Basic Chemical Calculations-Merged

2.
Basic Chemical Calculations
2. Basic Chemical Calculations
2.1 Introduction:
In Chapter 1, an attempt was made to present various systems of units and their
Conversions from one system of units to another. Before discussing material and Energy
balances, it is important to understand basic chemical principles.
Matter exists in three different forms, viz., solids, liquids and gases. Most of the elements
and compounds can be had in all the three forms except a few, e.g., iodine and ammonium
chloride, for which the liquid state is not visible and the solid state is sublimated into
gaseous state. The easiest way of expressing the quantity of matter is mass. For solids and
liquids, this can be done by weighing on a balance. However, a gas occupies the entire
volume available to it, and hence it is customary to specify the volume along with its
temperature and pressure. Very often, liquid volumes are also specified, in which case,
additional information regarding its density is required to compute the mass of the liquid.
2.2 Mole, Atomic Mass & Molar Mass:
Although measurement in terms of mass is of direct interest to the engineers, matter is

basically made up of atoms and molecules. However, since the discovery of the
fundamental laws of chemistry, chemists considered it significant to express quantity of
matter in atoms and molecules rather than in terms of auxiliary properties, such as mass
and volume. For instance, 'gram atom' and gram mole' have been used to specify amounts
of chemical elements or compounds. These units have a direct relationship with 'atomic
weights' and 'molecular weights' which are, in fact, relative masses.
Originally, the atomic mass of oxygen was taken as a reference base and its numerical value
was fixed at 16. However, the physicists discovered different isotopes of oxygen which
created a conflict between the physicists & the chemists. In 1959-60, this controversy come
to an end and both the groups of scientist finally agrees on a standard based on carbon-12.
The table of elements based on this scale was formulated in which atomic masses (m) were
listed.
The amount of substance of a system which contains as many elementary entities as there
are atoms in 0.012 kg of carbon-12 is defined as a mole. A mole is the base unit in SI units.
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2.2.1 Atomic weights of important elements:
Element Atomic Wt. Element Atomic Wt. Element Atomic Wt.

Aluminum (Al) 27 Gold (Au) 196.96 Oxygen (O) 16
Argon (Ar) 40 Helium (He) 4 Phosphorus (P) 31
Barium (Ba) 137.3 Hydrogen (H) 1 Potassium (K) 39
Beryllium (Be) 9 Iodine (I) 127 Silicon (Si) 28
Bromine (Br) 80 Iron (Fe) 55.845 Silver (Ag) 107.86
Calcium (Ca) 40 Lead (Pb) 207.2 Sodium (Na) 23
Carbon (C) 12 Magnesium(Mg) 24.3050 Sulfur (S) 32
Chlorine (Cl) 35.453 Manganese(Mn) 54.93 Tin (Sn) 118.71
Chromium (Cr) 52 Mercury (Hg) 200.59 Uranium (U) 238
Cobalt (Co) 59 Nickel (Ni) 58.59 Zink (Zn) 65.4
Copper (Cu) 63.546 Nitrogen (N) 14
2.2.2 Atomic Weight:

The atomic weight of an element is the mass of an atom on a scale that assigns carbon a
mass of exactly twelve. .
2.2.3 Molecular Weight:

The molecular weight of a compound is the sum of the atomic weights of atoms that
constitute a molecule of a compound.
2.2.4 The Gram atom:

It is used to specify the amounts of chemical elements. It is defined as a mass in gram of an
element which is equal numerically to its atomic weight.
weight in gram of A
gram atom of element A =
Atomic weight of A
weight in kilogram of A
kilogram atom of element A =
Atomic weight of A
For chemical compounds, a mole is defined as the amount of substance equal to its
molecular weight/formula weight.
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2.2.5 The Gram mole:

It is used to specify the amounts of chemical compounds. It is defined as the mass in grams
of substance that is equal numerically to its molecular weight.
weight in grams of B
gram mole of compound B =
Molecular weight of B
weight in kilograms of B
kilogram mole of compound B =
Molecular weight of B
The number of atoms present in a mole can be obtained from Avogadro's number.
1 mol = 6.022 1367 x 1023 atom/mol
Note: In these notes, gram moles & kilogram moles will be specified as mol & kmol
respectively.
2.2.6 Basis of Calculation:

Before we start solving the problems on material and energy balances of a given process,
we must assume a suitable basis on which further calculations are based. The calculations
must be presented by assuming some specific quantity or flow rate of stream entering or
leaving the process as problems involve providing the values of some input or output
stream variables and calculation of other variables. If the basis is specified in the problem
(with respect to which we have to calculate other unknowns of process) e.g., flow rate etc.,
assume it as a basis of calculation. If basis of calculation is not specified, assume suitable
basis which will simplify the given problem. While assuming new basis of calculations, we
have to search out a stream of which maximum information is given.
Ex 2.1) How many grams of NH4Cl are there in 5 mol?

Solution
Molar mass of NH4Cl = 14 + 4 + 35.5 = 53.5 g
5 mol of NH4Cl = 5 x 53.5 = 267.5 g NH4Cl
Ex 2.2) Convert 499 g CuSO4.5H2O into mol. Find equivalent mol of CuSO4 in the crystals.
Solution:
Molar mass of CuSO4 = 159.5 g
Molar mass of CuSO4.5H2O = 159.5 + 5 (1 x 2 + 16) = 249.5 g
Moles of CuSO4.5H2O = 499/249.5 = 2 mol
In the formula of CuSO4.5H2O, the moles of CuSO4 are equal (one in each) and hence, the
equivalent moles of CuSO4 in the crystals are also 2.0 mol.
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Ex 2.3) How many moles of K2CO3 will contain 117 kg K?

Solution:
Atomic mass of K, MK = 39
∴ Atoms of K = 117/39 = 3 kg atom
Each mole of K2CO3 contains 2 atoms of K.
2 atoms of K ≡ 1 mole of K2CO3 (The sign ≡ refers to 'equivalent to' and not 'equal to')
3 Moles of K2CO3 = 3/2 = 1.5 kmol
Ex 2.4) How many atoms are present in 416.6 gm barium chloride?

Solution:
Molar mass of BaCl2 = 137.3 + 2 x 35.5 = 208.3
Moles of BaCl2 = 416.6/208.3 = 2 mol
Atoms present in the mass of 416.6 g BaCl2 = 2 x 6.022 X 1023 = 12.044 X 1023 Ans.
Ex. 2.5) Convert 499 g of CuSO4 .5H2O into moles.

Solution:
Basis: 499 g of CuSO4 .5H2O
Atomic Weight: Cu = 63.5, S = 32, O = 16 and H = 1
Molecular Weight of CuSO4 . 5H2O = 1 x 63.5 + 1 x 32 + 4 x 16 + 5(2 x 1 + 1 x 16) = 249.5
499
Moles of CuSO4 . 5H2O = 249.5 = 2 mol.
Ex. 2.6) 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
Atoms of S = = = 2 katom
Atomic weight of S 32
Each mole of H2SO4 contains one atom of S.
1 kmol H2SO4 ≡ 1 katom of S
1
∴ Moles of H2SO4 = 1 𝑥2 = 2 kmol
OR
Molecular weight of H2SO4 = 98
1 katom of S ≡ 1 kmol of H2SO4
On weight basis, we have:
32 kg of S ≡ 98 kg of H2SO4
64 kg of S ≡ ?
98
Amount of H2SO4 = 𝑥 64 = 196 kg
32
196
Moles of H2SO4 = = 2 kmol
98
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Ex. 2.7) Find moles of K2CO3 that will contain 117 Kg of K?

Solution:
Basis: 117 Kg. of K
Atomic weight of K = 39
117
Atoms of K = = 3 katom
39
Each mole of K2CO3 contains 2 atom of K.
2 atom of K ≡ 1 mole of K2CO3
2 katom of K ≡ 1 kmol of K2CO3
1
Moles of K2CO3 = 𝑥 3 = 1.5 kmol
2
Ex. 2.8) Find equivalent moles of Na2SO4 in 644 g of Na2SO4 .10H2O crystals.
Solution:
Basis: 644 g of Na2SO4 .10H2O crystals
Molecular weight of Na2SO4 = 2 x 23 + 1 x 32 + 4 x 16 = 142.
Molecular weight of Na2SO4.0H2O = 142 + 10(2 x 1 + 1 x 16) = 322
644
Moles of Na2SO4.10H2O = = 2 mol
322
The relationship between Na2SO4 and Na2SO4. 10H2O is:
1 mol of Na2SO4.10H2O ≡ 1 mol Na2SO4
2 mol of Na2SO4 .10H2O ≡ ?
Moles of Na2SO4 = 2 mol
In the above formula of Na2SO4.10H2O, the moles of Na2SO4 are equal (one in each) and
hence, the equivalent moles of Na2SO4 in crystals are 2 mol.
Ex. 2.9) Find kilogram of C2H6 that contain 4 katom of carbon.

Solution:
Basis: 4 katom carbon
Molecular weight of C2H6 = 30
Relationship between C2H6 and C is
2 katom of C ≡ 1 katom of C2H6
∴ 4 katom of C ≡ ?
1
Moles of C2H6 = 2 × 4 = 2 kmol
Weight of C2H6 = kmol of C2H6 x Molecular weight of C2H6
= 2 x 30
= 60 kg
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2.3 Equivalent weight:

Equivalent weight of an element or compound is defined as the ratio of the atomic weight
or molecular weight to its valence. The valence of an element or a compound does depend
on the number of hydrogen ions (H+) accepted or the hydroxyl ion (OH-) donated for each
atomic weight or molecular weight.
Molecular weight
∴ Equivalent weight =
Valence
Ex 2.10) Find the equivalent mass of (a) PO4 radical & (b) Na3PO4.
Solution:
Molar mass PO4 radical = 31 + 4 x 16 = 95
Valence of PO4 radical =3
Equivalent mass of PO4 radical = 95/3 = 31.67
Molar mass of Na3PO4 = 3 x 23 + 95 = 164
Valence of Na3PO4 =3
i.e. Equivalent mass of Na/mole = 3
Equivalent mass of Na3PO4 = 164/3 = 54.67
Ex 2.11) Find the equivalent of 3 kmol of AlCl3

Solution:
Aluminium ion will accept three hydroxyl ions Equivalents = (moles) x 3 = 3 x 3 = 9 keq
Ex. 2.12) Find the equivalent weight of (1) HCL, (2) NaOH (3) Na2CO3 and (4) H2SO4
Solution:
(1) HCL:
Molecular weight of HCL = 1 x 1+1 x 35.5 = 36.5
Valence of HCl =1
Equivalent weight of HCl = 36.5/1 =36.5
(2) NaOH:
Molecular Weight of NaOH = 1 x 23+1 x 16+1 x 1 = 40
Valence of NaOH =1
Equivalent weight of NaOH = 40/1 =40
(3)Na2CO3:
Molecular Weight of Na2CO3 = 2 x 23+1 x 12+3 x 16 = 106
Valence of Na2CO3 =2
Equivalent weight of Na2CO3M = 106/2 =53
(4) H2SO4:
Molecular weight of H2SO4 = 2 x 1+1 x 32+3 x 16 = 98
Valence of H2SO4 =2
Equivalent Weight of H2SO4 =98/2 = 49
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Ex. 2.13) Calculate the equivalent weight of following compound:

(1)H3PO4 , (2)CaCl2 , (3)FeCl3 , (4)Al2(SO4)3 , (5)KMnO4
Atomic weights: K=39 , Ca=40 , P=31 , H=1 , O=16 , Al=27 , S =32 , Cl=35.5 , Fe=56 , Mn=55.
Sol: (1)H3PO4:
Molecular weight of H3PO4 = 3 x 1 + 1 x 31 + 4 x 16 = 98
Valence of H3PO4 =3
Equivalent weight of H3PO4 =98/3 = 32.67
(2) CaCI2:
Molecular weight of CaCl2 = 1 x 40 + 2 x 35.5 = 111
Valence of CaCl2 =2
Equivalent weight of CaCl2 = 111/2 =55.5
(3) FeCl3:
Molecular weight of FeCl3 = 1 x 56 + 3 x 35.5 =162.5
Valence of FeCl3 =3
Equivalent weight of FeCl3 = 162.5/3 = 54.17
(4) Al2(SO4)3 :
Molecular weight of Al2(SO4)3 = 2 x 27 + 3 x 32 + 12 x 16 = 342
Valence of Al2(SO4)3 =6
Equivalent weight of Al2(SO4)3 = 342/6 = 57
(5)KMnO4 :
Moleqular weight of KMnO4 = 1 x 39 + 1 x 55 + 4 x 16 = 158
Valence of KMnO4 =5
Equivalent weight of KMnO4 = 158/5 = 31.6
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2.4 Methods of expressing the Composition of Solid Mixtures and Solutions:

The composition of solid systems and 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 l06 parts) is used specifying the contents of trace impurities in solids or
liquids.
2.4.1 Composition of solid mixture:

Consider a binary system composed of components A and B.
Weight percent:
It is the weight of any component expressed as the percentage of total weight of a system.
Weight of A
∴ Weight % of A = x 100
Total weight of system
Weight fraction: It is the ratio of weight of individual component to the total weight system.
Weight of A
∴ Weight fraction of A =
Total weight of system
∴ Weight % of A = Weight fraction of A x 100
Mole percent:
It is the moles of any component expressed as the percentage of the total moles of a system.
moles of A
∴ mole % of A = x 100
Total moles of system
Mole fraction: It is the ratio of moles of individual components to the total moles of system.
For binary system of A and B,
moles of A
mole fraction of A =
Total moles of system
∴ Mole % of A = Mole fraction of A x 100
WA WB
MA MB
xA + xB = + =1
WA WB WA WB
MA + MB MA + MB
∴ Sum of mole fractions of components present in the system is equal to unity.
n
∴ ∑ xi = 1
i=1
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Ex 2.14) Sodium chloride weighing 600 kg is mixed with 200 kg potassium chloride. Find
the composition of the mixture in (a) mass % (b) mole %.
Solution
Basis: 600 kg NaCl and 200 kg KCl
Mass of NaCl in the mixture = 600 kg
Mass of KCl in the mixture = 200 kg
Total mass of the mixture = 600 + 200 = 800 kg
Mass % of NaCl, WA = (600/800) x 100 = 75

Mass % of KCl, WB = 100 -75 = 25
Molar mass of NaCl, MA = 23 + 35.5 = 58.5

Moles of NaCl = 600/58.5 = 10.26 kmol
Molar mass of KCl, MB = 39 + 35.5 = 74.5
Moles of KCl = 200/74.5 = 2.68 kmol
Total moles in the mixture = 10.26 + 2.68 = 12.94 kmol
Mole % NaCl = (10.26/12.94) x 100 = 79.23

Mole % KCl = 100 – 79.23 = 20.77
Ex. 2.15) Find nitrogen (N) content of 100 kg urea sample containing 96.43% pure urea.
Solution:
Basis: 100 kg urea sample
It contains 96.43 kg of urea
Molecular weight of urea [NH2CONH2] = 60
1kmol of NH2CONH2 ≡ 2 katom of N
60 kg of NH2CONH2 ≡ 28 kg of N
∴ 96.43 kg of NH2CONH2 ≡ ?
28
Nitrogen content of 100 kg sample = 𝑥 96.43
60
= 45 kg
Ex. 2.16) The available nitrogen (N) in the urea sample is found to be 45% by weigh.
Calculate the actual urea content in the sample
Solution:
Basis: 100Kg of urea sample
It contains 45Kg Of nitrogen as N
Atomic weight of N = 14,
Molecular weight of NH2CONH2 =60
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1Kmol NH2CONH2 ≡ 2Katom N

60 Kg of NH2CONH2 ≡ 28 Kg N
Actual urea in sample = 60/28 x 45 = 96.43 Kg
Weight % actual urea content of sample = (Kg urea/ Kg sample) x 100
= 96.43/100 x 100 = 96.43
Ex. 2.17) Calculate the available nitrogen content of solution having 30% urea, 20%
Ammonium sulphate & 20% ammonium nitrate.
Solution:
Basis: 100 Kg of the solution.
It contains 30 Kg urea, 20Kg ammonium sulphate & 20Kg ammonium nitrate.
Molecular weight of urea (NH2CONH2) =60
1Kmol NH2CONH2 ≡2 Katom of N
60 Kg NH2CONH2 ≡ 28 Kg N
Nitrogen available from urea = 28/60 * 30 = 14Kg
Molecular weight of (NH4)2SO4 =132
1Kmol (NH4)2SO4 ≡ 2 Katom N
132 Kg (NH4)2SO4 ≡ 28 Kg nitrogen (on weight basis)
Nitrogen available from (NH4)2SO4 = 28/132 * 20 = 4.24Kg
Molecular weight of NH4NO3 = 80
1 Kmol NH4NO3 ≡ 2K atom of N
80Kg of NH4NO3 ≡ 28Kg of N (on weight basis )
Nitrogen available from NH4NO3 = 28/80 x 20 = 7Kg
Total nitrogen available from the solution = 14+ 4.24 + 7 = 25.24 Kg
Nitrogen available from the solution = 25.24 /100 *100 =25.24%
Ex 2.18) A sample of light diesel oil (LDO) from a refinery is found to contain 0.68 mass%
sulphur (as S). Its density is 0.85 kg/L at 303.15 K (30oC). Convert this impurity into ppm.
Solution:
Sulphur content = 0.68% = 0.68 g S / 100 g LDO
= (0.68g/100g) x (1000 mg/1g) x (1000 g/1kg) x 0.85 kg/L
= 5780 mg/L or ppm
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Ex. 2.19) Spent acid from fertilizer plant has the following composition by weight:
H2SO4 = 20%, NH4HSO4 = 45%, H2O = 30% and organic compounds = 5%.
Find the total acid content of the spent acid in the terms of H2SO4 after adding the acid
content, chemically bound in ammonium hydrogen sulphate.
Solution:
Basis: 100 kg of spent acid.
It contains 20 kg of H2SO4 and 45 kg of NH4SO4.
1 kmol NH4SO4 ≡ 1 kmol of H2SO4
115 kg NH4SO4 ≡98 kg H2SO4
 H2SO4 chemically bound in NH4SO4 = 98/115 x 45 = 38.35 kg
H2SO4 from the spent acid = Free H2SO4 + H2SO4
chemically bound in NH4SO4 = 20 + 38.35 = 58.35 kg
Total acid content of the spent acid as weight % H2SO4
= 58.35/100 x 100 = 58.35
Ex 2.20) Caustic soda flakes obtained from a manufacturer are found to contain 60 ppm
silica (SiO2). Convert this impurity into mass %.
Solution:
Impurity = 60 ppm = 60 g SiO2/1000000 g total solids
Mass % of SiO2 = (60/1000000) x 100 = 0.006
Ex. 2.21) A Sample of Caustic soda flakes contains 74.6% Na2O by weight. Determine the
purity of the flakes.
Solution:
Basis :100 Kg of caustic soda flakes
It contains 74.6 Kg of Na2O
2NaOH → Na2O+H2O
2kmol of NaOH ≡ 1kmol of Na2O
80 kg of NaOH ≡ 62kg of Na2O
80
∴ Amount of NaOH in the flakes = ×74.6 = 96.26 kg
62
Kg of NaOH
%Purity of flakes = ×100
Kg of flakes
96.2
= × 100
100
= 96.26
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Ex. 2.22) What will be % Na2O content of lye containing 73% (by weight) caustic soda?
Solution:
Basis: 100 kg of lye.
It contains 73 kg of caustic soda (NaOH).
2 NaOH → Na2O + H2O
Molecular weight of NaOH = 40, Molecular weight of Na2O = 62.
2 kmol NaOH ≡ 1 kmol Na2O
80 kg NaOH ≡ 62 kg Na2O
Amount of Na2O in the lye = 62/80 x 73 = 56.675 kg
Weight % Na2O in the lye = 56.675/100 x 100 = 56.675
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2.4.2 Composition of liquids & solutions:

The mass % and mole% of components are expressed for liquids and solutions, the former
being more common. In addition to these two, the volume % of a component is sometimes
given, e.g., the alcohol content in wine. The trace impurities are either expressed in mg/L or
ppm.
Volume percent:
It is the pure component volume of any component expressed as a percentage of the total
volume of a system.
Pure component volume of A
∴ Volume % of A = x 100
Total volume of system
Ex 2.23) A saturated solution of salicylic acid in methanol contains 64 kg salicyclic acid per
100 kg methanol at 298.15 K (25°C). Find (a) the mass %, and (b) mole % composition of
the solution.
Solution:
Basis: 100 kg methanol
Solution contains 64 kg salicylic acid
Mass of the solution = 100 + 64 = 164 kg
Mass % salicylic acid = (64/164) x 100 = 39.02
Mass % methanol = 100 - 39.02 = 60.98
Molar mass methanol (CH3OH) = 32
Molal mass of salicylic acid (HOC6H4COOH) = 138
Moles or methanol = 100/32 = 3.125 kmol
Moles of salicylic acid = 64/138 = 0.464 kmol
Total amount = 3.125 + 0.464 = 3.589 kmol
Mole % methanol = (3.125/3.589) x 100 = 87.07
Mole % salicylic acid = 100 - 87.07 = 12.93
In water analysis, impurities such as alkalinity, hardness, etc. are expressed in mg/L. In
effluent analysis, BOD, COD, TOC, TOD, and ThOD are expressed in mg/L. Among these
parameters, TOC and ThOD can be theoretically calculated. TOC refers to the total organic
carbon present in the solution, while ThOD refers to the theoretical oxygen demand of
organic compounds present in the solution.
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Ex 2.24) Glycerin, weighing 600 mg, is dissolved in pure water to make a final solution of 1
litre. Find the TOC and ThOD of the solution.
Solution:
Basis: 1 litre of solution
The structure of glycerin is
CH2OH - CHOH – CH2OH
1 kmol of glycerin contains 3 atom (or kmol) of carbon.
Molar mass of glycerin = 92
Glycerin concentration in the solution = 600 mg/L
Total carbon present in the solution (TOC) = (3 x 12/92) x 600 = 234.8 mg/L Ans.
The oxygen requirement of the compound (for complete combustion) can be determined
by writing the combustion reaction as:
C3H8O3 + 3.5 O2 → 3 CO2 + 4H2O
The O2 requirement of glycerin present in the solution.
ThOD = (3.5 x 32 x 600)/92 = 730.4 mg/L
In the case of water analysis, the alkalinity or hardness is expressed in equivalent ppm of
CaCO3 although the actual values of alkalinity and hardness in terms of the compounds
present will be different.
Ex 2.25) By titration, it was found that sample of water contains hardness equivalent to
500 mg/L (ppm) CaCO3. Assuming that the water contains temporary hardness in 60%
Ca(HCO3)2 form, and 40% Mg(HCO3)2. Find the concentration of both in water.
Solution:
Molar mass of CaCO3 = 100
Valence of CaCO3 =2
Equivalent mass of CaCO3 = 100/2 = 50
Molar mass of Ca(HCO3)2 = 162
Valence of Ca(HCO3)2 =2
Equivalent mass of Ca(HCO3)2 = 162/2 = 81
Actual content of Ca(HCO3)2 in the
sample of water = (81/50) x 500 x 0.6 = 486 mg/L
Molar mass of Mg(HCO3)2 = 146.3
Valence of Mg(HCO3)2 =2
Equivalent mass of Mg(HCO3)2 = 146.3/2 = 73.15
Actual content of Mg(HCO3)2in the
sample of water = (73.15/50) x 500 x 0.4 =292.6 mg/L
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Ex. 2.26) Nitric acid and water forms maximum boiling azeotrope containing 62.2 % water
by mole. Find the composition of the azeotrope in weight %.
Solution:
Basis : 100 kmol of HNO3 + Water azeotrope.
It contains 62.2 kmol of water and 37.88 kmol of HNO3.
Molecular weight of HNO3 = 63,
Molecular weight of H2O = 18
Amount of HNO3 in azeotrope = 37.8 x 63 = 2381.4 kg
Amount of H2O in azeotrope = 62.2 x 18 = 1119.6 kg
Amount / weight of azeotrope = 2381.4 + 1119.6 = 3501 kg
Weight of HNO3 in azeotrope = (2381.4/3501) x 100 = 68.02
Ex. 2.27) An aqueous solution contains 15% ethanol by volume. Find the weight % ethanol
if densities of ethanol and water are 0.79 g/cm3 and 1.0 g/cm3 respectively.
Solution:
Basis : 100 cm3 of aqueous solution.
Volume of ethanol in solution = 0.15 x 100 = 15 cm3
Volume of water in solution = 0.85 x 100 = 85 cm3
Amount of ethanol in solution = Volume x Density = 15 x 0.79 = 11.85 g
Amount of water in solution = 85 x 1 = 85 g
Total amount of solution = 11.85 + 85 = 96.85 g
Weight % ethanol in solution = (11.85/96.85) x 100 = 12.23
Ex. 2.28) The Strength of a Phosphoric acid sample is found to be 35% P2O5 by weight.
Determine the actual concentration of H3PO4 (by weigh) in the acid.
Solution:
Basis: 100Kg of phosphoric acid sample
It contains 35 Kg of 𝑃2 𝑂5
2H3PO4 → 2 P2O5 +3 H2O
Molecular weight of H3PO4 = 98
Molecular weight of P2O5 = 142
2kmol H3PO4 ≡ 1kmol P2O5
196 Kg of H3PO4 ≡ 142 Kg of P2O5
196
∴ Amount of H3PO4 in Sample = ×35 = 48.31 Kg
142
48.31
Weight % of H3PO4 in Phosphoric acid sample = ×100
100
= 48.31
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Ex. 2.29) The concentration of CO2 is measured to be 0.206 kmol per kmol
monoethanolamine (MEA) in a 20% (by mass) aqueous MEA solution. Assuming the
density of the solution to be nearly 1.0 kg/L, find the concentration of CO2 as mass % and
mol % in the solution.
Solution:
Basis: 100 kg aqueous MEA solution
The solution contains 20 kg MEA.
Chemical formula of MEA = NH2CH2CH2OH
Molar mass of MEA = 61
Moles of MEA in the solution = 20/61 = 0.3279 kmol
CO2 dissolved in the solution = 0.206 x 0.3279 = 0.0675 kmol
Mass of CO2 = 0.0675 x 44 = 2.97 kg
Moles of water = (100 - 22.97)/18 = 4.2794 kmol
Composition of Lean MEA

Component kmol Mole Molar Mass kg Mass %
ni % mass (ni.Mi)
Mi
Water 4.2794 91.54 18 77.027 71.03
MEA 0.3279 7.02 61 20 20.00
CO2 0.0675 1.44 44 2.973 2.97
Total 4.6748 100.00 123 100.00 100.00
Ex. 2.30) Ethanol & water forms a azeotrope containing 96% by weight ethanol. Find
composition of azeotrope by mole%
Solution:
Basis: 100 kg of ethanol-water mixture
It contains 96 kg of ethanol & 4 kg of water
Molecular weight of H2O = 18
Molecular weight of C2H6OH = 46
Moles of ethanol = 96/46 = 2.087 kmol
Moles of water = 4/18 = 0.222 kmol
Moles of azeotrope mixture = 2.087 + 0.222 = 2.309 kmol
Mole% ethanol in azeotrope mixture = (2.087/2.309) x 100 = 90.38
32
PPP_DOTSUK
2.4.3 Concentration of solutions:

Concentration of solution containing solid or liquid solute can be expressed in terms of
normality, molarity and molality.
Normality (N):
It is defined as the number of gram-equivalents of solute dissolved in one litre of solution.
gram equivalent of solute
Normality(N) =
Volume of solution in litre
Molarity (M):
It is defined as the number gram moles of the solute dissolved in one litre of solution.
gram moles of solute
Molarity(M) =
Volume of solution in litre
Molality (Molal):
It is defined as gram-moles (mol) of the solute dissolved in one kilogram or solvent.
Molality =
mass of solvent in kg
From the definition of normality, thus, it is possible to find concentration of solute in g/l.
Concentration (g/l) = Normality x Equivalent weight
Ex 2.31) A solution of sodium chloride in water contains 20% NaCl (by mass) at 333 K
(60°C). The density of the solution is 1.127 kg/L. Find the molarity, normality and molality
of the Solution.
Solution:
Basis: 100 kg solution of sodium chloride
∴ The solution contains 20 kg NaCl
Density of the solution = 1.127 kg/L
Volume of the solution =100/l.l27 = 88.73 L
Moles of NaCl in the solution = 20/58.5 = 0.342 kmol = 342 mol
Molarity, M = moles of solute/volume of solution = 342/88.73 = 3.85
For NaCl, since it is univalent,

Molar mass = equivalent mass
Therefore,
Normality (N) = molarity (M) = 3.85
Molality = Moles of solute/mass of solvent = 342/80 = 4.275 mol/kg
33
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Ex. 2.32) Aqueous solution of triethanolamine (TEA), i.e. N(CH2CH2OH)3, contains 50%
TEA by mass. Find the molarity of the solution if the density of the solution is 1.05 kg/L.
Solution
Basis: 100 kg TEA solution
∴ The solution contains 50 kg TEA.
Molar mass of TEA = 149
Moles of TEA present in the solution = 50/149 = 0.3356 kmol
Volume of the solution = 100/1.05= 95.24 L
Molarity of the solution = (0.3356/95.24) x 1000 = 3.524 M
Ex. 2.33) A solution of caustic soda contains 20% NaOH by weight. Taking density of the
solution as 1.196 kg/lit, find the normality, molarity and molality of the solution.
Solution:
basis: 100 kg of solution
The solution contain 20 kg NaOH and 80 kg water (solvent)
Density of solution is 1.196 kg/lit
100
Volume of solution = = 83.62 lit
1.196
20
moles of NaOH in solution = = 0.5 kmol = 500 mol
40
gram moles of NaOH 500
Molarity(M) = volume of solution in litre = = 5.98
83.52
For NaOH as valance =1
Equivalent weight = Molecular weight
∴ Normality (N) = Molarity (M) =5.98
gram moles of NaOH 500
Molality = = = 6.25 mol/kg
kg of solvent 80
Ex. 2.34) a chemist is interested in preparing 500 ml of 1 normal 1 molar and 1 molal
solution of H2SO4 H2SO4. Assuming the density of H2SO4 solution to be 1.075 g/𝑐𝑚3 ,
calculate the quantities of H2SO4 to be taken to prepare these solutions.
Solution:
Basis: 500 ml of H2SO4 solution
Volume of solution = 500 ml =0.5 l
gram equivalents of H2 SO4
Normality =
volume of solution
Gram-equivalent of H2SO4 = Normality * volume of solution

= 1*0.5
98
Equivalent weight = = 49
2
34
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Amount of H2SO4 required for 1 Normal solution

= 0.5 x 49 = 24.5 g
gram moles of H SO
Molarity = volume of solution2in litre
4
Moles of H2SO4 = Molarity x Volume of solution

=1 x 0.5 = 0.5 mol
Amount of H2SO4 required for 1 Molar solution
= 0.5 x 98= 49g
Let x be the quantity in grams of H2SO4 required for making 1 molal solution
Density of solution = 1.075 g/cm3
Quantity of solution = 500 x 1.075=537.5g
Grams of solvent = gram of solution- gram of solute
= 537.5 - x
Weight of solvent = (537.5-x) x 10-3 kg
x
Moles of H2SO4 = 98 mol
Molality = weight of solvent in kg
x/98
= (537.5−x) x 10−3
= 58.3 g
Solving we get,
Amount of H2SO4 required for preparing 1 molal solution
= 58.3 g
Ex. 2.35) 2000ml solution of strength 0.5N H2SO4 is to be prepared in laboratory by adding
98 % H2SO4 (specific gravity= 1.84) to water. Calculate the ml of 98% to be added to get
solution of required strength.
Solution:
Basis: 2000 ml of 0.5 N H2SO4 solution
gm.equivalent of H SO
Normality = volume of solution in2 liter
4
Volume of solution = 2000 ml = 2 lit.

Gram equivalent of H2SO4 = normality × volume of solution in lit.
= 0.5 × 2
= 1 gm. Equivalent
Amount of H2SO4 required = 1×49
= 49 gm.
49
Amount of 98% H2SO4 required = 0.98 =50 gm.
Specific gravity of 98% H2SO4 =1.84
gm.98% H2SO4 50
Volume of 98% H2SO4 solution = specific gravity = 1.84 = 27.2 ml
35
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Ex. 2.36) 2 lit. of NH3 at 303 k &20.265kpa is neutralized by 135 ml of solution of H2SO4.
Find the normality of the acid.
Solution:
Basis: 2 lit of NH3
PV = nRT
Where
P = 20.265Kpa
T = 303K
R = 8.31451 kPa.lit/mol.K
V = 2lit.
20.265×2
Moles of NH3 = 8.31451×303 = 0.01609 mol
For neutralization of 2 moles of NH3, 1mole of H2SO4 is required
1
Moles of H2SO4 required = 2 × 0.01609
= 0.008045 mol
Gram of H2SO4 required = 0.00845×98
= 0.788 gm
0.788
Gram equivalents of H2SO4 required = = 0.01609
49
Volume of H2S04 solution = 135 ml
= 0.135 lit.
0.01609
Normality of acid =
0.135
= 0.12 N
Ex. 2.37) A sample of Na2CO3.H2O weighing 0.62 grams is added to 100 ml of 0.1 N H2SO4
solution. Will the resulting solution acidic, basic or neutral?
Solution:
Basis: 100 ml of 0.1 N H2SO4 solution and 0.62g of Na2CO3.H2O sample
Normality of H2SO4 solution = 0.1N
Volume of H2SO4 solution = 100ml = 0.1 l
Gram equivalents of H2SO4 = Normality  Volume of solution
= 0.1  0.1 = 0.01g
Amount of H2SO4 in solution = 0.01  49 = 0.49g
Molecular weight of Na2CO3 = 124
Na2CO3 . H2O + H2SO4 → Na2SO4 + 2H2O + CO2
1 mol Na2CO3 .H2O ≡ 1 mol H2SO4
124 g Na2CO4 .H2O ≡ 98 g H2SO4
0.62 g Na2CO3 . H2O = ?
Amount of H2SO4 required for 0.63 g Na2CO3 . H2O = (98/124)  0.62 = 0.49g
36
PPP_DOTSUK
For neutralizing, we need 0.49 g of H2SO4 as per reaction and we have added solution
containing 0.49 g H2SO4. None of the component is in excess. Hence, resulting solution is
neutral.
Ex. 2.38) Make the following conversions:

(a) 294 g/l H2SO4 to normality.
(b) 5N H3PO4 to g/l.
(c) 54.75 g/l HCL to molarity.
(d) 3M K2SO4 to g/l
(e) 4.8 mg/ml CaCl2 to normality
Solution:
(a) 294 g/l H2SO4 to normality.
Basis : 1 litre of solution.
H2SO4 in solution = 294 g
Gram equivalents of H2SO4 = (294/49) = 6g eq
Normality = (6/1) = 6N
(b) 5N H3PO4 to g/l.

Molecular weight of H3PO4 = 98
Valence of H3PO4 =3
Equivalent weight of H3PO4 = (98/3) = 32.67
Concentration in grams per litre of solution = Normality  Equivalent weight
Concentration of solution = 5  32.67 = 163.35 g/l
(c) 54.75 g/l HCl to molarity.

Basis: 1l of HCl solution
Amount of HCl in it = 54.75 g
Moles of HCl = (54.75/36.5) = 1.5 mol
Molarity = (1.5/1) = 1.5 M
(d) 3MK2SO4 to g/l.

Basis: 1l of solution
Moles of K2SO4 = 3  1 = 3 mol
Molecular weight of K2SO4 = 174
Amount of K2SO4 = 3  174 = 522g
Concentration of solution = (522/1) = 522 g/l
37
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(e) 4.8 mg/ml CaCl2 to normality

Basis: 1l of solution
4.8 mg/ml CaCl2 = 4.8 g/l CaCl2
CaCl2 in solution = 4.8 g
Molecular weight of CaCl2 = 111
Equivalent weight of CaCl2 = (111/2) = 55.5
gram equivalent of CaCl2 = (48/55.5) = 0.0865
Normality = (0.0865/1) = 0.0865 N
Ex. 2.39) an aqueous solution of K2CO3 is prepared by dissolving 43 kg K2CO3 in 10 kg

water at 293(20oC). Find molarity, normality & Molality of solution. Take density of
solution as 1.3 kg\l.
Solution:
Basis: 43 kg of K2CO3 & 100 kg of water
Weight of K2CO3 solution = 43+100 = 143 kg
Volume of solution = 143 / 1.3 = 110 liter
Mol. Weight of K2CO3 = 138
Equivalent weight of K2CO3 = 138 /2 =69
Moles of K2CO3in solution = 43/138 = 0.3116 kmol = 311.6 mol.
Molarity of solution = 311.6/110 = 2.832
Gm Equivalent of K2CO3 = (43/69) x 1000 = 623.19
Normality of solution = 623.19/110 = 5.665
Molality of solution = 311.6/100 = 0.3116
Ex. 2.40) An aqueous solution contains 20% ammonia, 60% ammonium nitrate & 5% urea
by weight. Find the available nitrogen content of the solution.
Solution:
Basis: 100 Kg of aqueous solution.
It contains 20 Kg NH3, 60 Kg NH4NO3 & 5Kg NH2CONH2.
1 Kmol NH2CONH2 ≡ 2 K atom N
60 Kg Urea ≡ 28 Kg N
28
∴ Nitrogen from urea = × 5 = 2.33Kg
60
1 K mol NH3 ≡ 1 Kg atom N
70Kg NH3 ≡14 Kg N
14
∴ Nitrogen from NH3 = 17 × 20 = 16.47 kg
1 Kmol NH4NO3 ≡ 2 K atom N
80 Kg NH4NO3 ≡ 28 Kg of N
28
∴ Nitrogen from NH4NO3 = 80 × 60 = 21 Kg
38
PPP_DOTSUK
Total Nitrogen available from the solution = 2.33 + 16.47 + 21 = 39.8 kg

39.8
∴ Nitrogen content of solution = 100 × 100 = 39.8%
39
PPP_DOTSUK
Questions from theory examination:
2.1) How many Kg moles of H2SO4 will contain 64 Kg of sulphur ?

(At. wt. of sulphur = 32)
2.2) A compound having molecular weight of 123, analyses: C = 58.536%, Hydrogen =

4.065%, Nitrogen = 11.382%, Oxygen = 26.016%. The data is in mass percent. Obtain the
molecular formula of the compound.
2.3) The analysis of a sample of glass yields 7.8% Na2O, 7.0% MgO, 9.7% ZnO, 2.0% Al203,
8.5% B2O3, 65% SiO2. Convert this composition into mole percent.
Data: Atomic weights are given below.
Na = 23, Mg = 24, Zn = 65, AI = 27, B = 11, Si = 28.
2.4) An aqueous solution of acetic acid (CH3COOH) of 35 % concentration by weight has

density 1.04 kg/lit at 298 K. Find the molarity, normality and molality of the solution.
2.5) Convert the following into equivalent PPM CaCO3 :

i) 800 PPM NaHCO3 in water ii) 85 PPM CaSO4 in water.
2.6) An aqueous solution of soda ash containing 20% by wt soda ash. Express the
composition as % Na2O. [Mol. Wt. Na2O = 68.0, For NaOH = 40.0 ]
2.7) An aqueous solution contains 19.0% NH3, 65.6% NH4N03, and 6.0% urea (by weight).
Calculate the available nitrogen content of solution.
2.8) A tank for deep sea diving consists of 60% He (atomic weight 4.00), 20% N 2 and 20%
O2. The weight of the gas in the tank, excluding the tank weight is 1.437 Kg. What is the
mass fraction of each component in the tank?
2.9) A compound whose molecular weight is 103 analyses as following:

Compound C H N
% weight 81.5 4.9 13.6
What is its formula?
2.10) Given a water solution that contains 1.704 Kg. of HNO3 per kg. of H2O and has a
specific gravity of 1.382 at 20°C. Express composition in following ways:
i) Wt. % HNO3.
ii) Kg. of HNO3/m3 of solution at 20°C.
iii) Molarity of solution.
40
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2.11) It is desired to prepare a solution of sodium chloride in water, having a molarity of

1.8. Calculate the weight of sodium chloride that should be placed in 1 lit. volumetric flask
in order that the desired concentration will be obtained by subsequently filling the flask
with water keeping the temperature of the solution at 30° C.
2.12) Ammonium phosphomolybdate (NH4)3PO4.12MoO3.3H2O is made up of the radicals

NH3, H2O, P2O5 and MoO3. What is the percentage composition of the molecule with respect
to-these radicals? [P - 31, MO – 95.95, N -14, H -1, O -16]
2.13) A compound whose molecular weight is 103 analyzes C=81.5%, H:4.9%,N:13.6%.

What is its chemical formula?
Exercise:
2.1) Find the moles of oxygen present in 500 g.[Ans. 15.625 mol]
2.2) How many grams of carbon are present in 600 g CaCO3? [Ans. 72 g]
2.3) Find the molar mass of KMnO4. [Ans. 158]
2.4) A mass of 100 g each of HNO3 and H2SO4 is filled in two separate bottles. Which bottle
contains more atoms? How many more?
[Ans. Bottle containing HNO3 will have 0.567 mol or 3.415 x 1023 atoms more than the
other bottle.]
2.5) How many kilogram of carbon disulphide will contain 3.5 kmol carbon? [Ans. 266 kg]
2.6) What is the equivalent mass of Al2(SO4)3? [Ans. 57]
2.7) How many equivalents are there in 500 g KMnO4? [Ans. 15.82 g eq]
2.8) The analysis magnesite ore obtained from Chalk Hill area, Salem district, yields 81%
MgCO3, 14% SiO2 and 5% H2O (by mass), Convert the analysis into mole %.
[Ans. 65.3% MgCO3, 15.8% SiO2, 18.9% H2O (mole basis)]
2.9) The analysis of a sample of glass yields 7.8% Na2O, 7.0% MgO, 9.7% ZnO, 2.0% A12O3,
8.5% B2O3 and 65.0% SiO2 (by mass). Convert this composition into mole%
[Ans. 7.65% Na2O, 10.57% MgO, 7.25% ZnO, 1.19% A12O3, 7.43% B2O3 and 65.91 % SiO2
(mole basis)]
41
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2.10) A sample of sea water contains 35 000 ppm solids. Express the concentration of the
solids as mass percentage. [Ans. 3.5% (mass)]
2.11) A sample of milliolite limestone, obtained from Porbandar, Gujarat, is found to

contain 54.5% CaO (by mass). If this CaO is present as CaCO3 in the limestone, find the
content of CaC03 in the limestone. [Ans. 97.32 mass %]
2.12) Calculate the available nitrogen in the following:

(a) Commercial ammonium sulphate (96% pure)
(b) Pure sodium nitrate (100%) [Ans. (a) 20.36%; (b) 16.47% (mass basis)]
2.13) A sample of caustic soda flakes contains 74.6% Na2O (by mass). Find the purity of the
flakes. [Ans. 96.26% NaOH]
2.14) Nitric acid and water forms a maximum boiling azeotrope containing 62.2 mole %
water [boiling temperature = 403.6 K (130.6°C)]. Find the composition of the azeotrope by
mass.
[Ans. 68.02% HNO3 (mass)]
2.15) An aqueous solution of common salt (NaCl) contains 25% salt (by mass) at 298.15 K
(25°C). Find the mole % of NaCl in the solution. [Ans. 9.3 mol% NaCl]
2.16) An aqueous solution contains 19.0% NH3, 65.6% NH4NO3 and 6.0% urea (by mass).
Calculate the available nitrogen content solution. [Ans. 41.41 % Nitrogen]
2.17) Ethanol is present in the aqueous solution to the extent of 1000 mg/L.
Find TOC and ThOD of the solution in mg/L. [Ans. TOC = 522 mg/L; ThOD = 2087 mg/L]
2.18) The strength of a phosphoric acid sample is found to be 35% P2O5 (by mass). Find out
the actual concentration of H3PO4 (by mass) in the acid [Ans. 48.31 % H3PO4 (by mass)]
2.19) Spent acid from a fertilizer unit has the following composition by mass;
H2SO4: 20%, NH4 HSO4: 45%, H2O: 30% and organic compounds: 5%. Calculate the total
acid content of the spent acid in terms of H2SO4 after adding the acid content, chemically
bound in ammonium hydrogen sulphate. [Ans. 58.35% (mass)]
2.20) A sample of aqueous triethanolamine (TEA) solution contains 47% TEA (on volume
basis). If the density of pure TEA is 1125 kg/m3, find the mass % of TEA in the solution.
[Ans. 49.94% (mass)]
42
PPP_DOTSUK
2.21) A sample of wine contains 20% alcohol (ethanol) on volume basis. Find the mass % of
a alcohol in the wine. Assume the densities of alcohol and alcohol free liquid (essentially
water) to be 0.79 kg/L and 1.0 kg/L, respectively. [Ans. 16.49% alcohol]
2.22) Convert the following into equivalent ppm CaCO3:

(a) 800 ppm Na2CO3 in water (b) 85 ppm MgSO4 in water
[Ans. (a) 754.7 ppm CaCO3; (b) 70.7 ppm CaCO3]
2.23) Make the following conversions:

(a) 294 g/L H2SO4 to normality (N)
(b) 4.8 mg/ml CaCl2 to normality (N)
(c) 5 N H3PO4 to g/L
(d) 54.75 g/L HCl to molarity (M)
(e) 3 M K2SO4 to g/L
[Ans. (a) 6 N; (b) 0.0865 N; (c) 163.35 g/L (d) 1.5 M (e) 522 g/L]
2.24 An aqueous solution of acetic acid of 35% concentration (by mass) has density 1.04
kg/L at 298.15 K (25°C). Find the molarity, normality and molality of the solution.
[Ans. 6.066 M; 6.066 N; 8.974 Molality]
2.25) An aqueous solution of monoethanolamine contains 20% MEA (by mass). It is utilised
for the absorption of CO2, Rich solution from the absorber contains 40 volume CO2.
Calculate CO2 loading in terms of moles CO2 dissolved per mole MEA assuming that the
density of the solution is 1.011 kg/L [Hint: 40 volumes CO2 concentration means that a litre
solution will liberate 40 L CO2 at 101.325 kPa a and 273.15 K [Ans. 0.5385 mol CO2/mol
MEA]
2.26) The strength of an aqueous hydrogen peroxide solution is 60 volumes. Its density is
measured to be 1.075 kg/L at 293 K (20oC). Find the mass & of the H2O2 in the solution
[Hint: A quality of 1 L of 60 volume hydrogen peroxide will liberate 60 L oxygen at 101.325
kPa a & 288.75 K (15.6oC) [Ans. 16.02 mass %]
43
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2. Cauchy's Integral Theorem
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3. Gaseous System
3. Gaseous System
The direct weighing of gases is ruled out in practice. The volume of a gas can be
conveniently measured and converted into mass from density of the gas. In order to know
the density of a gas, both pressure & temperature should be known. Various equations of
the state (also known as PVT relations) can be employed for this purpose.
3.1 Ideal Gas Law:
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.
P x V = Constant
Where, P is the absolute pressure and V is 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 a given pressure.
V
= constant
T
Where, T is the absolute temperature.
Combining the above two laws, an ideal gas can be formulated as

PxV
= constant
T
The constant of above equation is designated by the symbol R and is known as Universal
Gas Constant.
Therefore, PV = R T
When V is the volume in cubic meters of n kmol of gas, then ideal gas law is written as
PV = nRT
Numerical value of R:
8.31451 m3. kPa/(kmol.k)
0.008314 m3·MPa/(kmol.k)
0.08206 l.atm/(mol.k)
0.08206 m3·atm/(kmol.k)
1.987 kcal/(kmol.k)
8.31451 J/(mol.k)
44
PPP_DOTSUK
3. Gaseous System
When the mass of gas is not known and if we know the volume occupied by gas at specified
temperature and pressure and conditions are changed and we know two of the three
variables in final state, then the third one can be calculated by means of proportionality
indicated by ideal gas law.
Let V1, Tl and P1 be the volume, temperature and pressure of n kgmol of gas at condition-l
Let V2, T2 and P2 be the volume, temperature and pressure of n kgmol of gas at condition-2
then,
P1 V1 P2 V2
=
T1 T2
In an ideal gas law given by equation, V is called the molar volume. At 273.15 K and
101.325 kPa (l atm) volume occupied by 1 kmol of gas is 22.4136 m3 i.e. V = 22.4136
m3/kmol (or 22.4136 l/mol). These conditions are said to be normal temperature and
pressure (NTP)
In USA, 101.325 kPa (1 atm) and 288.7 K (15.6oC) are considered to be standard
temperature and pressure conditions (STP).
Ex. 3.1) 15 kg of carbon dioxide is compressed at a temperature of 303 K(300C) to volume

of 0.5 m3 . Calculate the pressure required for given duty. Assume ideal gas low is
applicable.
Solution:
Basis: 15 kg of carbon dioxide gas
Molecular weight of CO2 = 44
∴ Moles of CO2 = 15/44 = 0.341 kmol
PV = nRT
∴ P = nRT/V
Where,
n= 0.341 kmol, T=303 K, V=0.5 m3 , R= 8.31451 m3 .kPa/(kmol.K)
∴P = (0.341*8.31451*303)/0.5
=1718.16 kPa
Ex. 3.2) A gas contained in a closed vessel at a pressure of 121.59 kPa.g and 299 K (26oC) is
heated to a temperature of 1273 K (1000oC). Find the pressure to which a closed vessel
should be designed.
Solution:
Basis: A gas at 299 K in closed vessel
P1 V1 P2 V2
=
T1 T2
As vessel being closed, V1 = V2
45
PPP_DOTSUK
3. Gaseous System
P1 P2
∴ =
T1 T2
P1 T2
∴ P2 =
T1
Absolute pressure = gauge pressure + atmospheric pressure
∴ P1 = 121.59 + 101.325 = 222.915 kPa
222.915 x 1273
∴ P2 = = 949.07 kPa
299
Ex. 3.3) A sample of gas having volume of 0.5 m3 is compressed in such a manner so that
pressure is increased by 60%. The operation is done for a fixed mass of a gas at constant
temperature. Calculate the final volume of the gas.
Solution:
Basis: 0.5 m3 of gas sample
Since pressure increased by 60%
P2 = 1.6 P1
Temperature & mass are constant
∴P1V1 = P2 V2
P1 V1 P1 x 0.5
∴ V2 = = = 0.3125 m3
P2 1.6 P1
46
PPP_DOTSUK
3. Gaseous System
3.2 Gaseous Mixtures:

The composition of component gases present in gas mixture is generally expressed in
terms of volume percent. In case of gas mixture containing in closed vessel, the molecules
of each component gas are distributed throughout the entire volume of the container. The
total pressure exerted by entire mixture is equal to the sum of pressures exerted by each
component gas molecules.
Partial Pressure (pA):

The partial pressure of a component gas that is present in a mixture of gases is the pressure
that would be exerted by that component gas if it alone were present in the same volume
and at the same temperature.
Pure Component Volume (VA):

The pure component volume of a component gas that is present in a mixture of gases is the
volume that would be occupied by that component gas if it alone were present at the same
pressure and temperature as the mixture.
Dalton’s Law:
It states that the total pressure exerted by a gaseous mixture is equal to the sum of the
partial pressure component gases. Thus, it expresses the additive nature of partial
pressures.
Mathematically, P = pA + pB + pC +...
Where P is the total pressure and pA, pB and pC etc. are the partial pressures of the
component gases respectively.
Amagat's Law:
It states that the total volume occupied by gaseous mixture is equal to the sum of the pure
component volumes. It expresses the additive nature of pure component volumes of
component gases.
Mathematically, V = VA + VB + VC +...
Where V is the total volume and VA, VB and VC etc. are pure component volumes of
component gases A, B, C etc. respectively.
47
PPP_DOTSUK
3. Gaseous System
3.3 Relationship between Partial Pressure, 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 be the total pressure exerted by mixture.
VA,VB,VC etc. are pure component volumes of A, B, C, etc. respectively.
pA,pB,pC etc. are partial pressures of component gases A, B, C, etc. respectively.
Ideal gas law for component A is

pA V = nA RT (1)
Similarly for component B,
pB V = nB RT (2)
For component C,
pC V = nC RT (3)
Adding equations 1, 2 & 3 we get,

RT
pA + pB + pC = (nA + nB + nC ) (4)
V
Dividing equation 1 by 4
pA nA
= (5)
p A + p B + p C nA + nB + n C
∴ pA = x A P
Multiplying both sides of equation 5 by 100

pA nA
x 100 = x 100
pA + pB + pC nA + nB + nC
∴ Pressure % of A = Mole % of A
∴ for gases behaving ideally, Pressure % = Mole %
Ideal gas law for component A is also written as

VA P = nA RT (1)
Similarly for component B,
VB P = nB RT (2)
For component C,
VC P = nC RT (3)
Adding equations 1, 2 & 3 we get,
48
PPP_DOTSUK
3. Gaseous System
RT
VA + VB + VC = (nA + nB + nC ) (4)
P
Dividing equation 1 by 4
VA nA
= (5)
VA + VB + VC nA + nB + nC
∴ VA = xA V
Multiplying both sides of equation 5 by 100

VA nA
x 100 = x 100
VA + VB + VC nA + nB + nC
∴ Volume % of A = Mole % of A
∴for gases behaving ideally, Pressure % = Mole % = Volume %
3.4 Average molecular weight of gas mixture:

Consider a gas mixture consisting of component A, B & C
Let MA, MB, MC & xA, xB, xC are the molecular weights & mole fractions of component gases
respectively.
Let Mavg be the average molecular weight of gas mixture. Then
Mavg = MA.xA + MB.xB + MC.xC
i.e. average molecular weight of gas mixture is the sum of the product of molecular weight
& mole fraction of component gases.
In general,
n
Mavg = ∑ Mi xi
i=1
Ex 3.4) Calculate the average molar mass & composition by mass of air.
Solution:
An average composition of air at sea level by volume is given below.
Composition of Air at Mean Seal Level
Gas Mole%
Nitrogen 78.084
Oxygen 20.946
Argon 0.934
Carbon dioxide 0.033
Neon 18 x 10-4
Helium 5.2 x 10-4
49
PPP_DOTSUK
3. Gaseous System
Krypton 1.1 x 10-4

Hydrogen 0.5 x 10-4
Xenon 0.08 x 10-4
In general, it can be taken that oxygen; nitrogen & argon are present to the extent of 21%,
78% & 1%, respectively (on volume basis). For combustion calculations, air with average
composition of 21% oxygen & 79% nitrogen (by volume) is considered.
Basis: 100 kmol air
Composition of Air without Trace/Noble Gases:
Gas Formula Molar kmol Mass kg Mass%
Mass
Oxygen O2 31.9988 21 671.786 23.19
Nitrogen N2 28.0135 78 2185.051 75.43
Argon Ar 1 39. 948 1.38
100 2896.785 100.00
Average molar mass of air = 2897/100 = 28.97
3.5 Density of gas mixture:

Ideal gas law equation for gas mixture is:
PV = nRT
P n
∴ =
RT V
kg of gas mixture W
n= =
molecular weight of gas Mavg
W 1 P
∴ x =
Mavg V RT
W PMavg
∴ = ρgas =
V RT
Ex. 3.5) Cracked gases from a petroleum refinery has the following composition by volume:
methane 45%, ethane 10%, ethylene 25%, propane 7%, propylene 8%, n-butane 5%. Find
(a) the average molar mass of the gas mixture, (b) the composition by mass, and (c) specific
gravity of the gas mixture.
Solution:
In this type of problem, it is convenient to assume the basis of 100 kmol of cracked gas.
Since volume % equals mole %, methane present in the mixture is equal to 45 kmol.
Molar mass of methane = 12 + 4 = 16
50
PPP_DOTSUK
3. Gaseous System
Mass of methane = 45 x 16 = 720 kg

In a similar way, for all the components of the mixture, weights can be calculated.
These calculations are summarized in Table 2.7.
Composition of Refinery Gas
Gas Formula Molar kmol mass Mass
Mass kg %
Methane CH4 16 45 720 27.13
Ethane C2H6 30 10 300 11.30
Ethylene C2H4 28 25 700 26.37
Propane C3H8 44 7 308 11.61
Propylene C3H6 42 8 336 12.66
n-Butane C4Hl0 58 5 290 10.93
Total 100 2654 100.00
Average molar mass of gas mixture = 2654/100 = 26.54

Specific gravity of gas mixture = 26.54/28.97 = 0.9161
Ex. 3.6) A mixture of H2 & O2 contains 11.1% H2 by weight. Calculate a) Average

molecular weight of gas mixture & b) partial pressure of O2 & H2 at 100 kPa & 303k (300c)
Solution:
Mol. Weight of O2 = 32
Mol. Weight of H2 =2
11.1
Moles of H2 = = 5.55 Kmol
2
88.9
Moles of O2 = = 2.78 Kmol
32
Amount of gas mixture = 5.55 + 2.78 = 8.33 Kmol
2.78
Molefraction of H2 = XH2 = = 0.33
8.33
Mavg = average molecular weight of gas mixture
= MH2 × XH2 + MO2 × XO2
= 2 × 0.67+ 32 × 0.33 = 11.9
P = total pressure =100 KPa
Partial pressure of H2 = PH2 = XH2 × P
= 0.67×100 = 67 KPa
Partial pressure O2 = PO2 = XO2 × P
= 0.33 × 100 = 33 KPa
51
PPP_DOTSUK
3. Gaseous System
Ex. 3.7) A mixture of CH4 & C2H6 has the average molecular weight of 22.4. Find mole% of
CH4 & C2H6 in the mixture.
Solution:
Mavg = MCH4 × XCH4 + MC2H6 ×XC2H6
22.4 = 16XCH4 + 30 XC2H6 (1)
∑Xi = 1
XCH4 + XC2H6 = 1 (2)
XC2H6 = 1- XCH4 (3)
Put the value of XC2H6 from equation (3) into equation (1) and solve for XCH4.
∴ 22.4 = 16 XCH4 + 30 (1 - XCH4)
∴XCH4 = 0.543
∴XC2 H6 = 1-0.543 =0.457
Mole % of CH4 = Mole fraction of CH4×100
= 0.543×100 =54.30
Mole % of C2H6 = 0.457 × 100 = 45.70
Ex. 3.8) A gas mixture has the following composition by volume:

SO2 =8.5%, O2 = 10% and N2 = 81.5%
Find (a) the density of a gas mixture at a temperature of 473 K (200°C) and 202.65 Kpa.g
and (b) by weight.
Solution:
Basis: 100 kmole of gas mixture
For ideal gas Mole % = Volume %
𝟖.𝟓
It cotain 8.5 Kmol of SO2 = xSO2 = 𝟏𝟎𝟎 = 0.085
𝟏𝟎
Mole fraction of O2 = XO2 = 𝟏𝟎𝟎 = 0.1
𝟖𝟏.𝟓
Mole fraction of N2 = XN2 = 𝟏𝟎𝟎 = .815
Molecular weight of SO2 = MSO2 = 64
Molecular weight of O2 = MO2 = 32
Molecular weight of N2 = MN2 = 28
Mavg = Mso2 . XSO2 +MO2 . XO2 + MN2 . XN2
= 64 x 0.085+ 32 x 0.1 + 28 x 0.815 = 31.46
Absolute pressure = Gauge Pressure + Atmospheric pressure
P = 202.65+101.325=303.975Kpa
PMavg
Density of gas mixture, ρ =
RT
m3 .Kpa
Where, P=303.975 kPa , Mavg = 31.46 , R= 8.31451 Kmol.k , T=473 K
303.975 x 31.46
∴ρ = = 2.43 Kg/m3
8.31451 x 473
52
PPP_DOTSUK
3. Gaseous System
SO2 in gas mixture = 8.5 x 64= 544Kg

O2 in gas mixture = 10 x 32= 320 Kg
N2 in gas mixture = 81.5 x 28 = 2286 Kg
Amount of gas mixture = 3146 Kg
Kg of SO
Weight % SO2 in gas mixture = Kg of gas mixture
2
x 100
Composition by weight:
Component Quantity in Kg Weight %
SO2 544 17.30
O2 320 10.17
N2 2282 72.53
Total 3146 100
Ex. 3.9) A volume of moist air at a total pressure of 101.325 kPa and a temperature of
303K contains water vapour in such proportion that it’s partial pressure is 2.933 kPa.
Without total pressure being changed, the temperature is reduced to 298K and some of
water vapour is removed by condensation. After cooling, it is found that the partial
pressure of water vapour is 1.693 kPa. calculate (a) volume of air at 298 K and (b) weight
of water condensed.
Sol:
Basis: 30m3 of moist air at 303 K
Ideal gas law is: PV = nRT
PV
n = RT
where,
n=moles of moist air, P=101.325 kPa, R=8.31451 m3 . kPa /(Kmol. K), V= 30 m3, T=303 K
101.325∗30
Moles of moist air, n = 8.31451∗303 = 1.2066 Kmols
Let n1 be the kmole of air and = n2 be the kmoles of moisture/ water vapour
p1 = partial pressure of air at 303 K
=101.325 – 2.933 = 98.392 kPa
p2 = partial pressure of air at 303 K = 2.933 kPa
For ideal gas , pressure% = mole%
Pressure fraction = mole fraction
98.392 n1
For air, =
101.325 n
98.392
n1 = * 1.2066 = 1.172 kmol at 303K
101.325
For water vapour/moisture,
2.933 n2
=
101.325 n
2.933
n2 = 101.325 * 1.2066 = 0.035 Kmol at 303K
53
PPP_DOTSUK
3. Gaseous System
At 288 K, partial pressure of water vapour = 1.693 Kpa

Let n3 be the moles of water vapour at 288 K
Moles of moist air = 1.172 + n3
1.693 n
= 1.172+n
3
101.325 3
n3 = 0.02 kmol
Moles of air at 288 K = 1.172 +0.02 = 1.192 kmol
Let 𝑛 ′
= 1.192 kmol
PV = n′ RT
Where, V = volume of air at 288 K
n′ = 1.192, R = 8.31451 m3 .kpa/(kmol.K), T = 288 K, P = 101.325 kpa
n′ RT
V = P
1.192 x 8.31451 x 288
= = 28
101.325
Moles of water condensed = n2 − n3 = 0.035 - 0.02 = 0.015 kmol
Amount of water condensed = 0.015 x 18 = 0.27 Kg
Ex. 3.10) In Manufacture of hydrochloric acid, gas containing 20%, HCL and 80% air by
volume enters an absorption tower at a temperature of 323 K (50°C) and pressure of
99.325 kPa. 98% of HCL is absorbed in water and remaining gas leaves the tower at a
temperature of 293 K (20°C) and a pressure of 97.992 kPa. Calculate (a) the weight of HCL
absorbed/removed per m3 of gas entering the system and (b) the volume of gas leaving per
m3 of gas entering the system.
Solution:
Basis: 100 kmol of gas entering the absorption tower.
PV = nRT
V = nRT/ P
Where, V=Volume of gas entering, m3, n–100 kmol, R - 8.31451 m3kPa/(kmol.K),
P = 99.325; T = 323K
∴ V = (100x8.31451x323)/99.325 = 2704m3
Moles of HCL in gas entering = 20kmol
Moles of air in gas entering = 80 kmol
Moles of HCL absorbed/removed = 0.98 x 20 =19.6kmol
Moles of HCL unabsorbed and appearing in gas leaving = 20 -19.6 = 0.4 kmol
HCL absorbed based on 100kmol gas entering = 19.6 x 36.5 = 715.4 kg
Volume of 100kmol gas entering =2704 m3
Amount of HCL absorbed per 1m3 of gas entering
= (715.4 / 2704) x 1 = 0.2646 kg
Moles of gas leaving = 80 + 0.4 = 80.4 kmol
PV = nRT
54
PPP_DOTSUK
3. Gaseous System
V = nRT/P
Where, V = volume of gas leaving, m3, n = 80.4kmol; R=8.31451 m3.kPa/(kmol.K);
P=97.992 kPa, T=293 K
V = (80.4 x 8.31451 x 293)/ 97.992 = 1999 m3
Volume of gas leaving based on 100 kmol or 2704 m3 of gas entering system = 1999 m3
Volume of gas leaving per 1 m3, of gas entering the system
= (1999 / 2704) x 1 = 0.74 m3
Ex. 3.11) The analysis of the gas sample is given below (on volume basis):
CH4 66%, CO2=30%, NH4 =4%
Find (a) the average molecular weight of the gas and (b) density of the gas at 202.65 kPa g
pressure and 303 K (30°C)
Solution:
Basis: Gas sample containing CH4, CO2 and NH3
For ideal gases, Volume % =Mole %
Mole % of CH4 = 66, Mole % of CO2 = 30 Mole % of NH4 =4
Mole fraction of CH4 = XCH4 = (Mole % of CH4) / 100
= 66 / 100 = 0.66
Mole fraction of CO2 = XCO2 = (Mole % of CO2) / 100
= 30 / 100 = 0.30
Mole fraction of NH3 = XNH4 = (Mole % of NH3) / 100
= 4 / 100 = 0.04
Mavg = Average molecular weight of gas
= MCH4 · XCH4 + MCO2 · XCO2 + MNH4· XNH3
= 16 x 0.66 + 44 x 0.30 + 0.04 x 17 = 24.44
ρ = Density of gas = PMavg /RT
Absolute pressure = Gauge pressure + Atmosphere pressure
P = 202.65 + 101.325 = 303.975 kPa,
T = 303K, Mavg =24.44, R = 8.31451 m3 ·kPa/(Kmol·K)
∴ ρ = (303.975 x 24.44) / (8.31451 x 303)
= 2.95 kg/m3
Ex. 3.12) By electrolyzing mixed brine a gaseous mixture is obtained at the cathode having
the following composition by weight: Cl2 =67%, Br2=28% and O2=5%
Calculate (i)composition of gas by volume.(ii)average molecular weight and(iii)density of
gas mixture at 298K(25oC) and 101.325kPa. [At. Wt.:Cl=35.5,Br=80,O=16].
Solution:
Basis: 100 kg of gas mixture.
It contains 67kg of Cl2, 28 kg of Br2 and 5kg of O2.
55
PPP_DOTSUK
3. Gaseous System
Moles of Cl2 = 67/71=0.9437 kmol.

Moles of Br2 = 28/160=0.175 kmol.
Moles of O2 = 5/32=0.1562 kmol.
Composition of Gas Mixture by Volume:
Components Quantity in kmol. Volume %( mole %)
Cl2 0.9437 74.2
Br2 0.175 13.73
O2 0.156 12.25
Total: 1.2749 100
74.02
Mole fraction of Cl2 = xCl2 =
100
13.73
Mole fraction of Br2 =xBr2 = 100
12.25
Mole fraction of O2 =xO2 = 100
Mavg = Average molecular weight of gas mixture.
= MCl2.xCl2 + MBr2.xCl2+MO2.xO2
= 71 x 0.7402 + 160 x 0.1373 + 32 x 0.1225
Mavg = 78.44
kg of gas mixture
Mavg = kmol of gas mixture
100
= 1.2749
ρ = Density of gas mixture

P Mavg
= RT
Where P = 101.325kPa, Mavg = 78.44, R = 8.31451m3.kPa/kmol.K, T = 298K

101.325 x 78.44
∴ρ = = 3.208 kg/m3
8.31451 x 298
Ex. 3.13) The gas acetylene is produced according to following reaction:

CaC2 + 2H2O → C2H2 + Ca (OH)2
Calculate the number of hours of service that can be derived from 1 kg of calcium carbide in
an acetylene lamp burning 0.10 m3 of gas per hour at temperature of 298 K(25ºC) and
pressure of 99.325 kPa.
Solution:
Basis: 1 Kg of calcium carbide
CaC2 + 2H2O → C2H2 + Ca (OH)2
Molecular weight of CaC2 = 64
Moles of CaC2 = 1/64 = 0.01562 kmol
56
PPP_DOTSUK
3. Gaseous System
From reaction,
1 kmol CaC2 ≡ 1 kmol C2H2
Moles of C2H2 produced = (1 / 1) x 0.01562 = 0.01562 kmol
Now, PV = nRT
V = nRT / P
Where, n =0.01562, R = 8.31451 m3·kPa / (kmol·K), T = 298 K, P= 99.325 kPa
Volume of C2H2 gas produced = (0.01562 x8.31451 x 298) / 99.325
= 0.3896 m3
Acetylene gas burning rate = 0.10 m3/h
No. of hours of service = Volume of acetylene gas / Burning rate of acetylene
= 0.3896 / 0.1 = 3.896 h = 3.9 h
Ex. 3.14) In the manufacture of formaldehyde, O2, methanol and steam are mixed in
proportion 1.5:2:1.33(by weight) at 283 (10oc). The total pressure is 70.928 kPa.g
calculate the partial pressure of each of the components present in the mixture.
Solution:
Basis: 100 kg of mixture.
In gas mixture the proportion of O2: methanol: steam (H2O) is 1.5: 2: 1.3 by wt.
Therefore O2 in the mixture = (1.5/4.83) x 100= 31.06 kg.
= 31.06/32 =0.97kmol.
Methanol in mixture = (2/4.83) x 100=41.4 kg.
= 41.4/32 =1.3kmol.
Steam in mixture = (1.33/4.83) x 100=27.84 kg
= 27.54/18 =1.53kmol.
Moles of gas mixture = 0.97+1.3+1.53
= 3.8 kmol.
Mole fraction O2 =XO2 = 0.97/3.8 =0.256.
Mole fraction of methanol =XCH3OH = 1.3/3.8=0.342.
Total pressure = 70.928 kpa.g.
∴P = 70.928+101.325 =172.253 kpa.
Partial pressure of O2 =XO2. P
= 0.256 x 172.253 = 58.91 kpa.
Partial pressure of methanol = 0.342 x 172.253 = 58.91 kPa
Partial pressure of steam = 0.403 x 172.253 = 69.42 kpa.
57
PPP_DOTSUK
3. Gaseous System
Ex. 3.15) Cracked gas From a petroleum refinery contains 45% CH4, 10% C2H6 , 25% C2H4,
7% C3H8, 8% C3H6 & 5% C4H10 by volume. Calculate (1) The average molecular weight of
gas mixture (2) The composition by weight & (3) The sp. Gravity of the mixture taking
average Molecular weight of air as 28.84
Solution:
Basis: 100Kmol of cracked gas
It contains 45 kmol CH4, 10Kmol C2H6, 25 Kmol C2H4, 7 Kmol C3H8, 8 Kmol C3H6 and 5 kmol
of C4H10
Molecular weight Data:- CH4 = 16, C2H6 = 30, C2H4 = 28 , C3H8=44, C3H6 = 42, and C4H10 = 58
Composition of refinery gas:-
Component Kmol Mol. Wt. Kg Wt%
CH4 45 16 720 27.13
C2H6 10 30 300 11.30
C2H4 25 28 700 26.37
C3H8 7 44 308 11.61
C3H6 8 42 336 12.66
C4H10 5 58 290 10.93
Total 100 - 2654 100
Avg. molecular Wt. of refinery gas is

2654
Mavg = = 26.54
100
OR
Mavg = MCH4 × XCH4 + MC2H6× XC2H6 + MC2H4 × XC2H4 + MC3H8 × XC3H8 + MC3H6 × XC3H6 +
MC4H10 × XC4H10
= 16×0.45 + 30×0.1 + 28×0.25 + 44×0.07 + 42×0.08 + 58×0.05
sp. gravity of gas mixture
26.54
= 28.84 = 0.92
58
PPP_DOTSUK
3. Gaseous System
3.6 Vapour pressure:

The vapour pressure of a liquid is defined as the absolute pressure at which the liquid and
its vapour are in equilibrium at a given temperature.
Pure water exerts vapour pressure of 101.325 kPa (760 torr) at 373.15 K (100oC).
3.6.1 Estimation of vapour pressure:

a) Antoine equation:
An equation proposed by Antoine is as follows:
B
log10 Pv = A −
T+C
B
lnPv = A −
T+C
where Pv is the vapour pressure in kPa, T is the temperature in K and A, B and C are
constants. In these equations, constants do not necessarily have same values.
A graph having logPv (or InPv) on y-axis and l/T on x-axis is called the Cox chart. In another
words it is a representation of Antoine equation in the graphical form.
It is observed that barring some of the compounds (such as organic sulphur compounds),
the Antoine equation is proved to give the vapour pressure in the range of 1 to 200 kPa (10
to 1500 torr) of a variety of compounds well within the experimental uncertainty.
Ex 3.16) Calculate vapour pressure of (a) n-hexane at 305 K (32°C) and (b)water at 395 K
(l22°C) using Antoine constants
Solution:
(a) Vapour pressure of n-hexane: T = 305 K
2825.42
lnPv = 14.0568 − = 3.2847
305 − 42.7089
∴ Pv = 26.70 Kpa
(a) Vapour pressure of water: T = 395 K
1636.90
lnPv = 7.0436 − = 2.3229
395 − 48.25
∴ Pv = 208.76 Kpa
59
PPP_DOTSUK
3. Gaseous System
b) Clausius-clapeyron equation:
Effect of temperature on vapour pressure is given by clapeyron equation
dpv λ
=
dT [T(VG − VL )]
Where,
Pv - Vapour pressure
T – Absolute pressure
λ – latent heat of vaporization at T
VG – volume of gas
VL – volume of liquid.
If the volume of liquid is neglected and applicability of the ideal gas law assumed, the above
equation reduces to clausius -clapeyron equation.
dpv λdT
=
p RT 2
or
λ dT
d(ln pv ) = − ( 2 )
R T
where, R is gas law constant and λ, molal latent heat of vaporization.
When the temperature does not vary over wide range, it may be assumed that the molal
latent heat of vaporization is constant and the above equation may be integrated between
limits po & p and To & T
P
λ T dT
∴ ∫ d(ln pv ) = − ∫ ( 2 )
Po R To T
P λ 1 1
∴ ln ( ) = ( − )
Po R To T
Ex. 3.17) The vapor pressure of ethyl ether at 0oC is 185 mm Hg. Latent heat of
vaporization is 92.5 cal/g. Calculate vapor pressure at 20oC and 35oC.
Solution:
Basis:
Molecular weight of ethyl ether = 74
λ = (92.5 x 74) = 6845 cal/g mole
R = 1.99 cal/g mole. K
To = 273 K, T1 = 293 K, T2 = 308 K
At 20oC
P 6845 1 1
ln ( )= ( − )
185 1.99 273 293
∴P = 437 mm Hg
60
PPP_DOTSUK
3. Gaseous System
P 6845 1 1
ln ( )= ( − )
185 1.99 273 308
∴P = 773 mm Hg
3.7 Gas - Liquid System:

The approximate relationship that governs the distribution of a substance between a gas
and a liquid phase are Raoult's and Henry's laws which assume reasonably accurate results
in many cases.
Consider a component 'A' contained in a gas-liquid system in equilibrium at temperature T

and pressure P.
Let poA be a vapour pressure of pure liquid 'A'.
Let xA be the mole fraction of A in liquid phase and yA be the mole fraction of 'A' in vapour
phase.
Let PA be the equilibrium partial pressure of A in vapour phase.
Raoult's Law:
It states that the equilibrium partial pressure at component 'A' is equal to the product of
vapour pressure and mole fraction of 'A' in liquid phase.
Thus,
pA = yA.P = xA. poA
Henry's Law:
Henry's law states that the partial pressure of solute gas is proportional to mole fraction of
that component in liquid phase but proportionality constant is H.
pA = yA.P = xA.HA (T)
where HA(T) is the Henry's law constant for 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. It is also valid over entire range of compositions for mixtures of similar substances,
such as straight chain hydrocarbons of similar molecular weights.
Henry's law is valid when xA is close to zero i.e. for dilute solution of 'A'.
61
PPP_DOTSUK
3. Gaseous System
Ex 3.18) A ternary mixture of n-butane, I-butene and furfural is analyzed to find the
content of each in it. The mixture is stripped off with the help of carbon dioxide without
appreciable entrainment of furfural due to its very low vapour pressure. The stripped gases
are passed through an absorber column in which CO2 is absorbed in 25% (by mass) KOH
solution. The mixture of hydrocarbons, saturated with water vapour is collected in a
measuring burette.
The test data are as follows:
Sample mass = 6.5065 g
Volume of saturated gases collected at 296.4 K (23.25°C) and 102.5 kPa (769 torr) = 415.1
ml
n-Butane present in the hydrocarbons (dry) in the burette = 43.1 mol %
Find the analysis of the liquid mixture (both on mole and mass basis).
Data: Vapour pressure of water over 25% KOH solution at 296.4 K = 2.175 kPa
Solution:
Basis: 6.5065 g furfural-n butane-I-butene mixture
Partial pressure of water vapour in the saturated hydrocarbon gas mixture
= Vapour pressure of water over KOH solution
= 2.175 kPa
Partial pressure of n-butane and I-butene (p) = 102.5 - 2.175 = 100.325 kPa
If n is the total number of mol of n-butane and I-butene, then according to Eq. (2.23),
pV 100.325 x 415.1
n= = = 0.0169 mol
RT 8.314 x 296.4 x 1000
n-Butane in the hydrocarbon mixture = 0.0169 x 0.431 = 0.007 284 mol

Mass of n-butane in the mixture = 0.007 284 x 58 = 0.422 g
I-Butene in the hydrocarbon mixture = 0.0169 - 0.007 284 = 0.009 616 mol
Mass of I-butene in the mixture = 0.009 616 x 56 = 0.5379 g
Mass of furfural in the liquid mixture = 6.5065 - 0.422 - 0.5379 = 5.5466 g
Moles of furfural in the liquid mixture = 5.5466/96 = 0.057 78 mol

Composition of Ternary Mixture
Component Formula Molar mass mol Mole % Mass g Mass %
n - Butane C4HlO 58 0.007284 9.75 0.4225 6.49
I - Butene C4H8 56 0.009616 12.87 0.5379 8.27
Furfural C5H4O2 96 0.057780 77.38 5.5469 85.24
0.074680 100.00 6.5073 100.00
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Ex 3.19) The liquid mixture cited in the above example is boiled at 338.15 K (65oC) and 5.7
bar g. The mole fraction of n-butane in the ternary vapour mixture in equilibrium with the
liquid is found to be 49.1 volume%. Assuming ideal behavior of the liquid and vapour
mixture, find the composition of the vapour mixture.
Data: Vapour pressure of furtural at 338.15 K = 3.293 kPa = 24.7 torr
Solution:
Absolute total pressure = 5.7 + 1.01 = 6.71 bar
According to Raoult's law,
Actual vapour pressure of the furtural
= (vapour pressure of pure furtural at 338J5 K) x (mol fraction of furfural in the liquid
mixture)
= 3.293 x 0.7738 = 2.548 kPa
According to Dalton's law of partial pressures,

Mole fraction of furfural in the vapour mixture = 2.548 / (6.71 x 100) = 0.0038
Mole fraction of I-butene in the vapour mixture = 1.0000 - 0.0038 - 0.491 = 0.5052
Ex. 3.20) The liquid mixture contains n-butane, 1-butane and furfural. It is boiled at 338K
(65oC) and 570.46 kPa.g pressure. The mole fraction of n-butane in the ternary vapour
mixture in the ternary vapour mixture in equilibrium with the liquid is found to be
49.1%by volume. Assuming ideal behavior of the liquid and vapour mixtures find the
composition of vapour mixture.
Data: vapour pressure of furfural = 3.293 kPa at 338K(65oC)
Molefraction of furfural in liquid mixture = 0.7734
Apply Dalton’s law of partial pressure.
Solution:
Basis: Liquid mixture at 338K and 570.46kPa.g
Absolute total pressure =P = 570.46 + 101.325
= 671.785kPa
According to Raoult’s law:
Actual vapour = vapour pressure of x mole fraction of furfural
pressure of furfural pure furfural at 338K in liquid mixture
= 3.293 x 0.7734
= 2.547 kPa
According to Dalton’s law of partial pressure:
2.547
Mole fraction of furfural in vapour mixture = 671.785
= 0.0038
Mole % of n-butane in vapour mixture = 0.491
∑xi = 1
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Mole fraction of n-butane in vapour mixture

= 1-(0.0038 + 0.491)
= 0.5052
Composition of the vapour mixture:
Components Quantity in kmol. Volume in %( mole %)
n-butane 0.491 49.10
i-butane 0.5052 50.52
furfural 0.0038 0.38
Total: 1.0 100
Ex. 3.21) Ambient air on a particular day in Ahmedabad has the following condition
Total pressure = 100 kPa (750 torr)
Dry bulb temperature = 308.15 K (35°C)
Dew point = 294.45 K (21.3°C)
Find the absolute humidity of the air
Data: Vapour pressure of water at 294.45 K = 2.5326 kPa = 19 torr
Solution: -
Partial pressure of water vapour in the air, Pw = vapour pressure for water at dew point
= 2.5326 kPa
Now, according to Dalton’s law,
(Moles of water vapour) (Partial pressure of water vapour) 2.5326 2.5326
= = =
(Moles of dry air) (Partial pressure of air) 100 − 2.5326 97.4674
(Mass of water vapour) 2.5326 (Molar mass of water)

= x
(Mass of dry air) 97.4674 (Molar mass of air)
2.5326 18.0153 kg g water vapour

x = 0.01616 = 16.16
97.4674 28.9679 kg kg dry air
Ex. 3.22) A solution containing 55% benzene, 28% toluene and 17% xylene by weight is in
contract with its vapour at 373 K (100ºC). Calculate the total pressure and molar
composition of the liquid and vapour.
Data : Vapour pressure data at 373 K (100ºC)
Benzene = 178.60 kPa, Toluene = 74.60 kPa, Xylene = 28 kPa
Solution:
Basis: 100 kg of solution.
It contains 55 kg of benzene, 28 kg of toluene and 17 kg of xylene.
Molecular weight of benzene (C6H6) = 78
Molecular weight of toluene (C6H5CH3) = 92
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3. Gaseous System
Molecular weight of xylene [C6H6 (CH3)2] = 106

Composition by Mole
Component Amount in kg Amount in kmol Mole %
Benzene 5 0.7051 60.28
Toluene 28 0.3043 26.01
Xylene 17 0.1604 13.71
Total 100 1.1698 100
According to Raoult’s law :
Pi = P10 · xi
Where,
Pi = Partial pressure of component ‘i’ over a solution
Pi0 = Vapour pressure of pure ‘i’
xi = Mole fraction of ‘i’ in solution
Total pressure in vapour space = P = Σpi
Partial pressure of benzene = pB = 0.6028 x 178.60 = 107.66 kPa
Partial pressure of toluene = pr = 0.2601 x 74.60 = 19.4 kPa
Partial pressure of xylene = px = 0.1371 x 28 = 3.84 kPa
Partial pressure of vapours = Px = 107.66 + 19.4 + 3.84 = 130.9 kPa
Composition of vapour in mole % :
Mole % of benzene = (107.66 / 130.9) x 100 = 82.25
Mole % of toluene = (19.4 / 130.9) = 14.82
Mole % of xylene = (3.84 / 130.9) x 100 = 2.93
[Mole % - Mole fraction x 100 = Pressure fraction x 100]
Ex. 3.23) At a temperature of 299K(260c),ethanol exerts a vapour pressure of 8 kpa.

Calculate the composition of a saturated mixture of and ethanol vapour at a temperature of
299K(260c) and a pressure of 100 kpa in terms of : (1) volume (2) Weight (3) kg of vapour
per meter cube (4)kg of vapour per kg of vapour free air.
Solution:
Basis: 1M of gas mixture.
Pure component volume of ethanol vapours in 1 m of mixture
=1 x 8/100 = 0.08m3
Composition by volume:
Ethanol vapour 0.08 m3 8.0%
Air 0.92 m3 92%
Total 1.0 100
Amount of ethanol vapour present in 1 kmol of mixture
= 0.08 x 1
= 0.08 kmol.
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3. Gaseous System
= 0.08 x 46
= 3.68 kg
Amount of air in mixture = 0.92*1
= 0.92kmol
= 0.92*28.84
= 26.53kg.
Amount of mixture = 3.68+26.53=30.21 kg.
Composition by weight:
Ethanol vapour 3.68 kg 12.18%
Air 26.53 kg 87.72%
Total 30.21 100
PV = nRT
V = nRT/P
Volume of 1 kmol of mixture = nRT/p
Where
n=1kmol, R =8.31451 m.kpa/kmol.k, T =299k, P =100kpa
∴V = (1 x 8.31451 x 299)/100
= 24.86m3
Weight of ethanol vapour present per m of mixture
= 3.68/24.86
= 0.148kg.
Kg of ethanol vapour per kg of vapour free air = 3.68/26.353
= 0.1387.
Ex. 3.24) A binary mixture containing n-butane and furfural is analyzed to determine the
butane content in it. First, the n-butane present in the mixture is stripped off with the help
of CO2 (with very negligible entrainment of furfural). The mixture of CO2 and butane is then
passed through a 25% NaOH by weight solution in which CO2 is absorbed. The saturated
hydrocarbon is collected over the solution in a burette. The data obtained on a specific run
are given below:
Weight of sample (butane + furfural) = 9.082 g
Volume of saturated butane stripped off at 295.2 K (22.20C) and 101.75 kPa = 105.7 ml
Determine the amount of butane present in the liquid mixture on (i) mole and (ii) weight
basis.
Data: Vapour pressure of water over 25% NaOH solution at 295.2 K (22.2 oC)= 1.66 kPa.
Solution:
Basis: 9.082 g n-butane - furfural mixture
(Partial pressure of water vapour in saturated hydrocarbon)
= (vapour pressure of water over NaOH solution) = 1.66 kPa
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partial pressure of n-butane = 101.75-1.66 =100.084 kPa

If n is the moles of saturated n-butane then,
n = PV/RT
=100.084 x 105.7/8.314 x 295.2 x 100
= 0.00431 mol
Weight of n-butane in the mixture = 0.00431*58 = 0.25 g
Weight of furfural in the mixture = 9.082 - 0.25 = 8.832 g
Weight % of n-butane in liquid mixture = 0.25 x 100/9.082 = 2.75
moles of furfural = 8.832/96 = 0.092 mol
Total moles of liquid mixture = 0.00431 + 0.092 = 0.09631 mol
Mole % of n-butane in liquid mixture = 0.00431*100/0.09631 = 4.47
Assignment No. 2) 2a, 3a & b (S-175), 1b (S-181), 2A & 2B (O-650), 1b & 2a (G-23), 2a & 3a
(O-281), 1b & 4b (G-215), 2a,b & 3b (J-493), 2b (Z-461), 1c (K-42)
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3. Gaseous System
Questions from theory Examination:
3.1) For 1000 lit/s, of a gaseous mixture of the following composition:

CH4 -10%, C2H2 - 30%, H2 - 60% (volume %) at 30°C and 2000 mmHg.gauge.
Calculate:
i) the mole fr. of each component
ii) the concentration of each component gm.mole/cc
iii) the p.p. of each component, mm Hg
iv) the mass flow rate of mixture, kg/s.
3.2) A natural gas having the composition CH4 - 94% , C2H6 – 3% and N2 3% is piped from
the well at 25°C and 3.0 atm. Assuming ideal gas law, find out:
i) P.P. of N2 ii) Volume ofN2/100 cu.m of gas iii) Density of gas.
3.3) Methyl alcohol and ethyl alcohol at 100°C have V.P. 2710 mm and 1635 mm Hg
respectively. Calculate the total pressure and composition of the vapor in content with a
liquid containing 30% by wt. methyl alcohol and 70% by wt. ethyl alcohol at 100°C.
3.4) By electrolyzing mixed brine, a gaseous mixture obtained at the cathode has following
composition by weight: Cl2 = 67%, Br2 = 28%, O2 = 5%. Calculate:
a) Composition of the gas by volume
b) Average molecular weight
c) Density of the gas mixture at 25°C and 101.325 kPa
3.5) What will be the vapor pressure of cyclohexane at 300 k .

A B C Temperature in k
13.7865 2794.58 - 49.10 280 - 378
3.6) The vapor pressure of ethyl ether is given in the International critical tables as 2.5 x
104 N/m2. The latent heat of vaporization is 4.185 x 105 J/(kg) (K) at 0°C. Calculate the
vapor pressure at 20°C and at 35°C.
Data: Molecular wt. of Ethyl ether = 74.
3.7) The gas acetylene is produced according to following reactions

CaC2 + 2H2O → C2H2 + Ca(OH)2
Calculate the number of hours of services that can be derived from 1 kg of calcium carbide
in an acetylene lamp burning 100 liters of gas per hour at temperature 25oC and pressure
of 743 mm Hg. [Data M.W. of Ca = 40].
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3. Gaseous System
3.8) A natural gas having the composition CH4 - 94 %, C2H6 - 3% and N2 - 3% is piped from
the well at 25°C and 3.0 atm. pressure. Assuming that the ideal ,gas law is obeyed. Find out
i) Partial pressure of N2
ii) Volume of N2 per 100 cu.m of gas
Iii) Density of the gas.
3.9) Bottled liquid gas of the-following composition is sold for household use:
Component n - butane Propane Ethane
Composition (mole%) 50 45 5
V.P.at 30°C(bar) 3.4 10.8 46.6
Determine:
i) The pressure of the system and equilibrium vapor composition at 30oC.
ii) If all ethane removed from the liquid, the pressure of the system and the vapor
composition at 30oC. Assume Raoult's law applicable.
3.10) A mixture of acetone vapor and nitrogen contains 14.8 % acetone by volume.
Calculate the relative saturation and % saturation of the mixture at a temperature of 20 oC
and a pressure of 0.098 x 105 N/m2,
Data: V.P. of acetone at 20oC = 0.243 x 105 N/m2.
3.11) Calculate the density of chlorine gas at 230oC and 15.2 MPa. by using the ideal gas
law.
3.12) If 45 gm of iron react as Fe + H2SO4 → FeSO4 +H2, how many litres of hydrogen are
liberated at standard conditions?
3.13) A producer gas has the following composition by volume CO = 22 %, CO2 = 5 %, O2 =

3% and N2 = 70%. Calculate the volume of gas at 35°C and 101.325 kPa pressure per 10 kg
of carbon present.
3.14) The analysis of a sewage gas sample from a municipal sawage treatment plant is
given below (volume basis).
Component Methane Carbondioxide NH3 H2S SO2
% (volume) 68 30 2 Traces
Find i) the average molecular weight of the gas ii) The density of the gas at NTP.
3.15) A liquid mixture contains N-butane, 1 butane and furfural is boiled at 65°C and 5.63
atm(g) pressure. The mol. friction of N-butane in the ternary vapor mixture in equilibrium
with liquid is found to be 49.1% by volume. Assuming the ideal behavior of the liquid and
vapor mixtures, find the composition of vapor mixture.
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PPP_DOTSUK
3. Gaseous System
Data: V.P. of furfural at 65°C = 24.7 mm Hg,

Mole fraction of furfural in liquid mixture = 0.7734.
3.16) A weight of 1.10 kg of carbon dioxide occupies a volume of 33 litre at 300 K.

Using the Vander Walls equation of state, calculate the pressure.
Data: a = 0.3646 (m3)2 N/m2 mol2, b = 4.28 xl0-5m3/mol
3.17) In the manufacture of nitric acid, initially ammonia and air are mixed at 0.709 MPa g
and 923 K. The composition of the gas mixture by volume is as follows:
Nitrogen 70.5%, Oxygen 18.8%, Water 1.2% and Ammonia 9.5%
Find the density of the gas mixture using 1) ideal gas law, ii) also find the sp. gravity of the
gas mixture.
3.18) the mosanto process for the manufacture of formaldehyde, air, methanol and steam
are mixed in the proportion 4:2:1.3 (by weight) at 373 K. The total pressure is 68.6 KPa g.
Calculate the partial pressure of each of components present in the mixture.
3.19)A liquid mixture is having composition as follows:

Component n-butane I-butene Furfural
mole % 9.75 12.87 77.38
The temperature of mixture is 338 K and pressure 0.57 MPa g. The mole fraction of n-
butene in the ternary vapour mixture in equilibrium with the liquid is found to be 49.1 %
(Volume). Assuming ideal behavior of the liquid and vapour mixture, find the composition
of the vapour mixture.
3.20) Calculate the number of cubic meters of acetylene gas at a temperature of 40°C and a
pressure of 100 KPa, that may be produced from 10 Kg of calcium carbide.
3.21) An inert gas (mol. wt. 28) is admitted at a rate of 1000 Lit/minute at 202.65 KPa
pressure and 30°C to a pipeline in which natural gas is flowing. The analysis of this gas at a
very long distance shows 2.9% (volume) of an inert gas. Calculate the flow rate of natural
gas through tile pipeline per minute at 101.325 KPa and 30°C.
3.22) A gas containing 96% ethylene and 4% butene by volume is passed through a bed of
activated carbon, where 98% of the original butene is absorbed and none of the ethylene.
In five hours of operation, if quantity of butene removed is 0.5 K mol, find i) mole percent
ethylene in gas leaving carbon bed ii) molar flow rate of the gas to the carbon bed.
3.23) Aromatic hydrocarbons form 15 to 30% of the components of leaded fuels and as
much as 40% of non leaded gasoline. The carbon/hydrogen ratio helps to characterize the
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PPP_DOTSUK
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fuel components, If a fuel is 80% C and 20% H by weight, what is the C/H ratio in moles and
also calculate the Mavg of fuel (Average mol. wt).
3.24) A solution containing 55% benzene, 28% toluene and 17% xylene by weight; is in
contact with its vapor at 100oC. Calculate the total pressure and molar composition of the
liquid and vapor.
Data:
Component V. Pressure, KPa
C6H6 178.60
C7H8 74.60
C8H10 28.0
3.25) A gas mix has the following composition by volume

Component Ethylene Benzene Oxygen Methane Ethane Nitrogen
% volume 30.6 24.6 1.3 15.5 25.0 3.1
Find: i) the Mavg of gas mixture.
ii) the composition by wt
iii) density of mix in kg/m3 at NTP
iv) Sp. gravity of mixture.
3.26) Calculate the mass flow rate of NH3 through the pipe based on the following data.
A stream of oxygen is introduced into the NH3 pipe line at a rate of 4.5 m3/60 seconds. The
resulting mixture is sampled further downstream and found to contain 10% vol. O2. The
entering O2 is measured at 1.5 bar and 30°C. Calculate the flow rates of NH3 and oxygen in
kg/h.
3.27) A binary mixture of n-butane and furfural is analyzed to find the butane content in it.
First, the n-butene present in the mixture is stripped off with the help of carbon dioxide
with negligible entrainment of furfural. The mixture of carbon dioxide and butene is then
passed through the solution containing 25% NaOH (by weight) in which carbon dioxide is
absorbed. The saturated hydrocarbon is collected over the solution in a burette.
The test data on a specific run are given below:
Weight of sample (butane and furfural) = 9.082 g
Volume of saturated butene stripped off at 295.2 K and 101.75 KPa = 105.7 ml
Find the amount of butane present in the liquid mixture on molal and weight basis
Data: Vapor pressure of water over 25% NaOH solution at 295 K = 1.666 KPa.
3.28) Most processes for producing high energy content gas or gasoline from coal include
some type of gasification step to make hydrogen or synthesis gas, pressure gasification is
preferred because of its greater yield of CH4 and higher rate of gasification. Given that, a
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3. Gaseous System
50.0 Kg. test run of gas averages 10.00 % H2, 40% CH4, 30% CO and 20% CO2, What is the
average molecular weight of the gas?
3.29) The vapor pressure of ethyl ether is 2.5 x l04 N/m2 at 0°C. The latent heat of
vaporization is 4.185 x l05 J/Kg. K. at 0°C. Calculate the vapor pressure at 20°C and at 30°C.
3.30) Calculate the mass flow rate of ammonia through a pipe based on the following data:
A stream of oxygen introduced into NH3 pipeline at a rate of 4.5 m3/60 S. The resulting
mixture is sampled further downstream and found to contain 10% volume O2. The entering
oxygen is measured at 1.5 bar and 30°C. Calculate the flow rates of ammonia and oxygen in
Kg/h.
3.31) A natural gas has the following composition CH4-94%, C2H6-3% and N2-3% is passed
from the well at 25oC and 3 atm. pressure. Assuming that ideal gas law is obeyed, Find:
i) partial pressure of N2.
ii) volume of N2 per 100 m3 of gas.
iii) density of the gas.
3.32) A volume of moist air of 1000 m3 at a total pressure of 740 mmHg and a temperature
of 30°C contains water vapor in such proportions that its partial pressure is 22.0 mmHg.
Without the total pressure being changed, the temperature is reduced to 15°C and some of
the water vapor removed by condensation. After cooling it is found that the partial
pressure of the water vapor is 12.7 mmHg. Using the partial pressure method, Calculate:
i) Volume of the gas after cooling.
ii) Weight of water removed.
3.33) calculate the total pressure and the composition of the vapors in contact with a
solution at 100°C. Containing 35% benzene, 40% toluene and 25% O-xylene by weight.
Data : Vapor pressures at 100°C.
Benzene -1.763 x 105 N/m2
Toluene - 0.737 x 105 N/m2
O-xylene - 0.276 x 105 N/m2
3.34) Calculate total pressure and composition of the vapors in contact with solution at
100°C containing 35% benzene and 40% toluene and 25% O-xylene by weight.
Data:
V.P. at 100°C for
Benzene = 1340 mm Hg
Toluene = 560 mm Hg
O-xylene = 210 mm Hg
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3.35) The average molecular weight of flue gas sample is calculated by two different
engineers. One engineer use the correct molecular weight 28 for N2 and determine the
average molecular weight to be 30.08, the other engineer, using an incorrect value of 14,
calculate the average molecular weight to be 18.74
a) Calculate volume % of N2 in the flue gas.
b) If the remaining components of the flue gases are CO2 and O2, calculate the volume % of
each of them.
3.36) An equimolar liquid mixture of benzene and toluene is in equilibrium with its vapour
at 30oC. What is the system pressure and composition of the vapour? Use the following
Antoine equation and data:
B
log10 P = A −
T+C
where P in mmHg & T in °C.

Data:
Component A B C
Benzene 6.906 1211 220.8
Toluene 6.953 1343.9 219.38
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Exercise:
3.1) A gas mixture has the following composition by volume:
Ethylene 30.6% Benzene 24.5%, Oxygen 1.3%, Methane 15.5%, Ethane 25.0%, and
Nitrogen 3.1%. Find (a) the average molar mass of gas mixture, (b) the composition by maa
& c) density of the mixture in kg/m3 at NTP
[Ans. (a) 38.94; (b) ethylene 22.0%, benzene 49.07%, O2 07%, methane 6.37%, ethane
19.26%, nitrogen 2.23% (by mass); (c) 1.737 kg/m3
3.2) The analysis of a sewage gas sample from a municipal sewage treatment plant is given
below on a volume basis:
68% Methane, 30% Carbon dioxide, 2% Ammonia, Traces H2S, SO2 etc.
Find (a) the average molar mass of the gas and (b) the density of the gas at NTP. [Ans. (a)
24.42; (b) 1.09 kg/m3]
3.3) Calculate the density of chlorine gas at 503.15 K (230oC) and 152 bar a using the ideal
gas law
[Ans. 258.1 kg/m3]
3.4) In the manufacture of nitric acid, initially ammonia and air are mixed at 7.09 bar g and
923 K (650oC). The composition of the gas mixture (by volume) is as follows
Nitrogen 70.5%
Oxygen 18.8%
Water 1.2%
Ammonia 9.5%
Find (i) the density of the gas mixture using (a) ideal gas law, and (b) the van der Waals
equation and (ii) the specific gravity of the gas mixture.
[Ans. (i) (a) 2.912 kg/m3; (b) 2.907 kg/m3; (ii) 0.952]
3.5) A binary mixture of n-butane and furfural is analysed to find the butane content in it.
First, the n-butane present in the mixture is stripped off with the help of carbon dioxide
with negligible entrainment of furfural. The mixture of carbon dioxide and n-butane is then
passed through the solution containing 25% NaOH (by (mass) in which carbon dioxide is
absorbed. The saturated hydrocarbon is collected over the solution in a burette. The test
data on a specific run are given below:
Weight of sample n-butane and furfural = 9.082 g
Volume of saturated n-butane stripped off at 295.35 K (22.2°C) and 101.75 kPa (763.2 torr)
= 105.7 mL
Find the amount of n-butane present in the liquid mixture on mole and weight basis.
Data: Vapour pressure of water over 25% NaOH solution at 295.35 K (.22.2°C) = 1.666 kPa
(12.5 torr) [Ans. 4.48 mole % and 2.75 mass % n-butane]
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3.6) The Orsat (dry) analysis of the flue gas from a boiler house is given as (volume basis);
CO2: 10.0%, 02: 7.96%, N2: 82.0% and SO2: 0.04%. The temperature and pressure of flue
gases are 463 K (190°C) and 100 kPa (750 torr), respectively. The dew point of the gas is
found to be 320 K (20°C). Find the absolute humidity of the flue gases [Ans. 8.6 g/kg dry
flue gas]
3.7) The Monsanto process for the manufacture of formaldehyde, air, methanol and steam
are mixed in the proportion 4:2:1.33 (by weight) at 373 K ( 100oK). The total pressure is
68.6 kPa g. Calculate the partial pressure of each of the components present in the mixture.
[Ans. methanol 38.71; steam 45.78; oxygen 17.94; nitrogen 67.49 (kPa)]
3.8) A domestic liquefied petroleum gas (LPG) cylinder, conforming to IS:4576, is stored at
313.15 K (40oC). It is a mixture of 30% propane, 45% n butane and 25% i-butane by
volume. Calculate (a) average molar mass of LPG, (b) specific gravity of LPG & (c) pressure
in the cylinder.
Date: Vapour pressures of propane, n-butane and i-butane are 1350, 383 and 535 kPa,
respectively at 313.15 K( 40°C). [Ref. : Table 5.4] [Ans. : (a) 53.916, (b) 2.25 and (c) 7.11
bar a]
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5. Material Balance involving Chemical Reactions
5. Material Balances Involving Chemical Reactions
5.1 Introduction:
The process of manufacture of a desired product from a given raw materials involves series
of steps wherein a whole physical and chemical changes take place. The step where
chemical change takes place i.e. wherein raw materials undergo chemical
reaction/reactions (with or without catalyst) to produce a desired product is a heart of the
process as it decides the economics of the process as a whole. Material balances of the
processes wherein chemical reaction takes place are very important from the design point
of view of chemical reactor. The occurrence of chemical reaction makes the material
balances calculations complicated as in addition to input and output terms (at steady state)
the formation or disappearance term is involved in material balance equation.
In processes involving chemical reaction, the total mass of various compounds entering a
reactor is equal to the total mass of various components leaving the reactor but entering
moles of components need not be equal to the moles of components leaving. While doing
material balance calculations in such case it is very convenient to use basis of calculations
in molar units. Generally, calculations should be based on limiting reactant and quantity of
products formed should be calculated with the help of chemical reaction and amount of
limiting reactant reacted.
5.2 Definition of Terms Involved:
Stoichiometry:
It is a theory of the proportions in which chemical species combine with one another.
Stoichiometric Equation:
The stoichiometric equation of a chemical reaction is a statement indicating relative moles
of reactants and products that take part in the reaction.
For example, the stoichiometric equation
CO + 2H2 → CH3OH
indicates that one molecule (molar kmol) of CO reacts with two molecules (mol or kmol) of
hydrogen to produce one molecule (mol or kmol) of methanol.
Stoichiometric Coefficient:
It is the number that precede the formula of each component involved in a chemical
reaction.
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Thus, for example, in above cited reaction, the stoichiometric coefficient of CO is one, the
stoichiometric coefficient of H2 is two and stoichiometric coefficient of methanol is one.
The stoichiometric requirements of components are given as:
1 kmol CO ≡ 1 kmol CH3OH

≡ 2 kmol H2
Stoichiometric Ratio:
It is the ratio of stoichiometric coefficients of two molecular species/components in the
balanced reaction equation.
e.g. stoichiometric ratio of H2 to CO is 2/1 = 2.
Stoichiometric Proportion:
Two reactants, A and B, are said to be present in stoichiometric proportion if the ratio of
moles of A present to the moles of B present is equal to the stoichiometric ratio obtained
from the balanced reaction equation.
Consider a chemical reaction:
CO + 2H2 → CH3OH
For the reactants in the above reaction to be present in stoichiometric proportion, there
must be 2 moles of H2 for every mole of CO (so that nH2/nCO = 2/1) present in the feed to
the reactor.
When the reactants are fed to a reactor in stoichiometric proportion and the reaction goes
to completion, all of the reactants are consumed. In case of above cited reaction, for
example, if 200 moles of H2 and 100 mol of CO are initially present, the H2 and CO would
disappear at a same instant. It follows that if we start with 100 mol of CO and less than 200
mol of H2 (i.e. if H2 is present in less than its stoichiometric proportion) H 2 disappears
before the CO2, on the other hand if there are more than 200 mol of H2 initially present the
CO disappears first.
Limiting Reactant / Component:

The reactant that would disappear first if a reaction goes to completion is called the
limiting reactant. It is the one which decides the extent to which the reaction can proceed.
The limiting reactant is always present in less than its stoichiometric proportions relative
to other reacting components.
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Excess Reactant:
It is the one which is in excess of theoretical or stoichiometric requirement. The excess
component/reactants always found in product stream though the reaction proceeds to
completion. For example, consider a reaction:
C2H4 +1/2 O2 → C2H4O
In Industrial practice of producing ethylene oxide by oxidation of ethylene, oxygen/air fed

to reactor is always in excess of theoretically required. Thus, ethylene is a limiting reactant
and oxygen/air is a excess reactant.
Percent Excess:
The excess reactant involved in reaction is generally specified in terms of percent excess. It
is the amount in excess of stoichiometric (theoretical) requirement expressed as the
percentage of stoichiometric/theoretical requirement.
Consider a reaction A + B → C
where B is the excess reactant then
mole of B moles of B
( )−( )
Percent supplied theoretically required
∴[ ]=[ ] x100
excess of B moles of B
theoretically required
Conversion:
The conversion is always based on limiting reactant and it gives idea regarding degree of
completion of reaction. The unreacted quantities of raw materials are easily obtained
knowing the charged quantities with the help of conversion thus in turn it gives idea in case
of unit process whether recycling is to be done or not for process to be economically
feasible.
Consider a chemical reaction:
A+B→C
where A is a limiting reactant and B is a excess reactant. Then,
moles of A reacted
% conversion of A = x100
moles of A charged or supplied
Yield and Selectivity:

The terms yield and selectivity are used in case of multiple reactions to give information
regarding the degree to which a desired reaction predominates over side reaction or
reactions involved.
Consider a series reaction:
A+B→C
C+B→D
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or parallel reaction
A→C
A→D
Where C is a desired product, D is an undesired product and A is a limiting reactant.
Then percent yield of C is given as:
moles of A reacted to produce C
% yield of C = x 100
moles of A totally reacted
Selectivity of C relative to D
moles of C (desired product)formed
selectivity of C relative to D =
moles of D (undesired product)formed
Ex. 5.1) Monochloroacetic acid (MCA) is manufactured in a semibatch reactor by the action
of glacial acetic acid with chlorine gas at 373 K (100°C) in the presence of PCl 3 catalyst.
MCA thus formed will further react with chlorine to form dichloroacetic acid (DCA). To
prevent the formation of DCA, excess acetic acid is used. A small-scale unit which produces
5000 kg/d MCA, requires 4536 kg/d of chlorine gas. Also, 263 kg/d of DCA is separated in
the crystalliser to get almost pure MCA product. Find the % conversion, % of MCA and
selectivity.
Solution:
Basis: One - day operation
Reactions:
CH3COOH + Cl2 = CH2ClCOOH + HCl
Acetic acid Chlorine MCA Hydrogen Chloride
CH2ClCOOH + Cl2 = CHCl2COOH + HCl
MCA Chlorine DCA Hydrogen Chloride
In this example, the amount of chlorine determines the product distribution while acetic
acid is in excess. Hence, chlorine becomes the limiting component.
Chlorine charged = 4536/71 = 63.89 kmol
For each mole of MCA production, one mole of chlorine is consumed
Chlorine utilized for MCA production = 5000/94.5 = 52.91 kmol
Similarly, for each mole of DCA production, two moles of chlorine are consumed
Chlorine utilized for DCA production = (261 x 2)/129 = 4 08 kmol
Total chlorine utilized = 52.9 + 4.08 = 56.99 kmol
Conversion = (56.99 x l00)/ 63.89 = 89.2%
Yield or MCA = (52.91 x 100)/56.99 = 92.84%
Selectivity of MCA = 52.91/4.08 = 12.97
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Ex. 5.2) Bechamp process is classically known for reduction of nitro compounds to
corresponding primary amino compounds using iron in an acidic medium. Orthotoluidine
(OT) is manufactured from ortho-nitro toluene (ONT) by Bechamp process.
In a batch of 700 kg ONT, 800 kg iron turnings (containing 90% Fe) and 400 kg water is
added. Reaction mixture is heated to 333 K (60°C) and formic acid is added (approx. 6 kg)
as a catalyst in batches. The mixture is stirred for about 18 hours and then total mass is
allowed to settle in two layers. Upper layer of OT is sucked out by vacuum in a distillation
unit where it is purified by vacuum distillation.
Reactions:
CH3 CH3
NO2 NO2
HCOOH
4 + 9 Fe + 16 H2O 4 + 3 Fe(OH)2 + 6 Fe (OH)3
333 K
(60oC)
ONT OT
4 x 137 9 x 56 16 x 18 4 x 107 3 x 90 6 x 107
3 Fe(OH)2 + 6 Fe(OH)3 = 3 Fe3O4 + 12 H2

3 x 90 3 x 107 3 x 232 12 x 18
At the end of the batch, 505 kg 99% pure OT is obtained. Assuming 98% completion of
reduction, calculate (a) the yield of OT, and (b) excess quantity of iron powder
Solution
Basis: 700 kg ONT charged to reactor
OT produced = 505 x 0.99 = 500 kg
ONT required = (4 x 137 x 500)/(4 x l07) = 640.2 kg
ONT reacted = 700 x 0.98 = 686 kg
Yield of OT = 640.2 x 100/686 = ------ = 93 12%
Theoretical iron requirement = (9 x 56 x 700)/(4 x 137) = 643.8 kg
Iron charged = 800 x 0.9 = 720 kg
Excess iron = (720 – 643.8) x 100 / 643.8 = 11.84%
Ex. 5.3) Chlorobenzene is nitrated using a mixture of nitric acid and sulphuric acid. During
the pilot plant studies, a charge consisted of 100 kg chlorobenzene (CB), 106.5 kg 65.5%
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(by mass) nitric acid, and l08.0 kg 93.6% (by mass) sulphuric acid. After two hours of
operation, the final mixture was analyzed. It was found that the final product contained 2%
unreacted chlorobenzene. Also, the product distribution was found to be 66% p-
nitrochlorobenzene (p-NCB) and 34% o-nitrochlorobenzene (o-NCB)
Calculate: (a) the analysis of charge, (b) the percentage conversion of chlorobenzene, and
(c) the composition of the product mixture.
Basis: 100 kg chlorobenzene
The charge consists of chlorobenzene and mixed acid.
HNO3 in the charge = 106.5 x 0.655 = 69.758
H2SO4 in the charge = 108 x 0.936 = 101.088 kg
Water in the charge = l06.5 x 0.345 + 108.0 x 0.064 = 43.654 kg
The analysis of the reactants can be tabulated as shown in Table 4. 1.
Composition of Feed
Component Molar mass Charge, kg Mass
%
Chlorobenzene 112.5 100.000 31.80
HNO3 63.0 69.758 22.18
H2SO4 98.0 101.088 32.14
H2O 18.0 43.654 13.88
Total 314.500 100.00
The reactions taking place in the reactor are:
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PPP_DOTSUK
Cl Cl
NO2
+ HNO3 = + H2O
Chlorobenzene Nitric acid o - NCB water
Cl Cl
+ HNO3 = + H2O
NO2
Chlorobenzene Nitric acid p - NCB water
As given in the problem, the yield of p-NCB is 66%. Since the total charge (mass) remains
constant
Unreacted CB in the product = 314.5 x 0.02 = 6.29 kg
Amount of CB that has reacted = 100 – 6.29 = 93.71 kg
Conversion of CB = (93.71/100) x 100 = 93.71%
Sulphuric acid remains unreacted,
From the reaction, it is clear that,
1 kmol CB ≡ 1 kmol HNO3
≡ 1 kmol NCB
≡ 1 kmol H2O
Thus, 63 kg HNO3 will be consumed for converting 112.5 kg CB into NCB
Total HNO3 consumed = (63/112.5) x 93.71 = 52.478 kg
Unreacted HNO3 = 69.758 - 52.478 = 17.28 kg

Total NCB produced = (157.5/112.5)x 93.71 = 131.194 kg
p-NCB = 0.66 x 131.194 = 6.5S8 kg
o-NCB = 0.34 x 131.194 = 44.606 kg
Water produced = (18/112.5) x 93.71 = 14.994 kg
Total water in the product mixture = 43.654 + 14.994 = 58.648 kg
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The final analysis of the products is given in Table below:

Composition of Product Stream
Component Mass, kg Mass %
CB 6.290 2.00
p-NCB 86.588 27.53
o-NCB 44.606 14.18
HNO3 17.280 5.49
H2SO4 10 1.088 32.15
H2O 58.648 18.65
Total 314.500 100.00
Ex 5.4) The analysis of water has been given in Example 4.36. The same water is treated by
the lime-soda process. Calculate the theoretical (stoichiometric) amounts of chemicals
required for the treatment.
Solution Basis: 1 L of water
Since the water contains only temporary hardness, only lime addition is required The
reactions of lime with bicarbonates are:
Ca(HCO3)2 + CaO = 2CaCO3 + H2O
Mg(HCO3)2 + CaO = MgCO3 + CaCO3 + H2O
2 NaHCO3 + CaO = CaCO3 + Na2CO3 + H2O
From these equations, it is clear that 1 mole of lime is required for each mole of Ca(HCO 3)2
or Mg(MCO3)2 and for every 2 moles of NaHCO3
56 mg CaO ≡ 162 mg Ca(HCO3)2
≡ 146.3 mg Mg(HCO3)2
≡ 2 x 84 mg NaHCO3
Total lime required = (56/162) x 257.6 + (56/146.3) x 329.2 + (56/168) x 11.1 = 218.7 mg
Thus, theoretically, the lime dosage of the order of 218.7 mg/L is required to treat the
water. The dosage can be calculated by knowing the bicarbonate alkalinity in terms of
equivalent CaCO3
1 mole CaCO3 ≡ 1 mole CaO
100 mg CaCO3 ≡ 56 mg CaO
Lime required = (56/100) x 390.6 = 218.7 mg/L
Ex. 5.5) Tallow is essentially glyceryltristearates. It is desired to saponify the tallow with
caustic soda. For 100 kg tallow, calculate: (a) the theoretical requirement of caustic soda,
and (b) the amount of glycerine liberated.
Solution Basis: 100 kg tallow
The saponification reaction is
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CH2COOCH35C17 CH2OH
CHOOCH35C17 + 3 NaOH = 3 C17H35C00Na + CHOH
CH2COOCH35C1 CH2OH
Glyceryltristearate Caustic soda Sodium stearate Glycerine
890 3 x 40 3 x 306 92
3 x 40
caustic soda required = [ ] x 100 = 13.48 kg
890
92
Glycerine liberated = ( ) x 100 = 10.34 kg
890
Ex. 5.6) In manufacture of chlorine, feed containing hydrochloric acid and air are fed to
oxidizer. The product gas leaving the oxidizer are found to contain 13.2% HCl, 6.3% O2,
42.9% N2, 30% Cl2 and 7.6% H2O (by weight).
Calculate: -
a) Percent excess air used.
b) Composition by weight of gases entering the oxidizer.
c) Degree of completion of oxidation
Solution:
Basis: 100Kg of product leaving oxidizer
Reaction: 4HCl + O2 → 2Cl2 + 2H2O

Product gas contain 13.2 kg HCl, 6.3 kg O2, 42.9 kg N2, 30 kg Cl2 and 7.6 Kg H2O.
Quantity of HCl unreacted = 13.2 kg
We have, 4 Kmol HCl = 2 kmol Cl2
i.e. 146 Kg HCl = 142 Kg Cl2
Quantity of HCl reacted to produce 30 Kg Cl2 = 146/142 x 30 = 30.85 Kg
Material balance of HCl:
HCl charged = HCl reacted + HCL unreacted
= 30.85 + 13.2
=44.05 Kg
Moles of HCL charged = 44.05/36.5 = 1.2068 Kmol
We have,
4 Kmol of HCL ≡ 1 Kmol of O2
HCl 146 kg ≡ 32 kg of O2
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Quantity of O2 reacted = 32/146 x 30.85 = 6.76 Kg.

Material balance of O2:
O2 charged = O2 reacted + O2 unreacted = 6.76 + 6.3 = 13.06 Kg.
N2 charged = N2 in product gas = 42.9Kg.
Air charged = O2 + N2 in air charged = 13.06 + 42.9 = 55.96 Kg.
Moles air charged or supplied = 55.96/28.84 = 1.94 Kmol.
Theoretically O2 required for
1.2086Kmol of HCL = ¼ x 1.2068 = 0.3017 Kmol
Theoretically air required = 0.3017 x 100/21 = 1.45 Kmol.
% excess air = (Actually supplied – theoretically required) / (theoretically required) * 100
= (1.94-1.45)/1.45 x 100 = 33.8 %
Composition of Gas entering the reactors
Component Quantity in kg Weight %
HCl 44.05 44.05
O2 13.06 13.06
N2 42.90 42.90
Total 100 100
Degree of Completion of oxidation is nothing but percentage conversion of HClL gas

Degree of completion of oxidation = (30.85 /44.05) x 100 = 70%
i.e. oxidation is 70% complete.
Ex. 5.7) In production of chlorine gas by oxidation of hydrochloric acid gas, air is used 30%
excess of that theoretically required. Based on 4 kmol HCL, calculate: a) weight ratio of air
to HCL gas in feed. B) If oxidation is 80% complete, find the composition of product stream
on mole basis.
Solution:
Basis: 4 kmol of HCl fed to reactor

Reaction: 4HCl + O2 → 2Cl2 + 2 H2O
From reaction,
4 kmol HCl ≡ 1 kmol O2
1
∴ Stoichiometric requirement of O2 = x 4 = 1 kmol
4
% excess air = % excess O2
30
O2 in air supplied = 1 [1 + ] = 1.3 kmol
100
100
∴ Air supplied = 1.3 x = 6.19 kmol
21
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PPP_DOTSUK
N2 supplied in air = 6.19 x 0.79 = 4.89 kmol

Quantity of air fed to reactor = 6.19 x 28.84 = 178.52 kg
Quantity of HCl feed = 4 x 36.5 = 146 kg
178.52
∴ Weight ratio of air to HCl feed = = 1.22: 1
146
Since oxidation is 80% complete, % conversion of HCl is 80
HCl reacted = 4 x 0.8 = 3.2 kmol
HCl unreacted = HCl fed – HCl reacted
= 4 – 3.2
1
Oxygen reacted = x 3.2 = 0.8 kmol
4
Oxygen unreacted = Oxygen in air fed – Oxygen reacted
= 1.3 – 0.8 = 0.5 kmol
2
Chlorine produced by reaction = x 3.2 = 1.6 kmol
4
2
Water produced by reaction = x 3.2 = 1.6 kmol
4
N2 being inert, kmol N2 in air fed to reactor is equal to kmol N2 in product stream.
N2 in product stream = 4.89 kmol
Analysis of product stream:

Component Quality, kmol Mole %
HCl 0.8 8.52
O2 0.5 5.32
N2 4.89 52.08
Cl2 1.6 17.04
H2O 1.6 17.04
9.36 100.00
Ex. 5.8) Phosphorous is prepared by heating a mass of calcium phosphate[ca 3(po4)2 ] , sand
(sio2) and charcoal [c] . the react ion takes place as :
Ca3(PO4)2 + 3SiO2 +5C → 3CaSiO3 + 5CO + 2P
the amount of sand used is 15 weight percent excess of that theoretically required .
calculate : a) the percentage composition of original change.
b) the amount of phosphorous produced if the reaction is 75% complete, per 100 kg of
calcium phosphate charged .
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PPP_DOTSUK
Solution :
Basis: 100 kg of calcium phosphate charged.
1 kmol of Ca3(PO4)2 = 3 kmol SiO2
= 5 katom C
i.e. 310 kg Ca3(PO4)2 = 180 kg SiO2
= 60 kg C
Theoretical requirement of sand = 180/ 310 ×100
= 58.06 Kg
Amount of sand charged = 58.6 [1+15/100]
= 66.8 Kg
Theoretical requirement of charcoal
= 60/310 × 100
= 19.35 Kg
Amount of charcoal charged =19.35 [1+35/100]
=26.12 Kg
Analysis of charge:
Component Quantity In Kg Weight %
Ca3(PO4)2 100 51 .83
Sand 66.8 34.63
charcoal 26.12 13.54
Total 192.92 100
From reaction we have,

1 kmol Ca3(PO4)2 ≡ 2 Katom P
310 Kg Ca3(PO4)2 ≡ 62 Kg P
Ca3(PO4)2 reacted = 0.75 (100)
= 75 kg
Amount of phosphorous produced per 100 Kg of phosphate charged
= 62/310 ×75 = 15 Kg
Ex. 5.9) pure CO2 may be prepared by treating limestone with aqueous sulphuric acid. The
limestone used in such a process contained CaCO 3 and MgCO3, the remainder being inert
insoluble material. The acid used contained 12% H2SO4 by weight.
The residue from the process had the following composition:
CaSO4 – 8.56%, MgSO4 – 5.23, H2SO4 – 1.05%, Inerts – 0.53%, CO2 – 0.12% and water =
84.51%
During the process the mass was warmed and CO 2 and water vapour were removed
Calculate the analysis of limestone.
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PPP_DOTSUK
(Atomic weight: Ca = 40, Mg = 24)

Solution:
Basis: 1000 kg of residue from the process

Residue Contains : 85.6 kg CaSO4, 52.3 kg MgSO4, 10.5 kg H2SO4, 5.3 kg inerts , 1.2 kg CO2,
845.1 kg water
Reactions:
CaCO3 + H2SO4 → CaSO4 + H2O + CO2
MgCO3 + H2SO4 → MgSO4 + H2O + CO2
Limestone contains CaCO3, MgCO3 and inerts
Material balance of Inerts:
Inerts in limestone = Inerts in residue = 5.3 kg
(As inerts are not affected in the process)
According to Reactions:
1 kmol CaSO4 ≡ 1 kmol CaCO3 (mole basis)
136 kg CaSO4 ≡ 100 kg CaCO3 (weight basis)
CaSO3 in limestone = (100/136) x 85.6 = 62.94 kg
1 kmol MgSO4 ≡ 1 kmol MgCO3
120 kg MgSO4 ≡ 84 kg MgCO3
MgCO3 in limestone = (84/120) x 52.3 = 36.61 kg
Analysis of Limestone :
Component Quality kg Weight %
MgCO3 36.61 34.91
CaCO3 62.94 60.02
Inerts 5.3 5.05
Total 104.85 100.00
Ex. 5.10) In the Decon process for the manufacture of chlorine a dry mixture of
hydrochloric acid gas and is passed over a heated catalyst which promotes oxidation of
acid. Air used in 30% excess of that theoretically required. Calculate the weight of air
supplied per kilogram of acid.
(Atomic weight of chlorine = 35.5, Air contains 23.2% O 2 by weight)
Solution
Basis : 1 kg of hydrochloric acid gas charged
Oxidation Reaction: 4HCl +O2 → 2Cl2 + 2H2O
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PPP_DOTSUK
Moles of acid charged = 1/ 36.5 = 0.0274 kmol

From reaction, we have,
4 kmol HCL = 1 kmol O2
O2 theoretically required for oxidation of 0.0274 kmol acid
= (1/4) x 0.0274 = 0.00685 kmol
Air is used 30% excess
O2 is supplied air = theoretically required O2 [1+ ((% excess)/ 100)]
= 0.00685 [1+ (30/100)] = 0.0089 kmol
Air contains 21% by (Volume i.e. by mole) O2
Air supplied = 0.0089 x (100/21) = 0.0424 kmol
Molecular weight of air = 28.84
Air supplied per kg of acid = kmol air x molecular weight of air
= 0.0424 x 28.84 = 1.22 kg of air per kg of acid
Ex. 5.11) Calcium carbide is produced according to the reaction

CaO+3C → CaC2 + CO
Estimate the requirement of lime and cock for production of 1000 kg of calcium carbide
with the composition of 78% CaC2, 15% CaO, 3% C and 4% other impurities.
Solution:
Basis: 1000 kg of calcium carbide production.
It contains 780kg CaC2, 150kgCaO,30kg’C’ and 40kg other impurities.
Cao+3C→CaC2+CO
1kmol CaO ≡ 1kmolCaC2
56kg CaO ≡ 64 kg CaC2
56
Amount of CaO reacted = 64×780
= 682.5 kg
CaO appearing product =150kg
Lime contains 96%CaO therefore,
682.5 +150
Lime consumption =( )
0.96
= 867.2 kg
3 katom C ≡ 1kmole CaC2
36 kg C ≡ 64 kg CaC2
36
C reacted = [64] × 780
= 438.75 kg
C in product =30 kg
C content of cock is 90%
438.75+30
Consumption of cock = ( ) = 520.83 kg.
0.90
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Ex. 5.12) A sample of dry flue gas has the following composition by volume.
CO2=13.4%, N2=80.5%, O2 =6.1%
Find the per cent excess air supplied assuming that the fuel contained no nitrogen,
The nitrogen and oxygen in the gas must have come from air.
Solution:
Basis: 100 kmol of flue gas
It contains 13.4 kmol CO2, 80.5 kmol N2 and 6.1 kmol O2.
N2 in flue gas = N2 in supplied air
= 80.5 kmol.
80.5
Amount of air supplied = 0.79
=101.9 kmol
Amount of O2 in supplied air= 0.21(101.9)
= 21.4 kmol
Amount of O2 in flue gas = 6.1 kmol
Amount of O2 consumed in combustion of fuel
=21.4 - 6.1=15.3 kmol
6.1
Per cent excess air supplied = 15.3 × 100 =39.9.
Ex. 5.13) In the manufacturing of acetic acid, acetaldehyde is oxidized over silica gel
catalyst with the help of air. The feed mixture Is passed over catalyst at 387K (114°c).The
outgoing dry gases are analyzed to contain 8.65% acetaldehyde , 14.9% acetic acid , 4.85%
carbon dioxide ,2% oxygen and 69.05% nitrogen by mole (on dry basis).in order to carry
out analysis , water was first removed from the mixture. While water removal, some of the
acetic acid is also condensed.
Calculate : (a) the % conversion of acetaldehyde , (b) the % yield , of acetic acid , (c) the
ratio of air to acetaldehyde in the incoming feed on weight basis , (d) the % removal of
acetic acid during water removal and (e) the actual analysis of the gases leaving the
reactor
Solution:
Basis : 100 kmol of outgoing dry gas.
It contains 8.56 kmol acetaldehyde, 14.9 kmol acetic acid ,4.85 kmol CO2, 2.55 kmol oxygen,
69.05 kmol N2
Reactions:
𝟏
CH3CHO + 𝟐 O2 → CH3COOH
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PPP_DOTSUK
CH3CHO + 2.5 O2 → 2CO2 + 2 H2O

N2in out going dry gas = 69.05 kmol
N2 in air supplied = N2 in out going dry gas = 69.05 kmol
Air supplied = 69.05/0.79 =87.40 kmol
O2 in air supplied = 87.40-69.05=18.35 kmol
O2 totally reacted = 18.35-2.55 =15.8 kmol
From reaction (2),
2.5 kmol of O2 ≡ 2 kmol CO2
O2 reacted for CO2 = 2.5/2×4.85 = 6.06 kmol
O2 reacted for CH3COOH =15.80 - 6.06 = 9.74 kmol
1
Acetic acid actually produced =1/2 × 9.74 = 19.48 kmol
CH3COOH reacted to CO2 = ½ ×4.85 =2.425 kmol
H3CHO reacted to CH3COOH = 1/1 ×19.48 =19.48 kmol
CH3CHO totally reacted = 2.425 + 19.48 = 21.905 kmol
CH3CHO charged =21.905 +8.65 =30.555 kmol
21.905
% conversion of acetaldehyde = 30.555 ×100 = 71.7
19.48
% yield of acetic acid =21.905 × 100 =88.93
CH3CHO charged = 30.555 kmol =30.555 ×44 =1344.42 kg
Air supplied =87.40 kmol= 87.40 × 29=2534.6 kg
Ratio of air to acetaldehyde in coming feed (weight basis)
2534.6
= 1344.42 =1.885 =1.885:1
Acetic acid produced = 19.48 kmol
Acetic acid In dry gas = 14.9 kmol
Acetic removed =19.48 × 1409 = 4.58 kmol
4.58
% removal of acetic acid = 19.48 ×100=23.51
From reaction (2), 2 kmol CO2 = 2 kmol H2O
Water produced =2/2×4.85 = 4.85 kmol.
Actual analysis of gas leaving factor:
Component Quantity, kmol Mole%
CH3CHO 8.65 7.91
CH3COOH 19.48 17.80
CO2 4.85 4.43
H2O 4.85 4.43
O2 2.55 2.33
N2 69.05 63.10
Total 109.43 100.00
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5.3) Electrochemical Reactions:
Electrochemistry is an important branch of chemistry. The chlor-alkali industry, aluminium

industry, copper industry, etc, are the typical examples of electrochemical industries.
In an electrochemical cell, the amount of an electrolyte liberated depends on the current &
time. Theoretically, the amount of current required to liberate 1g eq of an electrolyte at
each pole is the faraday (F), which is equal to 96 485.309 coulombs/mol
1 coulombs = 1 ampere. second
In actual practice, 1 faraday will liberate less than 1 g eq electrolyte. The ratio of theoretical
faraday consumption to the actual faraday consumption is defined as the current efficiency
of the cell.
It may be noted that in electrochemical reactions, only the current is important for the
liberation of the electrolyte. Hence, in most electrolytic cells, for maximum utilization of the
power, the voltage is kept as low as possible while the current is kept to its maximum.
Ex. 5.14) In an electrochemical cell, the current is passed at the rate of 1130 amperes for
18000 s through a solution containing copper sulphate. At the end of the process 1.12 m3 of
oxygen (at NTP) is collected. Find (a) amount of copper liberated, and (b) the current
efficiency of the cell.
Solution:
Basis: 1.12m3 of oxygen at NTP
At NTP, the specific volume of oxygen = 22.4 m3/kmol
Oxygen liberated = 1.12 m3 = l.12 x (1/22.4) kmol
= 50 mol = 1600 g
Equivalent mass of oxygen 16/2 = 8
Oxygen liberated = 1600/8 = 200 a eq
This electrochemical reaction taking place in the cell are:
CuSO4 = Cu++ + SO4--
At the cathode: Cu++ + 2e = SO4
At the anode: SO4-- - 2e = SO4
SO4-- + 2H2O = H2SO4 + 2OH-
2OH- = H2O + ½ OH-
Thus, 1mole of O2 ≡ 2 moles of CuSO4
Equivalent mass of Cu = (63.5/2) = 31.75
Copper deposited = (31.75 x 1600)/8 = 6350 g
Total energy passed through solution in the cell = [(1130 x 18 000) / 96485] faradays
1130 x 18 000 x 31. 7 5
Theoretical liberation of Cu= ( ) =6693.1 g
96485
Cu liberated actually 6350
Current efficiency = ( ) x 100 = ( ) x 100 = 94.87%
theorcticalliberation of eu 6693.1
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Ex. 5.15) Typical operating data on the Hooker-type diaphragm cell are as follows:
Power characteristics: 3.25 V, 15000 A
Brine feed = 26.6% NaCl by mass at 338 to 343 K (65 to 70°C)
NaOH concentration in the cell liquor = 11.0% by mass
Salt/NaOH ratio in the cell liquor = 1.4: 1.0 by mass
Temperature of the cell liquor = 360 K (87oC)
Production of NaOH = 514.1 kg/(d.cell)
Based on the above data, find: (a) the current efficiency of the cell, (b) the amounts of
chlorine and hydrogen produced from the cell, and (c) the evaporation loss (of water) in
the cell.
Solution:
Basis: 1 day operation of the cell
The reactions taking place in the cell are:
NaCl = Na+ + Cl-
H2O = H+ + OH-
Na+ + OH- = NaOH-
H+ + e = ½ H2
Cl- - e = ½ Cl2
Total energy passed through the cell = (15 000 x 3600 x 24)/96 485 = 13 431.9 faraday/d
Theoretical (expected) NaOH formation = (15000 X 3600 x 24 x 40)/(96485 x 1000)
= 537.3 kg/d
actual NaOH produced 514.1
Current efficiency = ( ) x 100 = ( ) x 100 = 95.7%
theoretical NaOH production 537.3
35.5
Chlorine produced = ( ) x 514.1 = 456.2 kg/d
40
Hydrogen produced = 514.1/40 = 12.85 kg/d
Now, 40 g NaOH ≡ 58.5 g NaCl
NaCl consumed in the reaction = (58.5/40) x 514.1 = 751.9 kg/d
Cell liquor contains 11.0% NaOH
Total cell liquor = 514.1/0.11 = 4673.6 kg/d
NaCl that remained in the cell liquor = 514.1 x 1.4 = 719.7 kg/d
Total NaCl entering the system = 751.9 + 719.7 == 1471.6 kg/d
Total original feed contains 26.6% NaCl.
Brine feed rate = 1471.6/0.266 = 5532.3 kg/d
Water consumed in the reaction = (18/40) x 514.1 = 231.3 kg/d
Hence,
Loss of water due to evaporation = 5532.3 – (4673.6 + 231.3) = 627.4 kg/d
4.8 Metallurgical Applications

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Complex reactions takes place in the furnaces where the metal is extracted from the ore. It
is difficult to treat individual reactions as seen in various examples cited above. Overall
material balances are set for getting the desired information
Ex. 5.16) A blast furnace makes pig iron containing 3.6% C, 1.4% Si and 95% Fe. The ore
used contains 80% Fe2O3, 12% SiO2 and 8% Al2O3. The coke analysis shows the presence of
10% SiO and 90%C. The flux used is pure CaCO 3. The exit gases contain 28% CO & 14%
CO2. The coke ratio is 1kg/kg pig iron. Flux is 0.4 kg/kg pig iron. Calculate per tone of pig
iron: (a) the mass of the slag made, (b) the mass of the ore used, (c) the composition of slag,
& (d) the volume of the air required at NTP.
Solution
Basis: 1 tonne (= 1000 kg) of pig iron
Coke = 1000 kg
Flux = 400 kg
Fe in the pig iron = 0.95 x 1000 = 950 kg
Fe available per kg of ore = (112/160) x 0.8 = 0.56 kg
Ore required = 950/0.56 = 1696.43 kg
Silica balance: Si in the pig iron = 0.014 x 1000 = 14 kg as Si
SiO2 present in the pig iron = (60/28) x 14 = 30 kg
SiO2 present in the ore = 1696.43 x 0.12 = 203.57 kg
SiO2 present in the coke = 0.10 x 1000 = 100 kg
SiO2 present in the slag = 203.57 + 100 - 30 = 273.57 kg
Al2O3 balance: Al2O3 present in the ore = 1696.43 x 0.08 = 135.71 kg
Al2O3 present in the slag = 35.7 kg
CaO balance:
CaO comes into the slag due to the decomposition of CaCO 3
CaCO3 fed to the furnace = 400 kg
CaO present in the slag = (56/100) x 400 = 224 kg
The composition of the slag is given in Table 4.21.
Composition of Slag
Component Mass, kg Mass %
SiO2 273.57 43.20

Al2O 135.71 21.43
CaO 224.00 35.31
Total 633.28 100.00
Air requirement:
Total carbon available
= carbon present in the coke + carbon present in the CaCO 3 - carbon left over in pip iron
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= 0.90 x 1000 + (12/100) x 400 – 36 = 912 kg as C

In the blast, the ratio of CO to CO2 is 2:1. Therefore, two-third of 912 kg C will be burnt to
CO and one third to CO2
Carbon converted to CO2 = (1/3) x 912 = 304.0 kg
Carbon converted to CO = (2/3) x 912 = 608.0 kg
Oxygen required to form CO & CO2 = 608 x (16/12) + 304 x (32/12)
= 810.68 + 810.67 = 1621.35 kg as O2
Thus, the total requirement is 1621.35 kg. However, a part of the oxygen is available from
SiO2, Fe2O3 & and CaCO3
SiO2 = Si + 02
60 28 32
Oxygen derived from SiO2 = (32/28) x 14 = 16 kg
Fe2O3 = 2 Fe + 3/2 O2
160 112 48
Oxygen derived from Fe2O3 = (1696.43 x 0.8 x 48)/160 = 407. 15 kg
CaCO3 = CaO + CO2
100 44 56
CO2 = C + O2
44 12 32
Oxygen derived from CaCO3 = 400 x 32 / 100 = 128 kg
Total oxygen available = 16 + 407.15 + 128 = 551.15 kg
Oxygen to be supplied from air = 1621.35 - 551.15 = 1070.20 kg = 33.44 kmol
Air supplied = 33.44/0.21 = 159.26 kmol
At NTP, specific volume of air = 22.414 m3/kmol
Volume of air supplied at NTP = 159.26 x 22.414 = 3569.6 m3
5.3 Recycling operation:
Recycling involves feeding back the part of stream leaving the system along with the fresh
stream entering the system. Recycling is a common practice adopted in unit operation or
unit process for:
1. increasing the yield of the product,
2. maximum utilisation of raw material and hence for avoiding wastage,
3. enrichment of the product,
4. conserving the heat,
5. improving the performance of equipment or operation itself.
Recycling operation can be presented diagrammatically as follows:
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PPP_DOTSUK
Mixed feed (M) for recycling operation is a combination of fresh feed (F) and recycle feed
(R).
∴ M = F+R
Recycled Ratio: It is the ratio of quantity of recycle feed to quantity of fresh feed.
Recycle ratio = R/F
Combined feed ratio: It is the ratio of quantity of reactant in mixed feed or mixed feed to
the quantity of same reactant in fresh feed or fresh feed itself.
M
∴ combined feed ratio =
F
If the process stream contains inerts or impurities, the recycling of such streams leads to
gradual accumulation of such material in recycle loop which in turns affect the
performance of operation as decrease in conversion or favor side reactions
In such cases, accumulation of inerts or impurities beyond certain tolerable limits can be
avoided by bleeding off/purging a fraction of recycle feed.
Purge ratio: It is the ratio of quantity of purge stream to the quantity of recycle feed. It can
also be expressed on component present in purge stream and recycle feed.
P
purge ratio =
R
Ex. 5.17) formaldehyde is produced by dehydrogenation of methanol

CH3OH→HCHO +H2
The per pass conversion is 67%. The product leaving the reactor is fed to separation unit
battery where formaldehyde is separated from methanol and hydrogen. The separated
methanol is recycled to rector .If the production rate of formaldehyde is 1000 kg/h,
calculate; (a) combined feed ratio and (b) flow rate of methanol required to the process as
fresh feed.
Solution:
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PPP_DOTSUK
Basis: 1000 kg/h of formaldehyde.

CH3OH→HCHO +H2
Let F, R and M be the kmol/h of fresh feed recycle feed and mixed feed respectively .
F+R=M
Molecular weight of formaldehyde = 30 kg/kmol
Rate of formaldehyde production =1000/30 = 33.33 kmol/h
From reaction, we have,
1 kmol CH3OH ≡ 1 kmol HCHO
CH3OH reacted = (1/1) × 33.33 = 33.33 kmol/h
Methanol as mixed feed = M kmol/h
Conversion =67 %
Methanol reacted = 0.67 M kmol/h
0.67 M = 33.33
M = 49.74 kmol/h
Unreacted methanol = 49.74 – 33.33 =16.41 kmol/h
Unreacted methanol is the methanol recycled.
R =16.41 kmol/h
Methanol as a fresh feed is equal to the methanol reacted to produce formaldehyde
=33.33 kg/h
F =33.33 kmol/h
Combined feed ratio , (M/F) =(49.74/33.33) =1.492 = 1.5
Methanol to the process as fresh feed
= 33.33 kmol/h =1066.56 kg/h
Recycle ratio, (R/F) = (16.41/33.33) = 0.492
Ex. 5.18) In synthesis of ammonia, the fresh feed containing 24.75% nitrogen,74.25%
Hydrogen & 1% inert (on mole basis) is mixed with recycle feed entering into reactor
resulted in 25% conversion to ammonia. The product mixture is passed through condenser,
where ammonia gets condensed & the remaining gases are recycled after purging small
portion of gas stream to avoid built up of inerts. The recycle stream contains 12.5 mole %
inert. Calculate (a) recycle ratio (b) purge ratio & (c) combined feed ratio.
Solution:
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PPP_DOTSUK
Basis: 100 kmol of fresh feed

It contains 24.75 kmol H2 & 1 kmol inerts.
Reaction: N2 + 3H2 → 2NH3
Let M, R, F & P be the kmol of mixed feed, recycle feed, fresh feed & purge respectively.
F+R=M (1)
The proportion of N2 to H2 anywhere in process is 1:3 (on mol basis)
Inert in recycle = 0.125 R kmol
N2 - H2 in recycle = R – 0.125 R = 0.875 R kmol
N2 - H2 in fresh feed = 100-1 = 99 kmol
N2 - H2 in mixed feed = N2 - H2 in fresh feed + N2 - H2 in recycle feed
= 99 + 0.875 R
Conversion per pass = 25%
N2 - H2 reacted = 0.25 (99 + 0.875 R) kmol
N2 - H2 unreacted = 0.75 (99 + 0.875 R) kmol
Amount of gas leaving condenser = {0.75(99 + 0.875 R) +Inerts} kmol
Inerts will be unaffected during the course of reaction & condensation
Material balance of Inerts:
{Inert in fresh feed} + {Inert in recycle feed} = Inerts in mixed feed
1 + 0.125 R = Inerts in mixed feed
Inerts in gas leaving condenser = Inerts in mixed feed
= 1 + 0.125 R
Gas leaving condenser = 0.75 (99 + 0.875 R) + (1 + 0.125 R )
= 75.25 + 0.78125 R kmol
Material balance of Gas Leaving Condenser:
[ kmol Gas Leaving condenser ] = kmol gas purged + kmol gas recycled
75.25 + 0.78125 R = P + R (2)
So as to avoid to built up of inert in recycle loop, we must have,
Inert in fresh feed = inerts in purge
Inerts in purge = 1 kmol
Conc. of inerts in gas leaving condenser, in purge, & in recycle feed is same.
Mole % inerts in purge = 12.5
1
12.5 = 𝑃 × 100
P = 8 kmol
Put value of P in equation (2) and solve for R
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∴75.25 + 0.78125 R = 8 + R
∴R = 307.43 kmol
& M = 100 + R = 407.43 kmol
R
Recycle ratio = F = 3.0743 kmol
𝑃 mole of purge
Purge ratio = 𝑅 = Moles of recycle feed
8
= 307.43 = 0.026
M 407.43
Combined feed ratio = = = 4.0743
F 100
Ex. 5.19) In synthesis of methanol, fresh feed containing 32% CO, 64% H 2 & 4% inert (by
volume) is mixed with recycle feed mixed feed entering the reactor results in 20% per pass
conservation of CO. The product stream from reactor is fed to condenser where all
methanol formed gets condensed & the gases from condensed are recycled. In order to
prevent build up of inerts of recycle loop, a small portion of gases leaving the condenser is
continuously purged. If mixed feed contains 15 mole % inerts , Calculate : (a) recycle ratio
& (b) purge ratio.
Solution:
Basis: 100 kmol/h of fresh feed.

Let F, R, M&P be kmol/h of fresh, recycle feed, mixed feed, & purge respectively.
CO in fresh feed = 32 kmol/h
H2 in fresh feed = 64 kmol/h
Inerts in fresh feed = 4 kmol/h
Inerts in mixed feed = 0.15 M kmol/h
CO + H2 in mixed feed = 0.85 M kmol/h
M=F+R (1)
M = 100 + R (2)
CO + H2 reacted = 0.20 (0.85 M)
CO + H2 unreacted = (1-0.20) (0.85 M) = 0.68 M kmol
[CO + H2 + Inert leaving condenser per hour] = 0.68 + 0.15 =0.83 M kmol
0.15 M
[mol % inerts in gas leaving condenser ] = 0.83 M × 100 = 18.07 %
For steady state operation (so as prevent build up of inerts in recycle loop above certain
limit) we must have:
Inerts in purge = inerts in fresh feed
Inerts in purge = 4 kmol
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PPP_DOTSUK
Concentration of inerts in purge, recycle & gas leaving condenser is same. In purge stream
for inerts, we have,
4
18.07 = × 100
𝑃
P = 22.15 kmol/h
Material balance for gas leaving condenser:
Gas leaving condenser = gas purged + gas recycled
0.83 M = 22.14 +R
Material balance of inerts in F, R & M:
Inerts in mixed feed = inerts in fresh feed + inerts in recycle feed
0.15M = 4 + 0.1807 R
From equation (2) we have, M = 100 + R (4)
Equation (4) become,
0.15(100 + R) = 4 + 0.1807 R
R = 358.3 kmol/h
M = 100 + R = 458.3 kmol/h
𝑅 358.3
Recycle ratio = 𝐹 = = 3.58 ≈ 3.6
100
𝑃 22.14
Purge ratio = 𝑅 = 358.3 = 0.062
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5.1) 5 kg of limestone is mixed with one kg of coke and is being burnt in a kiln with 200%
excess air. The composition of limestone and coke are given below:
Lime stone Coke
CaC03 - 84.5% Carbon -76%
MgC03 - 11.5% Ash-2l%
Inerts - 4% Moisture 3%
The calcination of CaC03 is 95% complete. Calculate the composition of lime leaving the
furnace.
5.2) In the deacon process for the manufacture of chlorine, a dry mixture of HCI gas and air
is passed over a heated catalyst which promotes oxidation of the acid. Air is used in 30%
excess of that theoretically required.
Calculate:
i) wt. of air supplied per kg acid
ii) composition by wt. of gas entering
iii) Assume 60% oxidation is completed, composition of gases leaving the chamber.
5.3) In synthesis of ammonia the fresh feed containing 24.75% N2, 74.25% H2 and 1 % inert
(on mole basis) is mixed with recycle feed. Mixed feed entering in to reactor resulted in 25
% conversion to ammonia. The product mixture is passed through condenser, where
ammonia gets condensed and the remaining gases are recycled after purging small portion
of gas stream to avoid built up inerts. The recycle stream contains 12.5 mole % inerts.
Calculate i) recycle ratio ii) purge ratio iii) combined feed ratio.
5.4) In an electro chemical reaction the current is passed at the rate of 1130 amperes for
18000 sec through a solution containing copper sulphate. At the end of process 1.12m 3 of
oxygen (at NTP) is collected. Find i) the amount of copper liberated and ii) the current
efficiency of the cell.
5.5) A gas mixture entering an NH3 convertor contains H2 and N2 in a mole ratio of 4:1.
The mole ratio of these gases in the exit stream is found to be 4.20 : 1. What volume of
entering gas measured at 500oC and 1.013 bar must be fed to the converter to produce 100
tonnes of NH3 per day?
5.6) In production of sulfur trioxide 100 kgmoles of SO2 and 200 kg moles of O2, are fed to
reactor. The product stream is found to contain 80 kgmoles SO3. Find % conversion of SO2.
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PPP_DOTSUK
5.7) In production of chlorine gas by oxidation of hydrochloric acid gas, air is used 30%
excess of that theoretically required based 4 kg mole HCl.
Calculate
i) Weight ratio of air to HCl gas in feed.
ii) If oxidation is 80% complete, find the composition of product stream on mole basis. 12
5.8) 200 kg of pure sulphur is burnt with 25 % air in excess of that required to convert all
the sulphur to SO2, 4.5% of sulphur is oxidized to SO 3 and 95.5% to SO2.The air is assumed
to be dry. Calculate the composition (mole %) of the gas leaving the burner.
5.9) Ethylene oxide is produced by oxidation of ethylene. 100 kmol of ethylene (C2H4) are
fed to the reactor and the product is found to contain 80 kmole ethylene oxide and 10 kmol
CO2. Calculate:
a) % conversion of ethylene
b) % yield of ethylene oxide.
Data:
C2H4 + 0.5O2 → C2H4O
C2H4 + 3O2 → 2CO2 + 2H2O
5.10) Phosphorous is prepared by heating a mass of Calcium phosphate [Ca 3(PO4)2], Sand
[SiO2] and charcoal [C]. The reaction takes place as
Ca3(PO4)2 + 3SiO2 + 5C → 3CaSiO3 + 5CO + 2P.
The amount of sand used is 15 wt% excess and charcoal used is 35 weight% excess of that
theoretically required.
Calculate:
a) The % composition of the original charge.
b) The amount of phosphorous produced if the reaction is 75% complete, Per 100 kg of
calcium phosphate charged.
Data:
Atomic weights P = 31, Si = 28, Ca = 40.
5.11) The analysis of the gas entering the secondary converter in a contact sulfuric acid
plant is 4% SO2, 13%O2, and 83%N2 on volume basis. The gas leaving the converter
contains 0.45% SO2 on a SO3 free basis by volume. Calculate a) the percent of SO 2 entering
the converter, getting converted to SO 3 b) the actual analysis of gases leaving the converter
on volume basis.
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PPP_DOTSUK
5.12) Exist gases from an ethylene oxide reaction had the following analysis (mol % on dry
basis).
Ethylene - 2.3, ethylene oxide - 0.9, nitrogen - 79.0, oxygen - 12.3, carbon dioxide - 5.5
Calculate.
a) Percent selectivity
b) Percent overall conversion
c) Air to ethylene mole ratio in the feed mixture.
5.13) Sodium phosphate is produced by neutralized phosphoric Acid in two stages:

Stage 1: H3PO4 + NaCO3 → Na2HPO4 + CO2 + H2O
Stage 2: Na2HPO4 + NaOH → Na3PO4 + H2O
The process is carried out as follows:
Soda ash (Na2CO3) is dissolved in water and the solution is reacted with commercial
phosphoric Acid containing 85% H3PO4 (rest water) to complete the first stage.
In the second stage disodium phosphate solution with 50% caustic soda (NaOH) resulting
in a trisodium phosphate solution having concentration of 20%
To produce 1000 kg of the trisodium phosphate; calculate
a) composition of soda ash fed
b) the ratio in which phosphoric acid (85 % ) and the soda ash solution to be mixed
c) the weight of caustic soda needed
Atomic weights P = 31, Na = 23, C = 12, O = 16, H = 1.
5.14) In a production of chlorine gas by oxidation of HCl (gas), air is used 30 % in excess of
that theoretically required. Based on 4 Kmol HCl, calculate:
i) Weight ratio of air to Hel gas in feed.
ii) If oxidation is 80% complete, find the composition product stream on mole basis.
(molecular weight of air = 29.0)
5.15) In manufacturing soda ash the wet sodium bicarbonate is dried and calcined in a
single stage.
2NaHCO3 → Na2CO3 + CO2 + H2O
In an experimental investigation wet NaHCO 3 containing 8% water is pre-mixed with dry
soda ash (Na2CO3) so as to reduce the water content to 4%, before introducing onto the
calciner. The calciner is fed with 100 kg of wet bi -carbonate per hour.
Calculate
i) kg of soda ash produced per hour as the final product.
ii) the total quantity of the off gases (containing CO 2 and H2O only) produced per hour.
ill) kg of soda ash recycled per hour.
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PPP_DOTSUK
iv) the mol ratio CO2/H2O in the off gas.
5.16) In manufacture of acetic acid by oxidation of acetaldehyde, 100 Kmol of acetaldehyde

is fed to the reactor per hour. The product leaving the reactor contains 14.81%
acetaldehyde, 59.26% acetic acid and rest oxygen on mole basis. Find the percentage
conversion of acetaldehyde. The reaction is
CH3CHO + ½ O2 → CH3COOH
5.17) In synthesis of methanol, fresh feed containing 32% CO, 64% H2, 4% inerts, 64% H2
and 4% inerts (by volume) is mixed with recycle feed. Mixed feed entering the reactor
results in 20% per pass conversion of CO. The product stream from the reactor is fed to
condenser where all methanol gets condensed and the gases from the condenser are
recycled. In order to prevent build up of inerts in recycle loop, a small portion of gases
leaving the condenser is continuously purged. If mixed feed contains 13 mole % inerts.
Calculate a) recycle ratio (b) purge ratio.
5.18) BaCl2 + Na2SO4 → BaSO4 + 2NaCl.

i) How many grams of BaCl2 will required to venet with 5.0 gram of Na2SO4
ii) How many grams of BaCl2 are required for the precipitation of 5.0 gram of BaSO 4
ill) How many grams of BaCl2 are needed to produce 5.00 gram of NaCl.
iv) How many grams of Na2SO4 are necessary for the precipitation of the barium of 5.00
gram of BaCl2.
Data -At. wt. for Ba = 137.327, S = 32.0, O =16.0, Na = 22.98, Cl = 35.45.
5.19) A phosphate rock, chiefly a mixture of Ca3(PO4)2 and inerts contains 32% P2O5 and is
treated with 95% H2SO4 to produce H3PO4:
Calculate:
i) the weight and composition of H3PO4 produced.
ii) the weight and composition of the solid residue
iii) to recover H3PO4 as 40% acid from the reacted mass, how much of H2O is to be added?
5.20) In the Deacon process for manufacturing chlorine, hydrochloric acid gas is oxidized
with air. The reaction taking place is:
4HCl + O2 → 2Cl2 + 2H2O
If the air is used excess of 30% of that theoretically required, and if the oxidation is 80%
complete, calculate the composition by volume of dry gases leaving the reaction chamber.
5.21) Nitrogen and hydrogen react under certain conditions to form ammonia, according to
the following equation:
147
PPP_DOTSUK
N2+3H2 → 2NH3
If 280 kg of nitrogen and 64.5 kg of hydrogen are brought together and allowed to react at
515oC and 300 atm. pressure and it is found that there are 38 kg mole of gases present at
equilibrium:
i) How many kg moles of nitrogen, hydrogen and ammonia are present at equilibrium?
ii) Which is the limiting reactant and which is the excess reactant?
iii) What is the amount of theoretically required hydrogen and what is the percent excess
hydrogen?
iv) What is the degree of the completion of the reaction?
5.22) Two pure organic chemicals A and B are introduced into a reactor for the purpose of
making the compound AB. The products from the reactor are sent to phase separator. From
the phase separator, the stream containing AB is withdrawn. Unreacted A is recycled and
mixed with make-up stream of A and B and fed to the reactor again. Stream flows are
adjusted so that the mole ratio of A to B is 4: 1. At the temperature and pressure employed,
this mole ratio effects complete consumption of B. 90% of B form AB. The remainder forms
A2B useless by product. A2B is incapable of further reaction. The effluent stream from the,
reactor is cooled to 20°C, at which temperature A and AB are completely immiscible. A2B,
however, is soluble in A and in AB. The distribution coefficient is K = C A/CB = 6.
where CAB = mole A2B/mole AB, and
CA = mole A2B/mole A.
Calculate the amount of all materials flowing in each stream per 100 Kg mol of desired
product All in product stream from phase separator.
5.23) Diborane, B2H6, a possible rocket propellant can be made by using lithium hydride
(LiH)
6 LiH +2BCl3 → B2H6 + 6LiCl
If you mix 200 kg of LiH with 1000 kg of BCl 3 and if you recover 45.0 kg of B2H6
Determine:
i) limiting reactant.
ii) excess reactant.
iii) % excess reactant.
iv) the degree of completion of reaction. [Li-6.94, B-1O.81, CI-35.5, H-l]
5.24) Brine on Electrolysis produces caustic soda, chlorine and hydrogen.

2 NaCI → 2 Na + Cl2
2 Na + H2O → 2 NaOH + H2
A cell is being fed with a brine solution, sp.gr. 1.19 containing 24% NaCl and produces a
caustic lye of sp.gr. 1.14 analysing 16.3% NaCl, 5.7% NaOH. The caustic lye is concentrated
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PPP_DOTSUK
to 50% NaOH during which NaCl crystallises out and is recycled. If the feed rate to the cell
be 3 X 10-2 m3 per hour, calculate:
a) How much 50% NaOH solution is produced?
b) How much NaCl is recycled?
c) How much Cl2 and N2 measured at S.T.P. are produced?
5.25) A Limestone analyses: CaCO3 -92.89 %, MgCO3 -5.41 % insoluble 1.70%

a) How many kg of CaO can be made from 5 tons of this limestone?
b) How many kg or CO2 can be recovered per kg of limestone?
c) How many kg of limestone are needed to make 1 tonne of lime?
Data:
i) Molecular weight of CaCO3 = 100.1
ii) Molecular wt. of MgCO3 = 84.32
iii) Molecular weight of CaO = 56.08
iv) Molecular wt. of MgO = 40.32
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PPP_DOTSUK
Exercise:
5.1) A pilot plant reactor was charged with 50 kg naphthalene and 200 kg (98% by mass)
H2SO4. The reaction was carried out for 3 hours at 433 K (160 oC). The reaction goes to near
completion. The product distribution was found to be 18.6% monosulphonate naphthalene
and 81.4% disulphonate (MSN) and disulphonate (DSN) products, and (b) the complete
analysis of the product. [Ans. (a) 19.51 kg MSN & 85.4 kg DSN (b) 7.81 % MSN, 34.16%
DSN, 51.47% H2SO4 & 6.56% H2O]
5.2) Dinitro-o-sec-butyl phenol (DNOSBP) is manufactured by the nitration of sec-butyl

phenol (SBP) in presence of zinc chloride and hydrogen chloride.
CH3 CH3
OH OH
C2H5 O2N C C2H5

C
+ 2HNO3 = + 2H2O
H H
SBP DNOSBP
NO2
CH3 CH3
OH OH
C2H5 O2N C C2H5

C
+ 2HNO3 = + 2H2O
H H
NO2
SBP
DNPSBP
After the reaction is complete a sample from the reactor is analyzed as follows:
Table 4.22 Analysis of Reactor Product
Component Mass
%
Nitric acid 15
sec-Butyl phenol 65
4,6 Dinitro-o-sec- butyl phenol 18
(DNOSBP) 2
150
PPP_DOTSUK
3,6 Dinitro-p-sec-butyl phenol (DNPSBP)
Calculate: (a) Conversion and (b) Yield of ortho and para products. [Ans. (a) Conversion =
41.2% (b) Yield of o-product = 90.04% and of p-product = 9.96%]
5.3) Ethyl alchohol is industrially produced by fermentation of molasses. A sample of

molasses contains 45% (mass) fermetable sugars (in the form of sucrose). The reactions
taking place in the fermenter are as follows:
C12H22O11 + H2O = C6H12O6 + C6H12O6
Sucrose d-Glucose d-fructose
C6H12O6 = 2 C2H5OH + 2 CO2
Monosaccaride Alcohol
Calculate the theoretical production of rectified spirit (having density of 0.785 kg/L) in
liters per tone of molasses. [Ans. 308.41 L]
5.4) Selective dehydrogenation of alkanes to alkenes is a well established process. In this

process, dehydrogenation of i-butane is carried out on a platinum impregnated catalyst at
50 kPa g and 773 K (500°C). The feed to the reactor is pure i-butane along with 0.75 kmol
H2 per kmol i-butane. Hydrogen stream contains 90% H2 and 10% methane (by mole).
Following reactions are known to take place.
i-C4H10 = i-C4H8 + H2
Butane i-Butylene Hydrogen
i-C4H10 = C3H6 + CH4
i-Butane Propylene Methane
literature reports 50% per pass conversion in a battery of three reactors with 88% yield of
i-butylene. Calculate the composition of the product stream leaving the final reactor.
[Ans. (mole %) i-C4H10: 21..43%, i-C3H8: 18.86%, C3H6: 257%, H2: 51.01 % and CH4: 6.11%]
5.5) In the BASF oil quench process to manufacture acetylene, pure oxygen and pure
methane are fed to the acetylene burner. The cracked gas from the burner has the following
composition:
H2: 56.5%, CH4: 5.2%, C2H4: 0.3%, C2H2: 7.5%, C3H6: 0.5%, CO: 25.8%, CO2: 4.0% and O2:
0.2% (mole% on dry basis).
Assume that formation of other compounds, such as aromatics, is negligible.
151
PPP_DOTSUK
For 100 kmol cracked gas, calculate (a) methane requirement, (b) oxygen requirement, (c)
production of water, (d) conversion of methane, and (e) yield of acetylene production.
[Ans. (a) 52.1 kmol CH4, (b) 30.95 kmol O2 (c) 27.7 kmol H2O (d) 90.02%, and (e) 31.98%]
5.6) The analysis of limestone gives 60% CaCO 3, 33.5% MgCO3 and rest inerts. It is treated
with 12% aqueous sulphuric acid (by mass) to obtain pure CO 2. An excess of 15% of the
acid over the stoichiometric amounts is used to ascertain that the reaction goes to
completion. Based on the treatment of 500 kg limestone, calculate: (a) the amount of 100%
(by mass) sulphuric acid required, (b) the amount of the residue, (c) the analysis of the
residue left in the vessel, and (d) the moles of CO2 produced.
[Ans. (a)562 kg (b) 4964.2 kg (c) CaSO 4: 8.21%, MgSO4: 4.82%, H2SO4: 1.48%, H2O: 84.84%,
Inerts 0.65% (by mass); (d) 5 kmol]
5.7) In the Deacon process for manufacturing chlorine, hydrochloric acid gas is oxidized
with air. The reaction taking place is:
4 HCl + O2 = 2 Cl2 + 2 H2O
If the air is used in excess of 30% of that theoretically required, and if the oxidation is 80%
complete, calculate the composition by volume of dry gases leaving the reaction chamber.
[Ans. HCl: 10.27%, O2: 6.42%, Cl2: 20.53%, and N2: 62.78%, (by volume)]
5.8) The gaseous reaction A = 2B + C takes place in a constant pressure reactor. Starting
with a mixture of 75% A and 25% inerts (by volume), in a specified time the volume
double. Calculate the conversion achieved. [Ans. 66.67%]
5.9) The shift reaction is a very important reaction in the gas processing industry.
CO + H2O = CO2 + H2
If a and b are the percent carbon monoxide in the dry inlet and outlet gas mixtures to and
from the shift converter respectively, prove that moles of CO converted (x) per 100 moles
of inlet gas mixture can be calculated by using the formula,
100(a − b)
x=
100 + b
5.10) The analysis of the gas entering the secondary converter in a contact sulphuric acid
plant is 4% SO2, 13% O2 and 83% N2 (on volume basis). The gas leaving the converter
contains 0.45% SO2 on SO3-frec basis (by volume). Calculate the percentage of SO2
entering the converter getting converted to SO3 [Ans. 89.35%]
5.11) A mixture of pure carbon dioxide and hydrogen is passed over a nickel catalyst. The
temperature of the catalyst bed is 588 K (315°C) and the reactor pressure is 2 MPa g. The
analysis of the gases leaving the reactor showed
152
PPP_DOTSUK
CO2:57.1%, H2: 41.1%, CH4:1.68% & CO: 0.12% (by volume) on a dry basis. The reaction
taking place in the reactor are:
CO2 + 4 H2 = CH4 + 2 H2O
and CO2 + H2 = CO + H2O
Find (a) the conversion of CO2 per pass,(b) yield of CH4 terms of CO2 reacted, and (c) the
composition of the feed (volume basis) [Ans. (a) 3.06% (b) 93.33%; (c) CO 2: 55.13%, H2:
44.87% (volume basis)]
5.12) Acetaldehyde is oxidized over silica gel with the help of air. The mixture is passed
over that catalyst at 387 K (l14°C). The outgoing dry gases are found to contain 4.85% CO2,
8.65% acetaldehyde, 14.9% acetic acid, 2.55% O2 & 69.05% N2 by volume (on dry basis).
For carrying out dry analysis, water was first removed from the, mixture. During the water
removal, some acetic acid is also condensed.
Calculate: (a) the percentage conversion of acetaldehyde, (b) the percentage yield of acetic
acid, (c) mass ratio of air to acetaldehyde in incoming feed, (d) the percentage removal of
acetic acid during the removal of water, and (e) actual analysis of the gases leaving the
reactor.
[Ans. (a) 71.7% (b) 89% (c) 1.884: I (d) 23.6% (e) COZ: 4.43%,
5.13) It is desired to produce hydrogen from methane by partial oxidation in the presence
of steam. The reactor is charged with 100kg of methane at 698K (425oC), 100kg of oxygen
at 698K (425oC) and 100kg of steam at 1253K (980oC). The product gases are assumed to
leave the reactor at 1198K (925oC) in chemical equilibrium. Based on kinetic consideration
at 1198K (925oC), the equilibrium constant value is 0.7, i.e.
(𝐲𝐂𝐎𝟐 )(𝐲𝐇𝟐 )
𝐊𝐩 =
(𝐲𝐂𝐎 )(𝐲𝐇𝟐𝐎 )
Where y stands for the mole fraction of the component. Calculate the kmol of various
components present in the product gas.
[Ans. CO2: 1.15, CO: 5.10, H2:13.65 & H2O: 4.4 all in kmol]
153
PPP_DOTSUK
6. Energy Balance on Nonreactive Processes
6.1 Introduction:
Energy is defined as a capacity a material object possesses for doing work. Industrially,
thermal-or (indirectly) electrical energy is produced by combustion of solid, liquid or
gaseous fuel. One has to be very cautious during the production and utilization of energy as
its wastage leads to reduced profits. During design of a process, we must account for
energy flowing into and out of operations and must determine overall energy requirement
of the process as a whole.
The energy requirement of the process can be calculated by writing energy balances on the
process, in much the same way as we write material balances to account for the material
entering and leaving the process.
The basis of energy balance of a particular system is the law of conservation of energy,
which states that energy can neither be created nor destroyed but transformation of
energy from one form into other is possible or the total energy of an isolated system
remains constant. This law is also called the first law of thermodynamics.
6.2 General Energy Balance Procedure:

(1) Assume suitable basis of calculation.
(2) Draw the block diagram of the process and label the streams.
(3) Determine the quantity or flow rates of all stream components with the help of
material balances.
(4) Determine the enthalpies of each stream component entering and leaving.
(5) If chemical reaction is involved wherein heat is evolved or absorbed, it must be
included in energy balance equation.
(6) If heat capacity data is provided for components involved choose the reference
temperature on which they are based for computational convenience.
6.3 Sensible Heat and Heat Capacities:

Sensible heat is the heat that must be transferred to raise or lower the temperature of a
substance or mixture of substances.
Heat Capacity is the amount of heat required to increase the temperature of one kg of
substance by 1 kg.
It is denoted by a symbol 'C'. It's unit is kJ/(kmol.K) or kJ/(kmol.K)
For pure water, heat capacity is 4.1855 kJ/(kg.K) at 288 K (15 °C)
Specific heat of the substance is the ratio of the heat capacity of a particular substance to
that of water.
153
PPP_DOTSUK
6.4 Heat capacity of gases at constant pressure:

Heat capacity at constant pressure is given by equation:
dQ = Cp.dT
Integrating the above equation between two temperatures Tl and T2
T2
Q = ∫ Cp . dT (1)
T1
6.4.1 Empirical Equation for Heat Capacities:

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 a symbol Cpo and is given by a equation:
Cpo = a + bT + cT 2 + dT 3
where T is in Kelvin, and a, b, c and d are constants.
Equation (1) becomes:

T2
Q = ∫ (a + bT + cT 2 + dT 3 )dT
T1
For n moles,
T2
Q = n ∫ (a + bT + cT 2 + dT 3 )dT
T1
b c d
∴ Q = n [a[T2 − T1 ] + [T22 − T12 ] + [T23 − T13 ] + [T24 − T14 ]] (2)
2 3 4
6.4.2 Mean Molal Heat Capacities of Gases:

Calculation of heat change during heating or cooling a gas between two temperatures with
the help of equation (2) is a lengthy procedure. To avoid it, it is convenient to use mean
molal heat capacity. Assume any arbitrary base temperature To (in K) and if T and To are
the two temperatures between which heat change is desired then 𝐂𝐩𝐦 𝐨
(mean molal heat
capacity) is given as,
T
∫T Cp0 dT
o 0
Cpm =
(T − T0 )
T
∫T (a + bT + cT 2 + dT 3 )dT
o 0
∴ Cpm =
(T − T0 )
b c d
a(T − T0 ) + 2 (T 2 − To2 ) + 3 (T 3 − To3 ) + 4 (T 4 − To4 )
o
∴ Cpm =
(T − T0 )
In most cases, To is selected as 298 K (25 C).
o
154
PPP_DOTSUK
Heat change between two temperatures, Tl and T2 with the help of Cpm o
data is calculated as
follows.
Let T2 < T1
Let Cpm1
o
and Cpm2
o
be the mean molal heat capacity of gas between T2 and To, and T1 and To.
Let Ql be the heat change between Tl and To, and Q2 be the heat change between T2 and To
then net heat change for 'n' kmol of gas is given as:
Q = Q2 - Ql
Q = n [Cpm2
o
(T2 - To) - Cpm1
o
(Tl - To)]
6.4.3 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 mixture in following
manner:
n
Cpo mix 0
= ∑ xi Cpi
i=0
Ex. 6.1) A stream of nitrogen flowing at a rate of 100 kmol/h is heated from 303 K to 373 K.
Calculate the heat that must be transferred.
Date: Cpo for nitrogen = 29.5909 – 5.141 x 10-3 T + 11.1829 x 10-6 T2 – 4.968 x 10-9 T3
Solution:
Basis: 100 kmol/h of nitrogen gas
b c d
Q = n [a[T2 − T1 ] + [T22 − T12 ] + [T23 − T13 ] + [T24 − T14 ]]
2 3 4
When n = 100 kmol/h, T2 = 373 K, T1 = 303 K
5.141 x 10−3
∴ 𝑄 = 100 [29.5909[373 − 303] − [3732 − 3032 ]
2
11.1829 x 10−6 4.968 x 10−9 4
+ [3732 − 3033 ] − [𝑇2 − 𝑇14 ]]
3 4
Q = 202587.2 kJ/h = 56.274 kJ/s = 56.274 kW
155
PPP_DOTSUK
Ex. 6.2) Heat capacity data for gaseous SO2 is given by following equation:
o −3
105
Cp = 43.458 + 10.634 x 10 T − 5.945 x 2
T
Solution:
Basis: 1 kmol pure SO2 gas.
Q = heat required
T2
Q = ∫ Cp . dT
T1
T2
−3
105
Q = n∫ (43.458 + 10.634 x 10 T − 5.945 x 2 ) dT
T1 T
10.634 x 10−3 2 1 1
= n [43.458 (T2 − T1 ) + (T2 − T12 ) + 5.945 x 105 ( − )]
2 T2 T1
When n = 1 kmol, T1 = 300 K, T2 = 1000 K
10.634 x 10−3
Q = 1 [43.458 (1000 − 300) + (10002 − 3002 )
2
1 1
+ 5.945 x 105 ( − )]
1000 300
Q = 1[30420.6 + 4838.47 – 1386] = 33873.07 kJ/kmol
Ex. 6.3) Toluene is heated from 290 K (17°C) to 350 K (77°C) at the rate of 0.25 kg/s.
Calculate the heat required to be added to toluene using constants given below
Solution:
Basis: 0.25 kg/s toluene heated from 290 K to 350 K
Molar flow rate, qm = 0.25/92 = 2.717 X 10-3 kmol/s
−3 −3
[3502 − 2902 ]
Q = 2.717 x 10 [1.8083(350 − 290) + 812.223 x 10
2
3
[350 − 290 ] 3 [3504 − 2904 ]
− 1512.67 x 10−6 + 1630.01 x 10−9 ]
3 4
= 2.717 x 10-3 [108.5 + 15594.7-9321.1+3232.9]

= 2.717 x 10-3 x 9615 kJ/s = 26.124 kW
Ex. 6.4) How much heat must be added in order to raise the temperature of a 20% (mass)
caustic soda solution from 280 K (7°C) to 360 K (87oC).
Solution:
Basis: 1 kg 20% NaOH Solution
From fig. 5.4, for 20% caustic soda solution,
Clm = 3.56 kJ/(kg .K) at 280 K
156
PPP_DOTSUK
and Clm = 3.71 kJ/(kg .K) at 360 K

(3.56 + 3.71)
Mean heat capacity, Clm = = 3.635 kJ/(kg. K)
2
Heat required to raise the temperature of 1 kg 20% NaOH solution
= 1 x 3.635 (360 - 280) = 290.8 kJ
Ex. 6.5) Chlorinated diphenyl (Diphyl A-30) is heated from 313 K (40°C) to 553K (280oC)
at the rate of 4000 kg/h in an indirectly fired heater. In this particular temperature range
the heat capacity of the fluid is given by the equation
C1 = 0.7511 + 1.465 x 10-3 T kJ/(kg.K)
Where T is in K
Also, the heat capacity data of Diphyl A-30 at 313 K (40oC) and 553 K (280oC) are 1.1807
and 1.5198 kJ/(kg.K) respectively.
Calculate the heat to be supplied to the fluid in the heater using the heat capacity equation.
Also calculate the % error involved in using the mean heat capacity data for the heat
change calculations.
Solution:
Basis: 1 kg Diphyl A-30
Sensible heat change
Q = ∫ C1 dT
533
=∫ (0.7511 + 1.465 X 10−3 )dT
313
−3
(5532 − 3132 )
= 0.7511(533 − 313) + 1.465 x 10
2
= 180.26 + 152.24 = 332.50 kJ/kg
For the mass flow rate of 4000 kg/h,
∅ = 4000 x 332.50 = 133 x 104 kJ/h = 369.44 kW
Clm = (1.l807+1.5198) / 2 = 1.3503 kJ/(kg K)
∅ = Clm (T2 - T1)
= 1.3503 (553 - 313) = 324.06 kJ/kg
324.06 − 332.50
% error = [ ] x 100 = −2.54
332.50
The heat capacities of solids are lower than liquids and increase with the, increase in
temperature as is the case with liquids or gases.
Ex. 6.6) Pyrites fines are roasted in a chamber plant for making sulphuric acid. The gases
leaving the roaster are at 775 K (502°C) and have molar composition SO2 7.09%, O2
10.55%, SO3 0.45% and N2 81.91%. Calculate the heat content of 1 kmol of gas mixture over
298.15 K (25°C), using the heat capacity data
157
PPP_DOTSUK
Basis: 1 kmol gas mixture,

(a) In the first instance, take the value of Cmp
o
= f(T)
T2
o
Heat change Q = ∫ Cmpmix
dT
T1
Sulphur dioxide:
ySO Compmix = 0.709 (24.7706 + 62.9481 x 10-3 T - 44.2582 X 10-6 T2 + 11.122 x 10-9 T3)
2
= 1.7562 + 4.4630 x 10-3 T - 3.1379 X 10-6 T2 + 0.7885 x 10-9 T3
Oxygen:
yO Compmix = O.1055 (26.0257 + 11.7551 x 10-3 T - 2.3426 x 10-6 T2 - 0.5623 x 10-9 T3
2
= 2.7457 + 1.2402 x 10-3 T - 0.2471 x 10-6 T2 - 0.0593 x 10-9 T3
Sulphur trioxide:
ySO Compmix = 0.0045 (22.0376 +121.624 x 10-3 T - 91.8673 x 10-6 T2 + 24.3691 x 10-9 T3)
3
= 0.0992 + 0.5473 x 10-3 T - 0.4134 x 10-6 T2 + 0.1097 x 10-9 T3
Nitrogen:
yN Compmix = 0.8191 (29.5909 – 5.141 x 10-3 T + 13.1829 x 10-6 T2 – 4.968 x 10-9 T3
2
= 24.2379 – 4.2110 x 10-3 T – 10.7891 x 10-6 T2 – 4.0693 x 10-9 T3
Summing up
∑ yi Compi = 28.833 + 2.0395 x 10-3 T + 6.9997 x 10-6 T2 - 3.2304 x 10-9 T3.
T1 = 298.15 K and T2 = 775 K
[T22 − T12 ] [T23 − T13 ]
Q = 28.833(T2 − T1 ) + 2.0395 x 10−3 + 6.9997 x 10−6
2 3
[T 4 4]
2 − T1
− 3.2304 x 10−9
4
= 13749.0 + 536.4 + 1024.2 – 285.0
= 15 024.6 kJ/mol
Ex. 6.7) A mixture of aniline and water, containing 11.8 (mass %) aniline, is subcooled in
the overhead condenser of the distillation column from 373 K to 313K (100 to 40oC) with
the help of cooling water at the rate 8000 kg/h. Find the heat removal rate of the sub-
cooling zone of the condenser.
Solution:
Basis: 8000 kg/h mixture is to be cooled.
Aniline and water are practically immiscible in each other and hence the additivity rule can
be used for calculations.
aniline in the mixture = 0.118 x 8000 = 944 kg/h = kmol/h
water in the mixture = 8000 – 944 = 392 kmol/h
T1 = 373 K and T2 = 313 K
Heat extraction rate
158
PPP_DOTSUK
(T12 − T22 )
−3 −6
(T13 − T23 )
Q = 10.151 [206.27(T1 − T2 ) − 211.5065 x 10 + 564.2902 x 10 ]
2 3
(T12 − T22 )
+ 392 [50.845(T1 − T2 ) + 213.08 x 10−3
2
(T13 − T23 ) (T14 − T24 )
− 631.398 x 10−6 + 648.746 x 10−9 ]
3 24
= 10.151 (12376.2-4352.8+393.4) + 392 (3050.7 + 4385.2 – 4468.4 + 1581.4)
= 121.982 + 1783 168.8
= 1905 151.3 kJ/h = 529.21 kW
Ex. 6.8) A stream flowing at rate of 15000 mol/h containing 25 mole % N2 and 75 mole %
H2 is to be heated from 298K (25°c) to 473K (200°c). Calculate the heat that must be
transferred using C°p data given below:
C°p =a+bT+cT 2 +dT 3 , kJ/(Kmol.k)
Gas a b x 103 c x 106 d x 109
H2 29.5909 -5.41 13.1829 -4.968
N2 28.6105 1.0194 -0.1476 0.769
Solution:
Basis: 15000mol/h of N2 − H2 mixture
Molal flow rate of gas mixture = 5 Kmol/h
25
XN2 = 100 =0.25
75
XH2 = 100 =0.75
C°p mix = Σ C°p mix .xi = xN2 C°p N2 + xH2 C°p H2
=0.25(29.5909-5.141 x 10−3 T+13.1829 x 10−6 T 2 -4.968 x 10−9 T 3 )
+0.75(28.6105+1.0194 x 10−3 T-0.1476 x 10−6 T 2 + 0.769 x 10−9 T 3 )
=28.8556-0.5207 x 10−3 T+3.185 x T 2 − 0.6652 x 10−9 T 3
Q = Heat transferred
T
= n∫T 2 C°P mix .dT
1
T
= n∫T 2(28.8556-0.5207 x 10-3T+3.185 x10-6 T2 – 0.6652 x 10-9T3) dT
1
(T12 − T22 ) (T13 − T23 )
Q = n [28.8556(T1 − T2 ) − 0.5207 x 10−3 + 3.185 x 10−6
2 3
(T14 − T24 )
− 0.6652 x 10−9 ]
4
Where, n=15 Kmol/h, T1 = 298 K, T2 = 473 K
159
PPP_DOTSUK
−3
[4732 − 2982 ] −6
[4733 − 2983 ]
Q = 15 [28.8556(473 − 298) − 0.5207 x 10 + 3.185 x 10
2 3
[4734 − 2984 ]
− 0.6652 x 10−9 ]
4
= 15(5049.73 - 35.13 + 84.25 - 7.01)
=76377.6 KJ/h =21.216 kJ/s = 21.216kW
Ex 6.9) A natural gas has the following composition on mole basis:

CH4 =84%, C2H6=13%, and N2=3%
Calculate the heat to be added to heat 10 kmol of natural gas 298 K(250C) to
523K(2500C) using heat capacity data given below:
C0p =a+bT+cT2+Dt3, kJ/(kmol.K)
Gas a b x 103 c x 106 d x 109
CH4 19.2494 52.1135 11.973 -11.3173
C2H6 5-4129 178.0872 - 67.3749 8.7147
N2 29.5909 -5.141 13.1829 -4.968
Solution:
Basis: 10 kmol of natural gas.
C0 p mix = ∑xi C0pi
XCH4 =84/100=0.84
XC2H6 =13/100=0.13
XN2 =3/100=0.03
XCH4 . C PCH4
0 =0.84(19.2493+52.1135 x 10-3T+11.973 x 10-6T-11.3173 x 10-9T3)
=16.1695+43.7753 x 10-3T+10.057 x 10-6T2-9.5068 x 10-9T3
XC2H5 . C0P C2H6 =0.13(5.4129+178.O872 x 10-3T-67.3749 x 10-6T2+8.7147 x 10-9T3)
=0.7037+23.1513 x 10-3T-8.7587 x 10-6T2+1.1329 x 10-9T3)
XN2 . COPN2 =0.03(29.5909-5.141 x 10-3T+13.1829 x 10-6T2-4.968 x 10-9T3)
=0.8877-0.1542 x 10-3T+0.3955 x 10-6T2-0.1490 x 10-9T3
COP mix = XCH4 .C0PCH4 + XC2H5. C0P C2H6 + XN2 . COPN2
=(16.1695+43.7753 x 10-3T+10.057 x 10-6T2-9.5065 x 10-9T3)
+(0.7037+23.1513 x 10-3T-8.7587 x 10-6T2+1.1329 x 10-9T3)
+ (0.8877-0.1542 x 10-3T+0.3955 x 10-6T2-8.5226 x 10-9T3)
Q =Heat to be added
𝑇2
= n ∫𝑇1 𝐶 OP mix dT
𝑇2
= n ∫𝑇1 (17.7609+66.7724 x 10-3T+1.6938 x 10-6T2-8.5226 x 10-9T3) dT
160
PPP_DOTSUK
−3
(T12 − T22 ) −6
(T13 − T23 )
Q = n [17.0609(T1 − T2 ) + 66.7724 x 10 + 1.6938 x 10
2 3
(T14 − T24 )
− 8.5226 x 10−9 ]
4
Where, n = 10 Kmol, T1= 298 K , T2=523 K

[5232 − 2982 ]
Q = 10 [17.7609(523 − 298) + 66.7724 x 10−3
2
3 3
[523 − 298 ] [5234 − 2984 ]
−6 −9
+ 1.6938 x 10 − 8.5226 x 10 ]
3 4
= 10(3996.20 + 6167.26 + 65.83 – 142.61)

= 100866.8 kJ
Ex. 6.10) A natural gas has following composition on mole basis:
CH4=84%, C2H6=13% and N2=3%.
Calculate:
The heat added to heat 2 kmol of gas mixture from 311K (380) to 533K (2600C)
(b) The heat to be added to heat 200 kg of natural gas from 311K ( 380C) to 533 K (2600C)
Data: C0pm values in kJ/kmolK
Gas C0pm (311-298K) C0pm (533-298)
CH4 36.0483 41.7800
C2H6 53.5240 67.4954
N2 29.1317 29.3578
Solution:
Basis: 2 kmol of natural gas
Mole fractions:
XCH4 = 84/100 = 0.84, XC2H6 = 13/100 = 0.13, XN2 = 3/100 = 0.003
C0pm (mix)1 = Mean molal heat capacity of mixture between 311-298K
= ∑ xi C0pmi
= 0.84×36.0483 + 0.13×53.5240 +0.003 ×29.1317
= 38.1126 kJ/kmol.K
C pm (mix)2
0 = Mean molal heat capacity of mixture between 533-298K
= ∑ xi C0pmi
= 0.84×41.78 + 0.13×67.4954 +0.003 ×29.357
= 44.7503 kJ/ kmol.K
Q = Heat added
= n [C0pm (mix)2 (T2 – T0) - C0pm (mix)1(T2 – T0)]
Where n = 2 kmol, T1 = 311K, T2 = 533K
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Q =2[44.7503(533-298) - 38.1126(311-298)]
Q = 2(10516.32-495.46)
= 20041.72 kJ
Basis: 200 Kg of natural gas
Mavg of gas = XCH4.MCH4+XC2H6.MC2H6+XN2.MN2
= 0.84×16+0.13×30+0.03×28
= 18.18
Moles of natural gas = 200/18.18 = 11 kmol.
Q = Heat added
= n [C0pm (mix)2 (T2 – T0) - C0pm (mix)1(T2 – T0)]
= 11[44.7503(533-298) - 38.1126(311-298)]
= 110236
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6.5 Phase Change Operation:

Phase changes such as fusion, vaporization and condensation are accompanied by large
changes in enthalpy. When matter undergoes a phase change (vapour to liquid, liquid to
solid etc.), the enthalpy change associated with unit amount of matter at constant
temperature and pressure is known as the latent heat of phase change.
When matter changes from one phase to another, the latent heat is either absorbed or
rejected. For example, ice melts at 273 K (0 °C) by supplying heat to produce water.
Similarly water at 101.325 kPa and 373 K (100°C) produces vapour if heat is continuously
supplied to it.
6.5.1 Latent heats of phase changes are defined as follows:

1. Latent heat of vaporization:
It is the heat required to vaporize a unit amount of liquid at constant temperature and
pressure or it is the heat removed to condense a unit amount of vapour into liquid at
constant temperature and pressure. The condensation is a reverse of vaporisation and
hence, latent heat of condensation must be the negative of the latent heat of vaporisation.
2. Latent heat of fusion:

It is the heat required to melt a unit amount of solid to liquid or removed to convert a unit
amount of liquid into solid at constant temperature and pressure.
3. Latent heat of sublimation:

It is the heat required to vaporize a unit amount of solid at constant temperature and
pressure.
Latent heats are generally expressed in kJ/kg. The latent heat of phase change does vary
considerably with temperature but hardly varies at all with pressure at the transition point.
6.5.2 Energy Balance during Phase Change Operation:

Suppose vapour at its saturation temperature (Ts) and pressure (P) is used to heat process
stream and if condensed liquid is not subcooled, then
Heat removed from vapour = Heat gained by a process stream
ṁv λv = ṁp Cpp (T2 − T1 )
where,
ṁv - vapour flow rate) kg/h
λv - latent heat of condensation of vapour, kJ/kg
ṁp - mass flow rate of process stream, kg/h
Cpp - specific heat of process stream, kJ/(kg· K)
T2 and Tl - final and initial temperature of process stream.
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PPP_DOTSUK
If condensed vapours are subcooled to temperature T then:

ṁv λv + ṁc Cpp (Ts − T) = ṁp Cpp (T2 − T1 )
Where,
ṁc - mass flow rate of condensed liquid, kglh
Cpp - specific heat of condensed liquid, kJ/(kg· K) c i.e. latent as well as sensible heat will be
transferred to process stream.
Ex. 6.11) Tin is melted in an open pan using a jacket. The jacket is fed with the vapours of
an eutectic mixture of diphenyl-diphenyl oxide at 171 kPa.a. Tin is fed to the pan at 303K
(30°C). Calculate the quantity of eutectic mixture of the diphenyl-diphenyl oxide condensed
per 100 kg of tin melted at its melting temperature. Assume no subcooling of vapours.
Data for Tin:
Molar mass, M = 118.7
Melting point = 505 K
Latent heat of fusion, λf = 7201 kJ/kmol
Heat capacity of solid tin, Cms = 21.14 + 0.02T kJ/(kmol.K)
where T is in K.
Solution:
Basis: 100 kg tin
For melting tin, the temperature of tin must be raised from 303K to the melting point
(505K). At the melting point, the heat of fusion must be supplied to melt it.
Sensible heat for raising the temperature,
T2
Q1 = n ∫ Cms dT
T1
100
n= = 0.8425 kmol
118.70
T1 = 303K, T2 = 505K
T2
Q1 = 0.8425 ∫ (21.14 + 0.02T) dT = 4972.9 kJ
T1
Latent heat supply
Q2 = n x λf = 0.8425 x 7201 = 6066.8 kJ
Q = Q1 + Q2
= 4972.9 + 6066.8
= 11 039.7 kJ
This amount of heat is supplied by condensation of the diphenyl-diphenyl oxide vapours at
171 kPa. At this pressure, latent heat, λv = 278 kJ/kg.
Since no subcooling is allowed, only latent heat transfer takes place.
11039.7
Amount of vapour condensed = = 39.7 kg
278
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Ex. 6.12) 100 kg/h of methanol liquid at a temperature of 303 K (300C) is to obtained by
Removing heat from saturated methanol vapour. Find out the amount of heat to be
removed in this case.
Data: Boiling point of methanol =337.8 (64.80C)
Latent heat of condensation of methanol =1101.7kJ/kg
Specific heat of methanol =2.7235kJ/(kg.K)
Solution:
Basis: 100kg/h of liquid methanol.
Q =Heat to be removed,
= ṁ λ + mC(TB -T)
Where, ṁ=100 kg/h, T=303K , TB=337.8 K, C=2.7235kJ/(kg.K), λ=1101.7 kJ/kg
Q = 100 x 1101.1 +100 x 2.7235 x (337.8 - 303)
= 11967.78 kJ/h
= 33.235 kJ/s = 33.235 kW
Assignment No. 5) 6b & 7a (S-175), 6a (S-481), 5 (H-32), 6 & 7 (Q-271), 7 (O-281), 6 & 7 (K-
42)
165
PPP_DOTSUK
Question from theory examination:
6.1) Tin is melted in an open pan using a jacket. The jacket is fed with vapors of an eutectic
mixture of diphenyl-diphenyl oxide at 171 KPa.a. Tin is fed to the pan at 303 k. Calculate
the quantity of eutectic mixture of the diphenyl-dipheynl oxide condensed per 100 kg of tin
melted at its melting point temperature. Assume no subcooling of vapors.
Data- Mo1.wt. = 118.7
melting point = 505 k.
latent heat of furon dF - 7201 kJ/kmol
heat capacity of tin, C = 21.14 + 0.02 T kJ/kmole k.
6.2) One kg of water is heated from 250 k to 400 k at one standard atmosphere pressure.
How much heat is required for this? The mean heat capacities of ice between 250 k and 273
k is 2.037 kJ/kg k, the mean heat capacity of water between 273 k and 373 k is 75.726
kJ/kg k and the heat capacity of water vapor (kJ/kmol k) is
Cp = 30.475 + 9.652 x 10-3T + 1.189 x 10-6T2.
Where T is in k.
The latent heat of fusion and vaporization of water are respectively, 6012 kJ/kmol and
40608 kJ/kmol.
6.3) A stream of nitrogen flowing at a rate of 100 kgmole/h is heated from 30oC to 100oC.
Calculate the heat must be transferred.
Data:
Cpo for nitrogen = 6.457 + 1.389 x 10-3T – 0.069 x 10-6 T2
6.4) At what rate in Kcal/hr must heat be removed from a saturated methanol vapor (B.P.
64.7°C) to generate 100 kg/h of methanol liquid at a temperature of 30oC?
Data:
i) Latent heat of condensation of methanol = 263.4 Kcal/kg
ii) Sp. heat of CH3OH = 0.6505 Kcal/kgoC.
6.5) Calculate the heat that must be added to 3 kg mole air to heat it from 25°C to 200°e.
Data: CPm(200 - 25°C) for air = 7.021 kcal/kg mole K.
6.6) Pure ethylene is heated from 30°C to 250oC at atmospheric pressure. Calculate the heat
added per kmol ethylene using data given below
Cpo = 4.1261 + 155.0213 x 10-3 T - 81.5455 x 10-6 T2 + 16.9755 x 10-9 T3
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PPP_DOTSUK
6.7) Chlorinated diphenyl is heated from 40oC to 280oC at the rate of 4000 kg/h in an
indirectly fired heater. The heat capacity of the fluid is given by the equation
C = 0.7511 + 1.465 x 10-3 T KJ/Kg K
where T is in Kelvin.
Calculate the heat to be supplied to the fluid in the heater using the heat capacity equation.
6.8) A solution containing 3 kg salt per 100 kg of solution in evaporated to 15% in an

evaporator. The heat capacity of the solution 4100.32 J/Kg°C and that of the 15% solution
is 3765.6 J/Kg°C. The feed temperature is 20°C. Boiling point in the evaporator is 104°C. It
requires 2259360 J to evaporate 1 kg of water from the boiling solution.
The steam gives up only its latent heat of vaporization 2196 600 J/kg.
How many kg of steam is required per kg of feed?
6.9) A stream at a rate of 15000 mol/hr containing 25 mole % N2 and 75 mole % H2 is to be

heated from 25 to 200oC. Calculate heat that must be transferred using Cpo data given
below:
Cpo = a + bT + cT2 + dT3
Gas a bx103 cx106 dx109
N2 25.5909 -5.41 13.1829 -4.968
H2 28.6105 1.0194 - 0.1476 0.769
6.10) SO3 has a molal heat capacity of

Cp = 34.33 + 42.86 x l0-3 T - 13.21 X 10-6 T2
where Cp is in J/mol K and T is absolute temp.
i) Calculate the true molal heat capacity at 373.16 K
ii) Calculate the mean molal heat capacity between the temperatures 273.16 K and 373.16
K.
iii) How many joules are needed to heat 60 kg of SO3 vapour from 273.16 K to 373.16 K?
6.11) Calculate the heat required to raise the temperature of 1 mole of ethylene gas from
370 K to 970 K at the standard pressure using the following data:
T (K) 298 500 700 1000
Cp (J/mol K) 45.58 63.47 78.54 94.49
6.12) If 50 kg of caustic soda (100% NaOH) is dissolved to form a 25% solution so that the
final temperature will be 40°C? Assume the solid NaOH to be at 0°C when added.
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PPP_DOTSUK
6.13) At what rate in Kcal/hr must heat be removed from saturated methanol vapor to
generate 100 kg/h of methanol liquid at temperature of 30°C.
Data:
i) Latent heat of condensation of methanol = 263.4 Kcal/kg
ii) Sp. heat of methanol = 0.6505 Kcal/kg °C.
6.14) A mixture of isomeric dimethyl diphenyloxide (Diphyl. DT*) is used as a thermic fluid
in a liquid phase heating system. The thermic fluid enters in an indirect fired heater at
180°C and leaves it at 260°C. The specific heat of fluid is given by:
Cp=1.485+0.00052 t kcal/kg °C where t is in oC.
i) Calculate the supply of heat in the heater per kg the liquid heated.
ii) If specific heats of Diphyl DT* at 180°C and 260°C are 0.485 and 0.527 kcal/kg°C
respectively, how much error will involved in computation of heat load using mean specific
heat value?
6.15) The heat capacity data for gaseous S02 is reported as follows;
Cpo = 10.38 + 2.54x10-3 T - 1.42x105/T
Calculate the heat required to raise the temperature of 1 kmol pure SO2 from 300 to l000 k.
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7. Energy Balance on Reactive Processes
7.1 Enthalpy Changes Accompanying Chemical Reaction:

Whenever a chemical reaction takes place, heat may either be evolved or absorbed and this
evolved or absorbed heat of reaction plays a major 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 and if enthalpy change is negative
then heat must be removed to keep reaction temperature from shooting:
a) Standard heat of Reaction:

The standard heat of reaction is the heat of reaction (i.e. enthalpy resulting from the
procedure of reaction) when both reactants and products are in their standard state i.e. at a
temperature of 298.15 K (25°C) and a pressure of 0.1 MPa.
It is represented by a symbol ∆HRo
The superscript 'o' indicates the standard state 298.15 K (25°C), 0.1 MPa.
b) Standard Heat of Formation:

It is the heat of reaction when one mole of a compound is formed from its elements in a
reaction beginning and ending at 298.15 K (250 C) and pressure of 0.1 MPa
It is expressed as ∆HRo
The heat of formation of every element in its standard state is arbitrarily taken to be zero.
c) Standard Heat of combustion:

The standard heat of combustion of substance is the heat of substance with molecular
oxygen to yield specified products with both reactants and reactants are in their standard
state' i.e. at 298.15 K (25°C) and 0.1 MPa.
d) Standard Heats of Reaction from Heats of Formation:

The standard heat of reaction may be calculated if the enthalpies of formation of all
components involved in a reaction are known in their standard state as given below:
Consider reaction,
na A + n b B = n c C + n d D
na, nb, nc and nd are number of moles of A, B, C and D respectively.
For this reaction, the standard heat of reaction, ∆HRo is defined as
∆HRo = Enthalpy of products - enthalpy of reactants
= Σ(ni . ∆Hfio )Products − Σ(ni . ∆Hfio )Reactants
= na ∆HfCo
+ nd ∆HfD o
− na ∆HfA o
− nb ∆HfB o
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PPP_DOTSUK
e) Standard Heat of Reaction from Heats of Combustion:

The standard heats of reaction where in organic compounds are involved can be
conveniently calculated with the help of standard heats of combustion of components
involved as:
∆HRo = Enthalpy of products - enthalpy of reactants
= Σ(ni . ∆Hci
o) o
Reactants − Σ(ni . ∆Hci )Products
Ex. 7.1) In the production of sulphuric acid from anhydrite, the gypsum roasted with clay
to obtain sulphur dioxide and cement clinker. The reaction proceeds as follows:
3 CaSO4(s) + SiO2(s) → 3 CaO.SiO2(g) + 3 SO2(g) + 3/2 O2(g)
Calculate the heat of reaction at 298.15 K (25°C).
Solution:
Basis: 1 mol SiO2(S) reacted
Thermodynamic Data
Component Phase ∆Hfo at 298.15 K (25°C) kJ/mol
CaSO4 Solid - 1432.7
SiO2 Solid - 903..5
3 CaO.SiO2 (amorphous) - 2879.0
SO2 Solid (clinker) - 296.81
O2 Gas 0.0
Standard heat of reaction at 298.15K,

∆HRo = Σ(ni . ∆Hfio )Products − Σ(ni . ∆Hfio )Reactants
3
= [−2879.0 + 3(−296.81) + 2 x0] − [3(−1432.7) + 1(−903.5)]
= 1432.17 kJ/mol SiO2 = 477.39 kJ/mol CaSO4
Since is positive, the reaction is highly endothermic.
Ex. 7.2) Calculate the standard heat of reaction at 298.15 K (25C) of the following
reaction.
Na2CO3 (s) + Fe2O3 (s) → Na2O. Fe2O3 (s) + CO2 (g)
Data :
Component ∆Hfo , kJ/mol at 298.15 K (25C)
Na2CO3 (s) -1130.68
Fe2O3 (s) -817.3
Na2O. Fe2O3 (s) -1412.2
CO2 (g) -393.51
Solution:
Basis: 1 mol of Na2CO3 (s).
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H0R = Standard heat of reaction

∆HRo = Σ(ni . ∆Hfio )Products − Σ(ni . ∆Hfio )Reactants
= [1 x (−1412.2) + 1 x (−393.51)] − [1 x (−1130.68) + 1 x (−817.3)]
= -1805.71 + 1947.987
= 142.27 kJ/mol Na2CO3 or kJ/mol Fe2O3
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7.2 Hess's Law of Constant Heat Summation:

It states that the enthalpy change (i.e. heat evolved or absorbed) in a particular reaction is
same whether the reaction takes place in one or several steps. The total change in enthalpy
depends on the pressure, temperature and state of aggregation and is independent of the
number of intermediate reactions.
According to this principle, the heat of reactions can be added or subtracted algebraically.
While applying this law, the stoichiometric equations are treated as algebraic equations
and the stoichiometric equation of a desired reaction can be obtained by algebraic
operations (multiplication by constants, addition and subtraction) on stoichiometric
equations of series of other reactions. For getting heat of desired reaction, same operations
are performed.
For example,
According to Hess's law,

∆H = ∆H1 + ∆H2 + ∆H3 + ∆H4
With the help of this principle, it is possible to calculate the heats of formation of
hydrocarbons as it is practically impossible to measure the same.
Ex. 7.3) Calculate the standard heat of formation of n- propanol liquid using the following
data.
Standard heat of formation of CO2 (g) = -393.51 kJ/mol
Standard heat of formation of H2O (l) = -285.83kJ/mol
Standard heat of combustion of n- propanol liquid = -2028.19 kJ/mol
Solution:
Basis: 1 of n- propanol liquid.
1. C(s) + O2 (g) → CO2 (g) ∆H1 = -393.51 kJ/mol
2. H2 (g) + 1/2 O2 (g) → H2O (l) ∆H2 = -285.83kJ/mol
3. C3H7OH (l) + 4.5 O2 (g) → 3CO2 (g) + 4H2O (l) ∆Hoc = -2028.19 kJ/mol
4.3C (s) +4 H2 (g) + 1/2 O2 (g) → C3H7OH (l) ∆H4 = ∆H C3H7OH (l)
∆H C3H7OH (l) = heat of formation of n- propanol (l) at 298 K (25oC)
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PPP_DOTSUK
Reaction (4) = 3Reaction (1) + 4 Reaction (2) – Reaction (3)

∆H C3H7OH (l) = 3∆H1 + 4 ∆H2 - ∆Hoc
=3 (-395.51) + 4(-285.83) - (-2028.19)
= -2323.85 +2028.19
= -295.66 kJ/mol
Ex. 7.4) Calculate the standard heat of formation of chloroform gas from its element using
Hess’s law.
Data :
C(s)+O2 (g) → CO2 (g) ∆H1 = -393.51 kJ/mol
H2 (g)+ ½ O2 → H2O ∆H2 = -285.83kJ/mol
½H2(g)+ ½ Cl2(g) → HCl(aq) ∆H3 = -167.57kJ/mol
CHCl3 + ½ O(g)+H2O →CO2(g)+3HCl(aq) ∆HoC = -509.95kJ/mol
Sol:
Basis: 1 mole of chloroform gas
C(s)+O2(g) → CO2(g) ∆H1 = -393.51kJ/mol
H2+½ O2(g ) → H2O ∆H2 = -285.83kJ/mol
½ H2(g)+½ CI2(g) → HCl(aq) ∆H3 = -167.57kJ/mol
CHCl3(g)+½ O2(g)+H2O → CO2(g)+3HCl(aq) ∆Hc = -509.95kJ/mol
C(s)+½ H2(g)+ 3/2Cl2(g) → CHCl3(g) ∆H4 =?
∆H4 = ∆Hof CHCl3(g)=Standard heat of formation of chloroform gas

Reaction(5) = Reaction(1) + 3Reaction(3) – Reaction(2) – Reaction(4)
∴ ∆Ho f CHCl3(g) = ∆H1 + 3∆H3 – ∆H2 – ∆Hoc
= (-393.51)+3(-167.57)-(-285.83)-(-509.95)
= (-393.51)+(-502.71)+285.83+509.95
= -896.22+795.78
=-100.44 kJ/mol
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7.3 Effect of Temperature on Heat of Reaction

When the heat balance is to be made with reactants & products at 1 bar pressure but at
temperature other than 298.15 K (25oC), the following procedure is recommended.
Consider again the reaction,

na A + n b B = n c C + n d D
There can be two possibilities. In one case, both the reactants and products are at
temperature T K, while in another case both are at different temperatures, say the reactant
enter the reactor at T1 K while products leave it at T2 K. In either case, the method of
calculation is essentially the same.
Step 1: Assume that reactants are cooled to 298.15 K (25°C). Calculate the Enthalpy of
(∆H1) of reactants at T1 K over 298.15 K (25°C).
Step 2: Calculate the standard heat of reaction (∆HRo ) using data given in Appendix IV. If
more than one reaction is taking place, the standard heat of reaction for each of them
should be calculated and summed up algebraically.
Step 3: Assume that products are heated from 298.15 K (25°C) to temperature T 2 K.
Calculate the enthalpy (∆ H2) of products at T2 K over 298.15 K (25°C).
The algebraic sum of enthalpies of all the three steps yield the heat balance, as Enthalpies
are point (state) functions.
Case (1): T 1 = T2 = T
For this case, the heat balance yields the heat of reaction at T K. It is possible to develop
empirical relation for heat of reaction at T K using the equation for heat capacity as
described below.
T1
o
∆H1 = ∫ (Σni . Cmpi ) dT
Reactants
To
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PPP_DOTSUK
T2
o
∆H2 = ∫ (Σni . Cmpi ) dT
Products
To
Now at constant pressure (at 1 bar),
o
∆HRT = ∆HRo − ∆H1 + ∆H2
Where ∆HRT
o
is the heat of reaction at reference temperature.
T2 T1
o o
∆H2 − ∆H1 = ∫ (Σni . Cmpi ) dT − ∫ (Σni . Cmpi ) dT
Products Reactants
To To
When T1 = T2 = 298.15 K & To = 0 K
o
∆HR0 = Standard heat of reaction at 0 K
= ∆HRo + (∆H2 − ∆H1 )
0
= ∆HRo + ∫298.15(∆a + ∆bT + ∆cT 2 + ∆dT 3 )dT
T
o o
∴ ∆HRT = ∆HR0 + ∫ (∆a + ∆bT + ∆cT 2 + ∆dT 3 )dT
0
o o
∆b 2 ∆c ∆d
∴ ∆HRT = ∆HR0 + ∆aT + ( ) T + ( ) T3 + ( ) T4
2 3 4
Case (b) T1 ≠ T2
The enthalpy change accompanying a chemical reaction can be expressed in terms of an overall
energy balance. Hence, for constant pressures or flow processes wherein kinetic, potential and
surface energy changes are negligible and no work is performed:
Q = ∆H = ΣHR + ΣHRo − ΣHp
Where,
ΣHR - sum of enthalpies of all materials entering the reaction relative tc standard state 298.15
K(25°C) and 0.1 MPa.
o
ΣHR - Standard heat of reactions involved.
ΣHp - Sum of enthalpies of all products relative to standard state [298.15 K (25°C) and 0.1
MPa].
Ex. 7.5) Obtain an expression relating the heat of reaction and the temperature of the
reaction
SO2(g) + ½ O2(g) = SO3(g)
Using the same expression, calculate the heat of reaction at 775 K (502 0C).
Data: Cpo = a+bT+cT2+dT3, kJ (kmol.K)
Component a b x 103 c x 106 d x 109
SO3 22.036 121.624 -91.867 24.369
SO2 24.771 62.948 -44.258 11.122
O2 26.026 11.755 -2.343 -0.562
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PPP_DOTSUK
component ∆Hfo , kJ/kmol

SO3(g) -395720
SO2(g) -296810
Solution:
Basis: 1 kmol reacted
∆a = 22.036 - 24.771 - 0.5 (26.026) = - 15.748
∆b x 10 = 121.624 - 62.948 - 0.5 (11.755) = 52.799
3
∆c x 106 = - 91.867 - (- 44.258) - 0.5 (- 2.343) = - 45.438

∆d x 109 = 24369- 11.122- 0.5 (- 0.562) = 13.528
∆HRo = 395 720- (- 296 810) = - 98 910 k.l/kmo]
0
o
∆HR0 = ∆HRo + ∫ (−15.748 + 52.799 x 10−3 T − 46.438 x 10−6 T 2
298.15
+ 13.528 x 10−9 T 3 )dT
52.799 x 10−3 46.438 x 10−6
= −98910 + 15.748 x 298.15 − ( ) (298.15)2 + ( ) (298.15)3
2 3
13.528 x 10−9
+( ) (298.15)4
4
= - 98910 + 4695 - 2347 + 410 - 27
= 96 178 kJ/kmol
o
∆HRT = 96178 − 15.748 T + 26.4 x 10−3 T 2 − 15.48 x 10−6 T 3 + 3.382 x 10−9 T 4
Substituting T = 775 K
o
∆HRT = −96178 − 12205 + 15857 − 7206 + 1220 = −98512 kJ/kmol
Ex. 7.6) Calculate the heat of reaction at 773 K(5000C) for the following reaction :
CO2(g) + 4H2(g) → CH4(g) + 2H2O(g)
ΔH R = -165.1 kJ/kmol.K
O
Heat capacity data:

C0P = a + bT + cT2 + dT3, kJ/kmol.K
Component a b×103 c×106 d×109
CO2 21.3655 64.2841 -41.0506 9.7999
H2 28.6105 1.0194 1.0194 0.769
CH4 19.2421 52.1135 11.973 -11.3173
H2O 32.4921 0.0976 13.2107 -4.5474
Solution:
Basis: 1 mol of CO2 gas.
ΔH0R = -165.1 kJ/kmol.K = -165100 J/mol
Heat of reaction at any temperature T (ΔHT) is given by ,
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PPP_DOTSUK
Δb Δc Δd
ΔHT = ΔH0 + Δa T + T2 + T3 + T4
2 3 4
Δa = [ 1×19.2494 + 2×32.4921 ] – [ 1×21.3655 + 4×28.6105 ]
= -51.5739
Δb = [ 1×52.1135 + 2×0.0976 ]×10-3 - [ 1×64.2841 + 4×1.0194 ]×10-3
= -16.089×10-3
Δc = [ 1×11.973 + 2×13.2107 ]×10-9 - [ 1×(-41.0506) + 4× (-0.1476) ]×10-9
= -32.288×10-9
Δd = [1× (-11.3173) + 2×(-4.5474)] × 10-9 –[1×9.7999 + 4 ×0.769] ×10-9
= -32.288×10-9
16.089 × 10−3 80.0354 × 10−6 32.288 × 10−9
ΔHT = ΔH0 - 51.5739 T – T2 + T2 - T4
2 3 4
= ∆H0 – 51.5739 T – 8.0445 × 10-3 T2 + 26.6784 × 10-6 T3 – 8.072 × 10-9 T4
ΔHT at 298 k (250C) = -165100J/mol
Evaluate ∆H0 by putting ΔHT = -165100 at T = 298 K
-165100 = ∆H0 – 51.5739 ×298 – 8.0445 × 10-3 × (298)2 + 26.6784 × 10-6 × (298)3 - 8.072
×10-9 × (298)4
-165100 = ∆H0 - 15441.06
∆H0 = -149658.94
Empirical equation for calculating heat of reaction J/mol at any temperature T is:
ΔHT = -149658.94 – 51.5739 T - 8.0445 × 10-3 × T2 + 26.6784 ×10-6 × T4
ΔHT =773k = heat of reaction at 773 K
= - 149658.94 – 51.5739 × 773 - 8.0445 × 10-3 × (773)2 + 26.6784 × 10-6 × (773)3
– 8.072 × 10-9 × (773)4
= -184891.94 J/mol
= -184.892 kJ/mol
Ex. 7.7) Methane is oxidized with air to produce formaldehyde as per the following
equation:
CH4 (g) + O2 (g) → HCHO (g) + H2O (g)
∆Ho R = - 283.094 KJ/mol
100 mol of methane are fed to the reactor at 311 K (38 oC), air is used 50% excess and is
supplied at 373 K (100o C). If the percent conversion is 60, calculate the heat that must be
removed for the product stream to emerge at 478 K (205 oC).
Data:
Component Copm (311-298 K) Copm (478-298 K)
CH4 36.044 40.193
N2 - 29.2866
O2 - 30.0821
HCHO - 41.2902
H2O - 34.2396
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CoPm for air (373-298 K) = 29.2908 kJ/(kmol.K)

Solution:
Basis: 100 mol of methane fed to the reactor
∆Ho R = - 283.094 KJ/mol = - 283094 J/mol
1
Theoretical O2 requirement = 1 𝑥 100 = 100 mol
50
O2 in supplied air = 100(1+100 ) = 150 mol
100
Air supplied = 150 x = 714.3 mol
21
N2 in supplied air = 714.3 – 150 = 564.3 mol
CH4 reacted = 0.60 x 100 = 60 mol
1
HCHO produced = 1 x 60 = 60 mol
1
H2O produced = 1 x 60 = 60 mol
1
O2 reacted = 1 x 60 = 60 mol
O2 unreacted = 150- 60 = 90 mol
∆H R for 60 mol CH4 reacted
o = 60 X (-283094) = -16985640 J
Enthalpy of reactants ∑ HR over 298 K (25o C)
∑ HR = nCH4 CopmCH4 (T1 – To) + nair Copmair (T1-To)
= 100 x 36.044 x (311-298) + 714.3 x 29.2908 x (373-298)
= 1616038.6J
∑ HP = Enthalpy of products over 298 K (25o C)
∑ HP = (nCH4 Co pmCH4 + nN2 Co pmN2 + nO2 Co pmO2 + nHCHO CopmHCHO + nH2O CopmH2O) x (T2 -To)
= (40x4040.193+564.3x29.2866+90x30.0821+ 60x41.2902 + 60 x34.23961) x
(478-298)
= 4567198.6 J
H = Net enthalpy change = Heat to be removed
= ∑Hp + ∑ ∆HoR - ∑ HR
= 4567198.6+ (-16985640) – 1616038.6
= - 14034480 J
= - 14034.48 kJ
Heat to be removed = 14034.48 kJ
178
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7.4 Adiabatic Process:

A process in which no heat can leave or enter the system i.e. the system does not give heat
to the surroundings nor does the system receive heat from surroundings.
Adiabatic Reaction:
It is the reaction which proceeds without loss or gain of heat. When the adiabatic reaction
is exothermic, the temperature of the product stream rises and when the adiabatic reaction
is endothermic, the temperature of product stream decreases.
Industrially important steam-hydrocarbon reforming reaction, thermal reduction of
hydrogen sulphide to sulphur, dehydrogenation of ethylbenzene, etc. are endothermic. The
dissolution of common salt in water is also endothermic. In actual industrial practice,
except for a few reactions, the reaction temperature controlled either by the addition or
removal of heat as the case may be.
Adiabatic Reaction Temperature:

It is the temperature of the products under adiabatic conditions of reaction.
Adiabatic Flame Temperature:

When a fuel is burned, a considerable amount of heat energy is released. Some of this
energy is transferred as a heat through the walls of reactor and remainder causes a rise in
temperature of the reaction products. If less amount of heat is transferred, higher will be
the product temperature. If the reactor is adiabatic, the highest achievable temperature is
reached.
This temperature is called the adiabatic flame temperature or theoretical flame
temperature.
In industrial practice, though the fuel is burned in well insulated furnaces etc. the heat loss
is bound to be there due to radiation from the surface and hence, the actual flame
temperature is less than the adiabatic/theoretical flame temperature.
Ex. 7.8) In a commercial process, chlorine is manufactured by burning hydrogen using air.
The reaction place in the burner is:
4 HCl(g) + O2(g) = 2 H2(g) + 2 Cl2(g)
For good conversion, air is used in 35% excess of that theoretically (stoichiometrically)
required. Assume that the oxidation is 80% complete and the dry air and hydrogen
chloride gas enter the burner at 298.15 K (25°C). Calculate (a) the composition of dry gases
leaving the burner and (b) the adiabatic reaction temperature
Solution:
Basis: 4 kmol hydrogen chloride gas
Theoretical O2 requirement = 1 kmol
Actual O2 supply = 1 x 1.35 = 1.35 kmol
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79
Nitrogen supply through air = 21 𝑥 1.35= 5.08 kmol
Total air supply = 1.35 + 5.08 = 6.43 kmol
Conversion in the burner is 80%.
HCI burnt = 0.8 x 4 = 3.2 kmol
Composition of Product Gas Stream
Component Product gas stream, kmol Composition on dry
Wet (ni) Dry basis (mole %)
HCl 4 – 3.2 = 0.8 0.8 9.96
O2 1.35 – 0.8 = 0.55 0.55 6.85
Cl2 0.8 x 2 = 1.6 1.60 19.93
H2O 0.8 x 2 = 1.6 -- --
N2 5.08 5.08 63.26
Total 9.63 8.03 100.00
Now assume base temperature to be 298.15 K (25°C).
Enthalpy of the reactants at 298.15 K (25°C), ΔH1 = 0 kJ
Standard heat of reaction at 298.15 K (25°C),
∆HRo = - 241.82 x 2 - 4.0 (- 92.31)
= - 114.4 kJ/mol O2 consumed
This represents the exothermic nature of the reaction.
Total heat liberated = 114.4 x 1000 x 0.8 = 91 520 kJ
Total enthalpy of product stream ΔH2 = 0 + 91 520 = 91 520 kJ
Heat Capacity Equation:

Constants for Product Gas Stream
Component ni, kmol Heat capacity equation constants
ai.ni bi.ni x 103 ci.ni x 106 ai.ni x 109
HCl 0.8 24.247 -6.087 10.609 -3.467
O2 0.55 14.314 6.465 -1.288 -0.309
Cl2 1.6 45.674 38.207 -34.181 10.356
H2O 1.6 51.987 0.127 21.137 -7.276
N2 5.08 150.322 -26.116 66.969 -25.237
Total 9.63 286.544 12.596 63.246 -25.933
Enthalpy of product stream over 298.15 K (25°C),

0
∆H2 = ∫ (286.544 + 12.596 x 10−3 T + 63.246 x 10−6 T 2 − 25.933 x 10−9 T 3 )dT
298.15
= 91520
∴ T = Adiabatic reaction temperature = 599.5 K or 326.5°C
180
PPP_DOTSUK
Ex. 7.9) Chlorine is manufactured by burning hydrogen chloride gas using air. The reaction
taking place in the burner is:
4HCl(g) + O2 → Cl2(g) +2H2O(g)
Air is used in 35% excess of that theoretical / stoichiometrically required. Assuming that
the oxidation is 80% complete and the dry air and hydrogen chloride gas enter the burner
at 298 K(25oC), calculate the adiabatic reaction temperature of the product gas stream.
Data:
Component ∆Hfo , KJ/mol
H2O(g) -241.82
HCl(g) -92.31
Heat capacity data:

C0p = a + bT + cT2 + dT3, kJ/(kmol.k)
Component a b×103 c×106 d×109
HCl 30.3088 -7.609 13.2608 -4.3336
O2 26.0257 11.7551 -2.3426 -0.5623
Cl2 28.5463 32.8795 -21.3631 6.4726
H2O 32.4921 0.0976 13.2107 -4.5474
N2 29.5909 -5.141 13.1829 -4.9680
Solution:
Basis: 4 kmol of hydrogen chloride gas entering burner.
4HCl(g) + O2(g) → 2Cl2(g) + 2H2O(g)
1
Theoretical O2 requirement = × 4 = 1 kmol
4
% excess O 2 = % excess air = 35
35
O2 in supplied air = 1× [ 1 + 100 ] = 1.35 kmol
79
N2 in supplied air = 21× 1.35 = 5.08 kmol
Oxidation is 80% complete,
HCl reacted = 0.8 × 4 = 3.2 kmol
HCl in product gas = 4 - 3.2 = 0.8 kmol
1
O2 reacted = 4× 3.2 = 0.8 kmol
O2 in product gas = 1.35 – 0.8 = 0.55 kmol
2
Cl2 in product gas = 4× 3.2 = 1.6 kmol
2
H2O in product gas = 4× 3.2 =1.6 kmol
N2 in product gas = 5.08 kmol
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PPP_DOTSUK
Enthalpy of reaction over 298 K (250 C) = 0.0 (as the reactants are at 298 K (250 C)
ΔH0R = 2ΔH0f(H2O)g - 4 ΔH0f(HCl)g As ΔH0f for both O2 and Cl2 is zero
= 2 × (-241.82) – 4 × (-92.31)
= -114.4 kJ/4 mol HCl reacted
−114.4
ΔH0R = × 3.2 × 1000 = -91520 kJ
4
Heat liberated = 91520 kJ
∑ HP = Enthalpy of product gas over 298 K (250C)
= HHCl + HCl2 + HO2 + HN2
b c d
H = n [a ( T – T0 ) + 2 ( T2 –T02 ) + 2( T3 – T03 ) + 2 ( T4 –T04 )]
T = adiabatic reaction temperature
T0 = 298 K (250 C)
0.007069 13.2608×10−6 4.3336 ×10−9
HHCL = 0.8 [30.3088 (T- 298) - (T2 – 2982) + (T3 – 2983) –
2 3 4
(T4 - 2984)]
23.8795×10−3 21.3631 ×10−6
HCL2 = 1.6 [28.5463 (T-298) + (T2 – 2982 ) – (T3 – 2983 ) +
2 3
6.4726 ×10−9
(T4 – 2984 ) ]
4
11.7551×10−3 2.3426×10−6
HO2 = 0.55 [ 26.257 (T-298) + (T2- 2982 ) - (T3 – 2983 ) –
2 3
0.5423×10−9
(T4 – 2984 ) ]
4
5.141×10−3 13.1829×10−6 4.968×10−9
HN2 = 5.08 [29.5909 (T-298) – (T2 – 2982) + (T3 -2983) –
2 3 4
(T4 – 2984)
ΔH = ∑ Hp + ∑ ΔH0R – ∑ H R
0.0 = ∑ Hp ∑ ΔH0 R - 0.0
∴ ∑ H p = -∑ H0 R
286.544 T + 6.298×10-3 T2 + 21.082 ×10-6 T3 – 6.483 ×10-9 T4 - 86456.2 = - (-91520)
286.544 T + 6.298 × 10-3 T2 + 21.082 ×10-6 T3 – 6.483 × 10-9 T4 = 177976.2
Adopting a trial and error procedure for getting LHS & RHS approximately equal by
selecting various of temperature (T) we get
T = 600.4 K
Adiabatic reaction temp. = 600.4 K (327.40C)
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Ex. 7.10) Heat of combustion of C2H5OH =-1368kJ/mol.100g of C2H5OH is completely

combusted and heat supplied to water at 298 k(25˚C) to convert it to steam at 373
K(100˚C).Find the amount of water which could be converted to steam.
Solution:
Basis: 100 g of C2H5OH
Amount of C2H5OH =100/46=2.174mol
Amount of heat liberated by combustion =1368 x 2.174
=2974 kJ
2974 x 10 3 = mCpΔT +mλ
2974 x 10 3 =m[4.187*(373-298)+2261]
Mass of water converted into steam (m) =1154.8g =1.55 kg
Assignment No. 6) 7b (S-175), 6b & 8b (S-481), 6 (H-32), 7 (Q-271), 7 (Y-487), 7b (G-23), 7b

(O-281), 7a & 7b (G-215), 8A & 8B (J-493), 7b (Z-461), 7b (Q-223), 7b (K-42)
183
PPP_DOTSUK
7.1) In the production of sulfuric acid from anhydrite, the gypsum is roasted with clay to
obtain sulphur dioxide and cement clinker. The reaction proceeds as follows:
3CaSO4 + SiO2 -+3CaO.SiO2 + 3SO2 + 3/2O2
Calculate the heat of reaction at 298.15 k.
Component ∆Hfo at 298.15 k in kJ/mol
CaSO4 - 1432.5
SiO2 - 903.5
3CaO.SiO2 - 2879
SO2 - 296.81
O2 0.0
7.2) Heat of combustion of C2H5OH = -1368 kJ/mol 100 gm of C2H5OH is completely

combusted and heat supplied to water at 298 k to convert it to steam at 373 k. Find the
amount of water which could be converted to steam.
Data: λv = 2261 kJ/mol Cp = 4.187 kJ/mol k.
7.3) Calculate the standard heat of reaction for the following reaction: (8)
C5H12 (l) + 8O2 (g) → 5CO2 (g) + 6H2O (l)
Data:
Component C5H12 (l) CO2 (g) H2O (l)
∆Hfo (cal/gmol) -41370 - 94051 - 68315
7.4) Calculate the standard heat of reaction of the following reaction

CH3(OH)(l) + ½ (O2)(g) → HCHO(g) + H2O(l)
Data component CH3(OH)(l) HCHO(g) H2O(l)

∆Hfo (cal/gmole) -57130 -27700 -68315
7.5) On the basis of the data and the chemical reactions given below, find the heat of
formation of ZnSO4 from elements
i) Zn + S (rhomb) → ZnS ∆H = - 44 kcal/kg mol.

ii) 2 ZnS + 3O2 → 2ZnO + 2SO2 ∆H = - 221.8 kcal/ kg mol
iii) 2SO2 + O2 → 2SO3 ∆H = - 46.88 kcal kg mol
iv) ZnO + SO3 → ZnSO4 ∆H = -55.10 kcal kg mol
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7.6) Calculate the standard heat of formation of chloroform gas from its elements using
Hess's Law. Data:
C(s) + O2(g) → 7CO2(g) ∆H1 = -393.51 KJ/mol
H2(g) + 0.5O2(g) →7H2O(l) ∆H2 = -285.83 KJ/mol
0.5 H2(g) + 0.5 Cl2(g) → 7HCI(aq.) ∆H3 = -167.57 KJ/mol
CHCl3(g) + 0.5O2(g) + H2O(l) →7CO2(g) + 3HCI(aq.) ∆Hco = - 509.95Kllmot
Atomic weights C =12, H = 1, CI = 35.5
7.7) Calculate the heat of formation of ethane gas at 25° C from its elements using Hess's
law. Data:
Heat of formation of CO2(g) = -393.51 KJ/mol
Heat of formation of H2O(1) = -285.83 KJ/mol
Heat of combustion of Ethane(g) at 25°C = -1560.6g KJ/mol
7.8) Pure CO is mixed with 100% excess air and burnt only 80% of CO bums. The reactants
are at 100°C and products are at 300°C. Calculate the amount of heat added or removed per
kmol of CO fed to the reactor.
Data mean metal specific heats between 25° C and ToC (given below in kJ/mol.k) are
Gas T = 100°C T= 300°C
CO 29.22 30.61
CO2 43.77
O2 29.64 43.77
N2 29.17 29.66
Standard heat of formation at 25°C in kJ/k mol/are
CO = - 110524
CO2 = - 393514
7.9) Calculate the ∆HRo of the following reaction.

2FeS2(s) + ½ O2(g) → FeZO3(s) + 4SO2(g)
Data:
Component 2FeS2(s) FeZO3(s) 4SO2(g)
∆Hf (kJ/mol)
o -178.02 -822.70 -296.81
7.10) Calculate ∆HRo for the following reaction from the ∆HFo
4NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O (g)
Data
Gas NH3 (g) O2 (g) NO (g) H2O (g)
∆HF o - 46.22 KJ 0 +90.43 KJ - 243 KJ
185
PPP_DOTSUK
7.11) Calculate the standard heat of formation of acetic acid from its elements using heat of
formation of CO2 and H2O
Data
Substance ∆Hfo KJ/mol at 298.5° K
Water (liquid) -285.83
CO2(g) -393.51
7.12) Calculate the heat of reaction at 773 K for the following reaction.
CO2(g) + 4H2(g) → 2H2O(g) + CH4(g)
Cp data
Gas a b x 103 cx106 mol
CO2 26.54 42.25 -14.29 1
H2 26.89 4.35 - 0.3265 4
H2O 29.18 14.50 -2.022 2
CH4 13.41 77.08 -18.76 1
∆HR = -165 kJ
o
7.13) Calculate the standard heat of reaction of the following reaction at 25 oC.
HCI(g) + NH3(g) → NH4Cl(S)
Data:
The standard heat of reaction are for:
HCI(g), ∆Hf25oC = - 22063 Kcal/kgmole
NH3 (g), ∆Hf 25oC = - 11040 Kcal/kgmole
NH4CI(S), ∆Hf25oC = -75380 Kcal/kgmole
7.14) Calculate the heat of reaction at 773 K for the following reaction:
CO2 (g) + 4H2 (g) → 2H2O(g) + CH4 (g)
Data.
∆Hf : CO2 (g) 393.65 KJ
H2 (g) 241.9 KJ
H2O (g) 74.89 KJ
CH4 (g) 0
Cp data
Gas a b x 103 c xl06 mol.
CO2 26.54 42.25 -14.29 1
H2 26.89 4.35 -0.3265 4
H2O 29.18 14.50 -2.2022 2
CH4 13.41 77.08 -18.76 1
186
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7.15) Suppose heat of reaction are measured experimentally for the following set of
reactions: - - -- , 2A + B → 2C; ∆Hr1o = -1000 kJ/mole
A + D → C + 3E; ∆Hr2o = - 2000 kJ/mole
Use Hess's law to show that for
B + 6E → 2D ∆Hro =+ 3000 kJ/mole.
7.16) The heat capacity data for gaseous S02 is reported as follows;
Cpo = 10.38 + 2.54x10-3 T - 1.42x105/T
Calculate the heat required to raise the temperature of 1 kmol pure SO2 from 300 to l000 k.
7.17) Calculate the standard heat of reaction at 25°C for the following reaction:
Na2CO3 (S) + Fe2O3 (S) → Na2Fe2O3 + CO2 (g)
Data:
Component ∆Hfo kCal/gmol at 25°C
Na2CO3 (S) - 269.8
Fe2O3 (S) - 195.2
Na2Fe2O3 - 337.3
CO2 (g) - 94.05
187
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8. Fuels & Combustion
8.1 Introduction:
In process industry the fuel burnt in furnaces may be solid, liquid or gas. The furnace is a
enclosed space in which heat is produced by chemical oxidation of fuel. Some of the more
common fuels are:
a) Solid fuels:
The classical fossil fuel (natural) is coal. Lignite is also found in nature. It is an earthy-
brown fuel, generally low in mineral-matter content. Wood is used as a solid fuel in many
instances. Coke, bagasse, rice husk, saw dust, etc. are other examples of synthetic solid
fuels.
b) Liquid fuels:
Crude oil obtained from sub-soil drilling is a natural liquid fuel. Gasoline (petrol), diesel oil,
alcohols, kerosene, fuel oils and other organic liquids, man-made liquid fuels. Manufacture
of biocrude from organic waste using high pressure steam is a reality on a pilot scale.
Biodiesel obtained from catalytic transesterification of vegetable oils, is emerging as a
substitute for the traditional diesel fuel.
c) Gaseous fuels:
Natural gas (and associated gas) is an important natural gaseous fuel. Coke, oven gas,
producer gas, blast-furnace gas, liquefied petroleum gas (LPG) and refinery gas are
examples of synthetic gaseous fuels. Dimethyl ether (DME) is gaining popularity as a
synthetic gaseous fuel.
The rapid reaction of a fuel with oxygen is known as combustion. In combustion operation,
the union of carbon, hydrogen and sulphur of fuel takes place with oxygen. When a fuel is
burned, the carbon in the fuel reacts to form either CO 2 or CO, hydrogen reacts to form H2O
and sulphur reacts to form SO2. The combustion is termed as complete combustion if the
products of combustion are CO2, H2O and SO2. A combustion reaction in which CO is formed
from a fuel is referred to as partial or incomplete combustion of the hydrocarbon.
The significance of combustion reactions lies in the tremendous quantities of heat released
during course of combustion process. The heat released is used to produce steam, which is
then used to drive the turbines to produce electricity. In process industry, the heat released
by burning fuel is used to supply thermal, energy. For economic reasons, air is the source of
oxygen in most combustion operations. The product gas that leaves a combustion chamber
[containing CO2, CO, H2O, O2, SO2 (SO3) and N2] is referred to as the stack gas or flue gas.
188
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8.2 Calorific Values of Fuels:

The calorific value of a fuel also known as the heating value of a fuel is the negative of the
standard heat of combustion, usually expressed per unit mass of a fuel. Since the standard
heat of combustion is always negative, the calorific value (heating value) is positive.
The calorific value of a fuel is defined as the total heat produced when a unit mass of fuel is
completely burnt with pure oxygen.
When a fuel is burnt, the hydrogen in a fuel reacts with oxygen to produce water. When
water is present in flue gas as vapour, the latent heat of vaporization is lost and hence this
quantity of heat is not available for any useful purpose.
The net calorific value (net heating value or low heating value of a fuel) is the calorific value
of a fuel which is determined by considering that the water is present in the vapour form
i.e. it is −∆Hco with H2O (g or v) as a combustion product.
The latent heat of vaporization of water can be made available for useful purpose if water
vapours are condensed. The gross-calorific value (higher heating value or gross heating
value) of a fuel is the negative of standard heat of combustion with H 2O(l) as a combustion
product. i.e. it is equal to the net calorific value of a fuel to which latent heat of water
vapours is added. The gross calorific value is abbreviated as GCV, higher heating value as
HHV, lower heating value as LHV, net calorific value as NCV and net heating value as NHV.
The NCV and GCV of the fuels are usually reported at 298 K (25 oC). These may be expressed
in kJ/kg of fuel, kJ/mol of fuel or kJ/m3 of fuel.
To calculate net calorific value of a fuel from a gross calorific value of a fuel or vice-versa
we must calculate the moles of water produced when a unit mass of the fuel is burned.
If n is the mol of water produced, then
GCV = NCV + n ∆Hv [H2O, 298 K (25oC)] kJ/mol of fuel
where ∆Hv [H2O, 298 K (25oC)] is the heat of vapor is at ion of water at 298 K (25 oC) in
kJ/mol.
The GCV calculated will be kJ/mol. If 'm' is the quantity of water produced in kg when a unit
mass of a fuel is burned and 'λ' is the latent heat of water vapours at 298 K (25 oC) in kJ/kg
then GCV and NCV of a fuel in kJ/kg of a fuel are related by equation:
GCV = NCV + mλ
Latent heat of water vapours, A, at 298 K (25oC) is 2442.5 kJ/kg.
(wt % hydrogen)(9)(λ)
GCV = NCV +
100
189
PPP_DOTSUK
If a fuel contains a mixture of combustible substances, its heating value (HV) is

HV = Σ xi(HV)i
where (HV)i is the heating value of the ith combustible substance. When the heating values
are expressed in units of energy per unit mass, then the x i's are the weight fractions of the
fuel components, and when they are expressed in units of energy per mole then the x i's are
the mole fractions of the fuel components.
8.3 Coal:
Coal is the most important fossil fuel. Two different analyses of coal are reported, namely
proximate analysis & ultimate analysis.
a) Proximate analysis:
Normally the proximate analysis of air-dried coal is reported as follows:
An air-dried coal sample is one which is exposed to the atmosphere of a laboratory to bring
it in equilibrium with the humidity conditions of the laboratory so that the sample does not
gain or loose mass during analysis.
Moisture: Water expelled in its various forms when tested under specified conditions.
Volatile matter (VM): Total loss in weight minus the moisture in coal when coal is heated
under specified conditions.
Mineral Matter: Inorganic residue left over when coal or coke is incinerated in air to
constant mass under specified conditions. It is ordinarily referred to as ash.
Fixed Carbon (FC): Obtained by substracting from 100, the sum of the percentages by mass
of moisture, VM and mineral matter.
Ordinarily, percentage of sulphur (by mass) does not form a part of the proximate analysis.
However, due to the harmful effects of sulphur dioxide and sulphur trioxide produced by
burning sulphur to the environment, percentage sulphur (by mass) is also included when
only proximate analysis is to be specified.
b) Ultimate analysis:
The ultimate analysis of the coal gives the constituent elements, namely; carbon, hydrogen,
nitrogen & sulphur.
For the ultimate analysis, the coal sample is burnt in a current of oxygen. As a result, the
hydrogen, carbon & sulphur get oxidized to water, carbon dioxide and sulphur dioxide
respectively. Water and carbon dioxide are absorbed in suitable solvents and constituents
are determined gravimetrically. Sulphur products are retained by lead chromate.
Precaution has to be taken to eliminate the oxides of nitrogen which can form during
combustion. The nitrogen in the coal is determined by the Kjeldahl method.
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Ex. 8.1) Crude oil is found to contain 87.1 % carbon, 12.5% hydrogen and 0.4% Sulphur
(by mass). Its GCV at 298.15 K (25oC) is measured to be 45071 kJ/kg oil. Calculate its NCV
at 298.15 K (25°C).
Solution:
Basis: 1 kg crude oil
Hydrogen burnt = 0.125 kg
0.125
Water formed = x 18 = 1.125 kg
2
Latent heat of water vapour at 298.15 K (25oC)
mλ = 1.125 x 2442.5 = 2747.8 kJ
∴ NCV = GCV – latent heat of water vapour
= 45071 – 2747.8
= 42323.2 kJ/kg oil
Ex. 8.2) The GHV of gaseous propane is 2219.71 kJ/kmol at 298.15 K (25°C).
Calculate its NHV.
Solution:
Basis: 1 mol gaseous propane (formula: C3H8)
The combustion reaction is
C3H8 + 5O2 → 3 CO2 + 4 H2O
Thus, when 1 mole of propane is burnt, 4 moles of water are produced.
Mass of water produced = 4 x 18.0153 = 72.06 g
(72.06 x 2442.5)
NHV = 2219.71 − = 2043.7 kJ/mol
1000
Ex. 8.3) Calculate the gross and net calorific values of the natural gas at 298.15 K (25 oC)
which has the following molal composition:
CH4: 89.4%, C2H6: 5.0%, C3H6: 1.9%, iso-C4H10: 0.4% n-C4H10: 0.6%, CO2: 0.7% and N2: 2.0%
Component Heating Value
kJ/mol
GCV NCV
CH4 890.65 802.62
C2H6 1560.69 1428.64
C3H6 2219.17 2043.11
iso-C4H10 2868.20 2648.12
n-C4H10 2877.40 2657.32
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Solution:
Basis: 1 mol natural gas
In a mixture of gases, the heating value of the mixture is made up of the heating values of
individual gases present in it.
∴ Heating Values of Natural Gas
Component Mol Mass Kg Heating Value Total Heating Value
kJ/mol kJ
ni Mi ni. Mi GCV NCV n.GCV n.NCV
CH4 0.894 16.0425 14.0425 890.65 802.62 796.24 717.54
C2H6 0.050 30.069 1.503 1560.69 1428.64 78.03 71.43
C3H6 0.019 44.0956 0.838 2219.17 2043.11 42.16 38.82
iso-C4H10 0.004 58.1222 0.232 2868.20 2648.12 11.47 10.59
n-C4H10 0.006 58.1222 0.349 2877.40 2657.32 17.26 15.94
CO2 0.007 44.0095 0.308 - - - -
N2 0.020 28.0134 0.560 - - - -
Total 1.0 18.132 945.16 855.32
Alternate calculations for NCV:

Combustion reactions are:
CH4 + 2O2 → CO2 + 2H2O
C2H6 + 3.5O2 → 2CO2 + 3 H2O
C3H8 + 5 O2 → 3CO2 + 4 H2O
C4H10 + 6.5O2 → 4CO2 + 5 H2O
Total of water formed = 2 0.894 + 3 x 0.05 + 4 x 0.019 + 5 (0.004 + 0.006)
= 2.064 mol = 37.184 g
(37.184 x 2442.5) kJ
Heat lost due to vaporization of water = = 90.83 mol fuel
1000
Average molar mass of the natural gas = 18.132
(945.16 x 1000)
GCV = = 52126.6 kJ/kg
18.132
(855.32 x 1000)
NCV = = 47171.9 kJ/kg
18.132
Specific volume at 101.3 kPa and 298.15 K = 24.465 m 3/kmol
(945.16 x 1000)
GCV = = 38633.1 kJ/m3
24.465
(855.32 x 1000)
NCV = = 34920 kJ/m3
24.465
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Ex. 8.4) calculate the net calorific value(NCV) at 298 K (25°C) at a sample of a fuel oil
having C/H ratio 9.33(by weight) and containing sulphur to the extent of 1.3% by weight.
Data: the GCV of the fuel oil at 298K (25°C) = 41785kJ/kg
Latent heat of vapour at 298K (25°C) = 2442.5kJ/kg
Sol.: Basis: 1 kg of sample of fuel oil.
It contains 0.013 kg of sulphur and balance being C and H (as % S = 1.3)
Let x and y be kg of carbon and hydrogen in fuel oil.
Amount of C and H in fuel oil = 1- 0.013 = 0.987 kg
x + y = 0.987 and
x
= 9.33 (given C/H ratio by weight = 9.33)
y
x = 9.33 y
Therefore,
9.33y + y = 0.987
10.33y = 0.987
Therefore,
y = 0.09554 kg and x = 0.89164 kg
Amount of hydrogen burnt = 0.09554 kg
1
H2 + 2 O2 → H2 O
1 kmol H2 ≡ 1 kmol of H2 O
2 kg of H2 ≡ 18 kg of H2 O
18
Water produced = x 0.09554 = 0.8597 kg
2
NCV = GCV - mλ
= 41785 – (0.8597 x 2442.5)
= 39685.2 kJ/kg fuel oil
Ex. 8.5) The GHV (gross heating value) of gaseous n-butane is 2877.40 kJ/mol at 298K
(250C)calculate its NHV (net heating value) in kJ/mol &kJ/kg.
Latent heat of water vapour at 298 K = 2442.5 kJ/kg
Solution:
Basis: 1mol of gaseous n –butane (C4H10)
The combustion reaction is
C4H10 + 13.5 O2 → 4CO2 + 5H2O
Thus when 1mol of n-butane is burnt, 5mol of water are produced.
Weight of water produced = 5 x 18 = 90 g = 90 x 10-3 kg.
Latent heat of water vapour at 298 K = 90 x10-3 x 2442.5 = 219.825 KJ
NHV = GHV – latent heat of water vapour
= 2877.40 – 219.825 = 2657.575 kJ/mol C4H10
Molecular weight of C4H10 = 58
Amount of C4H10 = 1 x 58 x 10-3 = 0.058 kg
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PPP_DOTSUK
NHV of C4H10 = 2877.40/0.058

= 49610.3 kJ/kg
From reaction,
58 kg C4H10 ≡ 90 kg H2O
Water produced = 90/58 x 0.058 = 0.09 kg
NHV = GHV – mλ
= 49610.3 – 0.09 x 2442.5
= 49390.475kj/kg C4H10
Ex. 8.6) The analysis of a refinery gas by volume is:

H₂: 74%, CH₄: 13.5 %, C₂H₆: 7.4%, C₃H₈:3.6%, n-C₄H₁₀:1.2% and nC₅H₁₂: 0.3%
Data:
Component -∆H˚c ( gross ), kJ/mol -∆H˚c (net ), kJ/mol
CH₄ 890.65 802.62
C₂H₆ 1560.69 1428.64
C₃H₈ 2219.17 2043.11
n-C₄H₁₀ 2877.40 4657.32
n-C₅H₁₂ 3535.77 3271.67
∆H˚f of H₂O (g) = - 241.82 kJ/mol at 298K (25˚C)

∆H˚f of H₂O (l) = - 285.83 kJ/mol at 298K (25˚C)
Specific volume at 298K ( 25˚C) and 101.3 kPa= 24.465m³/kmol
Calculate the GCV and NCV of the refinery gas in KJ/mol, kJ/m³.
Solution:
Basis: 1 mol of refinery gas.
It contains 0.74 mol H₂,0.135 mol CH₄,0.074 mol C₂H₆,0.036 mol C₃H₈,0.012 mol n-C₄H₁₀
and 0.003 mol n-C₅H₁₂.
In a mixture of gases , the heating value of the gas mixture is made up of the heating values
of individual gases present in it. Heats of combustion are negative of heating values.
GCV = 0.74 × 285.83 + 0.135 × 890.65 + 0.074 × 1560.69 +0.036 × 2219.17 + 0.012 ×
2877.4 + 0.003 × 3535.77
=572.27KJ/mol refinery gas
NCV =0.74 × 241.82 + 0.135 × 802.62 + 0.074 × 1428.64 + 0.036 × 2043.11 + 0.012 ×
2657.32 + 0.003 × 3271.67
= 508.275 kJ/mol
Mole fraction of H₂ = XH₂ = 74/100 = 0.74
Mole fraction of CH₄ = XCH₄ = 13.5/100 = 0.135
Mole fraction of C₂H₆ = XC₂H₆ = 7.4/100 = 0.074
Mole fraction of C₄H₁₀ = XC₄H₁₀ = 1.2/100 =0.012
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PPP_DOTSUK
Mole fraction of C₃H₈ = XC₃H₈ = 3.6/100 = 0.036

Mole fraction of C₅H₁₂ =XC₅H₁₂ = 0.3/100 = 0.003
Mavg = Average molecular wt. of refinery gas
= 0.74 × 2 + 0.125 × 16 + 0.074 × 30 + 0.036 × 44 + 0.012 × 58 + 0.003 × 72
= 8.356
Gross calorific value of refinery gas on wt. basis:
GCV = GCV (kJ/mol)/Mavg × 100
= 572.27/8.356 × 1000 = 68486.12 kJ/kg
Similarly,
NCV (on wt. basis) of refinery gas
= 508.275/8.356 × 100 = 60827.55 kJ/kg
Specific volume at 298 K (25˚C) and 101.3 kPa = 24.465 m³/kmol
GCV = 572.27/24.465 × 1000 = 23391.4kJ/m³
Similarly,
NCV = 508.275/24.465 × 1000 = 20775.6 kJ/m³ refinery gas
Ex. 8.7) Calculate GHV and NHV at 298K (25oC) of the gas having following composition by
volume CH4 = 74.4% , C2H6 = 8.4% , C3H8 = 7.4% , i-C4H10= 1.7% , n- C4H10 = 2.0% , i-
C2H12 = 0.5% , n-C2H12 = 0.7 % , N2=4.3% , & CO 2 =0.9%
Data:
Component GCV ,KJ/mol NCV, KJ/mol
CH4 890.65 802.62.
C2H6 1560.69 1428.64
C3H8 2219.17 2043.11
i-C4H10 2868.20 2648.12
n-C4H10 2877.40 2657.32
i-C5H12 3528.83 3264.73
n-C5H12 3535.77 3271.37
Sp. Volume of gas = 298K (250C) & 101.3 Kpa = 24.465 m3/Kmol
Solution:
Basis: 1 Kmol of gas
It contains 0.744 mole CH4, 0.084 mol C2H6, 0.074 mol C3H8, 0.017mol i-C4H10, 0.02 mol n-
C4H10, 0.005 mol i-C5H12, 0.004 mol n-C5H12,0.043 mol N2 & 0.009 mol CO2
In a mixture of gases, the heating value of gas mixture is made up of the heating value of
individual gas present in it
GHV = 0.0744 × 890.65 + 0.084 × 1566.79 + 0.074 × 2219.17 + 0.017 × 2868.20 + 0.02 ×
2877.40 + 0.005 × 3528.83 + 0.004 × 3535.77
=1096KJ/mol
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PPP_DOTSUK
NHV = 0.744 × 802.62 + 0.084 + 1428.62 + 0.074 × 2043.11+ 0.017 × 2648.18 + 0.02 ×
2657.32 + 0.005 × 3264.74 + 0.004 × 3271.67
= 996 kJ/mol
MAvg = ∑xi Mi & xi = volume or mole %/100

Mavg = 0.744 × 16 + 0.084 × 30 + 0.074 × 44 + 0.017 × 58 + 0.02 × 58 + 0.005 × 72 + 0.004
× 72 + 0.043 × 28 + 0.009 × 44
= 22.074
1096
GHV = 22.074 × 1000 =49651.2 kJ/kg
996×1000
NHV = = 45120.9 kJ/Kg
22.074
Sp. Volume of gas of 298K (250C) & 101.3Kpa =24.465m3/kmol

1096×1000
GHV = = 44798.7 kJ/m3
24.465
996×1000
NHV = = 40711.2 kJ /m3
24.465
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8.4 Air Requirement:

For any combustion process i.e. for chemical oxidation of a fuel, oxygen is must which will
combine with carbon, hydrogen and sulphur. In normal practice, air is used for burning the
fuel as it being the inexpensive source of oxygen. Air contains about 21% oxygen and 79%
nitrogen by volume. It is normal practice to feed less expensive reactant in excess of
valuable one to increase the conversion of a valuable reactant. Hence, combustion reactions
are invariably run with more air than needed to supply oxygen in stoichiometric
proportion to the fuel.
Theoretical oxygen:
It is the amount of oxygen needed for complete combustion of all the fuel fed to the
combustion chamber, assuming that all carbon in the fuel reacts with oxygen to form CO2,
all hydrogen reacts to form H2O and all sulphur reacts to form SO2.
Theoretical air:
It is the quantity of air that contains the theoretical oxygen i.e. it is the minimum air
required to burn the fuel completely so that all carbon gets converted into CO2, all
hydrogen into H2O and all sulphur into SO2. Theoretical air demand of a fuel is calculated
as
Theoretical oxygen demand in moles
Theoretical air demand in moles = 0.21
In actual combustion practice, air is used in excess of that theoretically required to assure
complete combustion.
Excess air:
It is the amount by which the air fed to combustion chamber exceeds the theoretical air.
moles air supply − moles air theoretical
% excess air = ( ) x100
moles air theoretical
The quantity of actual air supply and theoretical air can be used either in weight units or in
molar units in the formula cited above.
The actual air supply is obtained knowing % excess and theoretical demand by the relation:
% excess
Actual air supply = Theoretical air [1 + ]
100
The actual percentage excess air depends on the fuel used for combustion.
Normally gaseous fuels require very less excess air. Liquid & solid fuels requires more
excess air than gaseous fuel. Current designs of combustion equipments permit gaseous
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PPP_DOTSUK
fuels to be burnt with 5 to 15% excess air while liquid & solid fuels requires 10 to 50%
excess air.
Flue gases are the product gases which are produced by burning a fuel. Normally flue gases
contain CO2, CO, H2O, O2, SO2, (SO3) and N2. SO3 is usually in very low concentration in the
flue gases.
Orsat Analysis:
The flue gases are analyzed with the help of an instrument called the Orsat analyzer. Since
the water of the flue gases interferes with the analysis, it is removed by sampling the gas
through a strong sulphuric acid container. The dry gases are collected in a measuring tube.
CO2 and SO2 are absorbed in aqueous K2CO3 solution from the gas. The reduction in the
volume of the sample gas gives the volume % (or mole %) of (CO 2 + SO2), expressed as CO2.
Pyrogalol is used for O2 measurement while the solution of Cu2Cl2 is used for CO
determination. By subtracting the sum of CO 2, O2 and CO from 100, the mole % of N2 can be
calculated. Thus, with an Orsat apparatus, the molar analysis of dry flue gases can be
obtained.
8.5 Thermal efficiency of boiler:
The thermal efficiency of boiler or a furnace is calculated, using the following equation:
useful heat gain
Thermal efficiency = ( ) x 100
total heat input
Ex. 8.8) The coal specified in Example 7.1 is burnt with 100% excess air. Calculate a) The
theoretical oxygen per unit mass of coal, b) the theoretical dry air requirement per unit
mass of fuel, c) the wet & Orsat analyses of flue gases when the coal is burnt with 100%
excess dry air.
Basis: 100 kg coal as-received
Oxygen Requirement of Coal
Constituents Mass kmol O2 requirement for
Kg complete combustion, kmol
Carbon 50.22 4.185 +4.185
Hydrogen 2.79 1.395 +0.698
Sulphur 0.37 0.012 +0.012
Oxygen 18.04 0.564 -0.564
71.42 6.156 4.331
Stoichiometric O2 requirement = 4.331 kmol = 138.6 kg
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PPP_DOTSUK
138.6
Theoretical O2 requirement to fuel ratio = 100
= 1.386 kg O2/kg coal
The above O2 is fed in the form of air. Therefore, N2 also enters with O2
21
N2 entering with O2 = 79 x 4.331 = 16.293 kmol
Total theoretical dry air requirement for complete combustion
= 4.331 x 32 + 16.293 x 28
= 138.6 + 456.2 = 594.8 kg
Average molar mass value of 29 for air yields theoretical dry air requirement of 598.1 kg
Theoretical air requirement 594.8
= = 5.948 kg/kg coal
Fuel 100
Actual air supply = 5.948 x 2 = 11.896 kg/kg coal

Actual O2 supply = 4.331 x 2 = 8.662 kmol
79
N2 accompanying O2 = 21 x 8.662 = 32.586 kmol
or = 2 x 16.293 = 32.586 kmol
2.05
N2 in the coal = = 0.073 kmol
28
Total N2 in the flue gas = 32.586 + 0.073 = 32.659 kmol
7.00
Total moisture in the flue gas = 1.395 + ( ) = 4.895 kmol
2
Composition of Flue Gases
Constituents kmol Wet Dry analysis
analysis, considering SO2 as CO2
mole% (orsat analysis) mole%
CO2 4.185 9.08 10.19
SO2 0.012 0.03 --
O2 4.331 9.40 10.52
N2 32.659 70.87 79.29
4.895 10.62 --
46.082 100.00 100.00
Ex. 8.9) The Orsat analysis of the flue gases from a boiler house chimney gives CO 2: 11.4%,
O2: 4.2%, and N2: 84.4% (mole %). Assuming that complete combustion has taken place, (a)
calculate the % excess air, and (b) find the C: H ratio in the fuel.
Solution:
C+O2 → CO2
H2+1/2O2 → H2O
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PPP_DOTSUK
Basis: 100 kmol dry flue gases

O2 accounted = O2 in CO2 + O2 in flue gas = 11.4 + 4.2 = 15.6 kmol
For the calculations of the actual supply of O 2 nitrogen is a tie component which provides
the clue as it comes from air.
21
O2 available from air = (79 ) x 84.4 = 22.435 kmol
Excess O2 = 4.2 kmol
O2 unaccounted = 22.435 -15.6 = 6.835 kmol
This O2 must have been utilized for the burning of hydrogen.
Hydrogen burnt = 2 x 6.835 = 13.67 kmol
Theoretical oxygen requirement = 11.4 + 6.835 = 18.235 kmol
or = 22.435 - 4.2 = 18.235 kmol .
(4.2 𝑥 100)
% excess air = = 23.03
18.235
Mass of hydrogen burnt = 13.67 x 2 = 27.34 kg
Mass of carbon burnt = 11.4 x 12 = 136.8 kg
136.8
Carbon/hydrogen (mass) ratio in the fuel = 27.34 = 5.00
Ex. 8.10) The ultimate analysis of a residual fuel oil (RFO) sample is as given below:
C: 88.4%, H:9.4%, and S:2.2%(by wt)
It is used as a fuel in a power generating boiler with 25% excess air.
Calculate:
a) The theoretical dry air requirement
b) The actual dry air supplied
c) The Orsat analysis of flue gases
Solution:
Basis: 100kg of Residual fuel oil.
It contains 88.4 kg carbon, 9.4 kg hydrogen and 2.2 kg sulphur.
Theoretical O2 requirement = O2 requirement for complete combustion
= 32/12*88.4+16/2*9.4+32/32*2.2
= 313.13kg
Theoretical O2 requirement = 313.13/32=9.785kmol
Theoretical air requirement =9.785/0.21=46.595kmol
Weight of dry air requirement = 46.595*29=1351.26kg
Theoretical dry air requirement to fuel ratio
= 1351.26/100 =13.5126 kg dry air/kg RFO
…...ans(a)
Actual air supplied = 46.595(1+25/100) = 58.294kmol
Weight of actual air supplied = 58.244 x 29=1689 kg
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PPP_DOTSUK
Ratio of Actual air supplied/ fuel =1869/100 = 16.89 kg dry air/kg RFO
CO2 produced = 44/12 x 88.4 = 324.13 kg
= 324.13/44 = 7.37 kmol
SO2 produced = 64/32 x 2.2 = 4.4 kg
= 4.4/64 = 0.069 kmol
N2 in air supplied = 0.79 x 58.244 = 46.013 kmol
O2 in air supplied = 58.244 - 46.013 = 12.231 kmol
O2 in flue gas = 12.231- 9.785 = 2.446 kmol
N2 in flue gas = 46.013 kmol
In the dry gas analysis, SO2 is considered as CO2 and composition of flue gas is specified
Composition of dry flue gases:
Component Kmol Orsat analysis(mol%)
CO2 7.37 13.31
SO2 0.069 -
O2 2.446 4.38
N2 46.013 82.31
Total 55.898 100.00
Ex. 8.11) A furnace is fired with fuel oil. The orsat analysis of the fuel gases (by volume) is
as given below: CO2: 10.6%, O2 :6% and N2 :83.4%
Calculate the percentage excess air and find the C: H ratio in the fuel oil, assuming that fuel
does not contain nitrogen.
Solution:
Basis: 100 kmol of flue gases
It contains 10.6 kmol CO2, 6 kmol O2 and 83.4 kmol
O2 accounted = O2 in CO2 +O2 in flue gases
= (1/1) x 10.6 +6
= 16.6 kmol
N2 in air supplied = N2 in flue gas
= 83.4 kmol
O2 in air supplied = (21/79) x 83.4
= 22.17 kmol
O2 unaccounted =22.17 – 16.6
= 5.57 kmol
% excess air = % excess O2
= [(22.17 - 16.17)/16.17] x 100
= 37.10
Weight of carbon burnt = 10.6 x 12 = 127.2 kg
Weight of hydrogen burnt = 11.14 x 2 = 22.28 kg
Carbon / Hydrogen (W/W) ratio in the fuel oil = 127.2/22.28 = 5.71
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PPP_DOTSUK
Ex. 8.12) The purge gas obtained from ammonia synthesis loop has 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: 100kmol of purge gases.
It contains 69 kmol H₂, 23 kmol N₂, 2.7 kmol Ar and 5.3 kmol CH₄.
H₂ + ½ O₂ → H₂O
CH₄ +2O₂ → CO₂ +2H₂O
Theoretical O₂ required = 0.5 ×69 +2 ×5.3 = 45.1 kmol
Theoretical air required = 45.1/0.21 =214.8 kmol
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
Theoretical air required = 6229.2/974.8 = 6.39 kg/kg purge gas
O₂ in air supplied = 45.1 × 1.20 = 54.12 kmol (20% excess air)
O₂ in flue gas = 54.12 – 45.1 = 9.02 kmol
N₂ in air supplied = (79/21) ×54.12 = 203.6 kmol
N₂ in flue gas =203.6 + 23 = 226.6 kmol
CO₂ in flue gas = 1/1 ×5.3 = 5.3 kmol
Ar in flue gas = Ar in purge gas = 2.7 kmol
Flue gas composition (on dry basis)
Composition Quantity , kmol Kmol %
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
Ex. 8.13) Synthetic natural gas has the following molar composition:
CH4: 95%, H2: 1.0%, CO2=2%, CO=2%
This gas is used to generate steam generated at 101.325kPa.
Find the quantity of steam generated per kg of gas if the boiler has efficiency of 75%.
Data: At 101.325 kPa, H of steam = 2676 kJ/kg
GCV of CH4 = 809.65kJ/mol
NCV of CH4 = 802.62kJ/mol
∆H0fco2 = -393.51kJ/mol
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∆H0fco = -110.53kJ/mol
∆H0fco = -285.83kJ/mol
Latent heat of vapour at 298K (250C) = 2442.5kJ/kg
Solution:
Basis: 1mol of natural gas.
It contains 0.95 mol CH4, 0.01 mol H2, 0.02 mol CO2 and 0.02 mol CO.
Water produced = (2/1) x 0.95+(1/1) x 0.01
=1.91mol
=1.91 x 18 x 10-3
= 0.03438 kg
Latent heat in water vapour = 0.03438 x 2442.5 = 83.97 kJ
NCV = GCV-latent heat lost in water vapour
= 854.64-83.97
= 770.67kJ/mol of natural gas
Mavg =Average molecular weight of natural gas
=0.95*16+0.01*2+0.02*44+0.02*28
=16.66
NCV = (770.67/16.6) x 1000 = 46258.7kJ/kg of natural gas
Efficiency = (Heat gained by water/NCV) x 100
Heat gained by water = 0.75 x 46258.7 = 34694 kJ
At 101.325kPa pressure, H of steam = 2676kJ/kg
Quantity of steam generated = (34694/2676) = 12.965kg
Quantity of steam generated per kg of natural gas = 12.965 kg
Assignment No. 7) 8a & b (S-175), 7 (O-650), 8a (G-23), 8a (O-281), 8a (G-215), 8a (Z-461),

8 (T-139), 8 (R – 297)
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PPP_DOTSUK
7.1) The orsat analysis of the flue gases from a boiler house chimney gives CO 2 - 11.4%, O2 -
4.2%, and N2 - 84.4% (mole). Assuming complete combustion, calculate:
i) % excess air ii) C : H ratio in fuel.
7.2) A producer gas with the composition by volume 27.3% CO, 5.4% CO 2, 0.6% O2, 66.7%
N2 is burnt with 20 % excess air. If the combustion is 98 % complete, calculate the
composition by volume of the flue gases.
7.3) A hydrocarbon gas is burned in a furnace with 15% excess air, yielding a flue gas
containing CO2 = 11.6%, CO = 2% , H2 = 1.6%, O2 = 4%, N2 by difference
Calculate:
i) Actual O2 supplied
ii) Theoretical O2 required.
7.4) Wood having an analysis of 46% carbon, 23% oxygen, 5% ash, the rest being moisture
and hydrogen is being burnt in a furnace. An orsat analysis of flue gas during a run showed
Component % mole
CO2 14.9
CO 1.65
O2 3.45
N2 80
Calculate:
i) The complete analysis of the wood used
ii) Fuel ratio by weight
iii) % excess air
iv) Composition of the stack gas.
7.5) The Orsat analysis of a flue gas from a boiler chimney by mole is given below:
CO2 = 11.4%, O2 = 4.2%, N2 = 84.4%.
Assuming complete combustion, Calculate:
a) The percent excess air b) C : H ratio in the fuel.
7.6) A sample of fuel oil has C/H ratio 9.33 (by weight) and contains 1.3% sulfur by weight.
The net calorific value of the fuel is 39685 KJ/Kg at 25° C. Calculate gross calorific value
using latent heat of water at 25°C.
Data: Latent heat of water at 25°C = 2442.5 KJ/Kg.
204
PPP_DOTSUK
7.7) A furnace is fired with fuel oil. The orsat analysis of flue gases by volume is given
below. CO2 = 10.6%, O2 = 6%, N2 = 83.4 Calculate:
i) % excess air ii) The C : H ratio in fuel oil, assuming fuel oil doesn't Contain Nitrogen.
7.8) The purge gas obtained from ammonia synthesis loop has the composition
H2: 69%, N2 : 23%, Ar : 2.7% and CH4: 5.3% (mole). It is burnt with 20% excess air.
Calculate
i) Theoretical air required.
ii) The molar composition of the dry flue gas.
7.9) A sample of coal is found to contain 65% carbon and 12.7% ash by wt. The refuse
obtained after burning the fuel is found to have 8.6% carbon. Assume that negligible O2 is
present in the coal. Flue gas analysis showed
CO2 = 10.6%, O2 = 8.7% and N2= 80.7% (by vol)·
Calculate
i) the actual weight of dry air used to burn the coal
ii) the actual weight of flue gases produced by burning the coal.
7.10) A fuel gas constituents of CO2: 3.4%,. C2H4 : 3.7%, C6H6 : 1.5%, O2 : 0.3%, CO: 17.4%,
H2 : 36.8%, CH4: 24.9% and N2 : 12.0% (on molal basis). It is burn with air in a furnace. The
fyrite analyzer indicated 10.0 mole % CO 2 (on dry basis) in the fine gases. Find: a) the %
excess air used and b) the complete orsat analysis.
7.11) The steam raising plant of a refinery uses 5000 Kg/h of tar as a fuel. An analysis of the
tar indicates that it contain 88% carbon and 0.5% sulfur by weight; the remainder being
combustible hydrogen, moisture and ash. The ash content of this tar is usually four times
the moisture content. For a given test runs the following data were obtained:
Flue gas orsat analysis
Component % (mole)
CO2 14.5 %
CO 1.5%
O2 2.5 % and
N2 81.5 %
Air inlet conditions 30°C and 1.1 bar,
Calculate:
a) The combustible hydrogen, moisture and ash content of the tar.
b) % excess air used
c) The Kg. of water/Kg. of dry flue gas.
(Assume air to be dry)
205
PPP_DOTSUK
7.12) A hydrocarbon gas is burned in a furnace with 15% excess air yielding a flue gas
containing CO2 11.6%, CO 2%, H2 1.6%; O2 4%, N2 by difference. Comment on the data
reported and the furnace performance.
7.13) The purge gas obtained from ammonia synthesis loop has the following composition.
H2: 69%, N2: 23%, Ar : 2.7% and CH4 : 5.3% (Mole basis). It is burnt with 20% excess air
calculate:
a) The GCV and NCV at 298 of the purge gas.
b) Theoretical- air required and
c) The molar composition of the dry flue gases.
7.14) An orsat analysis yields the following dry basis composition:

N2 65%, CO2 14%, CO 11%, 02 10%
A humidity measurement shows that the mole fraction of H2O in the stack gas is 0.07.
Calculate the stack gas composition on a wet basis.
7.15) Crude oil is found to contain 87.1 % carbon, 12.5% hydrogen and 0.4% sulphur (by
wt.). Its GCV at 25°C is measured to be 10765 kcal/kg. Calculate its NCV at 25°C.
206
PPP_DOTSUK

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2.

Basic Chemical Calculations

2. Basic Chemical Calculations

2.2 Mole, Atomic Mass & Molar Mass:

Although measurement in terms of mass is of direct interest to the engineers, matter is

2.2.1 Atomic weights of important elements:

Element Atomic Wt. Element Atomic Wt. Element Atomic Wt.

2.2.2 Atomic Weight:

2.2.3 Molecular Weight:

2.2.4 The Gram atom:

2.2.5 The Gram mole:

2.2.6 Basis of Calculation:

Ex 2.1) How many grams of NH4Cl are there in 5 mol?

Ex 2.3) How many moles of K2CO3 will contain 117 kg K?

Ex 2.4) How many atoms are present in 416.6 gm barium chloride?

Ex. 2.5) Convert 499 g of CuSO4 .5H2O into moles.

Ex. 2.6) How many moles of H2SO4 will contain 64 kg of S?

Ex. 2.7) Find moles of K2CO3 that will contain 117 Kg of K?

Ex. 2.9) Find kilogram of C2H6 that contain 4 katom of carbon.

2.3 Equivalent weight:

Ex 2.11) Find the equivalent of 3 kmol of AlCl3

Ex. 2.13) Calculate the equivalent weight of following compound:

2.4 Methods of expressing the Composition of Solid Mixtures and Solutions:

2.4.1 Composition of solid mixture:

∴ Weight % of A = Weight fraction of A x 100

∴ Mole % of A = Mole fraction of A x 100

Mass % of NaCl, WA = (600/800) x 100 = 75

Molar mass of NaCl, MA = 23 + 35.5 = 58.5

Mole % NaCl = (10.26/12.94) x 100 = 79.23

1Kmol NH2CONH2 ≡ 2Katom N

2.4.2 Composition of liquids & solutions:

ThOD = (3.5 x 32 x 600)/92 = 730.4 mg/L

Composition of Lean MEA

2.4.3 Concentration of solutions:

Molarity, M = moles of solute/volume of solution = 342/88.73 = 3.85

For NaCl, since it is univalent,

Molality = Moles of solute/mass of solvent = 342/80 = 4.275 mol/kg

Gram-equivalent of H2SO4 = Normality * volume of solution

Amount of H2SO4 required for 1 Normal solution

Moles of H2SO4 = Molarity x Volume of solution

Volume of solution = 2000 ml = 2 lit.

Ex. 2.38) Make the following conversions:

(b) 5N H3PO4 to g/l.

(c) 54.75 g/l HCl to molarity.

(d) 3MK2SO4 to g/l.

(e) 4.8 mg/ml CaCl2 to normality

Ex. 2.39) an aqueous solution of K2CO3 is prepared by dissolving 43 kg K2CO3 in 10 kg

Total Nitrogen available from the solution = 2.33 + 16.47 + 21 = 39.8 kg

Questions from theory examination:

2.1) How many Kg moles of H2SO4 will contain 64 Kg of sulphur ?

2.2) A compound having molecular weight of 123, analyses: C = 58.536%, Hydrogen =

2.4) An aqueous solution of acetic acid (CH3COOH) of 35 % concentration by weight has

2.5) Convert the following into equivalent PPM CaCO3 :

2.9) A compound whose molecular weight is 103 analyses as following:

2.11) It is desired to prepare a solution of sodium chloride in water, having a molarity of

2.12) Ammonium phosphomolybdate (NH4)3PO4.12MoO3.3H2O is made up of the radicals

2.13) A compound whose molecular weight is 103 analyzes C=81.5%, H:4.9%,N:13.6%.

2.3) Find the molar mass of KMnO4. [Ans. 158]

2.6) What is the equivalent mass of Al2(SO4)3? [Ans. 57]

2.11) A sample of milliolite limestone, obtained from Porbandar, Gujarat, is found to

2.12) Calculate the available nitrogen in the following:

2.22) Convert the following into equivalent ppm CaCO3: