (b) 501.88 (c) 625.84 (d) 425.78
Sol: Using Kopp’s rule;
C Na 2SO4 10H2O 2 C Na CS 4 CO 20 CH 10 CO
C Na 2SO4 10H2O 2 26.04 22.6 4 16.8 20 9.6 10 16.8
501.88 J/g-atom K
Ans: b
ENTHALPY CHANGE OF PHASE CHANGES
A phase is "a homogeneous, physically distinct, and mechanically separable portion of
matter present in a nonhomogeneous physical-chemical system". For our purposes,
we can consider three phases of matter, solid, liquid, and gaseous.
Vaporization
Vaporization is the conversion of a liquid to a gas. Vaporization is an
endothermic process, since energy must be supplied to overcome the
intermolecular forces that hold molecules together as a liquid. The difference
in enthalpy per mole of molecules between the gaseous and liquid states of a
substance is called the enthalpy of vaporization.
H vapourisation H gaseous H liquid
Condensation
Condensation is the process of conversion of a gas to a liquid.
H condensation H vaporization
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Energy Balance
Fusion (Melting)
Fusion is the conversion of a solid to a liquid. Fusion, like vaporization, is
always an endothermic process, since energy must be supplied to overcome the
intermolecular forces that hold molecules together as a solid. The difference in
enthalpy per mole of molecules between the liquid and solid states of a
substance is called the enthalpy of fusion.
H fusion H liquid H solid
Freezing
Freezing is the process of conversion of liquid to the solid.
H freezing H fusion
Sublimation
Sublimation is the conversion of a solid directly to a gas without going through
the liquid state. Sublimation, like fusion and vaporization, is always an
endothermic process, since energy must be supplied to overcome the
intermolecular forces that hold molecules together as a solid. The difference in
enthalpy per mole of molecules between the gaseous and solid states of a
substance is called the enthalpy of sublimation.
H Sublimation H gaseous H solid
Note:
The change from a solid to a liquid, is not as drastic as the change from
a liquid to a gas, enthalpies of fusion are smaller than enthalpies of
vaporization for the same substance.
The change from a solid to a gas is a larger change than vaporization or
fusion; enthalpies of sublimation are larger than enthalpies of
vaporization or fusion for the same substance. In fact, the enthalpy of
sublimation is the sum of the enthalpies of vaporization and fusion.
H Sublimation H vapourisation H fusion
Phase changes can occur between any two phases of matter.
All phase changes occur with a simultaneous change in energy.
All phase changes are isothermal.
Heating Curve
A plot of the temperature versus the amount of heat added is known as a heating
curve. These are commonly used to show the relationship between phase changes and
enthalpy for a given substance.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Energy Balance
In the figure, the solid gains kinetic energy and consequently rises in temperature as
heat is added. At the melting point, the heat added is used to break the attractive
intermolecular forces of the solid instead of increasing kinetic energy, and therefore
the temperature remains constant. After all the solid has melted, once again, the heat
added goes to increasing the kinetic energy (and temperature) of the liquid molecules
until the boiling point. At the boiling point, once again, the heat added is used to break
the attractive intermolecular forces instead of supplying kinetic energy, and the
temperature remains constant until all liquid has been turned to gas.
Hess's Law
One of the key ideas of looking at state functions like the enthalpy is that the changes
are the same regardless of the process taken from the initial to the final state. This
allows us to take advantage of existing data to calculate the enthalpy changes for
reactions we may not have been able to perform or study. This is because even if we
cannot directly measure the change in the enthalpy, we can imagine a new process
which involves a number of steps that can (or have) been measured. The enthalpy
change for the overall process is the sum of the enthalpy change of the steps in the
process. This is known as Hess's Law and is given in the following equation
H reaction H1 H 2 H 3 H n
Enthalpy of formation
Enthalpy of formation (Sometimes also abbreviated as Heat of formation) is defined
as the enthalpy change when one mole of a compound is formed from the elements in
their stable states.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Energy Balance
Standard enthalpy of formation Ĥ of is heat evolved/absorbed when one mole of a
compound is formed from its elements in a reaction beginning and ending at 25C
and at a pressure of 1 atm.
For example, the heat of formation of water vapor is defined by the reaction:
1
H2 g O2 g H2O g
2
Even though we generally want the coefficients of balanced reactions to be whole
numbers, the definition of heat of formation specifies one mole of the product, so we
leave the 1/2. This reaction releases 241.8 kJ of heat when one mole of water vapor is
produced. The heat of formation of water vapor is -241.8 kJ. (Why is this negative? -
heat is released!)
Enthalpy of Reaction
Enthalpy of reaction (Sometimes also abbreviated as Heat of reaction) is the change in
the enthalpy of a particular chemical reaction that occurs at a constant pressure. Heat
of a chemical reaction can therefore be defined as the heat evolved in the surroundings
or absorbed when the reaction takes place at constant pressure and temperature.
Standard enthalpy of reaction Ĥ oreaction is given by
reaction H f, product H f, reactant
ˆo
H ˆo ˆo
Note: The standard enthalpy of formation for an element in its standard state is
ZERO.
Examples
Q.1 What is the standard heat of reaction for the following reaction?
Zn s Cu 2 aq Zn 2 aq Cu s
H o
f for Cu 2 64.4 kJ / mol; H fo for Zn 2 –152.4 kJ / mol
(a) 216.8 kJ released per mole (b) 88.0 kJ released per mole
(c) 88.0 kJ absorbed per mole (d) 216.8 kJ absorbed per mole
Sol: Standard enthalpy of reaction Ĥ oreaction is given by
reaction H f, product H f, reactant
ˆo
H ˆo ˆo
ˆo
H ˆo
H 152.4 64.4 kJ/mol = 216.8 kJ/mol
f, Zn
2+
f, Cu
2+
Hence, 216.8 kJ released per mole
Ans: b
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
GATE QUESTIONS
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Q.1
100 kg of a feed containing 50 wt % of a solute C is contacted with 80kg of a solvent
containing 0.5 wt % of C in a mixer-settler unit. From this operation, the resultant extract
and raffinate phases contains 40 wt % and 20 wt % of C, respectively, If E and R denote the
mass of the extract and raffinate phases, respectively, the ratio E/R is
(GATE-2019)
(A) 1/4 (B) 1/2 (C) 2/3 (D) 1
Q.2
The ammonia NH3 oxidation process occurs over a catalyst as
4NH3 5O2 6H2O 4NO
Air supplied such that oxygen O2 is 20% in excess of that required for complete
conversion of NH3 . The mole fraction of O2 in inlet gas mixture NH3 air is ____________.
(rounded off to third decimal place)
(GATE-2018)
Q.3
An aqueous salt — solution enters a crystallizer operating at steady state at 25C . The feed
temperatures 90C and the salt concentration in the feed is 40 weight %. The salt crystallizes
as a pentahydrate. The crystals and the mother liquor leave the crystallizer. The molecular
weight of the anhydrous salt is 135. The solubility of the salt at 25C is 20 weight %. The
feed flowrate required for a production rate of 100 kg/s of the hydrated salt, rounded to the
nearest integer, is __________ kg/s.
(GATE – 2017)
Q.4
A liquid mixture of ethanol and water is flowing as inlet stream P into stream splitter. It is
split into two streams, Q and R as shown in the figure below
The flow rate of P, containing 30 mass % of ethanol is 100 kg/h. What is the least number of
additional specification(s) required to determine the mass flow rates and compositions
(mass %) of the two exit streams?
(GATE - 2016)
(A) 0 (B) 1 (C) 2 (D) 3
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Q.5
A binary liquid mixture of benzene and toluene contains 20 mol% benzene. At 350 K the
vapour pressures of pure benzene and pure toluene are 92 KPa and 35 KPa, respectively. The
mixture follows Raoult's law. The equilibrium vapor phase mole fraction (rounded off to the
second decimal place) of benzene in contact with this liquid mixture at 350K is__________
(GATE – 2016)
Q.6
A catalytic reforming plant produces hydrogen and benzene from cyclohexane by de-
hydroaromatization. In order to increase the production of hydrogen, the owner plans to
change the process to steam reforming of the same feedstock that produces hydrogen and
carbon dioxide. Stoichiometrically, what is the maximum ratio of pure hydrogen produced
in the process to that in the existing process?
(A)1 (B) 2 (c)5 (D)6
(GATE – 2016)
Questions 7 and 8 are linked Questions
Q.7
A reverse osmosis unit treats water (F) containing fluoride and its output consists of a
permeate stream (P) and a reject stream (R). Let CF , CP and CR denote the fluoride
concentration in the feed, permeate, and reject streams, respectively. Under steady state
conditions, the volumetric flow rate of the reject is 60% of the volumetric flow rate of the
inlet stream, and CF = 2 mg/L and CP = 0.1 mg/L . The value of CR in mg/L, upto one digit
after the decimal point, is ___________
(GATE-2013)
Q.8
The fraction f of the feed is bypassed and mixed with permeate to obtain treated water
having a fluoride concentration of 1mg/L. Here also the flow rate of the reject stream is 60%
of the flow rate entering the reverse osmosis unit (after the bypass). The value of f, upto 2
digits after the decimal point, is__________
(GATE-2013)
Questions 9 and 10 are linked Questions
Thereaction A liq B gas C liq D gas , is carried out in a reactor followed by a
separator as shown below
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Notations:
Molar flow rate of fresh B is FFB
Molar flow rate of A is FA
Molar flow rate of recycle gas is FRG
Molar fraction of B in recycle gas is YRB
Molar flow rate of purge gas is FPG
Molar flow rate of C is FC
Here, FFB 2 mol / s;FA 1 mol / s; FB / FA 5 and A is completely converted
Q.9
If YRB 0.3 , the ratio of recycle gas to purge gas YRB 0.3 is
(A) 2 (B) 5 (C) 7 (D) 10
(GATE – 2012)
Q.10
If the ratio of recycle gas to purge gas FRG / FPG is 4 then YRB is .
(A) 3/8 (B) 2/5 (C) 1/2 (D) 3/4
(GATE – 2012)
Questions 11 and 12 are linked Questions
Ammonia is synthesized at 200 bar and 773 K by the reaction N2 3H2 2NH3 . The yield
of ammonia is 0.45mol/mol of fresh feed. Flow sheet for the process (along with available
compositions) is shown below.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Q.11
The single pass conversion for H2 in the reactor is 20%. The amount of H2 lost in the purge
as a PERCENTAGE of H2 in fresh feed is
(A) 10 (B)20 (C) 45 (D)55
(GATE – 2011)
Q.12
The following combustion reactions occurs when methane is burnt
CH4 2O2 CO2 2H2O
2CH4 3O2 2CO 4H2O
20% excess air is supplied to the combustor. The conversion of methane is 80% molar ratio
of CO to CO2 in the flue gas 1:3. Assume air to have 80 mol % of N2 and rest O2 . The O2
consumed as a percentage of O2 entering the combustor is
(A) 20 (B) 62.5 (C) 80 (D) 83.3
(GATE – 2011)
Q.13
The products of combustion of methane in atmospheric air 21% O2 and 79% N2 have the
following composition on a dry basis:
Products Mole%
CO2 10.00
O2 2.37
CO 0.53
N2 87.10
The ratio of the moles of CH4 to the moles O2 in the feed stream is
(A) 1.05 (B) 0.60 (C) 0.51 (D) 0.45
(GATE – 2010)
Q.14
The fractional yield of CO2 is (where fractional yield is defined as the ratio of moles of the
desired Product formed to the moles that would have been formed if there were no side
reactions and limiting had reacted completely)
(A) 0.7 (B) 0.88 (C)1 (D) 3.5
(GATE – 2008)
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Q.15
The fractional conversion of methane is
(A) 0.4 (B)0.5 (C)0.7 (D) 0.8
(GATE – 2008)
Q.16
A simplified flowsheet is shown in the figure for production of ethanol from ethylene. The
conversion Of ethylene in the reactor is 30% and the scrubber following the reactor
completely separates ethylene (as top stream) and ethanol and water as bottoms. The last
(distillation) column gives an ethanol-water Azeotrope (90 mol% ethanol) as the final
product and water as waste. The recycle to purge ratio is 34.
C2H4 g H2O C2H5OH g
The reaction is :
For an azeotrope product rate of 500mols/hr, the recycle gas flowrate in mols/hr is
(A) 30 (B) 420 (C) 1020 (D)1500
(GATE – 2007)
Q.17
A process flow sheet analysis results in the degrees of freedom having a value of -2, which
one of the following steps must be next carried out?
(A) Identify and add two new independent equation from process model
(B) Remove two equations that have been wrongly assumed to be independent
(C) Assign values of two variables in the process
(D) Assign value to one variable and remove one equation that was wrongly assumed to be
Independent
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
(GATE – 2007)
Q.18
A metal recovery unit (MRU)of intake capacity 5000Kg/hr treats liquid products from a
plant and recovers 90% of the metal in the metal in the pure form. The unrecovered metal
and its associated liquid are sent to a disposal unit along with the untreated product from
the plant (see figure below). Find flow rate m6 and the weight fraction of the metal w 6 .
The liquid product flow rate is 7500 higher of composition 0.1(wt fraction), Assume steady
state.
(A) m6 7500 kg / hr, w6 0.0 (C) m6 4500kg / hr, w6 0.1712
(B) m6 7050kg / hr, w6 0.04255 (D) m6 5600 kg / hr, w6 0.0314
(GATE – 2005)
Q.19
In the triangular diagram represented below for a batch separation process, a stream F is
mixed with solvent B to produce products R and E. Substance A is the carrier liquid and C is
the solute to be extracted. The amounts of B and E are 1 kg and 1.20 kg respectively. The
length FM is 8.5 units on the figure. The ratio R/E is estimated to be
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Note: Figure not to scale
(A) 1.285 (B) 2 (c) 0.751 (d)2.5
(GATE – 2005)
Q.20
A feed stream (S1) at 100 kg/hr and containing only A mixes with recycle stream (S5) before
entering the reactor (see figure below), where the reaction A B takes place. The operation
is at steady state. The stream S3 leaving the reactor is separated, without either phase or
composition change, into two streams S4 and 55. If the mass fraction of B in S4 is 0.95 and
total flow rate of S5 is 10 kg/hr, then the ratio of flow rates of streams (S3/55), and the flow
rate of A in S3 are, respectively.
(A) 11 and 110 kg/hr (B) 24 and 240 kg/hr
(C) 11 and 5.5kg/hr (D) 70 and 330 kg/hr
(GATE – 2005)
Q.21
A distillation column separates 10,000 Kg/h of benzen- toluene mixture as shown in the
figure below. In the figure XF , XD ,and Xw represent the weight fraction of benzene in the
feed, distillate and residue, respectively.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
The reflux ratio is
(A) 0.5 (B) 1.0 (C) 0.6 (D) 2.0
Q.22
The weight fraction of methanol in an aqueous solution is 0.64. The mole fraction of
methanol XM satisfies.
(A) XM < 0.5 (B) XM = 0.5 (C) 0.5 XM 0.64 (D) XM 0.64
(GATE – 2004)
Q.23
6 g of carbon is burnt with an amount of air containing 18 g oxygen. The product contains
16.5 g CO2 and 2.8 g CO besides other constituents. What is the degree of conversion on the
basis of disappearance of the limiting reactant?
(A) 100% (B) 95% (C) 75% (D) 20%
(GATE – 2003)
Q.24
An aqueous solution of 2.45% by weight H2SO4 has a specific of 1.011. The compoition
expressed in normality is
(A) 0.2500 (B) 0.2528 (C) 0.5000 (D) 0.5055
(GATE – 2003)
Q.25
Air at a temperature of 20 C is 750mm Hg pressure has a relative humidity of 80%. What is
its percentage humidity? Vapour pressure of water at 20 C is 17.5 mm Hg.
(A) 80.38 (B) 80 (C) 79.62 (D) 78.51
(GATE – 2003)
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Q.26
Na2SO4 , 10 H2O crystals are formed by cooling 100kgby weight aqueous solution of
Na2SO4 , 10 H2O . The final concentration of the solute in the solution 10%. The weight of
crystals is
(A)20 (B)32.2 (C)45.35 (D)32.2
(GATE – 2003)
Q.27
Methane is mixed with stoichiometric proportion of oxygen and completely combusted. The
number of additional specifications required to determine the product flow rate and
composition is
(A) 0 (B)1 (C) 2 (D) 3
(GATE – 2002)
Q.28
Fresh orange juice 12% (by weight) solids and rest water. 90% of the fresh juice is sent to
an evaporator to remove water and subsequently mixed with remaining 10% of fresh juice.
The resultant product contains 40% solids. The kg of water removed from 1 kg fresh juice is
(A) 0.4 (B) 0.5 (C) 0.6 (D) 0.7
(GATE – 2002)
Q.29
For the case of a fuel gas undergoing combustion with air, if the air/fuel ratio is increased,
the adiabatic flame temperature will
(A) Increase
(B) decrease
(C) increase or decrease depending on the fuel type
(D) not change
(GATE – 2001)
Q.30
A butane isomerization process produces 70kmol/h pure isobutene. A purge stream
removed continuously contains 85% n butane and 15% impurity (mole%). The feed stream
is n-butane containing 1% impurity (mole%). The flow rate of the stream will be
(A ) 3 kmol/h (B) 4 kmol/h (C) 5 kmol/h (D) 6 kmol/h
(GATE – 2001)
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
SOLUTIONS
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
(1) Ans: c
Overall material balance;
FS ER
100 80 E R
E R 180 ...1
Component C balance;
FXF SYs EYE RXR
1000.5 800.005 E 0.4 R 0.2
0.4E 0.2R 50.4 ...2
From equations (1) and (2);
R 108kg, E 72kg
72 2
E/ R
108 3
(2) Ans: 0.17 to 0.20
4NH3 5O2 6H2O 4NO
Basis = 4 moles NH3 entering the feed stream
The complete combustion of 4 moles NH3 , requires 5 moles of O2 .
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
4NH3 5O2 6H2O 4NO
Basis 4molNH3 entering thefeedstream
Forcompletecombustionof 4molNH3 O2 required 5mol
ExcessO2 tobesupplied 20%
O2 in feedstream 5 1.2 6mol
N2 entering with6molO2 in feedstream
79
6 22.57mol
21
FeedStreamcomposition
NH3______ 4mol
O2 ______ 6mol
N2______ 22.57mol
Total 32.57mol
6mol
y o2 0.184
32.57mol
(3) Ans: 198 to 202
Salt 5H2O
Mw 135 Hw 18
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
135
Xc 0.6
135 5 18
Overall material balance
F=C+L+V
Assuming no water loss by evaporation (@ 25C )
F=C+L
Salt balance
FxF C xc LxL
FxF C xc F c XL
C 100kg / s , XF 0.4, Xc 0.6, XL 0.2
F 0.4 C 0.6 F C 0.2
F 0.4 0.2 C 0.6 0.2
0.4
F C 100 2 200
0.2
(4) Ans: B
Independent equation
1) Overall material balance P Q R
2) Component material balance Px1 Q y1 R y2
Degreeof freedom ndf nunknown nindepequations nconstraints
where, nunknowns 6 P, Q, R, x1 , y1,y2 , nindepequation 2,
nconstraints 1 Streamsplitting all massfractions are equal x1 y1 y2
ndf 6 2 1 3
Twovariablevaluesare already known
P 100kg / h
x1 0.3
ndf 3 2 1
for a completely defined problemndf 0
To make ndf 0 , we need to define one more var iable.
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
(5) Ans: 0.40
pB XB PBvap pT xTPvap
T
P pB pT MixturefollowsRaoult ' s law
pB
YB
P
p Partial pressure
P Total pressure
xB pBvap
xBpBvap xTpvap
T
xB 0.2
xT 1 0.2 0.8
pBvap 92KPa
pTvap 35KPa
0.2 9.2
0.2 92 0.8 35
18.4
0.396 0.40
46.4
vapphasemol fractionof benzene 0.40
vapphasemol fractionof Toluene 0.60
(6) Ans: D
Process – 1: (Catalytic Dehydroaromatisation)
Process – 2:
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
MolesH2 produceinprocessII / molof C6H12 18
6
MolesH2 producedinprocessI / molof C6H12 3
(7) Ans: 3.27 to 3.28
Basis :F 100L, R 0.6F 60L
F P R P 100 60 40L
Fluoride balance :
F CF P Cp R CR
mg mg mg
100L 2 40L 0.1 60L CR
L L L
CR
200 4 3.27mg / L
60
(8) Ans: 0.264
Basis:
100L feed entering the reverse osmosis unit
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Feed (F’) split in two stream one stream F 100L, CF 2mg / L
Entering RO unit and a bypass stream CQ 2mg / L mixing with permeate
F' F Q
F 1 f F '
Q f F '
1 f F ' F 100L 1
Overall massbalance P'=P+Q
P ' 40 f F '
fluoridebalance
PCp QCQ P ' Cp
40 0.1 f F '2 40 f F ' 1mg / L
4 2f F ' 40 f F '
or fF ' 40 4 36
F ' 36 / f 2
1 f F ' 100.......Eqn 1
F ' 36 / f .......Eqn 2
36
1 f 100
f
f 0.264
(9) Ans: B
FB
5 FB 5 1mol / s 5mol / s
FA
A is completely converted, n A 0
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
FC 1 mol/s assuming that theseparatorseparatesallof C
nC 1 mol/s, nD 1 mol/s , nB ?
Making our overall material balance across the dashed line
FA FFB FC FPG
FPG FA FFB FC 1 2 1 2mol / s
Making material balance for component B at the point x
FFB YRB FRG FB
FB FFB 5 2
orFRG 10mol / s
YRB 0.3
YRB 0.3
10mol / s
FRG / FPG 5
2mol / s
(10) Ans: A
FRG
4
FPG
FRG 4 2 8mol / s
AgainFFB YRB FRG FB
F F 52 3
or, YRB B FB
FRG 8 8
(11) Ans: A
Basis=100 mol fresh feed
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Simplematerial balance
3
3 molH2 consumedin reactor toproduce 45mol
2
3
H2 exiting reactor n1 0.75 75 45 mol
2
H2 species balance around the splitting point
3
n1 0.75 75 45 n1 0.75 n2
2
3
or n2 75 45 7.5 mol
2
H lost in purgestream 7.5mol
% 2 100 10%
H2 in freshfeed 75mol
(12) Ans: B
Basis 1molCH4
CH4 2O2 CO2 2H2O ____ 1
2CH4 3O2 2CO 4H2O _____ 2
Basis : 1mol CH4 entering theoreticalO2 required 2mol
We don ' t consider the side reaction formingCO
O2 supplied=2mol 1.20=2.4mol
0.8molN2
N2 supplied=2.4 9.6mol
0.2molO2
Species nio ni
CH4 1 1 - 1 22
O2 2.4-2 1 -3 2
N2 9.6 9.6
CO 2 2
CO2 1
H2O 21 42
According to problem statement CH4 exiting the
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
reactor 1(1 0.8) 0.2 80% conversion
1 1 22 0.2
1
and moleratio CO / CO2 22 / 1
3
1 62
and1 62 22 0.2or 1 82 0.2
or82 0.8or 2 0.1, 1 0.6
O2 consumed 21 32 2 0.6 3 0.1 1.5
O2 supplied=2.4
O2 consumed / O2 supplied 1.5 / 2.4 0.625 62.5%
(13) Ans: D
Products Mol%
CO2 10.00 CH4 2O2 CO2 2H2 O
O2 2.37
3
CO 0.53 CH4 O2 CO 2H2O
2
N2 87.10
Methane air O2 , N2 CO, CO2 , unreactedO2 andN2
Basis: 100mol product of combustion
10molCO2 10molCH4 feed
0.5molCO 0.53mol CH4feed
10.53molCH4 burnt
O 10.53molCH4 feed
assuming allCH4 wasburnt
21molO2
O2 entered throughair 87.10molN2 inair
79molN2
23.153molO2 entered 23.153molO2 feed
CH4 feed 10.53mol
Ratio of 0.454mol
O2feed 23.153mol
(14) Ans: A
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Moles ofdesired product formed
Fractional yield
moles that would have been formed
If there were no side reactions and the limiting reactant had reacted completely
moles of desired product formed moles of CO2 formed 15.21 moles
Evaluation of the denominator
Moles of CO2 formed moles of CH4 consumed 15.21 mol
Moles of CO formed moles of CH4 consumed 2.17 mol
Moles of CH4 unreacted molesof CH4 consumed 4.35 mol
TotalCH4 in feed 21.73 mol
Total H2 in feed = 2 21.73 mol
43.46 mol
If 21.73 mol CH4 would have reacted to form CO2 only
then 21.73 mol CO2 would have been formed
15.21
Fractional yield 0.70
21.73
(15) Ans: C
Fractional conversion of methane
molesof CH4 reacted toformdesired product 15.21
= 0.7
molesof CH4 in feed 21.73
(16) Ans: C
Azeotrope product rate =500mol/hr
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
Ethanol product flowrate
500 0.9 450 mol / hr
Ethylene required to produce 450 mol / hr ethanol
450
= 1500 mol / hr 30%conversion
0.3
streamcontains
which required 450 mol / hr ethylene
450mol / hr ethanol
1500 450 1050 mol unreacted ethylene
and water not calculated
streamcontains 1050 mol unreacted ethylene
C
C D 1050 and 34 (given)
D
C 34 34
C D 34 1 35
34
C 1050 1020
35
(17) Ans: B
The degree of freedom of a process is given by
dF no of unknown no of independent equation
If dF is negative as here it is 2 , it means that two
equations have wrongly been assumed as independent
and they must be removed to make dF 0
(18) Ans: B
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
m2 m4 m5
m2 w2 m4 w 4 m5 w5 w 4 1 (Pure metal)
90%of metal(i.e.m2w2 )is recovered in pure form m4 w 4
m4 w 4 0.9 m2w2 m5w5
or, m5w5 m2w2 1 0.9 0.1 m2w2
m5w5 0.1 5000 0.1 50kg / h
Now, m2 m4 m5
5000 450 m5 ,m5 4550 kg / h
w5 50 / 4550 0.01098
m6 m3 m5 2500 4550 7050kg / h
m6 w6 m3w3 m5w5 2500 0.1 50 300
w6 300 / 7050 0.04255
(19) Ans: A
F BM FB FM
B FM FM
8.5 3.1
1.742
3.1
F 1.742 1kg 1.742 kg
F B R E(Material Balance)
R F BE
1.742 1 1.2
R 1.542
R 1.542
1.285
E 1.20
(20) Ans: C
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
S2 S1 S5 100 10 110Kg / h
S3 S2 110Kg / hr
XA4 0.05, XA5 0.05 andSA3 0.05
110
S3 / S5 11
10
Flow rateof Ain S3 S3 XA3 110 0.05 5.5 kg / h
(21) Ans: B
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
F D W overall material balance
FxF DZD WXw Benzene balance
DxD (F D)x w
F xF xw D xD xw
D x F x w 0.5 0.05
0.5
F x D x w 0.95 0.05
D F 0.5 10000 kg / h 0.5 5000kg / h '
8000
Again 8000 L0 D Lo / D 1
D
L 8000
Reflux ratio= 0 1 0.6
D 5000
(22) Ans: B
MW of methanol = 32 kg /kmol
Water =18 kg/kmol
Basis =1 kg aqueous solution
0.64 kg Heat 0.64 / 32 kmol
0.36 kg water 0.36 / 18 Kmol
0.64 / 32 kmol Heat
XM 0.5
0.64 0.36
32 18 kmol mixture
(23) Ans: B
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
(24) Ans: D
(25) Ans: C
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
(26) Ans: D
(27) Ans: A
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
(28) Ans:
(29) Ans: B
Excess air reduces Adriatic flame temperature (AFT) and is often introduced to complete
combustion and avoid excessively high flame temperature limited by the material of
construction of the chamber
(30) Ans: C
© Copyright Reserved Gateflix. No part of this material should be copied or reproduced without permission
You might also like
- Mechanical Operations in Chemical Engineering (Dr. Umesh Chandra Sharma)100% (8)Mechanical Operations in Chemical Engineering (Dr. Umesh Chandra Sharma)143 pages
- Aspen Plus® Simulation Software - A Basic Course For Beginners - Unit 4 - Week 2 - Basic Process Modelling - Simulation OverviewNo ratings yetAspen Plus® Simulation Software - A Basic Course For Beginners - Unit 4 - Week 2 - Basic Process Modelling - Simulation Overview3 pages
- Chemical Process Calculation by K Ashokan-1 PDF100% (3)Chemical Process Calculation by K Ashokan-1 PDF256 pages
- Mass Transfer Written Notes For Gate Aspirants80% (5)Mass Transfer Written Notes For Gate Aspirants153 pages
- GATE Solved Question Papers For Chemical PDFNo ratings yetGATE Solved Question Papers For Chemical PDF68 pages
- Barc Intrview Experience Chemical Engineering QuestionsNo ratings yetBarc Intrview Experience Chemical Engineering Questions69 pages
- Chemical Engineering Thermodynamics - PVT Behaviour of Pure Substances50% (6)Chemical Engineering Thermodynamics - PVT Behaviour of Pure Substances25 pages
- An Insight Into Chemical Engineering by M. Subbu100% (1)An Insight Into Chemical Engineering by M. Subbu198 pages
- Mass Transfer: Previous Year Question (2000-2020)100% (1)Mass Transfer: Previous Year Question (2000-2020)44 pages
- Chemical Reaction Engineering Lab Manuals PDFNo ratings yetChemical Reaction Engineering Lab Manuals PDF47 pages
- Assignment 1: Sonawane Vrushabh Rajendrabhai 21CH60R69No ratings yetAssignment 1: Sonawane Vrushabh Rajendrabhai 21CH60R6916 pages
- Viden Io Gate Chemical Engineering Formulas GTH CH 100 Formula Sheet PDFNo ratings yetViden Io Gate Chemical Engineering Formulas GTH CH 100 Formula Sheet PDF44 pages
- 679715390 Gate Flix Process CalculationNo ratings yet679715390 Gate Flix Process Calculation207 pages
- Physical Quantities - L 100 CSPC 132 Slide 1100% (1)Physical Quantities - L 100 CSPC 132 Slide 140 pages
- Content Marketed & Distributed By: Gupta Classes For Any Help Contact: 9953168795, 9268789880No ratings yetContent Marketed & Distributed By: Gupta Classes For Any Help Contact: 9953168795, 92687898806 pages
