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Process Calculation

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PROCESS CALCULATION
CHAPTER DESCRIPTION
1.1 Dimensions And System of Units 6

1
UNITS AND
1.2
1.3
1.4
Fundamental And Derived Units
Dimensional Consistency
Dimensional Equations
DIMENSIONS 1.5 Conversion Factor

2.1 Composition of Mixtures 10

2
2.2 Ideal Gas Laws And Its Applications
2.2.1 Dalton Law
2.2.2 Raoult’s Law
BASIC 2.2.3 Henry’s Law
CHEMICAL
2.3 Relationship Between Partial Pressure And
CALCULATIONS
Mole Fraction of Component Gas to Total Pressure

3.1 Material Balance 26


3.2 Material Balance Without Chemical Reaction
3.3 Material Balance Around Unit Operations
3.3.1 Distillation
3.3.2 Absorption

3
MATERIAL
3.3.3 Extraction
3.3.4 Drying
3.3.5 Evaporation
BALANCE 3.3.6 Crystallization
WITHOUT 3.3.7 Mixing / Blending
CHEMICAL 3.3.8 Filtration
REACTION 3.4 Material Balance With Recycle, Bypass And Purge
Streams
3.4.1 Recycling
3.4.2 Purging
3.4.3 Bypassing

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4.1 Concept of Limiting And Excess Reactants 50

4
MATERIAL
4.2 Conversion And Yield

BALANCE
INVOLVING 4.3 Material Balance Involving Reactions
CHEMICAL
REACTION

5.1 Heat 60
5.2 Heat Capacity
5.2.1 Relationship Between Cv And Cp for an ideal
gas
5.2.2 Empirical Equations For Heat Capacity

5
5.2.2.1 Heat Capacities of Gases at Constant
Pressure
5.2.2.2 Mean Molar Heat Capacities of Gases
5.2.2.3 Heat Capacities of Gaseous Mixture
ENERGY 5.3 Phase Transitions
BALANCE
5.4 Enthalpy Changes Accompanied By Chemical
Reactions
5.4.1 Heat of Reaction
5.4.2 Heat of Formation
5.5 Hess’s Law of Constant Heat Summation

6.1 Fuels 67
6.2 Types of Fuels
6.2.1 Liquid Fuels
6.2.1.1 Density
6.2.1.2 Specific Gravity

6
6.2.1.3 Viscosity
6.2.1.4 Flash Point
6.2.1.5 Pour Point
FUELS AND 6.2.1.6 Specific Heat
COMBUSTION 6.2.1.7 Calorific Value of Fuels
6.2.1.8 Sulfur
6.2.1.9 Ash Content
6.2.1.10 Carbon Content
6.2.1.11 Water Content
6.2.2 Solid Fuels

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6.2.2.1 Coal Classification


6.2.2.2 Physical And Chemical Properties of
Coal
6.2.3 Analysis of Coal
6.2.3.1 Proximate Analysis
6.2.3.2 Ultimate Analysis
6.2.4 Gaseous Fuels
6.3 Combustion
6.3.1 Principle of Combustion
6.3.2 3 T’s of Combustion
6.4 Theoretical Oxygen Requirement

7.1 Terminology and Definition 83

7
HUMIDIFICATION
10.2 Adiabatic Saturation Temperature

AND WATER 4.3 Material Balance Involving Reactions


COOLING

MULTIPLE CHOICE QUESTIONS


8 LEVEL 1 – CONCEPT BASED TEST 92
9 LEVEL 2 – CONCEPT BASED TEST 102

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PART A: NOTES

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CHAPTER 1
UNITS AND DIMENSIONS

1.1 DIMENSIONS AND SYSTEM OF UNITS

A dimension is a physical specification of a system (length, time, etc).


There are primary dimensions and secondary dimensions.

A primary dimension is one which is arbitrarily defined. For example, one


dimension is length which has units of foot. The foot was defined as the
physical length of a king's foot; a rather arbitrary definition.

A secondary dimension is one which is defined in terms of primary


dimensions; e.g., volume (secondary) is defined in terms of a cubic length
(primary).

Units give the magnitude of some dimension relative to an arbitrary


standard. For example, when we say that a person is six feet tall, we mean that
person is six times as long as an object whose length is defined to be one foot.

1.2 FUNDAMENTAL AND DERIVED UNITS

 Fundamental dimensions / units are those that can be measured


independently and are sufficient to describe essential physical quantities.

 Derived dimensions / units are those that can be developed in terms of


the fundamental dimensions / units.

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The following table shows the list of basic, derived and alternative units in SI
systems.

Physical Name of Unit Symbol Definition of Unit


Quantity for Unit

Basic SI Units

Length meter M
Mass kilogram Kg
Time second s
Temperature kelvin K
Molar Amount mole Mol

Derived SI Units

Energy joule J kg .m2 .s-2 Pa . m3


Force Newton N kg .m .s-2 J . m-1
Power watt W kg .m2 .s-3 J . s-1
Density Kilogram per cubic meter kg . m-3
Velocity Meter per second m . s-1
Acceleration Meter per second m . s-2
squared
Pressure Newton per square N . m-2 , Pa
meter, pascal
Heat Capacity Joule per (kilogram . J . kg-1 . K-1
kelvin)

Alternative Units

Time minute, hour, day, year min, h, d,


y
Temperature degree Celsius 0C

Volume litre (dm3) L


Mass tonne, ton (Mg), gram t, g

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1.3 DIMENSIONAL CONSISTENCY

Dimensions and units must be handled consistently in any algebraic


calculation. To be added, two quantities must have the same dimensions and
units. (Adding a volume and a mass is guaranteed to be wrong.) The factors in
a multiplication or division may have different units, and the combined
quantity will have units of the product or ratio of the factors. Equations
involving physical quantities must have the same dimensions on both sides,
and the dimensions must be the correct ones for the quantity calculated. The
units on both sides will usually also be the same, and must be at least
equivalent and correct.

Verifying dimensional consistency is often called “checking the units,”


and is a powerful technique for uncovering errors in calculations. For purposes
of checking consistency, dimensions or units may be considered algebraic
quantities. Some examples of this procedure are:

• Density is defined as the ratio of mass to volume, and must have dimensions
ofmass/(length)3, with corresponding units.

• Checking dimensions for the famous formula E = mc2

 energy  = mass  speed


2

 force length  = mass length/time 


2

mass  acceleration length  = mass length  /  time 


2 2

mass length/time  length  = mass length  /  time 


2 2 2

mass length  /  time  = mass length  /  time 


2 2 2 2

Hence, it is clear that the above equation is dimensionally consistence.

1.4 DIMENSIONAL EQUATIONS

A dimensional equation is one in which the units of measurement and


their powers are used rather than their actual numeric values. For example,
consider an object under constant acceleration: let u denote its initial velocity v
denote its final velocity a the acceleration and t the time between the initial
and final points of time.

Then v = u + a.t

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The dimensional equation is

[LT-1] = [LT-1] + [LT-2][T]

Where, L represents a dimension of length,

T represents a dimension of time


M which does not appear here, would represent mass.

Only terms with the same dimensions may be added or subtracted.

1.5 CONVERSION FACTOR

For converting one set of units to another is simply to multiply any


number and its associated units by ratios termed as conversion factors to arrive
at the desired answer and its associated units.

Conversion factors are statements of equivalent values of different units


in the same system or between systems of units used in the form of ratios.

E.g.

 Express a speed of 50 kilometers per hour as meters per second

50km 1000m 1h 1min


50 km / h   14 m / s
h km 60min 60s

 Convert a concentration of 220 mg / dl to grams / liter

220mg 1g 10dl
220 mg / dl   2.20 g / l
dl 1000mg l

Example 1.1 In a multiple effect evaporator system, the second effect is


maintained under vacuum of 475 torr, find the absolute pressure in kPa.

Solution: Absolute pressure = Atmospheric pressure – vacuum


= 760 – 475 = 285 torr
 101.325 kPa 
Absolute pressure = 285 torr   
 760 torr 
= 38 kPa.

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CHAPTER 2
BASIC CHEMICAL CALCULATIONS

A Process refers to any operation or a series of operations that cause


physical and / or chemical changes in a substance or group of substances. The
substance or a group of substances under consideration is termed as a system.

Unit operation only physical change can occur in unit process

eg distillation evaporation, drying, extraction

Unit process Both physical as well as chemical change

eg oxidation, reduction, hydrogenation, nitration, dehydrogenation

There are some common conventional terms used to describe the


physical properties of the materials.

 Atomic Weight :The atomic weight of an element is the mass of the atom
of this element based on the scale that assigns carbon a mass exactly
twelve.

 Molecular Weight :The molecular weight of a compound is the sum of


the atomic weights of atoms that constitute a molecule of the compound.

 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.

Weight in grams
Gram atoms of an element =
Atomic Weight

 Gram Mole :It is use to specify the amounts of chemical compounds. It


is defined as the mass in gram of a substance that is equal numerically
to its molecular weight.

Weight in grams
Gram moles of an element =
Molecular Weight

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 Equivalent Weight :It is defined as the ratio of atomic weight or


molecular weight to its valance. The valence of an element or a
compound depends on the number of hydroxyl ions (OH+) donated or the
hydrogen ions (H+) accepted for each atomic weight or molecular weight.

Molecular Weight
Equivalent Weight =
Valence

2.1 COMPOSITION OF MIXTURES

The concentration of a solution containing a solid or a liquid solute can


be expressed in terms o normality, molarity and molality.

 Normality: It is defined as the number of gram equivalents of solute


dissolved in one litre of solution. It is designated by the symbol ‘N’.

gram equivalents of solute


Normality, N =
Volume of solution in litre

 Molarity: It is defined as the number of gram moles of solute dissolved


in one litre of solution. It is designated by the symbol ‘M’.

gram moles of solute


Molarity, M =
Volume of solution in litre

 Molality :It is defined as the number of gram moles of solute dissolved in


one kilogram of solvent. It is designated by the symbol ‘m’.

gram moles of solute


Molality, m =
Mass of solvent in kg

 Concentration: It is defined as the amount of solute in gram dissolved in


one litre of solution. It is designated by the symbol ‘C’.

Mass of solute in gram


Concentration, C  g / l  =
Volume of Solution in litre

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The composition of solid systems (also of liquid systems) is expressed in


terms of weight percent (common) and also in terms of mole percent. The
composition of gases is expressed in terms of volume percent.

The method of expressing the composition in ppm (i.e. one part in 106 parts of
the system) is used to specify the contents of trace impurities in solids or
liquids.

 Weight Percent : It is the weight of any component expressed as a


percentage of the total weight of the system.

Weight of A
Weight % of A =  100
Total weight of system
WA
 Weight % of A =  100
W

Where, WA = weight of the component A

W = WA + WB = weight of system…… for a binary system of A and B.

 Volume Percent :It is the pure component volume of any component


expressed as a percentage of the total volume of the system.

Pure component vollume of A


Volume % of A =  100
Total volume of system
VA
 Volume % of A =  100
V

Where, VA = weight of the component A

V = Total volume of the system = VA + VB …… for a binary system of A


and B.

 Mole Percent :It is the moles of any component expressed as a


percentage of the total moles of the system.

For a binary mixture of A and B :

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Moles of A
Mole % of A =  100
Total moles of system
nA
 Mole % of A =  100
n
WA
MA
 Mole % of A =  100
WA WB

M A MB

Where, MA and MB are the molecular weights components A and B respectively.

The sum of the weight % of all the components present in a given system
is equal to unity, or

x
i 1
i  100%

2.2 IDEAL GAS LAWS AND ITS APPLICATIONS

There are several ideal gas laws:

 Boyle’s law states that for a given mass of an ideal gas, the product of the
pressure and volume is constant at constant temperature i.e.

Where P is the absolute pressure and V is the volume occupied by gas.

 Charle’s law states that for a given mass of an ideal gas, the ratio of the
volume to temperature is constant at given pressure.

Where, T is absolute temperature.

Combining the above two laws, an ideal gas can be formulated as

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The constant of above equation is designated by the symbol R and is known as


universal gas constant.

Therefore, PV = RT

When V is the volume in cubic meters of n kmol of gas then ideal gas law is
written as

Value of Universal Gas Constant (R):

Numerical Value of R Units


8.314 m3 .kPa / kmol . K
0.008314 m3 .MPa / kmol . K
0.08206 m3 .atm / mol . K
1.987 kcal / kmol . K
8.314 J / mol . K

When the mass of gas is not known and if we know the volume occupied
by the gas at specified temperature and pressure and condition are changed we
know two of three variables in final state then third can be calculated as by
means of proportionality indicated by ideal gas law.

Let V1, T1 and P1 be the volume, temperature and pressure of n kmol of


gas at condition-1.

Let V2, T2 and P2 be the volume, temperature and pressure of n kmol of


gas at condition-2.

Then,

Combining these two equations, we get

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In ideal gas law given by above equation, V is called molar volume. At 273.15 K
(00C) and 101.325 kPa (1 atm) volume occupied by 1 kmol of gas is 22.4136
m3. These conditions are said to be Normal Temperature and Pressure (NTP).

 Partial Pressure:

The partial pressure of component of gas that is present in a mixture of gases


is the pressure that would be exerted by that component gas if it is alone were
present in the same volume and at the same temperature.

 Pure Component Volume:

The pure component volume of a component of gas that is present in a mixture


of gases is the volume that would be exerted by that component gas if it is
alone were present at the same pressure and temperature as the mixture.

2.2.1 DALTON LAW

It states that the total pressure exerted by a gaseous mixture is equal to


the sum of the partial pressures of component gases.

Mathematically, P  pA  pB  pC  .......

where P is the total pressure and pA,pB, pC etc. are the partial pressures of the
component gases A, B, C etc. respectively.

2.2.2 RAOULT’S LAW

It states that the equilibrium partial pressure of the component A is


equal to the product of vapor pressure and mole fraction of component A in
liquid phase.

Where
= mole fraction of component A in gas phase,
= mole fraction of component A in liquid phase,
= vapor pressure of component A.

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2.2.3 HENRY’S LAW

It states that the partial pressure of solute gas is proportional to mole


fraction of that component in liquid phase but proportionality constant is H.

Where HA is the Henry’s law constant for component A in a specific solvent.

Raoult’s law is generally valid when XA is close to 1 i.e. when the liquid
phase is almost pure and Henry’s law is valid for dilute solutions.

2.3 RELATIONSHIP BETWEEN PARTIAL PRESSURE AND MOLE


FRACTION OF COMPONENT GAS TO TOTAL PRESSURE:

Consider a gas mixture consisting of component gases A, B, C, etc.


Let V be the total volume of gas mixture and P is the total pressure exerted
by the mixture. VA,VB, VC etc. are the pure component volumes of
component gases A, B, C etc. respectively. pA, pB, pC etc. are the partial
pressures of the component gases A, B, C etc. respectively.

Ideal gas law for component A, B and C is

Adding above equations, we get

According to Dalton’s law,

P  pA  pB  pC  .......

Dividing component A equation by, equation got from addition of two equation,

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In percentage form,

Similar procedure is done for volume and we got final relationship as

AVERAGE MOLECULAR WEIGHT OF GAS:

Consider gas mixture consisting of component gases A, B, C, etc.


Let MA,MB, MC etc. and XA, XB, XC etc. are the molecular weight and mole
fractions of component gases A, B, C etc.

Let Mavg be the average molecular weight of gas mixture. Then,

 DENSITY OF GAS MIXTURE:

For calculating the density one must know the average molecular weight
of the gas mixture.

Where

= Density of gas mixture,


= Average molecular weight of the gas mixture,
P = Total pressure in kPa,
T = Temperature in K

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Example 2.1 Calculate the kilograms of ‘Na’ of which the amount is specified
as 3 katom.

Solution: Basis: 3 katom ‘Na’

Atomic weight of Na = 23

kg of Na
katom of Na =
Atomic weight of Na
kg of Na = katom of Na  Atomic weight of Na
kg of Na = 3  23
kg of Na = 69

Example 2.2 How many moles of H2SO4 will contain 64 kg of S?

Solution: Basis: 64 kg of S.

Atomic weight of S = 32

kg of S 64
Aatoms of S    2 katom
Atomic weight of S 32
Each mol of H2SO 4 º1 katom of S
1
Moles of H2SO4   2  2 kmol
1

Example 2.3 98 grams of sulfuric acid are dissolved in water to prepare one
litre of solution. Find normality and molarity of solution.

Solution: Basis: 1 litre of solution.

Amount of H2SO4 dissolved = 98 g

Molecular weight of H2SO4 = 98

To find the normality we must know the gram equivalents of H2SO4. So find the
gram equivalents using equivalent weight of H2SO4.

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98
 Equivalent weight of H2SO 4   49
2
98
Gram equivalents of H2SO 4  2
49
gram equivalents of H2SO 4 2
 Normality (N)  
Volume of slution in litre 1
 Normality (N)  2
98
Moles of H2SO4  1
98
moles of H2SO 4 1
 Molarity (M)  
Volume of slution in litre 1
 Molarity (M)  1

Example 2.4 A solution of caustic soda contains 20 % NaOH by weight. Taking


density of the solution as 1.196 kg / l. find the normality, molarity and molality
of the solution.

Solution: Basis: 100 kg of solution.

The solution contains 20 kg NaOH and 80 kg water (solvent).

Density of solution = 1.196 kg / l

weight of solution 100


Volume of Solution =   83.62 l
Density of solution 1.196

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20
Moles of NaOH in solution   0.5 kmol  500 mol
40
moles of NaOH 500
 Molarity (M)  
Volume of solution in litre 83.52
 Molarity (M)  5.98
For NaOH as valence = 1,
Equivalent weight  Molecular weight
 Normality (N)  Molarity (M)  5.98
 Normality (N)  5.98
moles of NaOH 500
Molality = 
Weight of solvent in kg 80
 Molality (M)  6.25

Example 2.5 A solution of methanol in water contains 20 mol % methanol.


Express the composition as weight % methanol.

Solution: Basis: 64 kg of S.

Atomic weight of S = 32

kg of S 64
Aatoms of S    2 katom
Atomic weight of S 32
Each mol of H2SO 4 º1 katom of S
1
Moles of H2SO4   2  2 kmol
1

Example 2.6 98g of H2SO4 is dissolved in water to prepair 1l of solution. Find


Normality and molarity of the solution

wt
Moles 
mol wt
98
 1
98
Molarity  M  1m

N  M  valency
1 2
 2N

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Example 2.7 20g of caustic soda was dissolved in water to prepair 500ml of
solution. Find the Normality and molarity of the solution

wt 1000
M  
mol .wt V  in ml 

20 1000
  1
40 500
N  m  valency
1  1
 1N

Example 2.8 An aqueous solution of K2CO3 is prepared by dissolving 43kg of


K2CO3 in 100kg of water at 293K. Find N,M,M of the solution. Take
density of solution as 1.3 kg/l

Methods of expressing the composition of mixtures and solution.

1. Weight %

2. Volume %

3. More %

A, B
Binary system of A& B

weight of A
Weight % of A   100
Total wt
WA
  100
WA  WB

moles of A
mole % of A   100
Total moles of to system

WA

MA
100
WA WB

MA MB

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volumeof componentA
Volume % of Component A  100
Total volume
VA
 100
VA  VB

A mole of A
mole fraction of A  
 A B Total moleof system
WA
MA
XA
WA WB

M A WB

XA mole fraction of component ‘A’

moles of B
Mole fraction of ‘B’ 
Total moles of system
WB
MB
XB 
WA WB

MA MB

XB mole fraction of component B.

Example 2.9 An aqueous solution of NaCl is prepared by dissolving 15kg of


NaCl in 100 kg of water.

Find (i) weight %

25
 100  20% of NaCl
125

(ii) mole%

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25
 100
58.5
25 100

58.5 18
 7%

Example 2.10 200 kg of NaCl is mixed with 600 kg of KCl. Find the
composition of the mixture in weight % and mole%

200
W% of Nacl = 100  25%
4800
Wt% of KCl = 75%

200
58.5
Mole % of NaCl = 200 600 100

58.5 74.5
 29.8%

Past GATE Questions

1. Assuming CO2 obeys perfect gas low, calculate the density of CO2 (in
kg/m3, at 00C and 2 atm.
A) 1 B) 2 C) 3 D) 4

2. In a mixture of benzene vapour and nitrogen gas at a total pressure of


900 mm Hg, if the absolute humidity of benzene is 0.2 Kg benzene/kg
nitrogen, the partial pressure of benzene in mm Hg is :
A) 180 B) 60.3 C) 720 D) 200

3. A sample of well water contains 140 g/m3 Ca2+ ions and 345 g/m3 Na+
ions. The hardness of the sample of water, expressed in terms of
equivalent CaCO3 in g/m3 [assuming atomic masses of Ca : 40, Na : 23,
C : 12 and O : 16 ] is
A) 350 B) 485 C) 140 D) 345

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4. A solution of specific gravity 1.0 consists of 35% A by weight and the


remaining B. If the specific gravity; of A is 0.7, the specific gravity of B is
A) 1.25 B) 1.3 C) 1.35 D) 1.2

5. The molar composition of a gas is 10% H2, 10% O2, 30% CO2 and
balance H2O. If 50% H2O condenses, the final mole percent of H2 in the
gas on a dry basis will be
A) 10% B) 5% C) 18.18% D) 20%

6. An aqueous solution of 2.45% by weight H2SO4 has a specific gravity of


1.011. The composition expressed in normality is
A) 0.2500 B) 0.2528 C) 0.5000 D) 0.5055

7. 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

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Answer Key / Explanatory answer:


1-D 2-B 3-A 4-D 5-D 6-D 7-B
5.Ans: (D)
Explanation: Assuming 100 mol of the gas,
Then, n (H2) = 10
n (O2) = 10
n (CO2) = 30
n (H2O) = 50
n (dry gas) = 10 + 10 + 30 = 50
Mole per cent of H2 on a dry gas basis
10
= 
50
= 20 %
6. Ans: (D)
Explanation: Given,
Specific gravity = 1.011
 Density of the solution = 1.011 g/cm3
= 1.011  103 g/L = 1011 g/L
Since, H2SO4 is present as 2.45% by weight.
 Weight (H2SO4) in 1 L of solution
= 1011  0.0245 = 24.7695
24.7695
Normally of the solution = = 0.5055
49

7. Ans: (B)
Explanation: Assume, 100 g of aqueous solution,
Then, weight of methanol = 64 g
Weight of water = 36 g
Number of moles of methanol (CH3OH)
64
= = 2
32
36
Number of moles of water = =2
18
2
 Mole fraction of methanol = = 0.5
22

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Process Calculation

CHAPTER 3
MATERIAL BALANCE WITHOUT CHEMICAL REACTION

3.1 MATERIAL BALANCE

All material balance calculations are based on the law of conservation of


mass, which states that matter can neither be created nor destroyed during a
process (i.e. mass is conserved). The law of conservation of mass can also be
stated as:

 The total mass of all substances taking part in a process remains


constant.
 Within a given isolated system, the mass of the system remains constant,
regardless of the changes taking place within the system.
 The total mass of various components remains constant during an unit
operation or a chemical reaction.

According to the law of conservation of mass, we have for any process

Input = Output + Accumulation

For steady state operations / process where in the accumulation of the


material is constant or nil, equation becomes,

Input = Output

 Accumulation : It refers to change in mass or moles within the system


with respect to time (i.e. variables are time invariant).

3.2 MATERIAL BALANCE WITHOUT CHEMICAL REACTION

General methods for solving the material balance problems of the system
involving no chemical reactions are:

 Select a suitable basis of calculation.


 When the system involves a component material that appears in both the
incoming and outgoing streams, whose quantity does not change during
a given operation, the component is called tie component.

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Process Calculation

 Whenever we are dealing with the system involving an inert chemical


species, the calculation may be simplified by making material balance of
the inert chemical species.

3.3 MATERIAL BALANCE AROUND UNIT OPERATIONS

There are many unit operations used in chemical industries, and their
respective simplify block diagram.

3.3.1 DISTILLATION

This operation is used for the separation of the components of a liquid


mixture by partial vaporization and condensation. Distillation with rectification
or (fractional distillation) gives almost pure product. The product removed from
the top is called the distillate or overhead product and that removed from the
bottom is called the bottoms or bottom
product. Material balance is generally based
on the more volatile component. The vapor
phase is created by supplying thermal
energy to liquid to be distilled and this
method of separation depends on the
difference in vapor pressures of different
components at a given temperature.

Overall material balance :

F =D+B

Where, F = Feed Rate, D = Distillate Rate, W = Bottoms Rate

Material balance of component a :

A in feed = A in distillate + A in bottoms

xF .F  xD .D  xW .W

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Process Calculation

3.3.2 ABSORPTION

This operation is used in the chemical industry for the recovery /


removal of a solute gas component from its mixture with another component
gases (called as inert gases with respect
to absorption) with the help of a suitable
liquid solvent in which the solute gas is
absorbed. Mathematically agitated
vessels, packed columns, etc. are the
equipments commonly used for
absorption.

Material balance of inert gas :

Inert gas in gas mixture entering the tower

= Inert gas leaving the tower

Material balance of solute gas :

Solute removed by absorption = Solute in inlet gas – Solute in lean gas

3.3.3 EXTRACTION

This operation is used in the


chemical industry for the separation of
the components of a liquid mixture with
the help of a suitable liquid solvent
wherein the solute from the feed solution
is transferred in the solvent yielding the
raffinate phase (rich in the feed solvent)
and extract phase (rich in the solvent
used). It does not give a pure product and needs further processing. Mixer
settlers, packed columns etc. are used for liquid – liquid extraction.

Overall material balance :

Feed solution + Solvent = Extract phase + Raffinate phase

If A is the solute to be extracted, then the material balance of A for fresh


solvent is:

A in feed solution = A in extract phase + A in raffinate phase

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Process Calculation

Extraction operation is also carried out for


the removal of a soluble constituent of solids
with the help of a suitable liquid solvent. For
example, oil seed extraction or leaching of
valuable metals from mineral ores.

Material balance of solids :

Solids in seeds = Solids in meal

Material balance of oil :

Oil in seeds = Oil in meal + Oil in solvent

3.3.4 DRYING

This operation is carried out in the


chemical industry for the removal of residual
moisture (water) or volatile liquid associated
with wet solids with the help of hot air, or
inert gas (N2) (drying medium). When the hot
air is circulated over the wet solids, the
moisture from the solids evaporates and gets
added in the air. It is generally the last operation carried out in the industry.
Industrial dryers include tray dryer, spray dryer, etc.

Material balance of moisture :

Moisture removed from solids = moisture added in air

 Initial moisture in wet solids – Moisture in dried solids

= Moisture in outlet air – moisture in inlet air

Material balance of solids :

Solids in wet feed = Solids in dried product

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Process Calculation

3.3.5 EVAPORATION

This operation is used in the


chemical industry to enhance the
concentration of a weak liquor to
produce a thick liquor by
evaporating a portion of the solvent
by means of condensing steam. It
may be carried out in a single or a
multiple effect evaporation system.

Overall Material Balance :

Weak liquor = Water evaporated + Crystallized Product + Thick liquor

Material balance of solids :

Solids in weak liquor = Solids in thick liquor

3.3.6 CRYSTALLIZATION

It is formation of solid particles


within a homogeneous liquid phase.
Crystallization gives almost pure
product. Various equipments used
for carrying out crystallization are stirred tanks, vacuum crystallizer, Swenson
– walker crystallizer, etc. crystallization of dissolved solids from a solution is
based on the differences in solubility at different temperatures. It usually
consists of concentration of solution and cooling of solution until it becomes
super saturated.

Overall material balance :

Feed solution = Saturated solution + Crystals

Material balance of solute crystals :

Crystals in feed solution = Crystals obtained + Crystals in saturated solution

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Process Calculation

3.3.7 MIXING / BLENDING

This operation is carried out in the chemical industry to obtain a product


of the desired quality by mixing weak and concentrated streams. For example,
preparation of a desired mixed acid, blending of solids from various batches to
get solids of a specified quality, etc.

Suppose a product stream is to be


obtained by blending streams 1, 2 and
3, then

Overall material balance :

Feed Stream – 1 + Feed Stream – 2 + Feed Stream – 3 = Desired product stream

Component material balance :

A in Feed Stream – 1 + A in Feed Stream – 2 = A in desired product stream

3.3.8 FILTRATION

This operation is carried out in the industry for the separation of solids
from a suspension in a liquid. Wet solids
are the product of this operation. Various
equipments used for this purpose are:
centrifuge machines, drum – filter press,
etc.

Overall material balance :

Feed slurry = Wet solids + Filtrate

Material balance of solids :

Solids in slurry = Solids in wet solids product + Solids in filtrate

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Process Calculation

3.4 MATERIAL BALANCE WITH RECYCLE, BYPASS AND PURGE


STREAMS

3.4.1 RECYCLING

In recycling operation, Recycling


is returning back a portion of stream
leaving the process unit to the
entrance of a process unit for further
processing. This operation is carried
out under steady state.

A in fresh feed  A in net product


overall conversion =
A in fresh feed

A in mixed feed  A in gross product


single pass conversion =
A in mixed feed

 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 quantity of mixed feed stream to
the quantity of fresh feed stream.

M
Combined Feed Ratio =
F

3.4.2 PURGING

Purge stream is the fraction of recycled stream which is continuously


taken off in order to avoid an accumulation of inerts in the recycle loop.

At steady state,

Inerts in purge = Inerts in fresh feed

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Process Calculation

P
Purge Ratio =
R

3.4.3 BYPASSING

A stream that skips one or more stages of the process and goes directly
to another downstream stage.

Example 3.1 A single effect evaporator is fed with 10000 kg / h of weak liquor
containing 15 % caustic by weight and is concentrated to get thick liquor
containing 40 % by weight caustic. Calculate:

(a) kg / h of water evaporated and


(b) kg / h of thick liquor

Solution: Basis: 10000 kg / h of weak liquor.

Let x be the kg / h thick liquor obtained and y be the kg / h water evaporated.

Overall Material balance:

Total mass Input = Total mass output

kg / h weak liquor = kg / h water


evaporated + kg / h thick liquor

10000 =x+y

Material Balance of NaOH:

NaOH in the liquid stream = NaOH in output stream

NaOH in the weak liquor =NaOH in thick liquor

© CAREER AVENUES/ PROCESS CALCULATION 33


Process Calculation

0.15  10000  0.40 x


 x  3750 kg / hr
Hence,
 y  6250 kg / hr

Water evaporated = 6250 kg / h

Thick liquor obtained = 3750 kg / h

Example 3.2 The waste acid from a nitrating process contains 30% H2SO4,
35% HNO3 and 35% H2O w/w. The acid is to be concentrated to contain 39%
H2SO4 and 42% HNO3 by addition of concentrated sulfuric acid containing 98%
H2SO4 and concentrated Nitric acid containing 72 % HNO3. Calculate the
quantities of three acids to be mixed to get 1000 kg of desired mixed acid.

Solution: Basis: 1000 kg of desired mixed acid.

Let x, y and z be the kg of waste acid, conc. Sulfuric acid and conc. Nitric acid
required to make 1000 kg desired acid.

Overall Material Balance:

x + y + z = 1000…………..(i)

Material Balance of H2SO4:

0.3x + 0.98y = 0.39  1000


 0.3x + 0.98y = 390
……………..(ii)

Material Balance of HNO3:

0.35x + 0.72z = 0.42  1000  0.35x + 0.72y = 420……………..(iii)

From equations (i), (ii) and (ii), we get

x = 90.1 kg, y = 370.4 kg, z = 539.5 kg

Thus, Amount of waste acid required = 90.1 kg

Amount of conc. Sulfuric acid required = 370.4 kg

Amount of conc. Nitric acid required = 539.5 kg

© CAREER AVENUES/ PROCESS CALCULATION 34


Process Calculation

Example 3.3 Fresh juice contains 15% solids and 85 % water by weight and is
to be concentrated to contain 40% solids by weight.

In a single evaporation system, it is found that volatile constituents of


juice escape with water leaving the concentrated juice with a flat taste. In order
to overcome this problem, part of the fresh juice bypasses the evaporator. The
operation is shown schematically in figure given below:

Calculate:

(a) The fraction of juice that bypasses the evaporator.


(b) The concentrated juice produced (containing 40 % solids) per 100 kg of
fresh juice fed to the process.

Solution: Basis: 100 kg of fresh juice fed to the process.

Let x and y be the kg of juice fed to the evaporator and p be the kg of the
concentrated juice obtained.

Material balance over the separation of bypass stream

x + y = 100…………………(i)

Material balance of solids over Evaporator:

0.15x = 0.55z…………………(ii)

Overall material balance after Evaporator:

z + y = p…………………(iii)

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Process Calculation

Material balance of solids after Evaporator:

0.55z + 0.15 y = 0.40p…………………(iv)

From equation (i), (ii), (iii) and (iv), we get

x = 85.94 kg, y = 14.06 kg, z = 23.44 kg, p = 37.5 kg

Fraction of juice that bypass evaporator in %,

y 14.06
  100   100 = 14.06 %
100 100

Quantity of concentrated juice obtained finally

p = 37.5 kg

Example 3.4 In a particular drying operation, it is required to have the


moisture content of feed to a calciner at 15 % by weight in order to prevent
lumping and sticking. This is achieved by mixing the feed having 30% by
weight moisture with a recycle stream of dried material having 3% by weight
moisture. The drying operation is shown in figure. Find the fraction of the dried
product that must be recycled.

Solution: Basis: 100 kg of fresh feed.

It contains 70 kg solids and 30 kg moisture.

Let F, R and M be the kg of fresh feed, recycle feed and mixed feed respectively.

M=F+R

We’ve, F = 100 kg

© CAREER AVENUES/ PROCESS CALCULATION 36


Process Calculation

Material balance of moisture:

0.15 M = 0.30 (100) + 0.03 R = 30 + 0.03 R

We’ve M = 100 + R

 0.15 (100 + R) = 30 + 0.03 R

 R = 125 kg

And M = 100 + 125 = 225 kg

Let x be the kg of the product leaving the calciner. The solid balance about the
calciner gives

0.97 = 0.85  225

x = 197.2 kg

Fraction of the dried product that must be recycled

R 125
   0.634
x 197.2

= 63.4 %

Water removed from the calciner = 225 – 197.2 = 27.8 kg

Product obtained (P) = x – R

Product obtained (P) = 197.2 – 125 = 72.2 kg

© CAREER AVENUES/ PROCESS CALCULATION 37


Process Calculation

Example 3.5 An evaporator is fed with 15000 kg / hr of solution containing


10% NaCl and 15%NaoH and rest water. During the process, water is
evaporated and NaCl is precipitated as crystals. The thick liquid leaving the
evaporator contains 45% NaOH and 2% NaCl and rest water. Calculate

(a) Kg / hr of water evaporated

(b) kg/ hr of salt evaporated

(c) kg/hr of liquor obtained

Water evaporated
(x)
15,000 kg.hr Thick liquor (x)
Evaporator (y)45 % NaOH, 2 %
Feed Solution
NaCl
10% NaCl, 15%NaOH NaCl ppt as a
(z) crystcals

Overall balance of NaOH :-

0.15  15000 = 0.45Y

Material balance of NaCl :-

0.10  15000 = 0.02  500 + z

Z = 1400 kg / hr

Example 3.6

Water evaporated
(y)
wet
Drying
Solids Product solids
2000kg
1% moisture
70% solids
(x) 94% solids

2000 kg of wet solid containing 70% solids by weight are fed to the dryer where
it is dried by hot air. The product obtained is found to contain 1% moisture by
weight. Calculate.

(a) kg of water removed from wet solids

(b) kg of product obtained

© CAREER AVENUES/ PROCESS CALCULATION 38


Process Calculation

Overall Balance:-

2000  x  y
.70  2000  0.99 x
.70  2000
x
.99
x 1414.14
y  585.86

Example 3.7 100 kg seeds feed to extractor which contains 45% solids and
45% oil. The caps coming out from the extractor is found to contain 80% solids
and 5 % oil. Find the % recovery of oil.

X  kg of cake Obtained

material balanceof solid


solid in seeds  solid incake

.45 100  .80  x


0.45 100
56.25 kg  x
.8
Material balance of oil

Oil in seed = oil in cake + oil recovered

0.45100  O.R  .05 56.25


O.R  42.19kg

kg of oil re cov ered


% of oil recovered = 100
kg of oil in feed

42.19
  100
45
 93.7%

© CAREER AVENUES/ PROCESS CALCULATION 39


Process Calculation

Example 3.8

Soyabeam seed oil


100kg
Extractor
18.6 kg oil
6.9 kg solids (x)
12.4 kg moisture Cake
0.8 % oil
87.7 % solids
11.5% molsture

Soyabean seeds are extracted with hexane in batch extractor. The seed
containing 18.6% oil and 69% solids and 12.4% moisture. At the end of the
process, cake is separated from hexane – oil mixture. The cake analysis is given
as 0.8 oil, 87.7 % solids and 11.5% moisture. Find % of oil recovered. All % are
by weight.

x kg of cake

Balance of solids

0.069  100  0.877  x


0.069 100
x  78.67kg
0.877
oil in cake  0.00887.67

 0.63kg

balance of oil

oil in seed = oil in cake + oil recovered

O.R 18.6  0.63


17.97
17.97
%  100  95.61%
18.6

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Process Calculation

Past GATE Questions

1. 1000 kg of a solution containing 50% by weight of a salt dissolved in it is


cooled. 400 kg of anhydrous salt is separated out. The solubility of the
salt at the lower temperature is kg/100 kg of water is,
A) 80 B) 50 C) 40 D) 20

2. An evaporator while concentrating an aqueous solution from 10 to 40%


solids evaporates 30000 kg of water. The amount of solids handled by
the system in kgs is –
A) 4000 B) 9000 C) 4600 D) 3000

3. 1000 kg of wet solids are to be dried from 60% to 20% moisture (by
weight). The mass of moisture removed in kg is –
A) 520 B) 200 C) 400 D) 500

4. The reaction A + B  C has been conducted in a reactor as shown

A) Number of boundaries around which material balances can be


written are –
a. 1 b. 6 c. 3 d. 4

B) Number of independent balances (material) that can be made around


the reactor are –
a. 1 b. 2 c. 3 d. 4

© CAREER AVENUES/ PROCESS CALCULATION 41


Process Calculation

5. In the system as shown in Figure, each stream contains three


components.

The maximum number of independent material balances is


A) 3 B) 4 C) 6 D) 9

6. Fresh orange juice contains 12% (by weight) solids and the rest
water. 90% of the fresh juice is sent to an evaporator to remove water
and subsequently mixed with the 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

7. 1 kg of saturated aqueous solution of a highly soluble component A at


600C is cooled to 250C. The solubility limits of A are (0.6 kg A)/(kg
water) at 600C and (0.2 kg A)/(kg water) at 250C. The amount, is kgs, of
the crystals formed is
A) 0.4 B) 0.25 C) 0.2 D) 0.175

8. Na2SO4, 10 H2O crystals are formed by cooling 100 kg of 30% by weight


aqueous solution of Na2SO4. The final concentration of the solute in the
solution is 10%. The weight of crystals is
A) 20 B) 32.2 C) 45.35 D) 58.65

9. 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 equations 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.

© CAREER AVENUES/ PROCESS CALCULATION 42


Process Calculation

10. For the same process, if fresh H2O feed to the reactor is 600 mol/hr and
wash water for scrubbing is 20% of the condensables coming out of the
reactor, the water flow rate in mols/hr from the distillation column as
bottoms is
A) 170 B) 220 C) 270 D) 430

11. A 35 wt% Na2SO4 solution in water, initially at 50°C, is fed to a


crystallizer at 20°C. The product stream contains hydrated crystals
Na2SO4.10H2O in equilibrium with a 20 wt% Na2SO4 solution. The
molecular weights of Na2SO4 and Na2SO4.10H2O are 142 and 322,
respectively. The feed rate of the 35% solution required to produce 500
kg/hr of hydrated crystals is
A) 403 kg/ha B) 603 kg/hr C) 803 kg/hr D) 1103 kg/hr

12. A dehumidifier (shown below) is used to completely remove water vapor


from air.

Which ONE of the following statements is TRUE?


A) Water is the ONLY tie component.
B) Air is the ONLY tie component.
C) BOTH water and air are the components.
D) There are NO tie components.

13. A saturated solution at 30°C contains 5 moles of solute (M.W. = 50


kg/kmol) per kg of solvent (M.W. = 20 kg/kmol). The solubility at 100°C
is 10 moles of the solute per kg of the solvent. If 10 kg of the original
solution is heated to 100°C, then the weight of the additional solute that
can be dissolved in it, is
A) 0.25 kg B) 1 kg C) 2 kg D) 3.34 kg

Answer Key / Explanatory Answer:


1-B 2-A 3-C 4(a)-D4(b)-C5-C 6-D 7-C 8-D 9-B 10-B
11-C 12-B 13-C

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Process Calculation

6. Ans: (D)
Explanation: Assume the basis of 100 kg of fresh juice.
Material balance around the evaporator,

A + W = 90 … (i)
0.12  90 = XA + 0 + W
XA = 10.8 … (ii)
Also, B = A + 10 … (iii)
0.4 B = 0.12  10 + XA
Putting the value of xA from Eq. (ii),
0.4 B = 1.2 + 10.8
B = 30
From Eq. (iii), A = 20
From Eq. (i), W = 70
 Water removed from 1 kg fresh juice
70
= = 0.7
100

7. Ans: [c]
Explanation:

Solubility at 600C = 0.6 kg A/kg water


0.6
= kg A/kg water
1.6
0.375 kg A/kg water
Solubility at 250C = 0.2 kg A/kg water
0.2
= kg A/kg water
1.2
= 0.167 kg A/kg water
 Crystal formed = 0.375 – 0.167
= 0.2 kg

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Process Calculation

8. Ans: (D)
Explanation:

Overall material balance,


A=B+C
B + C = 100 … (i)
Material balance for Na2SO4
AxA = BxB + CxC … (ii)
Mol wt of Na 2SO4
Here, xB =
Mol wt of Na 2SO4 10 H 2O
(Since, B contains only crystals)
142
= = 0.441
322
From Eq. (ii),
100  0.3 = B  0.441 + (100 -B)  0.1
B = 58.65 kg

9. Ans: (B)
Explanation: Given,
The next step should be to remove two equations that have been wrongly
assumed to be independent.

11. Ans : (C)


Explanation:

Given, C = 500 kg/h


Applying overall material balance,
A=B+C
A = B + 500
Applying material balance for Na2So4,
142
0.35 A = 0.2 B + C 
322
142
0.35 A = 0.2 (A – 500) + 500 
322
A = 803 kg/h

12. Ans: (B)


Explanation: Air is the only tie component

© CAREER AVENUES/ PROCESS CALCULATION 45


Process Calculation

13. Ans: (C)


Explanation: Given,
Solubility at 300C
= 5 mol of solute/kg of solvent
50
= 5
1000
= 0.25 kg of solute/kg of solvent
0.25
=
1  0.25
= 0.2 kg of solute/kg of solution
Now,
Solubility at 1000C
= 10 mol of solute/kg solvent
50
= 10 
1000
= 0.5 kg of solute/kg solvent
Now, given 10 kg of solution at 300C
 Solute quantity = 0.2  10 = 2 kg
Solvent quantity = 10 – 2 = 8 kg
This solution is heated up to 1000C.
8 kg of solvent at 1000C can contain,
0.5  8 = 4 kg of solute.
Therefore, additional solute that can be dissolved in the solution
= 4 – 2 = 2 kg

© CAREER AVENUES/ PROCESS CALCULATION 46


Process Calculation

Past GATE Questions

1. Carbon black is produced by decomposition of methane:


CH4(g) → C (s) + 2H2 (g)

The single pass conversion of methane is 60%. If fresh feed is pure methane and 25% of
the methane exiting the reactor is recycled, then the molar ratio of fresh feed stream to
recycle stream is

A) 0.9 B) 9 C) 10 D) 90

2. A butane isomerization process produces 70 kmol/h of pure isobutane. 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 purge stream
will be
A) 3 kmol/h B) 4 kmol/h C) 5 kmol/h D) 6 kmol/h

3. A distillation column separates 10,000 kg/h of a benzene-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.

The reflux ratio is –

A) 0.5 B) 0.6 C) 1.0 D) 2.0

4. A simplified flow sheet 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.

© CAREER AVENUES/ PROCESS CALCULATION 47


Process Calculation

The reaction is: C2H4 (g) + H2O (g) → C2H5OH (g)

(a) For an azeotrope product rate of 500 mols/hr, the recycle gas flowrate in mols/hr is
A) 30 B) 420 C) 1020 D) 1500
(b) For the same process, if fresh H2O feed to the reactor is 600 mol/hr and wash water
for scrubbing is 20% of the condensables coming out of the reactor, the water flow
rate in mols/hr from the distillation column as bottoms is
A) 170 B) 220 C) 270 D) 430

© CAREER AVENUES/ PROCESS CALCULATION 48


Process Calculation

Answer Key / Explanatory Answer:


1-B 2-C 3-B 4(a)-C 4(b)-B
1. Ans: (B)
Explanation: M is the mixed feed and R is recycle.

Assume the basis of 100 mol of mixed feed (M).


CH4 (g)  C (s) + 2H2 (g)
Initial mol 100 0 0
After single 40 60 120
Conversion of 60%
Stream O will contain 40 mol of CH4.
Since, 25% of methane in exiting stream (O) is recycled back.
 R will contain 0.25  40 = 10 mol of CH4.
 Moles of CH4 in F = 100 – 10 = 90
R and F consist of only methane as given in problem.
90
Molar ratio of fresh feed to recycle = =9
10
2. Ans: (C)
Explanation: [c]

Overall material balance gives


A = B + 70 … (i)
And material balance for impurity
0.01  A = 0.15  B
Or A = 15 B
Or B + 70 = 15 B
B = 5 kmol/h

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CHAPTER 4
MATERIAL BALANCE INVOLVING CHEMICAL REACTION

The process of manufacture of a desired product from a given raw


material involves a series of steps wherein physical and chemical changes take
place in the materials under consideration.

4.1 CONCEPT OF LIMITING AND EXCESS REACTANTS

Limiting reactant is defined as the reactant that would disappear first if a


reaction goes to completion. It is the one which decides the extent to which a
reaction can proceed. The reactant can proceed. The limiting reactant is always
present in less than its stoichiometric proportion relative to other reacting
components.

Excess Reactant is defined as the reactant which is excess of the


theoretical or stoichiometric requirement as determined by the desired
reaction. The excess component always found in the product stream through
the reaction proceeds to completion.

 Percent Excess

The excess reactant involved in the reaction is generally specified in


terms of percent excess. It is the amount in excess of the stoichiometric
requirement expressed as a percentage of the stoichiometric requirement.

For any reaction A+B → C

Where B is the excess reactant, then

moles of B supplied  moles of B required theoretically


% excess of B =  100
moles of B required theoretically

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4.2 CONVERSION AND YIELD

Consider a chemical reaction:

A+B → C

The conversion or fractional conversion of reactant A is the ratio of the


amount of A reacted to the amount of A charged. The percentage conversion of
A is the amount of A reacted expressed as a percentage of the amount of A
charged.

moles of A reacted
% conversion of A = ×100
moles of A charged

 YIELD AND SELECTIVITY

The term yield and selectivity are used in case of multiple reactions to
give the information regarding the degree to which the desired reaction
predominates over the side reaction(s) involved.

Consider the series reactions:

A→C→D

Where C is the desired product, D is the undesired product and A is the


limiting reactant. Then the yield of C is given as:

moles of A reacted to produce C


Yield of C = ×100
moles of A totally reacted

Yield of the desired product is the quantity of the limiting reactant


reacted to produce is expressed as the percentage of the quantity of the limiting
reactant reacted totally.

Consider the parallel reactions:

A→C

A→ D

Where C is the desired product, D is the undesired product. Then the


selectivity is given as:

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moles of C formed
Selectivity of C related to D =
moles of D formed

Selectivity is the ratio of the moles of the desired product produced to the
moles of the undesired product produced.

4.3 MATERIAL BALANCE INVOLVING REACTIONS

Chemical reaction in a system requires the augmentation of general


material balance equation to take into account the effects of the reaction(s).
The general equation for the material balance for the systems involving
chemical reactions. These systems may contain some amount of accumulated
product and gain / loss of materials.

Generation
Accumulation  Input through the  Output through the    Consumption 
      within the    
within the system system boundaries system boundaries system  within the system
 

Example 4.1 In manufacture of acetic acid by oxidation of acetaldehyde, 100


kmol of acetaldehyde is fed to a reactor per hour. The product leaving the
reactor contains 14.81% acetaldehyde, 59.26 % acetic acid and rest oxygen (on
mole basis). Find the % conversion of acetaldehyde.

Solution: Basis:100kmol / h acetaldehyde charged to reactor.

Reaction: CH3CHO  21 O2 
CH3COOH

The product contains 14.81% acetaldehyde and 59.26 % acetic acid by mole.

Let x be the kmol of product stream obtained per hour.

Acetic acid formed = 0.5926x kmol / h

Acetaldehyde un-reacted = 0.1481x kmol / h

From the reaction, we have

1 kmol CH3CHO  1 kmol CH3COOH

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Process Calculation

i.e., to produce 1 kmol CH3COOH , 1 kmol CH3CHO must reactthus,


Acetaldehyde reacted to produce acetic acid

1
=  0.5926 x  0.5926 x kmol / h
1

Material balance of CH3CHO:

CH3CHO fed to th reactor = CH3CHO reacted 6+ CH3CHO un reacted

CH3CHO fed to th reactor = CH3CHO reacted 6+ CH3CHO un reacted


100 = 0.5926x + 0.1481x
x = 135 kmol / h
 Aceteldehyde reacted = 0.5926 (135) = 80 kmol / h
aceteldehyde reacted 80
%Conversion of aceteldehyde =  100   100
aceteldehyde charged 100

= 80 %

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Past GATE Questions

1. Methane is completely burned with air. The possible volume percent of carbon dioxide
(on dry basis) in the flue gases is,
A) 11.7 B) 21.0 C) 44.0 D) 28.0

2. Pure carbon is completely burnt in oxygen. The flue gas analysis is 70% CO2, 20% CO
and 10% O2. The percent excess oxygen used is
A) 20 B) 12.5 C) 0 D) 10

3. 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

4. 6 g of carbon is burnt with an amount of air containing 18 g oxygen. The products


contain 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 %

5. A sample of natural gas containing 80% Methane (CH4) and the rest Nitrogen (N2) is
burnt with 20% excess air. With 80% of the combustibles producing CO2 and the
remainder going to CO the Orsat analysis in volume percent is
A) CO2 : 6.26 CO : 1.56 O2 : 3.91 H20 : 15.66 N2 : 72.60
B) CO2 : 7.42 CO : 1.86 O2 : 4.64 N2 : 86.02
C) CO2 : 6.39 CO : 1.60 O2 : 3.99 H20 : 15.96 N2 : 72.06
D) CO2 : 7.60 CO : 1.90 O2 : 4.75 N2 : 85.74

6. 80 kg of Na2SO4 (molecular weight = 142) is present in 330 kg of an aqueous


solution. The solution is cooled such that 80 kg of Na2SO4. 10 H2O crystals separate
out. The weight fraction of Na2SO4 in the remaining solution is
A) 0.00 B) 0.18 C) 0.24 D) 1.00

7. 44 kg of C3H8 is burnt with 1160 kg of air (Mol. Wt. = 29) to produce 88 kg of CO 2 and
14 kg of CO and C3H8 + 5 O2 = 3 CO2 + 4 H2O
a] What is the percent excess air used?
A) 55 B) 60 C) 65 D) 68

b] What is the % carbon burnt?


A) 63.3 B) 73.3 C) 83.3 D) 93.3

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8. Air (79 mole % nitrogen and 21 mole % oxygen) is passed over a catalyst at high
temperature. Oxygen completely reacts with nitrogen as shown below,
0.5 N2(g) + 0.5 O2(g) → NO (g)

0.5 N2(g) + O2(g) → NO 2(g)

The molar ratio of NO to NO2 in the product stream is 2:1. The fractional conversion of
nitrogen is
A) 0.13 B) 0.20 C) 0.27 D) 0.40

9. Methane and steam are fed to a reactor in molar ratio 1 : 2. The following reactions take
place,
CH4(g) + 2H2O(g) →CO2(g) + 4H2(g)

CH4(g) + H2O(g)→CO (g) + 3H2(g)

where CO2 is the desired product, CO is the undesired product and H2 is a byproduct. The
exit stream has the following composition

Species CH4 H2O CO2 H2 CO

Mole % 4.35 10.88 15.21 67.39 2.17

(a) The selectivity for desired product relative to undesired product is


A) 2.3 B) 3.5 C) 7 D) 8

(b) 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 the limiting reactant had reacted completely)
A) 0.7 B) 0.88 C) 1 D) 3.5

(c) The fractional conversion of methane is


A) 0.4 B) 0.5 C) 0.7 D) 0.8

10. Dehydrogenation of ethane, C2H6 (g) → C2H4 (g) + H2 (g), is carried out in a continuous
stirred tank reactor (CSTR). The feed is pure ethane. If the reactor exit stream contains
unconverted ethane along with the products, then the number of degrees of freedom for
the CSTR is
A) 1 B) 2 C) 3 D) 4

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11. 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 of O2 in the feed stream is

A) 1.05 B) 0.60 C) 0.51 D) 0.45

Answer Key / Explanatory Answer:


1-A 2-C 3-A 4-B 5-B 6-B 7(a)-D 7(b)-C 8-B 9(a)-C 9(b)-A 9(c)-D
10-D 11-D
3. Ans: (B)
Explanation: CH4 + 2O2  CO2 + 2H2O
Number of additional specification required = 1
(Quantity of methane)

4. Ans: (B)
Explanation: C + O2  CO2
1
C + O2  CO
2
Weight of CO2 = 16.5 g
16.5
Moles of CO2 = = 0.375
44
Weight of CO = 2.8 g
Moles of C consumed
= Moles of CO2 and CO produced
= 0.375 + 0.1 = 0.475
Weight of carbon in the feed = 6g
6
Moles of carbon in the feed = = 0.5
12
18
Moles of oxygen present in the feed = = 0.5625
32
Since, 2 mol of C require 1.5 mol of CO2 to produce CO2 and CO,
0.5 mol of C require 0.375 mol of O2 to produce CO2 and CO.
Hence, O2 is in excess and carbon is limiting reactant.
Degree of conversion of carbon
Moles of C consumed
=  100
Moles of C in the feed
0.475
=  100 = 95%
0.5

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5. Ans: (B)
Explanation: [b] CH4 + 2O2  CO2 + 2H2O … (i)
3
CH4 + O2  CO + 2H2O … (ii)
2
Assume the basis of 100 mol of natural gas.
 nCH4 = 80, nN2 = 20
Now,
80% of CH4 produces CO2 and 20% produces CO
 nCO2 = 0.8  80 = 64
nCO = 0.2  80 = 16
Moles of O2 consumed
3
= 64  2 + 16  = 152
2
Now, 20% excess air is used considering complete combustion.
Moles of O2 required for complete combustion
= nCH4  2 = 80  2 = 160
Moles of O2 actually fed = 160  1.2 = 192
79
Moles of N2 in the air feed = 192  = 722.29
21
Since, N2 does not react.
 Total moles of N2 in the product
= 20 + 722.29 = 742.29
Moles of O2 remaining in the product
= 192 – 152 = 40
Or sat analysis
Mole Volume percentage
CO2 64 7.42
CO 16 1.86
O2 40 4.64
N2 742.29 86.08
Total moles 862.29
6. Ans: (B)
Explanation:

Overall material balance of the system,


A=B+C
330 = 80 + C
C = 250 kg
Material balance for Na2SO4 gives,
142
80 = 80  +x
322
x = 44.72 kg
Since, mole weight of Na2SO4 = 142
Mole weight Na2SO4  10 H2O = 322
The weight fraction of Na2SO4 in solution
44.72
C= = 0.18
250

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7. (a) Ans: (D)

Explanation: C3H8 + 5O2  3CO2 + 4H2O


Moles required 1 5
Given, weight of C3H8 = 44 kg
44
nC3H8 = = 1 mol
44
1160
And, nair = = 40 mol
29
Since, air contains 21% of O2 and 79% N2. Moles of O2 required in the reaction = 5
5
Corresponding moles of air required = = 23.8
0.21
40  23.8
 % Excess air used = = 68%
23.8

7(b). Ans: (C)


Explanation: nC3HB = 1 mol
 nC = 3 mol
Given, weight of CO2 = 88 kg
88
 nCO2 = = 2 mol
44
 Moles of C in CO2 = 2
And, weight of CO = 14 kg
14
 nCO = = 0.5 mol
28
 Moles of C present in CO = 0.5 mol
Total moles of C present in the product
= 2 + 0.5 = 2.5 mol
2.5
 % carbon burnt =  100 = 83.3 %
3

8. Ans: (B)
Explanation: Assume basis of 100 mol of air fed over the catalyst.
0.5 N2 (g) + 0.5 O2 (g)  NO (g)
Moles a a 2a
0.5 N2 (g) + O2 (g)  NO2 (g)
Moles 0.5 b b b
Total moles of O2 in the air = 0.21  100 = 21
Since, O2 completely reacts.
 a + b = 21 … (i)
Also given,
Moles of NO 2

Moles of NO2 1
2a
0r =2
b
a=b … (ii)
From Eqs. (i) and (ii),
a = b = 10.5
Moles of N2 reacted = a + 0.5 b = 15.75
Moles of N2 in the feed air = 79
15.75
 Fractional conversion of N2 =  100 = 20%
79

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9(a). Ans: (C)


Explanation: Selectivity
Moles of desired product  co2  formed 15.21
= = =7
Moles of undesired product  co  formed 2.17

9(b). Ans: (A)


Explanation: Assume the basis of 100 mol of exit stream.
CH4 (g) + 2H2O (g)  CO2 (g) + 4H2 (g)
Moles 15.21 15.21
At reaction
CH4 (g) + H2O (g)  CO (g) + 3H2 (g)
Moles 2.17 2.17
At reaction
Moles of CH4 in the exit stream = 4.35 (given)
Total moles of CH4 in the feed before any reaction taking place
= 15.21 + 2.17 + 4.35 = 21.73
 Moles of CO2 (that would have formed if there were no side reaction and CH 4 would have reacted
completely) = 21.73
15.21
The fractional yield of CO2 = = 0.7
21.73

9(c). Ans: (C)


Explanation: Fractional conversion of methane
Moles of CH 4 reacted 15.21  2.17
=  = 0.8
Moles of CH 4 in the feed 21.73
10 Ans: (D)
Explanation: C2H2 (g)  C2H2 (g) + H2 (g)
Degree of freedom, F = C – P + 2
Here, C = 3, P = 1
 F=3–1+2=4

11. Ans: (D)


Explanation: Assume basis of 100 mol of product
 nCO2 = 10, nCO = 0.53, nH2 = 87.10,
nO2 = 2.37
CH4 + 2O2  CO2 + 2H2O
For this reaction, moles of CH4 = moles of CO2
= 10
3
CH4 + O2  CO + 2H2O
2
For this reaction, moles of CH4 = moles of CO
= 0.53
Total moles of CH4 in the feed = 10 + 0.53
= 10.53
Total moles of O2 in the reaction required
3
= 2  10 +  0.53 = 20.795
2
Total moles of O2 in the feed
= 20.795 + 2.37 = 23.16
Ratio of moles of CH4 to the moles of O2 in the feed stream
10.53
= = 0.45
23.16

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CHAPTER 5
ENERGY BALANCE

5.1 HEAT

It is the energy in transit between a hot source and a cold receiver. Heat
is that form of energy which flows from one body to another as a result of a
temperature difference. Heat is the form of energy that flows from high
temperature body to a low temperature body.

5.2 HEAT CAPACITY

It is the amount of heat energy required to increase the temperature of 1


kg of substance by 1 K. heat capacity is generally expressed on a unit mass or
unit mole basis.

When it is expressed in unit mole basis, it is termed as molar heat


capacity. It is denoted by the symbol ‘C’. it has the units of kJ / (mol. K)

 Specific Heat

The ratio of heat capacity of a particular substance to that of water, is


termed as specific heat. Mathematically, it can be defined as:

dQ
C
dT

There are two types of heat capacity.

i. Molar Heat capacity at constant volume (Cv):

dQ
Cv 
dT

ii. Heat capacity at constant pressure (Cp):

dQ
Cp 
dT

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5.2.1 RELATIONSHIP BETWEEN Cv AND Cp for an ideal gas:

The ideal gas equation for n = 1mole is

PV  RT
dQ  CpdT
 dQ  dU  PdV
therefore,
 U   V 
Cp     P.  
 T  p  T  p
 U 
Cv   
 T v

For an ideal gas, the internal energy is independent of volume or


pressure.

 U   U 
   
 T  p  T v

Hence, Cp becomes,

 V 
Cp  Cv  P  
 T  p

The ideal gas equation for n = 1 is

PV = RT

Partial differentiation of the above equation with respect to T at constant P


yields

 V 
P  R
 T  p

Putting this in equation of Cp, we get

Cp  Cv  R
 Cp  Cv  R

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5.2.2 EMPIRICAL EQUATIONS FOR HEAT CAPACITIES

There are many empirical equations to determine the heat capacities of


various systems of mixture.

5.2.2.1 HEAT CAPACITY OF GASES AT CONSTANT PRESSURE

Heat capacity at constant pressure between two temperatures T1 and T2,


we get

T2
Q   Cp .dT
T1

 Heat capacities are function of temperature and are frequently expressed


in polynomial form over a temperature range of 298 K to 1500 K.

For ideal gases, Cp at 101.325 kPa is denoted by the symbol C po and may
be given by:

Cpo  a  bT  cT 2  dT 3

Where T is in kelvin and a, b, c and d are constants. For a temperature


range between T1 and T2, we get

a  bT  cT 
T2 T2
Q   Cp .dT  Q   2
 dT 3 dT
T1 T1

 b c d 
 Q  a(T2  T1 )  (T22  T12 )  (T23  T13 )  (T24  T14 )
 2 3 4 

5.2.2.2 MEAN MOLAR HEAT CAPACITIES OF GASES

Assume any arbitrary base temperature To (in K) and if T and To are the two
temperatures between which a heat change is desired then Cpmo
(mean molar
heat capacity) is given as

 C dT
o
p


o To
Cpm
T  To 

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5.2.2.3 HEAT CAPACITIES OF GASEOUS MIXTURES

In case of heating or cooling a gas mixture of known composition, the


heat change calculations may be simplified by calculating the heat capacity for
the mixture in the following manner:

n
o
Cpmix   xiC pio
i 1

Where xi is the mass fraction of ith component in the gas mixture.

Cpio and Cpmix


o
are the heat capacities of ith component and the mixture.

5.3 PHASE TRANSITIONS

Phase transitions occur from the solid to the liquid phase and from the
liquid to the gas phase, and the reverse. During these transitions very large
changes in the value of enthalpy (and internal energy) for a substance occur,
changes called latent heat changes, because they occur without any noticeable
change in temperature. For a single phase, the enthalpy varies as a function of
the temperature, as illustrated in figure
showing below. The enthalpy changes
that take place within a single phase are
often called “sensible heat” changes.

The enthalpy changes for the phase


transitions are termed heat of fusion (for
melting), Hfusion , and heat of vaporization
(for vaporization), H . The heat of
condensation is the negative of the heat of
vaporization and the heat of solidification
is the negative of the heat of fusion. The heat of sublimation is the enthalpy
change from solid directly to vapor.
Tfusion Tvaporization

Hˆ  Hˆ (T )  Hˆ (Tref )  
Tref

Cp,solid dT  Hˆ fustion  Tfusion
 
Tfusion

Cp,liquid dT  Hˆ vaporization 
Tvaporization

T
 
Tvaporization
Cp,vapor dT

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5.4 ENTHALPY CHANGES ACCOMPANIED BY CHEMICAL REACTIONS

Whenever a chemical reaction takes place, heat may either be evolved or


absorbed and this evolved or absorbed heat of reaction plays a vital role in the
economics of a chemical process.

 When the enthalpy change associated with a reaction is positive, then


heat must be added to keep the reaction temperature from dropping.
 When enthalpy change is negative, then heat must be removed from the
reaction system to keep the reaction temperature from shooting.

5.4.1 HEAT OF REACTION

The heat of reaction is the enthalpy change that occurs when


stoichiometric quantities of reactions at some T and P react to form products at
the same T and P.

The standard heat of reaction Hˆ rxn


o
 
is the name given to the heat of
reaction for one mole of a compound that reacts at 25 0C and 1 atm when
stoichiometric quantities of reactants in the standard state react completely to
produce products in the standard state.

 products 
 
reac tan ts
Hˆ rxn
o
   i Hˆ fo,i   i Hˆ fo,i 
250 C
 i i 

 The “heat of reaction” is actually an enthalpy change, and not necessarily


equivalent to heat transfer to or from the system.

5.4.2 HEAT OF FORMATION

It is the enthalpy change accompanying the formation of one mole of a


compound from its element at a given temperature and pressure.

 
The standard heat of formation Hˆ fo is heat evolved / absorbed when
one mole of a compound is formed from its elements in a reaction beginning
and ending at 25 0C and at a pressure of 1 atm.

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5.5 HESS’S LAW OF CONSTANT HEAT SUMMATION

The enthalpy change for any reaction depends only on the energy states
of the final products and initial reactants and is independent of the pathway or
the number of steps between the reactant and product.

According to this law, the heats of reactions can be added or subtracted


algebraically. While applying this law, stoichiometric equations are treated as
algebraic equations and the stoichiometric equations are treated as algebraic
operations on the stoichiometric equations of a series of other reactions. To
obtain the heat of desired reaction, the same algebraic operations are
performed on the heats of reactions.

Using this law, we can calculate the heat of formation of a compound


from a series of reactions that do not involve a direct formation of the
compound from its elements.

For example,

According to Hess’s law,

H  H1  H2  H3  H4

Example 5.1 Estimate the consumption of ammonia and air for production of
5000 kg of nitric acid per hour. The yield of NO is 97 %, the yield of HNO3 is
92% and the content of NH3 in the dry NH3 – air mixture is 7 % by weight.

Solution: Basis: 5000 kg / h of nitric acid production.

For material balance calculations, the net equation is:

NH3  2O2 
 HNO3  H2O

From the reaction : 1 kmol NH3  1 kmol HNO3


17 kg NH3  63 kg HNO3

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17
NH3 theoretically required =  5000  1349.21 kg / h
63

Yield of NO is 97% and that of nitric acid is 92%.

1349.21
Thus, Consumption of NH3 =  1511.9 kg / h
0.97  0.92

Ammonia content of the NH3 – air mixture = 7 %

Thus, Air content of the NH3 – air mixture = 93%

Consumption of air for oxidation of NH3 in the ammonia – air mixture

93
= 1511.9   20086.5 kg / h
7

20086.5 22.4
Consumption of air = 
28.84 1

 15601.3 m3 / h measured at NTP

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CHAPTER 6
FUELS AND COMBUSTION

6.1 FUELS

The various types of fuels like liquid, solid and gaseous fuels are
available for firing in boilers, furnaces and other combustion equipments. The
selection of right type of fuel depends on various factors such as availability,
storage, handling, pollution and landed cost of fuel. The knowledge of the fuel
properties helps in selecting the right fuel for the right purpose and efficient
use of the fuel. The following characteristics, determined by laboratory tests,
are generally used for assessing the nature and quality of fuels.

6.2 TYPES OF FUELS

This section describes types of fuels: solid, liquid, and gaseous.

6.2.1 LIQUID FUELS

Liquid fuels like furnace oil and LSHS (low sulfur heavy stock) are
predominantly used in industrial applications. The various properties of liquid
fuels are given below.

6.2.1.1 DENSITY

Density is defined as the ratio of the mass of the fuel to the volume of the
fuel at a reference temperature of 15 °C. Density is measured by an instrument
called a hydrometer. The knowledge of density is useful for quantitative
calculations and assessing ignition qualities. The unit of density is kg/m3.

6.2.1.2 SPECIFIC GRAVITY

This is defined as the ratio of the weight of a given volume of oil to the
weight of the same volume of water at a given temperature. The density of fuel,
relative to water, is called specific gravity. The specific gravity of water is
defined as 1. Since specific gravity is a ratio, it has no units. The measurement
of specific gravity is generally made by a hydrometer. Specific gravity is used in
calculations involving weights and volumes.

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6.2.1.3 VISCOSITY

The viscosity of a fluid is a measure of its internal resistance to flow.


Viscosity depends on the temperature and decreases as the temperature
increases. Any numerical value for viscosity has no meaning unless the
temperature is also specified. Viscosity is measured in Stokes / Centistokes.
Sometimes viscosity is also quoted in Engler, Saybolt or Redwood. Each type of
oil has its own temperature - viscosity relationship. The measurement of
viscosity is made with an instrument called a Viscometer.

Viscosity is the most important characteristic in the storage and use of


fuel oil. It influences the degree of pre- heating required for handling, storage
and satisfactory atomization. If the oil is too viscous, it may become difficult to
pump, hard to light the burner, and difficult to handle. Poor atomization may
result in the formation of carbon deposits on the burner tips or on the walls.
Therefore pre- heating is necessary for proper atomization.

6.2.1.4 FLASH POINT

The flash point of a fuel is the lowest temperature at which the fuel can
be heated so that the vapour gives off flashes momentarily when an open flame
is passed over it. The flash point for furnace oil is 66 0C.

6.2.1.5 POUR POINT

The pour point of a fuel is the lowest temperature at which it will pour or
flow when cooled under prescribed conditions. It is a very rough indication of
the lowest temperature at which fuel oil is ready to be pumped.

6.2.1.6 SPECIFIC HEAT

Specific heat is the amount of kcal needed to raise the temperature of 1


kg of oil by 10C. The unit of specific heat is kcal / (kg .0C). It varies from 0.22 to
0.28 depending on the oil specific gravity. The specific heat determines how
much steam or electrical energy it takes to heat oil to a desired temperature.
Light oils have a low specific heat, whereas heavier oils have a higher specific
heat.

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6.2.1.7 CALORIFIC VALUE OF FUELS

The calorific value is the measurement of heat or energy produced, and is


measured either as gross calorific value or net calorific value. The difference is
determined by the latent heat of condensation of the water vapor produced
during the combustion process.

calorific value    Heat of combustion 

Gross calorific value (GCV) assumes all vapor produced during the
combustion process is fully condensed. It is the calorific value of fuel when
water is present in liquid state in the combustion products.

Net calorific value (NCV) assumes the water leaves with the combustion
products without fully being condensed. It is the calorific value of fuel when
water in the combustion products is present in vapors form.

Fuels should be compared based on the net calorific value. Hence

NCV  GCV  n.

Where,  = latent heat of vaporization of water

The calorific value of coal varies considerably depending on the ash,


moisture content and the type of coal while calorific value of fuel oils is much
more consistent.

6.2.1.8 SULFUR

The amount of sulfur in the fuel oil depends mainly on the source of the
crude oil and to a lesser extent on the refining process. The normal sulfur
content for the residual fuel oil (furnace oil) is in the order of 2 – 4 %.

The main disadvantage of sulfur is the risk of corrosion by sulfuric acid


formed during and after combustion, and condensation in cool parts of the
chimney or stack, air pre – heater and economizer.

6.2.1.9 ASH CONTENT

The ash value is related to the inorganic material or salts in the fu el oil.
The ash levels in distillate fuels are negligible. Residual fuels have higher ash
levels. These salts may be compounds of sodium, vanadium, calcium,
magnesium, silicon, iron, aluminum, nickel, etc.

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Typically, the ash value is in the range 0.03 - 0.07 %. Excessive ash in
liquid fuels can cause fouling deposits in the combustion equipment. Ash has
an erosive effect on the burner tips, causes damage to the refractories at high
temperatures and gives rise to high temperature corrosion and fouling of
equipments.

6.2.1.10 CARBON RESIDUE

Carbon residue indicates the tendency of oil to deposit a carbonaceous


solid residue on a hot surface, such as a burner or injection nozzle, when its
vaporizable constituents evaporate. Residual oil contains carbon residue of 1
percent or more.

6.2.1.11 WATER CONTENT

The water content of furnace oil when it is supplied is normally very low
because the product at refinery site is handled hot. An upper limit of 1% is
specified as a standard. Water may be present in free or emulsified form and
can cause damage to the inside surfaces of the furnace during combustion
especially if it contains dissolved salts. It can also cause spluttering of the
flame at the burner tip, possibly extinguishing the flame, reducing the flame
temperature or lengthening the flame.

6.2.2 SOLID FUEL (COAL)


6.2.2.1 COAL CLASSIFICATION

Coal is classified into three major types namely anthracite, bituminous,


and lignite. However, there is no clear demarcation between them. Coal is
further classified as semi - anthracite, semi - bituminous, and sub -
bituminous.

Anthracite is the oldest coal from a geological perspective. It is a hard


coal composed mainly of carbon with little volatile content and practically no
moisture.

Lignite is the youngest coal from a geological perspective. It is a soft coal


composed mainly of volatile matter and moisture content with low fixed carbon.
Fixed carbon refers to carbon in its free state, not combined with other

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elements. Volatile matter refers to those combustible constituents of coal that


vaporize when coal is heated.

The chemical composition of coal has a strong influence on its


combustibility. The properties of coal are broadly classified as physical
properties and chemical properties.

6.2.2.2 PHYSICAL AND CHEMICAL PROPERTIES OF COAL

Physical properties of coal include the heating value, moisture content,


volatile matter and ash.

The chemical properties of coal refer to the various elemental chemical


constituents such as carbon, hydrogen, oxygen, and sulfur.

6.2.3 ANALYSIS OF COAL

There are two methods to analyze coal: ultimate analysis and proximate
analysis.

The ultimate analysis determines all coal component elements, solid or


gaseous.

The proximate analysis determines only the fixed carbon, volatile matter,
moisture and ash percentages.

The ultimate analysis is determined in a properly equipped laboratory by


a skilled chemist, while proximate analysis can be determined with a simple
apparatus.

6.2.3.1 PROXIMATE ANALYSIS

The proximate analysis indicates the percentage by weight of fixed


carbon, volatiles, ash, and moisture content in coal. The amounts of fixed
carbon and volatile combustible matter directly contribute to the heating value
of coal. Fixed carbon acts as a main heat generator during burning. High
volatile matter content indicates easy ignition of fuel. The ash content is
important in the design of the furnace grate, combustion volume, pollution
control equipment and ash handling systems of a furnace.

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There are following parameters used under this analysis:

 Fixed carbon:

Fixed carbon is the solid fuel left in the furnace after volatile matter is
distilled off. It consists mostly of carbon but also contains some hydrogen,
oxygen, sulphur and nitrogen not driven off with the gases. Fixed carbon gives
a rough estimate of the heating value of coal.

 Volatile matter:

Volatile matters are the methane, hydrocarbons, hydrogen and carbon


monoxide, and incombustible gases like carbon dioxide and nitrogen found in
coal. Thus the volatile matter is an index of the gaseous fuels present. A typical
range of volatile matter is 20 to 35%.

Volatile matter:

 Proportionately increases flame length, and helps in easier ignition of


coal
 Sets minimum limit on the furnace height and volume
 Influences secondary air requirement and distribution aspects
 Influences secondary oil support

 Ash content:

Ash is an impurity that will not burn. Typical range is 5% to 40%.

Ash:

 Reduces handling and burning capacity


 Increases handling costs
 Affects combustion efficiency and boiler efficiency
 Causes clinkering and slagging

 Moisture content:

Moisture in coal must be transported, handled and stored. Since it


replaces combustible matter, it decreases the heat content per kg of coal.
Typical range is 0.5 to 10%.

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Moisture:

 Increases heat loss, due to evaporation and superheating of vapor


 Helps to a certain extent with binding fines
 Aids radiation heat transfer

 Sulfur content:

Typical range is 0.5 to 0.8% normally.

Sulfur:

 Affects clinkering and slagging tendencies


 Corrodes chimney and other equipment such as air heaters and
economizers
 Limits exit flue gas temperature

6.2.3.2 ULTIMATE ANALYSIS

The ultimate analysis indicates the various elemental chemical


constituents such as carbon, hydrogen, oxygen, sulfur, etc. It is useful in
determining the quantity of air required for combustion and the volume and
composition of the combustion gases. This information is required for the
calculation of flame temperature and the flue duct design etc.

There are following parameters used under this analysis:

 % Carbon
 % Hydrogen
 % Nitrogen
 % Sulfur
 % Oxygen

6.2.4 GASEOUS FUELS

Gaseous fuels in common use are liquefied petroleum gas (LPG), Natural
gas, producer gas, blast furnace gas, coke oven gas etc. The calorific value of
gaseous fuel is expressed in Kilocalories per normal cubic meter (kcal / N.m3)
i.e. at normal temperature (20 0C) and pressure (760 mmHg).

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6.3 COMBUSTION
6.3.1 PRINCIPLE OF COMBUSTION

Combustion refers to the rapid oxidation of fuel accompanied by the


production of heat, or heat and light. Complete combustion of a fuel is possible
only in the presence of an adequate supply of oxygen.

Oxygen (O2) is one of the most common elements on earth making up


20.9% of our air. Rapid fuel oxidation results in large amounts of heat. Solid or
liquid fuels must be changed to a gas before they will burn. Usually heat is
required to change liquids or solids into gases. Fuel gases will burn in their
normal state if enough air is present.

Most of the 79% of air (that is not oxygen) is nitrogen, with traces of
other elements. Nitrogen is considered to be a temperature reducing dilutant
that must be present to obtain the oxygen required for combustion.

Nitrogen reduces combustion efficiency by absorbing heat from the


combustion of fuels and diluting the flue gases. It also increases the volume of
combustion by-products, which then have to travel through the heat exchanger
and up the stack faster to allow the introduction of additional fuel air mixture.

6.3.2 3 T’S OF COMBUSTION

The objective of good combustion is to release all of the heat in the fuel.
This is accomplished by controlling the "three T's" of combustion which are:

(1) Temperature high enough to ignite and maintain ignition of the fuel,

(2) Turbulence or intimate mixing of the fuel and oxygen, and

(3) Time sufficient for complete combustion.

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6.3 Too much, or too little fuel with the available combustion air may
potentially result in unburned fuel and carbon monoxide generation. A very
specific amount of O2is needed for perfect combustion and some additional
(excess) air is required for ensuring complete combustion. However, too much
excess air will result in heat and efficiency losses.

6.4 THEORETICAL OXYGEN REQUIREMENT

It is the amount of oxygen required for the complete combustion of the


total fuel charged to the combustion chamber.

But usually, we send the oxygen in excess amount to achieve the


maximum value of ultimate combustion of the fuel.

O2 supplied  O2 required
% excess of O2   100
O2 required

and note that

% excess of O2  % excess of N2

Example 6.1 Crude oil is analyzed to contain 87% carbon, 12.5% hydrogen
and 0.5% sulfur (w/w). calculate the net calorific value of crude oil at 298 K.

Data: Gross Calorific Value of crude oil at 298 K = 45071 kJ / kg oil.

Latent heat of vaporization at 298 K = 2442.5 kJ / kg.

Solution: Basis: 1 kg of crude oil.

Hydrogen burnt = Hydrogen in crude oil = 0.125 kg

H2  21 O2 
 H2O

1 kmol H2  1 kmol H2O


2 kg of H2  18 kg of H2O
18
Water Produced =  0.125  1.125 kg
2

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2442.5
Latent heat of water vapor at 298 K = 1.125   2747.8 kJ
1

Net calorific value = Gross calorific value – Latent heat of vaporization

= 45071 – 2747.8

% hydrogen by wt  9  
= GCV 
100
12.5  9  2442.5
 45071 
100

= 42323.2 kJ / kg oil

Example 6.2 The purge gas obtained from ammonia synthesis loop has the
following molar composition : H2 : 69%, N2 : 23%, Ar : 2.7% and CH4 : 5.3%

It is burnt with 20% excess air. Calculate the theoretical air required and molar
composition of the dry flue gases.

Solution: Basis: 100 kmol of purge gas.

It contains 69 kmol of H2, 23 kmol of N2, 2.7 kmol of Ar and 5.3 kmol of CH4.

H2  21 O2 
 H2O
CH4  2O2 
 CO2  2H2O

Theoretical O2 required = 0.5  69 + 2  5.3 = 45.1 kmol

45.1
Theoretical air required =  214.8 kmol
0.21

Weight of theoretical air required = 214.8  29 = 6229.2 kg

Mavg = average molecular weight of the purge gas

= 0.69  2 + 0.23  18 + 0.027  40 + 0.053  16

= 9.748

Weight of purge gas = 100  9.748 = 974.8 kg

6229.2
Theoretical air required =  6.39 kg / kg purge gas
974.8

O2 in the air supplied = 45.1  1.20 = 54.12 kmol

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O2 in the flue gas = 54.12 – 45.1 = 9.02 kmol

79
N2 in the air supplied =  54.12  203.6 kmol
21

N2 in the flue gas = 203.6 + 23 = 226.6 kmol

1
CO2 in the flue gas =  5.3  5.3 kmol
1

Ar in the flue gas = Ar in purge gas = 2.7 kmol

Flue gas composition:

Component Quantity, kmol Mol %


CO2 5.3 2.18
Ar 2.7 1.11
O2 9.02 3.70
N2 226.6 93.01
Total 243.62 100.00

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Past GATE Questions

1. 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

2. A rigid vessel, containing three moles of nitrogen gas at 300C, is heated


to 2500C. Assume the average heat capacities of nitrogen to be Cp =
29.1 J/mol0C and Cv = 20.8 J/mol0C. The heat required, neglecting
the heat capacity of the vessel, is

A) 13728 J B) 19206 J C) 4576 J D) 12712 J

3. Heat capacity of air can be approximately expresses as Cp = 26.693 +


7.365 x 10– 3 T where Cp is in J/(mol)(K) and T is in K. The heat given off
by 1 mole of air when cooled at 1 atmospheric pressure from 5000C to –
1000C is
A) 10.73 kJ B) 16.15 kJ C) 18.11 kJ D) 18.33 kJ

4. One mole of methane undergoes complete combustion in a stoichiometric


amount of air. The reaction proceeds as CH4 + 2O2 → CO2 + 2H2O. Both
the reactants and the products are in gas phase.
∆ H0298 = – 730 kJ/mol of methane.

(a) Mole fraction of water vapour in the product gases is about


A) 0.19 B) 0.33 C) 0.40 D) 0.67
(b) If the average specific heat of all the gases/vapour is 40 J/(mol k),
the maximum temperature rise of the exhaust gses in 0C would be
approximately equal to
A) 1225 B) 1335 C) 1525 D) 1735

5. 600 kg/hr of saturated steam at 1 bar (enthalpy 2675.4 kJ/kg) is mixed


adiabatically with superheated steam at 450°C and 1 bar (enthalpy
3382.4 kJ/kg). The product is superheated steam at 350°C and 1 bar
(enthalpy 3175.6 kJ/kg). The flow rate of the product is
A) 711 kg/ha B) 1111 kg/hr C) 1451 kg/hr D) 2051 kg/hr

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6. Pure water (stream W) is to be obtained from a feed containing 5 weight


% salt using a desalination unit as shown below:
Desalination Unit

If the overall recovery of pure water (through stream W) is 0.75 kg/kg


feed, then the recycle ratio (R/F) is

A) 0.25 B) 0.5 C) 0.75 D) 1.0

7. A flash distillation drum (see figure below) is used to separate a


methanol-water mixture. The mole fraction of methanol in the feed is
0.5, and the feed flow rate is 1000 kmol/hr. The feed is preheated in a
heater with heat duty Qh and is subsequently flashed in the drum. The
flash drum can be assumed to be an equilibrium stage, operating
adiabatically. The equilibrium relation between the mole fractions of
methanol in the vapor and liquid phases is y* = 4 x. The ratio of
distillate to feed flow rate is 0.5.

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7(a). The mole fraction of methanol in the distillate is


A) 0.2 B) 0.7 C) 0.8 D) 0.9

7(b). If the enthalpy of the distillate with reference to the feed is 3000
kJ/kmol, and the enthalpy of the bottoms with reference to the feed
is –1000 kJ/kmol, the heat duty of the preheater (Qh in kJ/hr) is
A) –2 × 106 B) –1 × 106 C) 1 × 106 D) 2 × 106

Answer Key / Explanatory Answer:


1-B 2-B 3-C 4(a)-A 4(b)-D 5-D 6-B 7(a)-C 7(b)-C
1. Ans: (B)
Explanation:
If excess air is used after air required for complete combustion, the adiabatic
flame temperature will decrease.

4(a) Ans: (A)


Explanation:
CH4 + 2O2  CO2 + 2H2O
Give,
Moles of CH4 = 1
 Moles of O2 required = 2
Air consists of 21% O2 and 79% N2.
79
 Moles of N2 = 2  = 7.52
21
Moles composition of product gases,
Mole fraction of water vapour in the product gases
2
= = 0.19
10.52

4(b). Ans: (D)


Explanation: Total moles in the product gases = 10.52
Given, (Cp)avg = 40 J/mol – K
 H = – 730 kJ/mol = – 730  103 kJ/mol
Maximum temperature rise (  T) will be at adiabatic conditions.
Energy balance,
10.52  40   T – 730  103 = 0
 T = 17350C
5. Ans: (D)
Explanation:

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Applying the material balance,


F 1 + F2 = P
600 + F2 = P … (i)
Applying the energy balance,
F1E1 + F2E2 = PEP
Putting values,
600  2675.4 + (P – 600)  3382.4
= P  3175.6
P = 2051 kg/h
6. Ans: (B)
Explanation:

Assume basis: F = 1 kg
 W = 0.75 kg
Overall material balance
F=W+E
1 = 0.75 + E
 E = 0.25 kg
Overall salt balance
0.05 F = 0  W + 0.01 x  E
0.05 1
X=  = 20%
0.01 0.25
Now, material balance around the unit
F+R=M
1+R=M … (i)
Salt balance around the unit
0.05 F + 0.2 R = 0.1 M
Or 5 F + 20 R = 10 (R + 1)
5  1 + 10 R = 10
R = 0.5

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Therefore, the recycle ratio


R 0.5
=  = 0.5
F 1
7(a) . Ans: (C)
Explanation: Applying overall material balance
F=L+V … (i)
V
Given, = 0.5
F
or V = 0.5 × 1000
V = 500 kmol/h

From Eq. (i),


L=F–V
L = 500 kmol/h
Applying methanol balance,
F xF = Lx + Vy*
Given, y* = 4x
∴ F xF = Lx + 4V x
Putting values,
1000 × 0.5 = 500x + 4 × 500 × x
x = 0.2
The mole fraction of methanol in the distillate,
y* = 4x
y* = 0.8

7(b). Ans: (C)


Explanation: Given, feed is reference point for enthalpy.
Applying energy balance,
F×0+ Qh = V × 3000 + L × (– 1000)
Qh = 500 × 3000 – 500 × 1000
Qh = 1 × 106 kJ/h

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CHAPTER 7

HUMIDIFICATION AND WATER COOLING


Conservation of water in a plant is done by cooling the warm water from heat
exchangers reactors, etc. and reusing it as shown schematically in Figure
10.1(b). Only a small quantity of makeup water is necessary to compensate for
the losses during use. The losses are mainly due to evaporative cooling. Cooling
of warm water is done by direct contact - with air in cooling towers. Water is
fed at the top of a cooling tower and air is drawn at the bottom or through the
side walls Evaporative cooling of water occurs in the tower, the latent heat of
vaporization being supplied mostly by the water itself. The air is humidified
and the water is cooled. Air – water contacting has four major applications.

1. Water cooling: Air-water contacting is done mostly for the purpose of cooling
the warm water before it can be reused.

Figure 10.1 Cooling water systems: (a) once – through cooling, and (b) a cooling
water circuit.

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2. Humidification: Air having a specified moisture content is necessary for


some process) applications – for example, in the drying of a solid under
controlled condition. The process of creasing the moisture content of air is
called ‘humidification’. A humidifier is also used at the inlet of an air-
ventilating system.

3. Dehumidification: Moist warm air may be relieved of a part of its moisture by


contacting with water at a lower temperature. Dehumidification has use in air
conditioning.

4. Gas cooling: A hot air stream can be cooled conveniently in contact with
water. However, its content changes in the process.

Each of the above operations involves ‘simultaneous transfer of heat and mass’.
In water cooling, for example, the air flowing through the cooling tower is
unsaturated’. Evaporation of water occurs and the water vapour is transported
to the bulk of the air thereby increasing its humidity. The water temperature
decreases, and some amount of heat transfer from the warm gas to the liquid
occurs. Before dealing with the theoretical principles of simultaneous heat and
mass transfer, we shall introduce several terms used in the description and
calculation of humidification and water cooling. Water, the transferable
component, is denoted by A and air is denoted by B.

10.1 TERMINOLOGY AND DEFINITIONS

‘Temperature’, ‘humidity’ and ‘enthalpy’ of air are the more important


quantities in dealing with humidification. The rate of transfer of water vapour
(generally to the air) depends upon the vapour pressure of the water and the
moisture concentration in air. Two types of temperature – the ‘dry-bulb’ and
the ‘wet-bulb temperature’ – are defined in connection with air – water
contacting. Moisture concentration is expressed in terms of ‘humidity’ which
can be defined in more than one ways.

Dry-bulb temperature: This is the temperature of air measured by a


thermometer whose ‘bulb is dry’ i.e. not in touch with water or any other liquid.
This is the true temperature of the air.

Wet-bulb temperature: It is the temperature attained by a small amount of


evaporating water in a manner such that the sensible heat transferred from the
air to the liquid is equal to the latent heat required for the evaporation. The
wet-bulb temperature is measured by passing air over the bulb of a
thermometer which is covered with a cloth-wick saturated with water. Hence
the name.

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Relative humidity: It is the ratio of partial pressure of water vapour (pA) in air
 
at a given temperature to the vapour pressure of water PA at the same
temperature. It can be expressed as a fraction or as a per cent.

PA PA
Relative humidity    100% (10.1)
PA PA

The relative humidity does not explicitly give the moisture content of a gas. It
rather gives the ‘degree of saturation’ of the gas at a given temperature.

Absolute humidity (or simply humidity): This is a direct measure of moisture


content in a gas. The mass of water vapour per unit mass of the ‘dry’ gas is
called its ‘humidity’ or ‘absolute humidity’. These two terms are used
interchangeably. We shall denote it by Y’ (The notation Y generally indicates the
gas-phase concentration in mole ratio unit. We use a prime to mean that the
moisture content is given in mass ratio unit.). Suppose the partial pressure of
moisture in air is PA and the total pressure is P. Then

PA P 18.02
Y and Y '  A  [M .wt.: water 18.02; air  28.97] 10.2 
P  PA P  PA 28.97

In industrial practice, the humidity is sometimes expressed in ‘grains per


pound of air’ (11b = 7000 grains).

Percentage humidity or percentage saturation: It is defined as


Y' PA 18.02
Percentage humidity   100%; YS'   10.3
YS' P  PA 28.97
'
Here Y’ is the humidity (i.e. the absolute humidity) of a sample of air and YS is
its humidity at the same temperature and pressure if saturated with water
vapour. The vapour pressure of water can be calculated using the Antoine
equation given below.

11.96481 3984.923
In PA  bar   whereT isin K 10.4
T  39.724
Dew point: If a vapour – gas mixture is gradually cooled at a constant pressure,
the temperature at which it just becomes saturated is called its ‘dew point’. The
partial pressure of water vapour in air is the same as the vapour pressure of

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water at this temperature. If the temperature is reduced even slightly,


condensation occurs and droplets (dew) of water appear.

Humid volume: The humid volume  H is defined as the volume of unit mass of
‘dry’ air with accompanying water vapour at a given temperature and pressure.
If Y’ is the humidity (i.e. absolute humidity) of a sample of air at atmospheric
pressure and temperature TG C i.e TG  273 K. its humid volume can be
O

calculated from the following equation assuming ideal gas behaviour (volume of
1 kmol of a gas at 1 atm and 0°C = 22.4 m3).

 1 Y'   TG  273 
H     22.4 
3
 , inm per kg dry air 10.5
 28.97 18.02   273 

Humid hear: The humid heat cH the heat energy required to raise the
temperature of unit mass of ‘dry air’ with the accompanying water vapour by
one degree. At ordinary temperature and pressure the heat capacity of dry air
may be taken as 1.005 kJ/kgK and that of water vapour as 1.88 kJ/kgK. If the
humidity of a sample of moist air is Y’, its humid heat can be calculated from
the following equation.

cH 1.005 1.88Y ', in KJ /  kg dry air  K  10.6 

Enthalpy: Enthalpy of a sample of air appears in the energy balance equation


of water cooling and many similar operations. Like humid volume and humid
heat, it is also expressed on the basis of unit mass of dry air. Thus the
statement “the enthalpy of a sample of air is H’ kJ/kg” means that 1 kg of ‘dry’
air with accompanying water vapour has a heat content of H’ kJ with respect
to the specified reference states of air and water. The reference states may be
chosen arbitrarily. The common choice is: dry air and liquid water, both at 0°C
and 1 atm (1.013 bar) pressure.

An equation for the calculation of enthalpy of a stream of moist air at 1 atm


pressure and of humidity Y’ and temperature TG°C is given below. It is assumed
that Y’ kg water is vaporized at the reference temperature T0 C and mixed o

o
with 1 kg of dry air at the same temperature, T0 C , to get (1 + Y’) kg moist air. If
0 is the latent heat of vaporization of water at the reference temperature.the
enthalpy is given as

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H' Y ' 0 CH TG  T0 

 Enthalpy    Latent heat    Sensibleheat  10.7 

Where cH is the humid heat of the air.

If the reference temperature is 0OC, we take 0 = 2500 kJ/kg; cH is given by


Eq. (10.7). So the enthalpy is

H '  2500Y '  1.005 1.88Y '  TG  T0  , in kJ per kg dry air 10.8 
The basis of Eq. (10.8) id schematically shown in figure 10.2

1  Y ' kg humid air atT0oC 1  Y ' kg waterTGoC

 cH TG  T0  kJ  0Y ' kJ

1kg dry air at T0oC Y ' kg water vapour at T0oC Y ' kg water at T0oC

10.2 ADIABATIC SATURATION TEMPERATURE

This is an important quantity in relation to air - water contacting. In order to


explain the quantity, we use the air-water contacting arrangement shown in
Figure 10.3.

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Water is continuously sprayed in the humdification chamber through the spray


pipe. The water at the bottom of the is chamber is recirculated by a pump as
shown. An air stream continuously enters into the chamber and is brought in
intimate contact with the water spray. The air stream attains thermal
equilibrium with the water at temperature Ts and also gets saturated with
water vapour at that temperature before it leaves the chamber. A small
quantity of water at the temperature Ts may be fed continuously in order to
compensate for the vaporization loss of water. The walls of the chamber are
well- insulated and the system operates adiabatically. The temperature TS
attained by the air (which is the same as the temperature of water) is called the
‘adiabatic saturation temperature’ (also denoted by Tas) Suppose Y’ is the
humidity of the inlet air and TG is its temperature; S is the heat of vaporization
of water at the adiabatic saturation temperature, TS. If TS is also the reference
temperature (chosen for convenience) and YS’ is the humidity of the saturated
exit air,
Enthalpy of the inlet air = CH (TG - TS) + S Y’ , In kJ per kg dry air

Enthalpy of exit air = CH (TS - TS) + S Ys’ = S Ys’


Because the water temperature does not change, its enthalpy remains constant. The
enthalpy of air also remains constant as there is no heat exchange with the
surroundings. At steady state we have

s
CH (TG - TS) + S Y’= S Ys’  (TG - TS) = (Ys’ – Y’) (10.5)
CH

Equation (10.9) may be used to make a plot of Y’ versus TG for a given set of
values of Ts and S . . Such a plot is called an ‘adiabatic saturation curve’. It is
slightly curved because of the dependence of cH on Y’. An adiabatic saturation
curve terminates on the 100% saturation curse of the ‘psychrometric chart’
shown in Figure 10.6(a) and discussed in Section 10.5.Thus, the adiabatic
saturation curve is the constant enthalpy locus of the point (TG, Y’)on the T-Y
 '

plane The point TS , YS lies on the 100% humidity curve.

WET-BULB TEMPERATURE
Consider a drop of water suspended in air at the tip of a thin wire. If the
vapour pressure of water at the temperature of the drop is higher than the
partial pressure of water vapour in the ambient air, evaporation of water will
occur. The latent heat required for evaporation will be supplied (i)partly by the
surrounding air by convective heat transfer to the water drop, and (ii) partly b
the water drop itself. The temperature of the drop falls as a result. As the

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temperature of the drop decreases with time, the vapour pressure of water in
the drop also decreases causing a reduction in the partial pressure driving
force and consequently in the evaporation flux. However, the temperature
driving force for heat transfer from the ambient air to the water drop will
increase. So the contribution of heat transfer from the ambient air towards the
latent heat of vaporization of water will gradually increase. If sufficient time is
allowed, the drop will eventually attain a steady-state temperature. At steady
state, the heat flux from the ambient is equal to the latent heat required for the
evaporation flux. The temperature of the drop does not decrease any further
under this condition. This temperature of the drop is the wet- bulb
temperature.

The wet-bulb temperature can be measured by a wet-bulb thermometer shown


in Figure 10.4. One end of a wick wraps the thermometer bulb and the other
end is dipped into a water pot. The wick remains wet by water by capillary
action. The steady-state temperature of the wick indicated by the thermometer
is the wet-bulb temperature. The dry-bulb temperature of air TG and its
humidity Y’, primarily determine its wet-bulb temperature. However, factors
such as air velocity and the shape of the thermometer bulb have some effect on
the wet-bulb temperature. At an air velocity above 30 km/h, the wet-bulb
temperature depends upon the dry-bulb temperature and the humidity of the
air only. The particular type of thermometer, called the ‘sling thermometer’
shown in Figure 10.4, gives the ‘true’ wet-bulb temperature. The thermometer
is kept fixed on a panel that can swing rapidly so that a relative air velocity
above 30 kmph may be maintained. A combination of a dry-bulb and a wet-
bulb thermometer is called apsychrometer. Heat and mass transport through
the air-film on the moist wick are illustrated in Figure 10.5.

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Figure 10.5(a) Schematic of the wick and the air-film ; (b) the profile of temperature
and partial pressure of water vapour in the air - film

We determine below the quantitative relation of the wet-bulb temperature with


the dry-bulb temperature. the humidity of the air, and the heat and mass
transfer coefficients. If the steady - state temperature of the wick (i.e. the wet-
bulb temperature) isTW, and the vapour pressure of Water at this temperature
is pw, the expressions for the heat flux and the evaporation mass flux can be
written as

Heat flux, q = hG TG  Tw  ; molar flux of water vapour,


N A  kG  p w  p A  10.10 

Since the heat flux is just sufficient to meet the requirement of latent heat of
vaporization of water at steady state,

hG TG  TW   w M w kG  pw  p A   wkY ' Yw'  Y '

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where

hG  heat transfer coefficient of the air  film

kG  mass transfer coefficient for moisture transport through the air  film

Mw  molecular weight of water

w  latent heat of vaporization of water

kY '  mass transfer coefficient for moisture, in kgmoisture /  m 2   h  Y ' 

Y'  humidity of the ambient air ,

Yw'  saturation humidity of air at temperatureTw '

From Eq. (10.11),


w Yw'  Y '
TG  Tw  10.12 
hG / kY '

The difference TG - Tw.is called the ‘wet-bulb depression’. The above equation
can be used to calculate the wet-bulb temperature if hG and kY are known or
are estimated using a suitable correlation. The quantities T w. and Y’ware
related through the vapour pressure equation. However the psychrometric data
show that under moderate conditions the ratio of the heat and the mass
transfer coefficient, hG / kY '  0.227 kcal.kg . C . This is again equal to the humid
O

heat of moist air cH at moderate humidities. This very useful and interesting
result can be expressed as

hG hG
 cH i.e.  10.13
kY ' cH kY '
The above equation is known as Lewis relation.If it is combined with Eq.
(10.12), we get an equation identical to Eq. (10.9), and it is found that TS Tw .
So the adiabatic saturation temperature and the wet-bulb temperature are
nearly equal for the air - water system. But this is certainly not true for any
other gas – liquid system. The following correlation can be used to estimate the
ratio hG / kY ' for any system

hG
1.231Sc0.56 kJ / kg. K 10.14
kY '

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CHAPTER 8 – CONCEPT BASED TEST


LEVEL 1

1. The total number of atoms in 8.5 gm NH3 is ………… 10 23

(a) 9.03 (b) 3.01

(c) 3.01 (d) 1.204

2. The number of atoms of oxygen present in 11.2 liters of ozone O3  at


N.T.P. are

(a) 3.01 x 10 22 (b) 6.02 x1023

(c) 9.03 x1024 (d) 1.20 x10 24

3. Measurement of the amount of dry gas collected over water form volume
of moist gas is based on the

(a) Charle’s law (b) Avogadro’s hypothesis

(c) Dalton’s law of partial pressure (d) Boyle’s law

4. Validity of the relationship, input = outputs holds good for the system at
steady state

(a) With chemical reaction (b) Without chemical reaction

(c) Without chemical reaction (d) None of these

5. N.T.P. corresponds to

(a) 1 atm absolute pressure & 0 C

(b) 760 mm Hg gauge pressure & 0 C

(c) 760 torr& 15 C

(d) 101.325 kPa gauge pressure & 0 C

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6. 1 bar is almost equal to ……….. Atmosphere

(a) 1 (b) 100

(c) 1000 (d) 10

7. Number of gm moles of solute dissolved in one liter of a solution is called


its

(a) Equivalent weight (b) Morality

(c) Molality (d) Normality

8. 2 liters of nitrogen at N.T.P. weighs …………grams

(a)14 (b) 2.5

(c) 28 (d) 1.25

9. 1 gm mole of methane CH4  contains

(a) 6.02 x1023 atoms of hydrogen (b) 4 gm atoms of hydrogen

(c) 3.01 x 10 23 molecules of methane (d) 3 gm of carbon

10. Kopp’s rule is concerned with the calculation of

(a) Thermal conductivity (b) Heat capacity

(c) Viscosity (d) Surface tension

11. The temperature of gas in a closed container is 27 . If the temperature of


the gas is increased to 300 C then the pressure exerted is

(a) Doubled (b) Halved

(c) Trebled (d) unpredictable

12. The total volume occupied by a gaseous mixture is equal to the sum of
the pure component volumes “this is the ………. Law.

(a) Dalton’s (b) Amgat’s

(c) Gay Lussac’s (d) Avogardro’s

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13. One of the specific gravity scales is “Brix” (used specifically for sugar
solution) it is defined as

(a) Brix = (400/G) – 400 (b) Brix = 200 (G – 1)

(c) Brix = 145 – (145/G) (d) None of these

14. Equal masses of CH 4 and H2 are mixed in an empty container. The partial
pressure of hydrogen in this container expressed as the fraction of total
pressure is

(a) 1/9 (b) 8/9

(c) ½ (d) 5/9

15. ……….equation gives the effect of temperature on heat of reaction

(a) Kirchhoff’s (b) Maxwell’s

(c) Antoine (d) Kistyakowsky

16. S.T.P. corresponds to

(a) 1 atm. Absolute pressure & 15.15 C

(b) 760 mm Hg gauge pressure & 15.5 C

(c) 760 torr& 0 C

(d) 101.325 kPa gauge pressure & 15.5 C

17. How many phases are present at eutectic point

(a) 1 (b) 2

(c) 3 (d) Unpredictable

18. A gas occupies a volume of 283 c.c at 10 C , If it is heated to 20 C . If it is


heated to 20 C at constant pressure the new volume of the gas will be
……….c.c

(a) 283 (b) 566

(c) 293 (d) 141.5

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19. Kinetic theory of gases stipulates that the

(a) Energy is lost during molecular collisions.

(b) Molecules possess appreciable volume

(c) Absolute temperature is a measure of the kinetic energy of molecules


none of these

(d) None of these

20. C for mono – atomicgases is equal to

(a) R (b) 1.5 R

(c) 2 R (d) 3 R

21. With rises in temperature the heat capacity of a substance

(a) Increases

(b) Decreases

(c) Remains unchanged

(d) Either (a) or (b): depends on the substance

22. For an ideal gas, the compressibility factor

(a) Decreases with pressure rise

(b) Is unity at all temperature

(c) Is unity at Boyle’s temperature

(d) Zero

23. Real gases approach ideal behavior at

(a) High pressure & temperature

(b) Low pressure & high temperature

(c) High pressure & low temperate

(d) Low pressure & low temperature

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24. Isotopes are atoms having the same

(a) Mass number (b) Number of neutrons

(c) Atomic mass (d) None of these

25. …………fuels requires the maximum percentage of excess air complete


combustion

(a) Solid (b) Liquid

(c) Gaseous (d) Nuclear

26. A sugar solution containing ……….percent sugar is equivalent to 10Brix.

(a) 0.01 (b) 0.1

(c) 1 (d) 10

27. …………chart is a graph related to Antoine equation

(a) Ostwald (d) Cox

(c) Moliere’s (d) Enthalpy concentration

28. The heat of solution depends upon the

(a) Nature of solvent (c) Nature of solution

(c) Nature of solute (d) All (a) (b) & (c)

29. Internal energy is independent of the ………. for an ideal gas.

(a) Pressure (b) Volume

(c) Both (a) & (b) (d) Neither (a) nor (b)

30. The heats of vaporization of CS2 .C2H5 OH & 26,8,38.6 & 40.6 KJ/kg mole
respectively the order of decreasing inter molecular force in these liquid
is

(a) H2O  C2H5OH  CS2 (b) CS2  C2H5OH  H2O

(c) H2O  CS2  C2H5OH (d) CS2  H2O  C2H5OH

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31. …………equation relates latent heat and boiling point.

(a) Antoine (b) Kistyakowsky

(c) Kopp’s (d) Trouton’s

32. A bypass stream in a chemical process is useful because it

(a) Facilitates better control of the process

(b) Improves the conversion

(c) Increased the yield of products

(d) None of these

33. Recycling in a chemical process facilitates

(a) Increased yield (b) Enrichment of product

(c) Heat conservation (d) All (a) (b) & (c)

34. The heat evolved in the combustion of benzene is represented by the


equation

C6H6  7.5 O2  6CO2  3H2O, H  3264.6 kJ / kg. mol

The heat energy change when 39 gm of C6H 6 Is burnt in an open


container will be ……….kJ / (kg.mol)

(a) + 816.15 (b) +1632.3

(c) -1632.3 (d) -2448.45

35. Pick out the correct statement

(a) Heat of solution is always positive

(b) At equilibrium G is zero

(c) For the reaction PCI5 PCI3  CI2 G is less than E

(d) The heating of water in a beaker is an example of an isolated system

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36. The heat capacity of a solid compound is calculated from the atomic heat
capacity of its constituent elements with the help of the

(a) Trouton’s rule (b) Kopp’s rule

(c) Antoine equation (d) Kistyakowsky equation

37. Enthalpy of formation of NH3 is – 46 kJ / (kg. mol). The enthalpy change


for the gaseous reaction 2NH3  N2  3H2 is equal to ……….kJ / (kg.mol)

(a) 46 (b) 92

(c) -23 (d) -92

38. Specific gravity on API scale is given by the relation

(a) API = 200(G-1) (b) API = (141.5/G)-131.5

(c) API = (140/G)-130 (d) API = 145 – (145/G)

Where, G = specific gravity at 15. 5 C

39. A limiting reactant is the one which decides the ………. In the chemical
reaction

(a) Equilibrium constant (b) Conversion

(c) Rate constant (d) None of these

40. Which of the following is the clauses Clayperon equation?

(a) PV  RT  B / V  y / V 2  ......

(b) (P  a / V 2 )(v  b )  RT

p   1 1
(c) loge    
p0 R  T0 T 

RT a
(d) P  
V  b TV 2

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41. Which of the flowing expressions defines he Baume gravity scale for
liquids lighter than water?

(a) Be = (140/G)-130 (b) Be  200(G  1)

(c) Be  145  (145 / G ) (d) Be  (400 / G )  400

42. The pH value of a solution 5.9 if the hydrogen ion concentration is


decreased hundred times the solution will be

(a) Basic (b) More acidic

(c) Neutral (d) Of the same acidity

43. Which of the following expressions defines the Baume gravity scale for
liquids heavier than water

(a) (141.5/g) – 131.5 (b) 145 – (145/G)

(c) 200/G-1) (d) (400/G) 400

44. A vapor that exists above its critical temperature is termed as a


…………vapor

(a) Saturated (b) Unsaturated

(c) Gaseous (d) Sub cooled

45. Pick out the wrong statement:

(a) A vapor is termed as a sutured vapor if its partial pressure equals its
equilibrium vapor pressure

(b) A vapor whose partial pressure is less than its equilibrium vapor
pressure is termed as a superheated vapor

(c) The temperature at which a vapor is saturated is termed as the boiling


point

(d) The difference between the existing temperature of a vapor its


saturation temperature (i.e. dew point) is called its degree of superheat

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46. Disappearance of snow in subzero weather exemplifies the process of

(a) Evaporation (b) Sublimation

(c) Vaporization (d) Melting

47. Coal containing 30% ash is fired in a boiler at a the rate of 1000 kg/hr
which operates 24 hrs/day if 5 % of the ash formed is carried away by
the flue gas the quantity of ash collected at the bottom of the boiler per
day

(a) 3420 (b) 6840

(c) 7280 (d) 8640

48. Addition of non volatile solute to a solvent produces a ……….its solvent

(a) Freezing point elevation (b) Boiling point depression

(c) Vapor pressure lowering (d) All (a) (b) & (c)

49. Boling point of a non homogenous mixture of immiscible liquids is


………. that of any of its separate components.

(a) Lower than

(b) Higher than

(c) Equal to

(d) Either (a) or (b) depends on the liquids

50. Othmer chart is useful in estimating the heat of

(a) Mixing (b) Wetting

(c) Adsorption (d) None of these

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ANSWER KEY

1 (a) 11 (d) 21 (a) 31 (d) 41 (a)


2 (c) 12 (b) 22 (b) 32 (a) 42 (a)
3 (c) 13 (a) 23 (b) 33 (d) 43 (b)
4 (c) 14 (b) 24 (d) 34 (c) 44 (c)
5 (a) 15 (a) 25 (a) 35 (b) 45 (c)
6 (a) 16 (a) 26 (c) 36 (b) 46 (b)
7 (b) 17 (c) 27 (b) 37 (b) 47 (b)
8 (b) 18 (c) 28 (d) 38 (b) 48 (c)
9 (b) 19 (c) 29 (c) 39 (b) 49 (a)
10 (b) 20 (b) 30 (a) 40 (c) 50 (c)

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CHAPTER 9 – CONCEPT BASED TEST


LEVEL 2

1. For water evaporating into unsaturated air under adiabatic conditions


and at constant pressure the ……….remains constant throughout the
period of vaporization

(a) Dry bulb temperature (b) Wet bulb temperature

(c) Humidity (d) Relative saturation

2. Which of the following has the least (almost negligible) effect on the
solubility of a solute in a solvent

(a) Temperature (b) Nature of solute

(c) Pressure (d) Nature of solvent

3. The crystallization of a solute form a solution be done by

(a) Removal of pure solvent by evaporation

(b) Change of temperature thereby causing supersaturation

(c) Changing the nature of the system by the addition of a more soluble
material

(d) All (a) (b) & (c)

4. The effect of pressure on the heat capacity of the gases ……….is


negligible

(a) At pressure below one atmosphere

(b) Below the critical temperature

(c) Product enrichment

(d) None of these

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5. Pick out the wrong statement

(a) The effect of pressure on heat capacity of gases at pressure above one
atmospheric pressure

(b) The value of Cp of gases increases with atmospheric pressure

(c) The value of Cp at critical temperature and pressure infinity

(d) All (a) (b) and (c )

6. At higher temperature molar heat capacities of most of the gases (at


constant pressure ),……….with increase in temperature

(a) Increase (b) Decreases

(c) Remains unchanged (d) Increases linearly

7. The vapor pressure of liquid of similar chemical nature at any particular


temperature with increase in the molecular weight

(a) Increases

(b) Decreases

(c) Remains unchanged

(d) Either (a) or (b) depends on the liquid

8. Pick out wrong statement

(a) Atomic heat capacities of the crystalline solid elements are nearly
constant and equal 6.2 kcal / kg-atom according to the law of Petit and
Dulong

(b) Atomic heat capacities of all solid elements decrease greatly with
decrease in temperature, approaching a value of zero at absolute zero
temperature, when in the crystalline state

(c) Generally, the heat capacities of compounds are lower in the liquid
than in the solid state

(d) The heat capacity of a heterogeneous mixture is an additive property,


but when solutions are formed this additive property may no longer exist

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9. In general the specific heats of aqueous solutions ……….with increase in


the concentration of the salute

(a) Increase (b) Decrease

(c) Remain unchanged (d) None of these

10. Which of the following is not a colligative property?

(a) Osmotic pressure (b) Depression of freezing point

(c) Lowering of vapor pressure (d) None of these

11. “The heat capacity of a solid compound is approximately equal to the


sum of the heat capacities of the constituent elements.”

This is the statement

(a) Law of Petit and Dulong (b) Kopp’s rule

(c) Nearnst heat theorem (d) Trouton’s rule

12. The atomic heat capacities of all solid elements…………with decrease in


temperature

(a) Increases (b) Decreases

(c) Remains unchanged (d) Approach zero at 0 C

13. Cox chart which is useful in the design of a distillation column


(particularly suitable for petroleum hydrocarbons) is a plot of the

(a) Temperature vs. log (vapor pressure)

(b) Vapor pressure vs. log (vapor pressure)

(c) Log (temperature) vs. log (vapor pressure)

(d) Vapor pressure vs. temperature

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14. The heat capacity of a substance is

(a) Greater for liquid state than for solid state

(b) Lower for liquid state than for gaseous

(c) Higher for solid state than for liquid

(d) Equal for solid and liquid states below melting point

15. Solutions having the same osmotic pressure sure are called……solutions

(a) Dilute (b) Ideal

(c) Isotonic (d) Saturated

16. Pick out the wrong statement

(a) Raoult’s law holds good for the solubility of polar gases in non-polar
liquids

(b) Molecules with symmetrical arrangement (e.g., CH4and CCI4 ) are non-
polar

(c) Most of the hydrocarbons are non-polar

(d) Generally, non-polar compounds are chemically inactive, conduct


electricity poorly and do not ionise.

17. One ‘Therm’ is equivalent to

(a) 105 BTU (b) 105 kcal

(c) 109 BTU (d) 109 kcal

18. API gravity of water at N.T.P. is about

(a) 0 (b) 1

(c) 10 (d) 100

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19. Pick out the wring statement:

(a) The integral heat of solution of either component cannot be calculated


from heat of mixing data

(b) The average value of heat of neutralization of dilute solutions of eak


acids and bases is much less compared to that for strong acids and
bases

(c) The standard heat of solution of the hydrate of a substance is the


difference between the heat of solution of the anhydrous substance and
its heat of hydration

(d) The accompanying enthalpy change when a solute is dissolved in


solvent depends upon the nature & amount of the solute & the solvent
on the temperature & on the initial & final concentrations the solution

20. Enthalpy change resulting when unit mass a solid is wetted with
sufficient liquid so that further addition of liquid produces no additional
thermal effect is called the heat of

(a) Mixing (b) Adsorption

(c) Wetting (d) Complete wetting

21. In osmosis through a semi- permeable membrane diffusion of the

(a) Solvent is form low concentration to high concentration region

(b) Solvent is form high concentration to low concentration region

(c) Solute takes place

(d) None of these

22. In a neutral solution

(a) H  Ions are absent

(b) OH  Ions are absent

(c) Both H  and OH  ions are present in very small bt equal


concentration

(d) None of these

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23. With increase in temperature the surface tension of water

(a) Increases (b) Decreases

(c) Remains constant (d) Increases linearly

24. A reduction process is accompanied with increase in the

(a) Number of electrons (b) Oxidation number

(c) Both (a) & (b) (d) Neither (a) nor (b)

25. For a neutral solution  pH  0  the value of H   OH   is equal to

(a) 0 (b) 1

(c) < 1 (d) > 1

26. A very dilute solution is prepared by dissolving ‘ x1 ’ mole of solute in ‘x2’


mole of a solvent the mole fraction of solute of is approximately equal to

(a) x1 (b) x2/x1

(c) 1 – (x1 / x2) (d) 1/x2

27. Pick out the wrong statement

(a) Heat capacity of a diameter gas is higher than that a mono-atomic gas

(b) Equal volumes of argon and krypton contain equal number of atoms

(c) Total number of molecules contained in 22.4 litres of hydrogen at NTP


is 6.023 x 10 23

(d) The binary mixture of a particular composition in both vapor and


liquid state is known as an azeotropic mixture

28. Diffusion of that property by virtue of which a perfume bottle opened up


in a room small if a perfume ‘X’ diffusion twice as fast molecular weight
of ‘Y’ what is the molecular weight of ‘Y’ if the vapor density of gas ‘X’ is 2
molecular weight of gas ‘X’ is to be assumed to be 2.

(a) 2 (b) 4 (c) 8 (d) 16

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29. Pick out the wrong statement

(a) The evaporation of aqueous solution of glucose causes its morality to


increase

(b) Both the freezing point as well as boiling point of sea water is more
than that of distilled water

(c) The solution containing equal masses of two liquids ‘X’ and ‘Y’ has the
same mole fraction of X’ and ‘Y’

(d) Both (b) and (c )

30. A metal oxide is refused by heating it in a stream of hydrogen after


complete reduction it is found that 3.15 gm of the oxide has yielded 1.05
gm of the metal it may be inferred that the

(a) Atomic weight of the metal is 4

(b) Equivalent weight of the metal is 4

(c) Atomic weight of the metal is 2

(d) Equivalent weight of the metal is 8

31. Unrestrained expansion of an ideal gas does not result in its cooling due
to the reason that the gas molecules

(a) Do not lose energy on collision

(b) Are above the inversion temperature

(c) Do not exert attractive force on each other

(d) Do work equal to loss in kinetic energy

32. According to Raoult’s law the vapor pressure exerted by component in a


solution is proportional to the mole fraction of that component Raoult’s
law is not applicable under the following assumption/condition

(a) No component is concentrated at the surface of the solution.

(b) The component molecules are non polar and are of almost equal size

(c) In the formation of solution chemical combination / molecular


association between unlike molecules takes place

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(d) The attractive forces between like and unlike molecules are almost
equal

33. A chemical process is said to occur under unsteady state if the

(a) Inventory changes do not take place

(b) Ratio of streams entering/living are independent of time

(c) Flow rates & composition both are time dependent

(d) None of these

34. In case of a ternary system involving two liquid components and a solute
the ratio of the concentration of the solute in the two phases at
equilibrium is called the distribution confident the distribution co-
efficient deepened upon the

(a) Solute concentration (b) Temperature

(c) Both (a) & (b) (d) Neither (a) nor (b)

35. Pick out the wrong statement

(a) Ten times dilution of a normal solution (N) reduces its normally to
N/10

(b) When equal weight of oxygen and methane are mixed in an empathy
reactor at room temperature than the fraction of total pressure exerted
by the oxygen is ½

(c) Volume occupied by 9.034 x 10 23 atoms of oxygen in ozone O3  at NTP


will be 11200 c.c.

(d) One kg mole of an ideal gas at N.T.P occupies 22400 N m3

36. Match equilibrium statements of various laws used in stoichiometry

List I

P. The equilibrium value of the mole fraction of gas dissolved in a liquid


is directly proportional to the partial pressure of the gas above the liquid
surface

Q. Equal volume of all gases contains the same number of molecules


under the same conditions of temperature and pressure

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R. The heat capacity of a solid compound is approximately equal to the


sum of the heat capacities of the constituent elements

S. The total volume occupied by a gaseous mixture is equal to the sum of


the partial volume of the component gases

List II

I. Avogadro’s law

II. Kopp’s rule

III. Henry’s low

IV. Amgat’s law

(a) P – I, Q – III, R – II, S – IV (b) P – III, Q – I, R – II, S – IV

(c) P – III, Q – I, R – IV, S – II (d) P – II, Q – I, R – III, S – IV

37. Match the following equation encountered in stoichiometric calculations

List I List II

P. Clayperon equation B
I. log P  A 
T C
Q. Antoine equation b
II.  8.75  4.571 log10Tb
Tb
R. Kistyakowsky equation b
III. K
Tb
S. Trouton’s rule dPsat 
IV. 
dT T (VG  VL )

(a) P – IV, Q – I, R – II, S – III (b) P – III, Q – I, R – II, S – IV

(c) P – III, Q – IV, R – I, S – II (d) P – IV, Q – II, R – III, S – I

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38. Match the values of following stoichiometric parameters

List I List II

P. The value of CP / Cv for monatomic I. 1.5 R


gases
Q. The value of Cv for monatomic II. 2.5 R
gases
R. The value of Cp for mono atomic III1.4
gases
S. The value of CP / Cv for diatomic IV. 1.67
gases

(a) P – I, Q – IV, R – III, S – II (b) P – III, Q – I, R – II, S – IV

(c) P – IV, Q – I, R – II, S – III (d) P – II, Q – IV, R – III, S – I

39. Pick out the wrong unit conversion of calorific value

(a) 1 kcal / kg = 1.8 BTU / Ib = 4.186 kJ / kg

(b) 1 BTU/ ft 3  8.9kcal / m 3

(c) 1 BTU / Ib = 2.3 kcal/kg

(d) 1 kcal / m3 = 0.1124 BTU / ft m3

40. Match the following stoichiometric variables

List I List II

P. It decrease with increase in I. Molality of a solution


temperature
Q. It gives the hydrogen concentration II. pH value of a solution
in a solution
R. It exemplifies the colligative III. Osmotic pressure of a solution
property of a solution
S. It does not change with the increase IV. Morality of a solution
in temperature

(a) P – IV, Q – II, R – III, S – I (b) P – III, Q – I, R – II, S – IV

(c) P – III, Q – IV, R – I, S – II (d) P – IV, Q – I, R – III, S – II

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41. Match the various types of processes encountered in a chemical process


system

List I List II

P. Steady state system I. The whole stream or a part of it is let


out of the processing zone due to build
up of non reacting components
beyond a permissible level in it.
Q. System employing recycle stream II. Some part of the product stream is
routed back for reprocessing
R. System with purge stream III. Some part of the reactant stream
escapes processing and joint the
product stream
S. System employing by pass IV. There is no change in process
parameters with time

(a) P – IV, Q – II, R – III, S – I (b) P – III, Q – I, R – II, S – IV

(c) P – III, Q – IV, R – I, S – II (d) P – IV, Q – II, R – I, S – III

42. A sample of well water contains 140 gm/ m3 Ca 2 ions and 345 gm/ Ca 2 Na+
ions the hardness of the sample of water expressed in terms of
equivalent CaCO3 in gm/ m3 is (assuming atomic masses of Ca 40, Na:23,
P: 12, 0: 16)

(a) 350 (b) 485

(c) 140 (d) 345

43. The reaction A+B  C has been conducted in a reactor as shown below

The number of boundaries around which material balance can be written


are

(a) 1 (b) 6

(c) 3 (d) 4

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44. A flowsheet is given in the following figure

The single pass once through conversion of to B is 20 % then the rate of


recycle R (moles/hr) is

(a) 300 (b) 400 (c) 500 (d) 600

45. Pick out the wrong statement about the recycle stream in a process

(a) Recycling in a process stream help in utilizing the valuable reactants


to the maximum with minimum loss of reactants

(b) The ratio of the quantity of a reactant present in the reactor feed of a
recycling operation to the quantity of the same reactant entering the
process as fresh feed is called combined feed ratio

(c) Recycling in a process does not help in getting higher extent of


reaction

(d) Recycling is exemplified by refluxing back a part of the distillate to the


distillation column to maintain the quantity of liquid within the column

46. At 100 C Water and methyl-cyclo-hexane both have vapor pressures of 1


atm. Also at 100 0C the latent heats of vaporization of water and 31.55
Kj/mole for methyl-cyclo-hexane the vapor pressure of water at 150 C is
4.69 atm at 150 C the vapor pressure of methyl-cyclo-hexane would be
expected to be

(a) Significantly less than 4.69 atm

(b) Nearly equal to 4.69 atm

(c) Significantly more than 4.69 atm

(d) Indeterminate due to lack of of data

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47. Pick out the wrong statement

(a) To make 100 kg of a solution containing 40 % salt by mixing solution


a (containing 25 % salt) and solution B (containing 25 % salt) and the
amount of solution A required is 40 kg

(b) 1.2 gm atoms of carbon and 1.5 gm moles of oxygen are reacted to
give 1 gm mole of carbon dioxide the limiting reactant is carbon the
percent limiting reactant is carbon the percent excess reactant supplied
is 25

(c) A gas bubble at a pressure of Pg is Passed through a solvent with a


saturation vapor pressure of Ps if the time of passage of the bubble is
long and air is insoluble in the solvent the mole fraction of solvent in the
bubble will be equal to Ps / Pg

(d) A supersaturated solution of a sparingly solution solute at a


concentration of C, is being fed to a crystallizer at a volumetric flow rate
of V the solubility of the salute is C1 the output rate of solid from an
efficient crystallizer is (C+C1)V.

48. If feed of 500 at 5 % concentration is fed to a crystallizer the product


abstained at 25 % concentration is equal to ……….hr

(a) 75 (b) 100

(c) 150 (d) 200

49. Match the process technique used with the proper reasons for them

List I List II
I. Purge steam P. To increase the reactant conversion
II. Recycle stream Q. To maintain inert conversion
R. To get highly enriched product
S. To enhance the production rate

(a) I – Q, II – P (b) I – Q, II – S

(c) I – S, II – R (d) I – R, II – P

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50. A sample of natural gas containing 80 % methane (CH 4 ) and the rest
nitrogen N 2  is burnt with 20 % excess air. With 80 % of the
combustibles producing CO2 and the remainder going to CO the Orsat
analysis in volume per cent is

(a) CO2 : 6.26, CO : 1.56, O2 : 3.91, H2O : 42, CO : 1.86, O2 : 4.64,

(b) CO2 : 7.42, CO : 1.86, O2 : 4364, N2 : 86.02

(c) CO2 : 6.39, CO : 1.60, O2 : 3.99, H2O : 15.96, N2 : 72.06

(d) CO2 : 7.60, CO : 1.90, O2 : 4.75, N2 : 85.75

ANSWER KEY
1 (b) 11 (b) 21 (a) 31 (c) 41 (d)
2 (c) 12 (b) 22 (c) 32 (c) 42 (a)
3 (d) 13 (a) 23 (b) 33 (c) 43 (d)
4 (c) 14 (a) 24 (a) 34 (c) 44 (c)
5 (a) 15 (c) 25 (b) 35 (d) 45 (c)
6 (a) 16 (a) 26 (a) 36 (b) 46 (c)
7 (b) 17 (a) 27 (b) 37 (a) 47 (d)
8 (c) 18 (c) 28 (d) 38 (c) 48 (b)
9 (b) 19 (a) 29 (d) 39 (c) 49 (a)
10 (d) 20 (d) 30 (b) 40 (a) 50 (b)

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