Course Notes PDF

CH 2254
CHEMICAL PROCESS CALCULATIONS
SYLLABUS
CH2254 CHEMICAL PROCESS CALCULATIONS
AIM
Every chemical reaction involves consumption of Materials and energy. The reactions are to be
balanced with correct quantity of materials and energy to achieve good percentage of conversion for
products. The aim of this course is to give fundamental knowledge on such material and energy
balances.
OBJECTIVES
To make them understand different types of laws of chemistry of materials and also prepare the
students to accurately calculate the Stoichiometric relations between the materials involved in a
physical and chemical reaction.
UNIT I UNITS AND DIMENSIONS 5

Basic and derived units, use of model units in calculations, Methods of expression, compositions of
mixture and solutions.
UNIT II GAS CALCULATIONS 7

Ideal and real gas laws - Gas constant - calculations of pressure, volume and temperature using ideal
gas law. Use of partial pressure and pure component volume in gas calculations, applications of real
gas relationship in gas calculation.
UNIT III MATERIAL BALANCE 7

Stoichiometric principles, Application of material balance to unit operations like distillation,
evaporation, crystallisation, drying etc., - Material balance with chemical reaction - Limiting and
excess reactants - recycle - bypass and purging - Unsteady state material balances.
UNIT IV HUMIDITY AND SATURATION 7

Calculation of absolute humidity, molal humidity, relative humidity and percentage humidity - Use of
humidity in condensation and drying - Humidity chart, dew point.
UNIT V FUELS AND COMBUSTION 6

Determination of Composition by Orsat analysis of products of combustion of solid, liquid and gas
fuels - Calculation of excess air from orsat technique, problems on sulphur and sulphur burning
compounds.
UNIT VI THERMO PHYSICS 6

Heat capacity of solids, liquids, gases and solutions, use of mean heat capacity in heat calculations,
problems involving sensible heat and latent heats, evaluation of enthalpy.
UNIT VII THERMOCHEMISTRY 7

Standard heat of reaction, heats of formation, combustion, solution, mixing etc., calculation of
standard heat of reaction - Effect of pressure and temperature on heat of reaction - Energy balance
for systems with and without chemical reaction. – Unsteady state energy balances.
TEXT BOOKS
1. Bhatt, B.L., Vora, S.M., “Stoichiometry”, Tata McGraw-Hill, 1976.
2. Himmelblau, D.M., “Basic Principles and Calculations in Chemical Engineering”,
EEE Sixth Edition, Prentice Hall Inc., 2003 (with CD containing programmes and problems).
REFERENCES
1. Process Calculation for Chemical Engineering, Second Revised Edition, Chemical Engineering
Education Development Centre, I.I.T., Madras, 1981.
2. Process Calculations, Venkataramani, V and Anantharaman, N, Prentice Hall of India Pvt. Ltd.,
2003.
Dr.K.P.GOPINATH
1
CH 2254
Dr.K.P.GOPINATH
2
CH 2254
UNIT – I
UNITS AND DIMENSIONS
Dr.K.P.GOPINATH
3
CH 2254
A unit of measurement is a definite magnitude of a physical quantity, defined and

adopted by convention and/or by law, that is used as a standard for measurement of the same
physical quantity. Any other value of the physical quantity can be expressed as a simple
multiple of the unit of measurement.
For example, length is a physical quantity. The metre is a unit of length that represents a
definite predetermined length. When we say 10 metres (or 10 m), we actually mean 10 times
the definite predetermined length called "metre".
The definition, agreement, and practical use of units of measurement have played a crucial
role in human endeavour from early ages up to this day. Different systems of units used to be
very common. Now there is a global standard, the International System of Units (SI), the
modern form of the metric system.
Principle of stoichiometry:
The mass and the gas volumetric relationships in chemical reactions are presented together
with the basic units for expressing charging in mass and composition.
1) 100g of chlorine gas is mixed with 10g of hydrogen gas. Calculate the mole fractions
of the two gases in the mixture.
Ans. Basis: 110g of gas mixture.
Component Gmmole Mol.Wt. Gm Mole Mole Fr.
Chlorine 100 71 1.41 0.219

Hydrogen 10 2 5 .00 0.781
----------------
6.41
----------------
2) Prove 1 J = 10^7 ergs.
Ans. 1 J = 1 Nm = 1 kgm^2/s^2 = 10^3 * (10^2)^2 10^7 ergs.
----------------------- =
1^2
3) Prove 1 W = 0.7376 ft lbf / sec .

Ans. 1 W = 1 J / sec = 1 Nm / s
1 N = ( 1 / 4.448222) lbf
1 m = (1/ 0.3048) ft
1 W = ( 1 / 4.448222) * ( 1 / 0.3048 ) = 0.7376 ft lbf / sec.
5) Convert the diffusion coefficient of 0.5 lb /ft^3.

Ans. 1 lbm = 0.4535 kg.
1 ft = 0.3048 m
0.5 lb / ft^3 = 0.5 * 0.4535
----------------- = 8.0076 kg / m^3.
0.3048^3
Dr.K.P.GOPINATH
4
CH 2254
6) What is the density of air at 40 degree Celsius and 760 mmHg?

Ans. Ideal gas law: PV = nRT
Pressure P = 760 mmHg
Temperature T = 40 + 273 = 313 K
Gas constant R = 62.396 mmHg l / gmol K
Volume V = nRT / P = 1 * 62.396 * 313 / 760 = 25.69 lit.
Mass of air = 0.21 * 32 + 0.79 * 28 = 28.84 g
Density = Mass / Volume = 1.12 g / lit.
Specific gravity of a liquid:

Specific gravity of a liquid is defined as the ratio of density of liquid to the density of water.
Specific gravity of liquid = Density of liquid / Density of water
Mole fraction:
Mole fraction of a component in a mixture is defined as the ratio of the number of moles of
that component to the total number of moles.
No. of moles of A
Mole fraction of a component A in (A+B) mixture = -------------------------
No. of moles of (A+B)
Volume percentage of a component in a mixture is defined as the ratio of volume

occupied by that component to the total volume occupied by the mixture.
Volume occupied by A
Volume % of component A in (A+B) mixture = ------------------------------------
Volume occupied by (A+B)
Molecular weight and equivalent weight:

The combined weight of all the atoms put together constitute the molecular
weight.Equivalent weight is defined as the molecular weight divided by valency of atoms.
Pbm: A solution of caustic soda contains 30% NaOH (by weight).The density of the solution
is 1.196 g/cc. Find the molarity and normality of the solution.
Ans. Basis: 100g of caustic soda solution.

Mass of NaOH = 30g
Density = Mass / Volume
Volume = Mass / Density = 30 / 1.196 = 25.08 cc
Molecular weight of NaOH = 40
Equivalent weight of NaOH = Mol.wt. / Valency = 40 / 1 = 40 g eqv.
Gram moles of NaOH = Mass / Molecular mass = 30 / 40 = 0.75 gmol
Gram moles of NaOH 0.75
Molarity of NaOH solution = ---------------------------------- = -------- = 0.0299 M
Volume of solution 25.08
Gram equivalents of NaOH 40

Normality of NaOH solution = ---------------------------------------- = ----- = 1.59
Volume of solution 25.08
Dr.K.P.GOPINATH
5
CH 2254
Concept of MOLARITY and MOLALITY:

Molarity is defined as the number of gram moles of solute dissolved in one litre of the
solution.
Molality is defined as the number of gram moles of solute dissolved in one kilogram of the
solvent.
ABSOLUTE temperature and RELATIVE temperature:

The Kelvin(K) and Rankine ( degree R) are the absolute temperature scales whose zero points
correspond to the lowest possible temperature whereas the Celsius and Fahrenheit scales are
relative temperature scales whose whose zero points are arbitrarily fixed by their inventors.
Pbm: A sample of wine contains 20% alcohol on volume basis. Find the weight percent of
alcohol in the wine. The density of alcohol and alcohol-free liquid are 0.79 g / cc and 1 g / cc
respectively.
Ans. Basis: 100 cubic metre of wine.
COMPONENT VOLUME DENSITY WEIGHT WEIGHT %

Alcohol 20 0.79 15.8 16.49
Non-alcohol 80 1 80 .0 83.51
----------
95.8
-----------
Pbm: Define the terms degree Baume , degree API and degree Twadell in the specific
gravity scale.
Ans. DEGREE BAUME
For liquids heavier than water
Degree Baume = 145 – ( 145 / ( S.G. 288.7/288.7) )
a) For liquids lighter than water

Degree Baume = (140 / S.G.(288.7 / 288.7)) – 130
DEGREE API
Degree API = ( 141.5 / S.G. ( 288.7 / 288.7)) – 131.5
DEGREE TWADELL
Degree Twadell = 200 ( (S.G.( 288.7 / 288.7) – 1)
Pbm: Convert the diffusion coefficient of 0.87 ft^2 / hr into MKS unit.
Ans. 1 ft = 0.3048 m
1 hr = 60 * 60 s = 3600 s
0.87t^2/ hr = 0.87 * 0.3048 ^ 2 / 3600 = 2.24 * 10 ^(-5) m^2 / s
0.88
Pbm: The available nitrogen in an urea sample is found to be 45% (by mass). Find the actual
urea content in the sample.
Ans. Basis: 100 kg of urea.
Urea molecular formula: NH2CONH2
Dr.K.P.GOPINATH
6
CH 2254
Molecular weight of urea: (2*14) + (4*1) + 12 + 16 = 60

28 kg nitrogen is present in 60 kg urea.
45 kg nitrogen will be present in 60 * 45/28 = 96.43 kg of urea.
Problems – Tutorials:
1) A limestone analysis CaCO3 - 94.52% , MgCO3- 4.16% and inert- 1.32%. Calculate (a)
kgs of calcium oxide could be obtained from 4 tons of limestone.
(b) How many kgs of CO2 are given off per kg of limestone?
Ans. Basis: 100 kg of limestone.

Equation: CaCO3  CaO + CO2
MgCO3  Mg O+ CO2
Molecular weights of (i) CaO : 40 + 16 = 56 MgO=40

(ii) CO2 : 12 + ( 2 * 16 ) = 44
(iii) CaCO3 : 40 + 12 + ( 3* 16) = 100 MgCO3=84
(a) 56 kg of CaO could be obtained from 100 kg CaCO3
4 tons ie. 4000 kg CaCO3 would produce 56
---- * 4000 = 2240 kg CaO
100
(b) 100 kg CaCO3 gives off 44 kg CO2
94.52 kg CaCO3 would give off 44
---- * 94.52 = 41.59 kg CO2
100
Amount of CO2 from MgCO3= 4.16x44/100=1.83 kg
The CO2 produced per 1 Kg = (41.59+1.83) /100= 0.434 Kg.
2) Cracked gas from a petroleum refinery has he following composition by volume :

Methane 40% , Ethane 20% , Ethylene 25% , Propane 5% and Propylene 10% . Find (a) the
average mol.wt. of gas mixture , (b) The composition by weight.
Ans. For gases, VOLUME % = MOLE %.
Basis : 100 kg mol of cracked gas.
COMPONENT KG -MOLE MOL.WT. WEIGHT WEIGHT %
Methane 40 16 640 24.81

Ethane 20 30 600 23.35
Ethylene 25 28 700 27.13
Propane 5 44 220 8.53
Propylene 10 42 420 16.28
-------- ---------
100 2580
-------- ------------
(a) Average molecular weight = Total weight 2580 kg
---------------------- = ------- = 25.8 ----
Total no. of moles 100 kg mol
Dr.K.P.GOPINATH
7
CH 2254
3) An aqueous solution of NaCl in water contains 28 g of NaCl per 100cc of solution at

20 degree C. Express the concentration of this solution in the following terms. The density at
20 degree C is 1.18 g / cc. Calculate i) Percentage of NaCl by weight ii) Percentage of water
by weight iii) mole fraction of NaCl iv) mole fraction of water.
Ans. Basis: 100 cc of NaCl solution.
Volume of solution = 100 cc.
Mass of NaCl = 28 g
Density of solution = 1.18 g / cc.
Mass of solution = Density * Volume
= 1.18 * 100 = 118 g / cc.
Mass of water = 118 – 28 = 90 g.
COMPONENT WEIGHT MOL.WT. Moles Mole fract.. Wt.%
NaCl 28 58.5 0.479 0.087 23.73

H2O 90 18 5 .00 0.913 76.27
-------- ----------
118 5.48
------- ----------
4) Two different persons calculate the average molecular weight of a flue gas sample.
One person used the correct molecular weight for nitrogen and found that that average
molecular weight as 30.08. The other person by mistake in the atomic weight for
nitrogen and found the value as 18.74. Calculate the composition of flue gases, if the
other gases are CO2 and O2.
Ans. Basis : 100 kg moles of flue gas sample.

Let x, y and z be the moles of N2, CO2 and O2.
COMPONENT MOLES MOL.WT. WEIGHT
PERSON 1 PERSON 2
N2 x 28 28x 14x
CO2 y 44 44y 44y
O2 z 32 32z 32z
--------- --------- ---------
100 3008 1874
--------- ---------- -----------
x+y+z = 100 --- (1)
28x + 44y + 32z = 3008 --- (2)
14 x + 44y + 32z = 1874 ---(3)
(2) – (3)  14x = 1134 Therefore x = 81%
(1) * 44  44x + 44y +44z = 4400 ---- (4)
(2) * 1  28x + 44y + 32 z = 3008 ----(5)
(4) – (5)  16x – 12z = 1392
Dr.K.P.GOPINATH
8
CH 2254
16 * 81 +12z = 1392 z = 8%
(1) - y = 100 – 81 –8 y=11%
N2=81% CO2=11% O2=8%
4) The composition of a gas mixture ( on volume basis) is : N2 –70.5% , O2 – 18.8% ,

H2O – 1.2% and NH3 – 9.5%. Calculate i) the composition im weight percentage ii)
the average molecular weight.
Ans. For gases , VOLUME% = MOLE%.
Basis: 100 kg mole of gas mixture.

COMPONENT MOLE MOL.WT. WEIGHT (i) WEIGHT%
N2 70.5 28 1974.0 71.55
O2 18.8 32 601.6 21.80
H2O 1.2 18 21.6 0.78
NH3 9.5 17 161.5 5.85
-------------- --------------
100 2758.7
--------------- --------------
ii) Average molecular weight = Total weight / Total no. of moles
= 2758.7 / 100 = 27.59 kg / kg mol.
Dr.K.P.GOPINATH
9
CH 2254
Dr.K.P.GOPINATH
10
CH 2254
Dr.K.P.GOPINATH
11
CH 2254
Dr.K.P.GOPINATH
12
CH 2254
Dr.K.P.GOPINATH
13
CH 2254
Dr.K.P.GOPINATH
14
CH 2254
Dr.K.P.GOPINATH
15
CH 2254
Dr.K.P.GOPINATH
16
CH 2254
Dr.K.P.GOPINATH
17
CH 2254
Dr.K.P.GOPINATH
18
CH 2254
Dr.K.P.GOPINATH
19
CH 2254
UNIT – II
GAS CALCULATIONS
Dr.K.P.GOPINATH
20
CH 2254
RaOult’s Law.
Rault’s law holds good for ideal and dilute solutions. According to this law, the vapour
pressure of the solvent in a solution is directly proportional to the mole fraction of the solvent
pi = Pi xi
Henry’s law.
According to this, for non-ideal solution (low concentration of gas in liquid), the partial
pressure of solute gas is proportional to the mole fraction of the solute in the solution
pi = Hi xi
By Pass Stream
It is a ream that skips one or more stages of the process and goes directly to another
stage with the purpose of controlling the composition of a final exit stream.
Purge Stream
A stream bled off to remove an accumulation of certain inerts or unwanted materials
that might otherwise build up in the Recycle Stream is called a Purge Stream.
Calculate the volume occupied by 30 lb of Chlorine at a pressure 743 mm Hg and
70F.
Solution:-
Volume of S.C. = 0.423  359 = 152 Cu.ft.
P1 T2
V2 = V1 
P2 T1
70 F = 530R
760 530
Volume of 743 MMHg, 70F = 152  
743 492
= 167 Cu.ft.
Calculate the weight of 100 cu. Ft. at water vapour, measured at a pressure of 15.5 mm
Hg and 23C.
Solution:-
15.5 273
Volume of S.C. = 100   1.88 Cu.ft.
760 296
Moles of H2O = 1.88  359 = 0.00523 lb – Mole
Weight of H2O = 0.00523  18 = 0.0942 lb.
Calculate weight of 100 Cu.ft. of water vapour. Measured at a pressure of 15.5 mm Hg.
and 23C.
Solution:-
Dr.K.P.GOPINATH
21
CH 2254
15.5 273
Volume of S.C. = 100   1.88 cu.ft.
760 296
Moles of H2O = 1.88  359 = 0.00523 lb mole
Weight of H2O = 0.00523  18 = 0.0942 lb
It is desired to compress 10 lb of carbon dioxide to a volume of 20 cu.ft. Calculate the

pressure in pounds per square inch that is required at temperature of 30C.
Solution:-
Volume of S.C. = 0.228  359  81.7 cu.ft.
V1 T2
P2  T1 
V2 T1
30C  303K
81.7 303
Pressure at 20 Cu.ft. = 14.7  
20 273
= 66.6 psi
Assuming the applicability of the ideal gas law. Calculate the maximum temperature
to which 10 lb of T2, enclosed in 30 cu.ft. chamber.
Solution:-
Volume at S.C. = 0.307  359
= 128.1 Cu.ft.
P2 V2
T2  T1 
T1 V1
150 30
= 273  
14.7 128.1
Temperature at 30 Cu.ft. = 652K (or) 379C
Define Partial Pressure.
The actual volume occupied by each of there components will always be exactly the
same as that of the entire mixture.
A volume of moist air 30m3 at a total pressure of 101.325 kPa and a temperature of
303K (30C) contains water vapor in such proportions that its partial pressure is 2.933
kPa. Without total pressure being changed the temperature is reduced to 288K (15C)
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 288K
(15C) and (b) weight of water condensed.
Solution:-
Basis: 30m3 of moist air at 303K.
Dr.K.P.GOPINATH
22
CH 2254
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 = 30m3
T = 303K
101.325  30
n = moles of moist air =
8.31451 303
= 1.2066 kmol.
Let n1 be the kmol of air
n2 be the kmol of moisture/water vapour.
p1 = Partial pressure of air at 303K
= 101.325 – 2.933
= 98.392 kPa
p2 = Partial pressure of moisture at 303K
= 2.933 kPa
For ideal gas,
Pressure % = mole %
 Pressure fraction = mole fraction
For air
98.392 n1

101.325 n
98.392
n1   1.2066
101.325
= 1.172 kmol at 303K
For water vapour/moisture.
2.933 n
 2
101.325 n
Dr.K.P.GOPINATH
23
CH 2254
2.933
n2 =  1.2066
101.325
= 0.035 kmol at 303K
At 288K,
Partial pressure of water vapour = 1.693 kPa
Let n3 be the moles of water vapour at 288K.
Moles moist air = 1.172 + n3
1.693 n3

101.325 1.172  n3
 n3 = 0.02 kmol
Moles of moist = 1.172 + 0.02
air at 288K = 1.192 kmol
Let n’ = 1.192 kmol
PV = n’RT
where V = Volume of air at 288K
n’ = 1.192 kmol
R = 8.31451 m3.kPa/kmol.K
T = 288K
P = 101.325 kPa
n'RT
V=
P
1.192  8.31451 288


101.325
 28.17 m3
Moles water condensed = n2 – n3
= 0.035 – 0.02
= 0.015 kmol.
Amount of water condensed = 0.015  18
= 0.27 kg.
Dr.K.P.GOPINATH
24
CH 2254
Calculate the density in pounds per cubic foot at 29 in. Hg and 30C of a mixture of
hydrogen and oxygen that contains 11.1% of H2 by weight.
Solution:-
H2 = 0.111 lb
O2 = 0.889 lb
Total Quantity
Volume of SC = 0.0833  359 = 29.9 cu.ft.
29.92  303
Volume of 29 inches 30 C = 29.9 
29.0  273
= 34.2 Cu.ft.
Density of 29 inches 30 C = 1

34.2
= 0.0292 lb per cu.ft.
A mixture of CH4 and C2H6 has density 1.0 kg/m3 at 273K (0C) and 101.325 kPa
pressure. Calculate the mole % and weight % CH4 and C2H4 in the mixture.
Solution:-
Basis : 1 kg/m3 density of gas mixture at 273 K and 101.325 kPa.
P Mave
Density of gas mixture =  =
RT
RT
 Mave =  .
P
where  = 1 kg/m3
T = 273 K
P = 101.325 kPa
R = 8.31451 m3. kPa/kmol. K
8.31451 273
Mavg. = 1 
101.325
= 22.4
Let x CH4 and x C2H6 be the mole fractions of CH4 and C2 H6 respectively.
Mavg =   Mi xi  MCH4 .xCH4  MC2H6 .xC2H6
22.4 = 16 xCH4  30xC2H6

….(1)
xi = 1
Dr.K.P.GOPINATH
25
CH 2254
xCH4  xC2H6  1
….(2)
xC2H6  1  xCH4
….(3)
Put the value of x c 2H6 from equation (3) in equation (1) and solve for x CH4 .
22.4 = 16xCH4  30 1  xCH4 

x CH4 = 0.543
 xC2H6 = 0.457
Mole % of CH4 = xCH4  100  0.543  100
= 54.3
Mole % of C2H6= 0.457  100
= 45.7
Weight of CH4 in 1 kmol mixture = 0.543  16
= 8.69 kg
Weight of C2H6 in 1 kmol mixture = 0.457  30
= 13.71 kg.
Weight of gas mixture = 22.4 kg
8.69
Weight % of CH4 in mixture =  100
22.4
= 38.8
Weight % of C2H6 in mixture = 100 – 38.8
= 61.2
In one case 26.6 litres of NO2 at 80 kPa and 298K (25C) is allowed to stand until the
equilibrium is reached. At equilibrium the pressure is found to be 66.662 kPa.
Calculate the partial pressure of N2O4 in the final mixture.
Solution:-
Basis : 26.6 lit. of NO2 at 80 kPa and 298 K.
Volume of NO2 = 26.6 lit. = 0.0266m3
P1V1 = n1RT1
P1V1
n1 = Initial moles =
RT1
Dr.K.P.GOPINATH
26
CH 2254
where P1 = 80 kPa, T1 = 298 K
R = 8.31451 m3. kPa/kmol. K
V1 = 0.0266 m3
80  0.0266
n1 =  8.6  104 kmol
8.31451 298
n1 = 0.86 mol
2 NO2 = N2O4
Let x be the mol of N2O4 in final gas mixture.
NO2 reacted = 2x mol
NO2 unreacted = 0.86 – 2x mol
Final moles = n2 = 0.86 – 2x + x
= 0.86 – x mol
For initial conditions – P1V1 = n1RT1
For final conditions – P2V2 = n2RT2
But here, V1 = V2 and T1 = T2
P1 n1
 
P2 n2
80 0.86

66.662 0.86  x
Solving we get x = 0.1434 mol.
Final moles = 0.86 – x
= 0.86 – 0.1434 = 0.7166 mol
Mole fraction of N2O4 in final gas mixture
 xN2O4  0.1434 / 0.7166
= 0.20
Partial pressure of N2O4 = xN2O4 .P
 0.20  66.662  13.33 kPa
Dr.K.P.GOPINATH
27
CH 2254
A closed vessel contain a mixture of 40% NO2 and 60% N2O4 at a temperature of 311K
(38C) and a pressure of 531.96 kPa. When the temperature is increased to 333K
(60C), some of N2O4 dissociates to NO2 and a pressure rises to 679.95 kPa. Calculate
the composition of gases at 60C by weight.
Solution:-
Basis : 100 kg of gas mixture at 311 K
NO2 in gas mixture = 40 kg
N2O4 in gas mixture = 60 kg
40
Moles of NO2 =  0.87 kmol
46
60
Moles of N2O4 =  0.652 kmol
92
Initial moles = n1 = 0.87 + 0.652 = 1.522 kmol
N2O4 = 2NO2
Let x be the kmols of N2O4 dissociated at 333K.
NO2 formed = 2x kmol
N2O4 at 333K = 0.652 – x kmol
N2O4 at 333K = 0.87 + 2x kmol.
Total moles at 333K = (0.652 – x) + (0.87 + 2x)
= 1.522 + x kmol
P1V1 = n1RT1 …(1)
P2V2 = n2RT2 …(2)
But V1 – V2 for it being closed vessel.
Taking ratio of equation (1) and (2) we get,
P1 n1 T1
 .
P2 n2 T2
where P1 = 531.96 kPa, P2 = 679.95 kPa
n1 = 1.522, n2 = 1.522 + x
T1 = 311K, T2 = 333K
Dr.K.P.GOPINATH
28
CH 2254
531.96 1.522 311

 
679.95 1522  x 333
Solving we get,
x = 0.295 kmol.
NO2 at 333K = 0.87 + 2x
= 0.87 + 2  0.295 = 1.46 kmol.
N2O4 at 333K = 0.652 – x
= 0.652 – 0.295 = 0.357 kmol.
Amount of NO2 at 333K = 1.46  46 = 67.16 kg
Amount of N2O4 at 333K = 0.357  92 = 32.84 kg.
Composition of Gases at 333K:
Component Quantity in kg. Weight %
NO2 67.16 67.16
N2O4 32.84 32.84
Total 100 100
Class Notes - Tutorials
1) A mixture of gases has the following composition by weight Cl2 – 65% Br2 –25% and O2 –
10%.Using ideal gas law calculate i) composition of gas mixture by volume ii) density of the
gas mixture in kg / m3 at 25oC and 740 mmHg iii) Specific gravity of the gas mixture.
Ans. For gases, VOLUME% = MOLE%.
Basis: 100 kg of gas mixture.
COMPONENT WEIGHT MOL.WT. KG.MOL. MOLE%

Cl2 65 71 0.92 66.19
Br2 25 160 0.16 11.51
O2 10 32 0.31 22.30
----------
1.39
-----------
ii) Density:
Pressure P = 740 mmHg
Gas constant R = 62.40 mmHg kgmol / kg mol K
Ideal gas law :
PV = nRT
Dr.K.P.GOPINATH
29
CH 2254
V= nRT / P = 1.39 * 62.40 * 298 / 740

Volume occupied by gas V = 34.93 m3 .
Density = Mass / Volume = 100 / 34.93 = 2.86 kg / m3 .
iii) Specific gravity:
Volume of air=1x62.40x298/740=25.13m3
Density of air = M/V=29/25.13= 1.154 kg / m3
Density of gas 2.86
Specific gravity = ----------------------- = ----------- = 2.478
Density of air 1.154
2) In the manufacture of hydrochloric acid , a gas is obtained which contains 25% HCl
and 75% air by volume.This gas is passed through an absorption system in which 98%
HCl is removed. The gas enters the system at a temperature of 49 degree C and a
pressure of 738 mmHg and leaves at 38 degree C and a pressure of 738 mmHg.
Calculate the following i) Volume of gases leaving per 100 m3 entering the system and
ii) weight of HCl removed per 100 m3 of the gas entering the absorption system.
Ans. Basis : 100 m3 of the gas.
For gases , VOLUME% = MOLE%.
Volume of HCl in the gas entering the system = 25 m3
Absorption of HCl = (98 / 100) * 25 = 24.5 m3
Volume of HCl entering = 25 – 24.5 = 0.5 m3
Total volume of gas entering = 75 + 0.5 = 75m3
Pressure at which gas enters P1 = 738 mmHg.
Pressure at which gas leaves P2 = 738 mmHg.
Temperature at which gas enters T1= 49 + 273 = 322 K
Temperature at which gas leaves T2 = 38 + 273 = 311 K
Ideal gas law :
PV = nRT
i) Volume of gas :
P1 V1 / T1 = P2 V2 / T2
738 * 75.5 / 322 = 738 * V2 / 311
V2 = 72.92 m3
ii) Weight of HCl removed :
PV = nRT Moles of HCl n = PV / RT
= 738 * 24.5 / (62.396 * 322) = 0.89 kg mol.
Weight of HCl removed = Moles * Mol.wt. = 0.89 * 36.5 = 32.485 kg.
3) Acetylene gas is formed according to the equation

CaC2 + 2 H2 O  C2 H2 + Ca (OH)2
Dr.K.P.GOPINATH
30
CH 2254
Calculate the number of hours of service that can be derived from 1 kg carbide in an
acetylene lamp burning 60 lit per hour of gas at a temperature of 30oC and a pressure of 725
mmHg. Assume ideal gas law obeys.
Ans. Molecular weight of CaC2 = 64
Pressure of gas P = 725 mmHg
Gas constant R = 62.40 mmHg l / gmol K
No.of Moles of Calcium carbide n = 1000/64=15.63gm-moles
Ideal gas law :
PV = nRT
V = nRT / P = 15.63 * 62.40 * 303 / 725
Volume of carbide V = 407.58 lit.
60 lit. of take 1 hour = 60 min
407.58 lit. would take = ( 60 / 60) * 407.58 = 408 min. = 6hr.48 min.
4) Calculate the total pressure and composition of vapour in contact with the solution at
100oC containing 40% benzene , 35% toluene and the rest ortho-xylene by weight.Vapour
pressure of benzene = 1340 mmHg , toluene = 560 mmHg and ortho-xylene = 210 mmHg.
Ans. Basis : 100 kg of mixture.
Component Weight Mol.Wt. Kg.Mol. Mole Fraction

Benzene 40 78 0.51 0.45
Toluene 35 92 0.38 0.34
O-Xylene 25 106 0.23 0.20
---------------
1.12
-----------------
Component Vapour Pres. Mole.Frn. Par.Pr. (ii)Vap%
Benzene 1340 0.45 603.0 71.33
Toluene 560 0.34 190.4 22.79
O-Xylene 210 0.20 42.0 5.03
(i) Total pressure = 835.4 mmHg.
Dr.K.P.GOPINATH
31
CH 2254
UNIT – III
MATERIAL BALANCE
Dr.K.P.GOPINATH
32
CH 2254
Define law of conservation of mass.

It states that the total mass of varies components in molted remains constant during an
unit operations (or) unit process.
Input = Output + accumulation
What is Distillation?
The operation is used for separation of components of liquid Mixture by partial
vaporization and condensation.
What is evaporation?
It is for concentration of week liquor to produce thick liquor by evaporating a produce
at solvent by means of condensing steam.
What is Absorption?
It is for Removal of solute gas component from its mixture with another component gores.
Define Extraction.
In the operation used in separation of components of liquid mixture with the help of
suitable liquid solvent.
Define Drying.
It is an removal of residual moisture (or) volatile liquid with vet solids with the help of hot
air.
What is filtration?
It is an separation of solids from suspension in liquid.
Define mixing.
It is obtain a product of derived quality by mixing the weak and concentrated streams.
What is dissolution?
In the operation carried out for dilation of concentrated stream by addition of solvent.
What is crystallization?
It is formation of solid particles within a homogeneous liquid phase.
What is limiting reactant?
The reactant present in such operation of proportions that its consumption will limit
the extent to which the reaction can proceed.
Define Reactant ratio.
The number of moles of an excess reactant per mole of limiting reactant in the reactor
feed.
Define selectively.
The quantity of the limiting reactant that goes to form the desired product in the
reactor effluent, expressed as a percentage of the total quantity of the limiting reactant.
Define yield per process.

The yield of an product is the reactant effluent expressed as a percentage of that
portion of the limiting reactant in the reactor feed which is converted and disappears during
the courge of reaction.
Dr.K.P.GOPINATH
33
CH 2254
Define recycle ratio.

The ration of the quantity of a reactant recycled to the quantity of the same reactant
entering a recycling operation as fresh feed.
Define fresh – feed conversion.

The percentage of the limiting reactant in the combined reactor feed that is converted
and disappears.
Define liquid volume velocity.
The liquid volume at 600 f at limiting reactant fed per for unit volume of effective
reactor (or) catalyst bed.
Define weight hourly space velocity.
The weight of limiting reactant feed per hour per unit weight of catalyst in the reactor.
Define catalyst resistance time.
The process period length in a fixed bad operation. In continuous motley – bed
operation it is equal to the at of catalyst.
Define space – time yield.
The net yield of a product from the reactor per hour per unit of effective reactor
volume
The spent acid from a nitrating process contains 33% H2SO4 36% HNO3 and 31%
water by weight. This acid is to be strengthened by the addition of concentrated
sulphuric acid containing 95% H2SO4and concentrated nitric acid containing 78%
HNO3. The strengthened mixed acid is to contain 40% H2SO4 and 43% HNO3.
Calculate the quantities spent and concentrated acids that should be mixed together to
yield 1500 kg of the desired mixed acid. (A.M.I.E. Exam. Summer 1975, Winter 1978
and summer 1979).
Solution:
Basis: 1500 kg of the desired mixed acid.
Let, x=wt. of waste acid (in kg) required
Y=wt. of conc H2SO4 (in kg) required
Z= wt. of conc. HNO3 (in kg) required
Overall material balance is,
X+y+z=1500 ….(1)
Sulphuric acid balance is,
0.33x+0.95y=0.4 1500=600 ……(2)
Nitric acid balance is,
Dr.K.P.GOPINATH
34
CH 2254
0.36x + 0.78z=0.431500=645 …..(3)
600-0.33x
From Eq. (2), y= .....(4)
0.95
645-0.36x
From Eq. (3), z= .....(5)
0.78
Putting (4) and (5) in Eq. (1)
600  0.33x 6.45  0.36x

x   1500
0.95 0.78
or, x-(0.347x+0.462x)
=1500-(631.58+826.92)
or 0.191x=41.5
41.5
Therefore, x=  217.3kg
0.191
From (4), y=556.1 kg
From(5), z=726.6 kg.
Weights of waste (spent) acid, conc. H2SO4 and co. HNO3 required are 217.3, 556.1 and
726.6 kg respectively.
A solution of potassium dichromate in water contains 13% K2Cr2O7 by weight, 1000 kg

of this solution is evaporated to remove some amount of water. The remaining solution
is cooled to 20oC. If the yield of K2Cr2O7 crystals is 80%, calculate the amount of water
evaporated. Solubility of K2Cr2O7 is 1.390 kg mole per 1000 kg water (at 20oC).Atomic
weights: K39, Cr52. (A.M.I.E.Exam. 1975Winter and Sambalpur Uni. 1978 May)
Solution:
Basis:1000 kg of 13% K2Cr2O7 Solution,
Assumption: No water of crystallization with K2Cr2O7 crystals.
Let, F= amount of feed solution, kg.
E= amount of evaporation, kg.
C= amount of crystals formed, kg.
M= amount of mother liquor left after crystallization, kg.
Mol. wt. of K2Cr2O7 =294.
Dr.K.P.GOPINATH
35
CH 2254
XF=0.13
XC=1.0
0.39  294
xM   0.103
0.39  294  1000
K2Cr2O7 in original solution = 130 kg.
Yield of crystals = 80%= 130 0.8=104kg
So, C=104kg
Overall material balance gives,
F=E+M+C=E+M+104 …..(1)
or M-(F-E-104) =(1000-E-104)=896-E
K2Cr2O7 balance gives,
FxF=MxM+Cxc ….(2)
(since, xE=0, ExE term is not there)
So, 10000.13=(896-E)  0.103+104
i.e., 0.103 E=92.29 + 104 – 130
E=643.6 kg
Amount of water evaporated = 643.6 kg.
1000 kg of sodium carbonate solution containing 25% Na2CO3 is subjected to

evaporative cooling, during which process 15% of the water present in the solution is
evaporated. From the concentrated solution Na2CO3, 10H2O crystallizes out. Calculate
how much crystals would be produced if the solubility of Na2CO3, 10H2O is 21.5 gm per
100gm of water. (Sambalpur Uni. 1982 May)
Solution:
Basic: 1000kg of sodium carbonate 25% solution (F).
Let C=crystals formed.
E=evaporated water
Dr.K.P.GOPINATH
36
CH 2254
M=mother liquor
Water present in the solution = 750kg.
Water evaporated = 750 0.15=112.5kg
F=C+E+M=C+112.5+M
Or, 1000=112.5=C+M
i.e., M=(887.5-C)
Mol. wt. of Na2 CO2, 10H2O=286
106
xC   0.371
286
21.5
xM   0.177
121.5
Na2CO3 balance is,
FxF=MxM+CxC
10000.25=(887.5-C)0.177+0.377C
Solving, C=479.4 kg.
Crystals formed = 479.4 kg.
Phosphorous is prepared by heating in the electric furnace a thoroughly mixed mass of

calcium phosphate, sand and charcoal. In a certain charge silica used is 10% in excess
of that theoretically required to combine with all the calcium to form the silicate and the
charcoal used is 40% in excess of that required to combine as carbon monoxide, with
the oxygen that would accompany all the phosphorous as the pentoxide.
(i)
Calculate the composition of the original charge.
(ii)
If the decomposition of the phosphate is 90% complete and the reduction of
the phentoxide is 70% complete, calculate the amount of phosphorous
produced per 100 kg of charge.
Atomic weights: P-31.0, Si-28.0, Ca-40.0. (A.M.I.E Exam. 1975 Winter)
Solution:
Basis: 1kg mol of calcium phosphate decomposed.
Reaction: (i) Ca3 (PO4)2+3SiO2  3CaSiO3+P2O5
(310) (360) 9142) …(1)
Dr.K.P.GOPINATH
37
CH 2254
(ii) P2O5 + 5C  2P +5CO
(142) (512) (231) …(2)
310 kg of Ca3 (PO4)2 require 180kg of SiO2
Since SiO2 is 10% excess.
So, SiO2 supplied = 180 1.1=198kg
142 kg of P2O5 require 60kg carbon.
Since charcoal (carbon) is 40% excess.
So carbon supplied = 60  1.4=84 kg.
(i) Charge analysis:
Constituents Amount kg Wt%
Ca3(PO4)2 310 52.36
SiO2 198 33.45
Charcoal 84 14.19
Total 592 100.00
(ii) 100kg. of charge contains 52.36 of calcium phosphate
Since the phosphate decomposition is 90%
Amount of P2O5 formed (reaction -1)
142
 52.36  0.9   21.58kg.
310
Reduction of P2O5 is 70% complete
P2O5 reduced = 21.58  0.7=15.11kg
From reaction (2),
142kg P2O5 produces 62kg. P.
62
15.11 P2O5 produces  15.11  6.6kg.
142
Amount of phosphorous produced = 6.6kg.
Dr.K.P.GOPINATH
38
CH 2254
Bottled liquid gas of the following composition is sold for house – hold use:
Component n-Butane Propane Ethane
Composition, Mole% 50 45 5
V.Pr. at 30oC, bar 3.4 10.8 46.6
Determine (i) the pressure of the system and the equilibrium vapour composition at
30oC and (ii) if all the ethane be removed from the liquid, the pressure of the system and
the vapour composition at 30oC. Assume Rault’s law is applicable. (A.M.I.E. Exam.
Summer 1976).
Solution:
Basis: 1kg mole of the bottled gas.
Components Mol frac. In liquid Vapour pr., bar Partial pr., bar
n-butane 0.50 3.4 1.7
Propane 0.45 10.8 4.86
Ethane 0.05 46.6 2.33
(i) Pressure of the system
=  partial pressure = 8.89 bar
Partial pressure
y
Pr essure of the system
Pbu tan s
ybu tan s 
Total pressure
Equilibrium vapour composition:
1.70
=  100  19.12%m
8.89
4.86
Similarly, y propane   100  54.67%m
8.89
2.33
y ethane   100  26.21%m
8.89
(ii) If ethane is removed, the liquid left will be
=1.0-0.05=0.95 kg mol.
Dr.K.P.GOPINATH
39
CH 2254
Components Amount mol Mol% in – liquid p.p., bar Vapour comp.

mol%
Butane 0.50 52.63 1.789 25.91
Propane 0.45 47.37 5.116 74.09
Total 0.95 100.00 6.905 100.00
Pressure of the system = p.p. = 6.905 bar.
Carbon tetrachloride is made as following:
CS2+3cl2  CCl4 + S2Cl2
The product gases are found contain

CCl4 S2Cl2 CS2 Cl2
Mol% 23.3 23.3 1.4 32.0
Calculate (i) The percentage of the excess reactants used.
(ii) The percentage of conversion.
(iii) The kg of CCl4 produced per 100kg of cl2 converted (A.M.I.E Exam Summer 1976)
Solution:
Basis: 100kg mol of product gas.
Product gas analysis:
Components Mol
CCl4 23.3
S2Cl2 23.3
CS2 1.4
Cl2 32.0
In this case CS2 is the limiting reactant and Cl2 is the excess reactant. From the product
analysis, it is seen that 23.3 kg mols of CS2 have been converted.
(i) CS2 unconverted = 1.4 kg mol

(ii) Percentage conversion
23.3  100
  94.33
23.3  1.4
Chlorine required for complete conversion of
CS2 = 24.7  3.0=74.1 kg mol.
Dr.K.P.GOPINATH
40
CH 2254
Chlorine used = 23.33=69.9 kg mol.
Chlorine in product = 32.0
Total chlorine used = 69.9+32.0=101.9 kg mol
Excess chlorine used = 101.9-74.1
= 27.8kg.mol.
(i) Percentage of the excess reactant used
27.8
  100  37.52
74.1
(ii) From the reaction,
371.0kg of cl2 yield 154 kg of CCl4
154
100kg of Cl2 yield  100
3  71.0
=72.3 kg of CCl4
SO2 reacts with pure O2 to form SO3. If the reaction is carried out with 100% excess
oxygen as necessary for complete oxidation, but under such low temperature and
pressure that the reaction goes only 60% to completion, calculate:
i. The mole fraction of SO2, O2 and SO3 in reactants and products

ii. The weight fraction of the three gases in reactants and products
iii. The average molecular weights of reactants and products.
iv. The partial pressure of the products if the total pressure is 2 atm.
v. If the products were cooled to 20C and the pressure reduced to 720 mm Hg.,
what volume of gas would be obtained from 100 kg of SO2.
(A.M.I.E. Exam. Summer, 1977)
Solution:-
Basis : 100 gm. Mol. of SO2 gas
1
Reaction : SO2 + O2  SO3
2
Oxygen required = 50 gm mol.
Oxygen supplied (by 100% excess) = 50  2 = 100 gm. mol.
Reaction is 60% complete
Dr.K.P.GOPINATH
41
CH 2254
SO3 formed = 60 gm mol.
(a) Oxygen left = 100 – 30 = 70 gm mol.
Analysis of reactants:-
Constituents Mol Mol fraction
SO2 100 0.500
O2 100 0.500
Analysis of products:-
Constituents Mol Mol fraction
SO2 40 0.235
SO3 60 0.353
O2 70 0.412
(b) Weight fraction of reactant gases:-
Constituents Mol Wr. in gm Wt. fraction
SO2 100 6400 0.667
O2 100 3200 0.333
Weight fraction of product gases:-
Constituents Mol Wr. in gm Wt. fraction
SO2 40 2560 0.267
SO3 60 4800 0.500
O2 70 2240 0.233
Dr.K.P.GOPINATH
42
CH 2254
(c) Average molecular weight of reactants
= 0.5  64 + 0.5  32 = 48.0
Average molecular weight of products
= 0.353  80 + 0.235  64 + 0.412  32
= 56.46
(d) Partial pressure = Total pressure  Mol fraction
p.p. SO2 = 2  0.235 = 0.470 atm.
p.p. SO3 = 2  0.353 = 0.706 atm
p.p. O2 = 2  0.412 = 0.824 atm
100
(e) 100 gm SO2 =  1.56 gm mol
64
170
100 gm mol of SO2 yield  1.56  2.65 gm mol of product
100
nRT
Volume of gas =
P
2.65  62.36  273  20 

=  67.25 litres
720
So, gas produced for 100 kg of SO2
= 67.25 1000  67,250 litres
Two pure organic chemicals A and B are introduced into the apparatus as shown in the
figure below for the purpose of making the compound AB. Stream flows are adjusted so
that mole ratios of A to B in the reactor is 4:1. At the temperature and pressure
employed, this mole ratio effects complete consumption of B, 90% of the B forms AB,
the desired product. The remainder forms A2B, a 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 immissible. A2B however is soluble in A and AB.
The distribution coefficient is
CAB
k 6
CA
Dr.K.P.GOPINATH
43
CH 2254
where, CAB = mol A2B / mol AB
CA = mol A2B/mol A.
Calculate the amount of all material flowing in each numbered stream, per 100 mole of
desired product AB in stream 4. (A.M.I.E. Exam. Summer.
1977)
Fig.
Solution:-
Basis : 100 mol of B reacted.
A + B 
 AB
Since, 90% of B forms AB, 90 mol of B reacts with 90 mol of A to give 90 mol AB
2A + B 
 A2B
10 mol B reacts with 20 mol A to give 10 mol A2B
Mole of A reacted = 90 + 20 = 110
For 90 mol AB produced, 110 mol A reacted
110
100 mol AB produced =  100  122 mol A reacted
90
Stream (1) = 122 mol.
Mol of B required for 100 mol AB,
100
  100  111
90
Stream (2) = 111 mol.
The only place that A2B can leave the process is with AB. After start-up, the
recycle stream composition will change constantly until a steady state has been reached.
Under steady state conditions,
10
Mol A2B with stream (4) =  100  11.0
90
Dr.K.P.GOPINATH
44
CH 2254
So, stream (4) will have 100 + 11 = 111 mol
Calculation for Stream (3):
Stream (3) and (4) are in equilibrium with respect to the concentration of A2B.
11
CAB 
100
CAB
 6 (given)
CA
11 mol A 2B
CA  
600 mol A
mol A 4
 ; mol A = 4  111 = 444
mol B 1
make-up A is 122 mol.
Hence recycle A = 444 – 122 = 322 mol
CA = concentration of A2B in stream (3)
= 11/600
11
Mol. A2B in stream (3) =  322  5.90
600
So, stream (4) will have
(i) 100 mol AB; (ii) 11 mol A2B
Stream (3) will have
(i) 322 mol A; (ii) 5.9 mol A2B
1000 kg of an impure limestone which analysis 96% CaCO3 and 4% inert material is
reacted with a sulphuric acid solution containing 70% sulphuric acid and 30% water.
The reacting mass is heated and all the CO2 generated is driven off together with some
of the water. The analysis of the final solid ‘cake’ is
CaSO4 – 86.54%
CaCO3 – 3.11%
H2SO4 - 1.35%
H2 O - 6.23%
Inerts - 2.77%
Calculate :-
(a) the degree of completion of the reaction

(b) mass of acid solution fed
Dr.K.P.GOPINATH
45
CH 2254
(c) mass of gas driven off

(d) composition of gases driven off
Solution:-
Basis : 100 kg of cake formed
Reaction : CaCO3 + H2SO4  CaSO4 + CO2 + H2O
Amount of CaSO4 formed = 86.54 kg.
100
CaCO3 consumed =  86.54  63.63 kg.
136
CaCO3 unconverted = 3.11
(a) Degree of completion of the reaction
63.63
  95.34
63.63  3.11
98
(b) Acid used =  86.54  62.36 kg.
136
Acid in cake = 1.35 kg.
Acid supplied = 62.36 + 1.35 = 63.71 kg.
Lime stone used = 63.63 + 3.11 + 2.77 = 69.51 kg.
69.51 kg limestone require 63.71 kg H2SO4
1000 kg limestone require
63.71
=  1000  916.56 kg H2SO4
69.51
916.56
Acid solution fed =  1309.37 kg.
0.7
(c) Water in acid = 1309.37 – 916.56 = 392.81 kg.
18
Water formed =  63.63
100
= 11.45 kg (per 69.51 kg, limestone)
Total water formed by reaction
11.45
=  1000  164.72 kg.
69.51
Dr.K.P.GOPINATH
46
CH 2254
Amount of water (acid solution and reaction)
= 392.81 + 164.72 = 557.53 kg.
Water left in cake per 1000 kg limestone
6.23
  1000  89.63 kg.
69.51
Water evaporated = 557.53 – 89.63 = 467.9 kg.
44
CO2 formed =  63.63  28.00 kg.
100
For 1000 kg of limestone,
28
CO2 formed =  1000  402.82 kg.
69.51
Mass of gas driven off = 467.90 (H2O) + 402.82 (CO2)
= 870.72 kg
(d) Composition of gases driven off:
Constituents Weight, kg Kg. mol. Mol%
CO2 402.82 9.155 26.06
H2 O 467.90 25.994 73.95
Total 35.149 100.00
For 1000 lit/sec of a gaseous mixture of the following composition:

CH4 – 10%, C2H6 – 30%, H2 – 60% (all by volume) at 30C and 2000 mm Hg gauge,
calculate,
(a) the mole fraction of each component
gm mol
(b) the concentration of each component,
CC
(c) the partial pressure of each component
(d) the molar density of the mixture
(e) the mass flow rate of the mixture
(f) the average molecular weight of the gas.
(A.M.I.I. Ch. Engg. Exam., C.P.P. March 1983)
Solution:-
Dr.K.P.GOPINATH
47
CH 2254
Basis : 1000 lit of the gaseous mixture
Pressure = 2000 mm Hg gauge
= 2760 mm Hg absolute.
(a) Let nCH4, nC2H6, nH2 be the moles of the components
From ideal gas law :-
PV mm Hg lit.
nCH4  , R = 62.36
RT gm mol K
2760  1000  0.1

=  14.61 gm mol
62.36   273  30 
2760  1000  0.3 

nC2H6   43.82 gm mol
62.36  303
2760  1000  0.6 
nH2 =  87.64 gm mol
62.36  303
14.61
Mol fraction of CH4 
14.61  43.82  87.64
14.61
=  0.10
146.07
43.82
Mole fraction of C2H6   0.30
146.07
87.64
Mol fraction of H2   0.60
146.07
(b) Concentration of CH4
14.61 gm mol
  1.46  105
1000  1000 cc
43.82 gm mol
Concentration of C2H6 =  4.38  10 5
1000  1000 cc
87.64 gm mol
Concentration of H2 =  8.76  10 5
1000  1000 cc
(c) Partial pressure of CH4 = 0.1  2760 = 276 mm Hg
Partial pressure of C2H6 = 0.3  2760 = 828 mm Hg.
Partial pressure of H2 = 0.6  2760 = 1656 mm Hg.
Dr.K.P.GOPINATH
48
CH 2254
146.07 gm mol
(d) Molar density of the mixture =  0.146
1000 lit.
(e) Mass flow rate of the mixture.
Constituents Mol Mol wt Weight
CH4 14.61 16 233.76
C 2 H6 43.82 30 1314.60
H2 87.64 2 175.28
Total 1723.64
Mass flow rate of the gaseous mixture
= 1723.64 gm = 1.724 kg.
(f) Average molecular weight = 16  0.1 + 30  0.3 + 2  0.6 = 11.8.
4000 kg of KCl are present in a saturated solution at a temperature of 80C. The

solution is cooled to 20C in an open tank. The solubilities of KCl at 80C and 20C are
55.0 and 35.0 parts per 100 of water respectively. Calculate:
(a) Assuming water equal to 3% by weight of solution is lost by evaporation, weight

of crystals obtained.
(b) The yield of crystals neglecting loss by evaporation.
KCL crystallizes without any water of crystallization.
(A.M.I.E. Exam. 1978 Summer)
Figure
Dr.K.P.GOPINATH
49
CH 2254
Solution:-
Molecular weight of KCl crystals
= 39 + 35.5 = 74.5
Let F, M, E and C represent the amounts of feed, mother liquor, evaporation and
crystals and xF, xM, xE and xC their solid fractions respectively.
55
xE  0 xF   0.355
100  55
35
x C  1.0 xM   0.259
100  35
Overall material balance is,
F=E+M+C ….(1)
KCl balance is, FxF = Mxm + Cxc ….(2)
Amount of KCl in feed = 4000 kg.
So, FxF = 4000
4000
i.e. F=  11,268 kg
0.355
(a) E = 0.03 F = 0.03  11,268 = 338 kg.
From equation (1),
(11,268 – 338 – C) = M ….(3)
Putting Equation (3) in (2),
4000 = (10,930 – C)  0.259 + C
C = 1578 kg.
(b) When E = 0,M = (11,268 – C)
Equation (2) gives 4000 = (11,268 – C)  0.259 + C
Solving, C = 1460 kg.
Dr.K.P.GOPINATH
50
CH 2254
UNIT – IV
HUMIDITY AND SATURATION
Dr.K.P.GOPINATH
51
CH 2254
The humidity (H) of a gas in generally defined as that of water per unit cut of moisture free gas.
Molar humidity
The number of molar of water per mole of moisture free gas
Relative humidity
It is defined as the ratio of the partial pressure of condensable vapour in gas phase to the vapour
pressure of liquid.
Saturation humidity
It is defined as the absolute humidity of vapour gas mixture at 100% saturation.
Absolute Humidity
This is defined as the weight of water vapour per unit weight of dry air in the mixture.
H = WA/WB = weight of water vapour / weight of dry air.
Percentage humidity
It is the ratio of the molal humidity at unsaturated conditions to the molal humidity at saturation.
%H = Hm /Hms x100 %
Humidification
The operation that is carried out increase the amount of vapour in a gas stream.
Dehumidification
It is carried to reduce the vapour content of gas stream is known as dehumidification.
Dew point
If an unsaturated mixture of vapour and gas is cooled the relative amounts of the components and
the percentage composition by volume will at first remain unchanged.
Dr.K.P.GOPINATH
52
CH 2254
The dry bulb temperature and dew point of ambient air were found to be 302 K (29oC)
and 291 K(18oC) respectively, Barometer reads 100 kPa. Calculate:
(a) The absolute molal humidity,

(b) The absolute humidity,
(c) % RH,
(d) % Saturation,
(e) Humid heat and
(f) Humid volume
Data: Vapour pressure of water at 291 K = 2.0624 kPa vapour pressure of water at 302
K=4.004 kPa.
Solution:
Air-water vapour mixture with DB = 302 K and DP = 291 K.
At DP, partial pressure of water in air is equal to vapour pressure of water.
PA = partial pressure of water vapour in air = 2.0624 kPa
P=total pressure = 100 kPa
PA
Absolute molal humidity = Hm 
P  PA
2.0624
=
100-2.0624
kmol water vapour
=0.02106
kmol dry air
.....Ans. (a)
Mol. Wt. H2O=18,Mol. Wt. air =29
Mol.wt.H2O
Absolute humidity =H= Hm 
Mol.wt.air
18
=0.02106 
19
kg water vapour
=0.0131
kg dry air
.....Ans. (b)
At saturation,
DB=WB=DP=302K
Vapour pressure at saturation i.e. at 302K=P6=4.004kPa.
Dr.K.P.GOPINATH
53
CH 2254
PA
% RH =  100
P6
2.0624
=  100
4.004
=51.51
.......Ans(c)
 P  Mol.wt.H2O
Saturation humidity = H8   8 
 P  P6  Mol.wt.air
 4.004  18
H8   
100  4.004  29
kg water vapour
=0.02589=
kg dry air
H
% saturation =  100
H5
0.0131
=  100
0.02589
….Ans.(d)
Humid heat = Ca = 1.006+1.84H
=1.006+1.884  0.0131
=1.03kJ/kg dry air K ….Ans. (e)
 H   1  
Humid volume = VH      22.4136
 MA   Ms  
 DB  101.325
 
 273  P
 0.0131 1   302  101.325
=   22.4136     100
 18 19   273 
=0.8846m3 / kg dry air .....Ans.(e)
Dr.K.P.GOPINATH
54
CH 2254
2. A mixture of benzene and dry air at a temperature of 303 K(30oC) and a pressure of
101.325 kPa is found to have a dew point of 288 K(15oC).
Calculate:
(a) Percentage by volume of benzene.

(b) Moles of benzene per mole dry air.
Data: Vapour pressure of benzene at 288K=7.999 kPa.
Solution:
Basis : A mixture of benzene and dry air at 101.325 kPa.
PA = Partial pressure of benzene in mixture.
= vapour pressure at 288 K.
= 7.999 kPa.
For ideal gas mixture,
Volume % = mole % = pressure %.
PA
Volume % of benzene=  100
P
7.999
=  100
101.325
=7.9
....Ans.(a)
1 mol of mixture
Benzene present = 0.0791=0.079 mol.
Dry air present = 1-0.079=0.921 mol.
0.079
Moles benzene per mole of air=
0.921
=0.086 ....Ans(b)
3. A mixture of acetone vapour and nitrogen contains 15.8% acetone by volume.

Calculate the relative and percent saturation of the mixture at a temperature of 293
K(20oC) and a pressure of 101.325 kPa.
Data: Vapour pressure of acetone at 293 K = 24.638 kPa.
Solution:
Basis: 1 mol of acetone nitrogen mixture.
Mol % acetone = volume % acetone = 15.8
Dr.K.P.GOPINATH
55
CH 2254
15.8
Molfraction of acetone in mixture = y =
100
P= total pressure = 101.325 kPa.
PA=partial pressure of acetone = y.P
=0.158  101.325
=64.98 …..(Ans)
Hm= Moles acetone per mole nitrogen in gas mixture
0.158

1  0.158
 0.1876
Consider one mole of saturated mixture at 293 K(20oC) and 101.325 kPa.
 Volume % acetone   Pr essure % acetone 

   
 in saturated mixture   in saturated mixture 
24.638
Volume % acetone =  100
101.325
=24.31
Mole % acetone in saturated mixture = volume % acetone
= 24.31
24.31
Acetone in saturated mixture = 1
100
=0.2431 mol
Nitrogen in saturated mixture = 1-0.2431
=0.7569 mol
HmS  moles acetone per mole nitrogen in saturated mixture
0.2431
=
0.7569
= 58.40 …..Ans.
Dr.K.P.GOPINATH
56
CH 2254
4. A gas mixture containing benzene vapour is saturated at 101.325kPa and 323

K(50oC). Calculate the absolute humidity if the other component of the mixture in (a)
nitrogen and (b) carbon dioxide.
Data: vapour pressure of benzene at 323 K=36.664 kPa.
Solution:
Basis : A gas mixture at 101.325 kPa and 323 K.
(a) Nitrogen and benzene vapour mixture.
Mol Wt. N2=28, Mol Wt. C6H6=78
As the mixture is saturated at 323K, the partial pressure of benzene is equal to vapour
pressure of benzene at 323 K.
 PA =36.664 kPa
P=101.325 kPa
PA
Hm 
P  PA
36.664
=
101.325-36.664
kmol benzene vapour
=0.567
kmol nitrogen
Mol wt.C6H6
Absolute humidity = Hm 
Mol wt. N2
78
=0.567 
28
kg benzene
=1.579 .....Ans.(a)
kg nitrogen
(b) Carbon dioxide – benzene vapour mixture.
Mol Wt. CO2 = 44
Dr.K.P.GOPINATH
57
CH 2254
PA = 36.664 kPa P =101.325 kPa

PA
Hm 
P  PA
36.664
=
101.325-36.664
Kmol benzene vapour
=0.567
kmol carbon dioxide
Mol wt. C6H6
Absolutehumidity  Hm 
Mol wt. CO2
78
=0.567 
44
kg benzene
=1.005 ....Ans(b)
kg carbon dioxide
5. The dry bulb temperature and dew point of ambient air were found to be 303
K(30oC) and 289 K(16oC) respectively. Calculate (i) the absolute molal humidity, (ii) the
absolute humidity, (iii) the % RH, (iv) the % saturation and (v) the humid heat.
Data: Vapour pressure of water at 289 K = 1.818 kPa
Vapour pressure of water at 303 K= 4.243 Kpa
Barometric pressure = 100 kPa
Solution:
Basis : Air – water mixture at DB = 303 K and DP = 289 K.
Partial pressure of water in air = Vapour pressure of water at DP
PA =1.818kPa
=Partial pressure of water vapour in air
P=total pressure
=100 kPa
PA
Absolute molal humidity = Hm=
P  PA
1.818

100  1.818
kmol water vapour
 0.01852 .....Ans.(i)
kmol dry air
Dr.K.P.GOPINATH
58
CH 2254
Mol Wt. H2O=18, Mol Wt. air = 29
Mol.Wt.H2O
 Hm 
Mol Wt. air
18
Absolute humidity = H  0.01852 
29
kg water vapour
 0.0115 ....Ans.(ii)
kg dry air
At saturation,
DB=WB=DP=303K
Vapour pressure of water at saturation = 4.243 kPa
i.e. at 303 K
Pa = 4.243 kPa
PA
  100
Pa
1.818
%RH=   100
4.243
 42.85 .....Ans(iii)
 P  Mol wt. H2O

  8 
 P  P3  Mol wt.air
 4.243  18
Saturation humidity = H8=   
100  4.243  29
kg water vapour
 0.0275
kg dry air
H
% Saturation =    100
 H8 
0.0115
=  100
0.0275
=41.82 .....Ans(iv)
Humid heat = C8  1.006  1.84H
=1.006+1.84  0.0115
=1.0272 kJ/kg dry air. K ......Ans(v)
Dr.K.P.GOPINATH
59
CH 2254
6. A mixture of benzene vapour and nitrogen gas at 297 K and 100 kPa has a relative
humidity of 60%. It is desired to recover 80% of benzene by cooling a mixture to 283
K(10oC) and compressing to a suitable pressure. Find out the pressure required for
above duty.
Data: Vapour pressure of benzene at 297 K=12.2kPa
Vapour pressure of benzene at 283 K = 6kPa.
Solution:
Basis: A mixture of benzene and nitrogen with 60% RH at 297 K.
PA
%RH   100
P8
where PA= partial pressure of benzene
P8 = vapour pressure of benzene
=12.2 kPa.
pA
60   100
12.2
pA = 8.32 kPa
at 297 K
In 1m3 of the benzene – nitrogen mixture
pA .MA
Mass of benzene = V
RT
where pA = 7.32 kPa
MA = 78
T =297 K
R =8.31451 m3. kPa/kmol. K
Dr.K.P.GOPINATH
60
CH 2254
7.32  78  1
Mass of benzene=
8.31451 297
=0.31kg
Mass of nitrogen =
100-7.32   28  1
8.31451 297
=1.051 kg
0.231
Hence,humidity=H=
1.051
=0.22kg/kg
PA
Hm 
P  PA
7.32
=
100-7.32
kmol benzene
=0.07898
Kmol nitrogen
Mol wt.C6H6
Humidity =H=Hm 
Mol wt. N2
78
=0.07898 
28
kg benzene
=0.22
kg nitrogen
In order to recover 80% of benzene, the humidity must be reduced to 20% of its initial
value. As the vapour will be in contact with liquid benzene, the nitrogen will be saturated with
benzene vapours and hence at 283 K.
20
Ho  0.22 
100
kg benzene
=0.044
kg nitrogen
Ho  humidity of saturated gas.
 p  M
Ho   s   A
 P  Ps  MB
where Ho=0.44
MA=78, MB=28
P= total pressure
Dr.K.P.GOPINATH
61
CH 2254
O8=6kPa at 283 K
(p.p. of benzene vapour in saturated gas is equal to vapour pressure of benzene at 283 K).
 6  78
0.044   
 P  6  28
0.044(P-6)=16.71
0.044P-0.264=16.71
P=385 kPa
Total pressure to which gas should be compressed = 385.8 kPa ….Ans.
7. A mixture of acetone vapour and nitrogen contains 14.8% acetone by volume,

calculate the following at 293 K (20oC) and a pressure of 99.33 kPa.
(a) Partial pressure of acetone.

(b) Moles of acetone per mole of nitrogen.
(c) Relative saturation of mixture at 293 K(20oC), and
(d) Percentage saturation of mixture at 293 K(20oC).
Data: Vapour pressure of acetone at 293K=24.638 kPa.
Solution:
Basis: 1 kmol of mixture of acetone vapour and nitrogen at 293K.
Mole % acetone in mixture = volume % acetone
= 14.8
Mole fraction of acetone in mixture = 14.8/100
=0.148
P =total pressure = 99.33 kPa.
PA=partial pressure of acetone vapour
Y =molefraction of acetone in mixture
PA=y.P
=0.1488  99.33
=14.7 kPa.
14.8
Acetone in mixture = 1
100
=0.148 kmol
Nitrogen in gas mixture = 1-0.148
=0.852 kmol.
Dr.K.P.GOPINATH
62
CH 2254
0.148
Hm  kmols acetone per kmol nitrogen =
0.852
=0.174 ....Ans(b)
Vapour pressure of acetone at 293K=24.638 kPa
P8= 24.638 kPa
pA
% relative saturation =  100
p8
14.7
=  100
24.638
=59.66 ...Ans(c)
Consider one kmol of saturated mixture at 293 K (20oC) and 99.33 kPa.
Volume % acetone = pressure % acetone
P3
  100
P
24.638
  100
99.33
 24.80
Mole % acetone = volume % acetone = 24.8
Acetone in saturated mixture = 0.248 1
=0.248 kmol
Nitrogen in saturated mixture = 1-0.248
=0.752 k mol
HmS  mole acetone per mole of nitrogen in saturated mixture
0.248

0.752
=0.329
Hm
Hms
0.174
=  100
0.329
=52.9 ....Ans.(d)
Dr.K.P.GOPINATH
63
CH 2254
8. An air – water vapour mixture has relative humidity of 80% at 293 K(20oC)
temperature and 100 kPa pressure. Calculate: (a) molal humidity of air, (b) molal
humidity of air if its temperature is reduced to 283 K(10oC) and the pressure is
increased to 174.65 Kpa condensing out some of the water, (c) Calculate the weight of
water condensed from 500 kg of original wet air in the process of part (b), (d) calculate
the final volume of the wet air of the part (c).
Data: Vapour pressure of water at 293 K(20oC) = 2.40 kPa Vapour pressure of water at
283K(10oC) = 1.266 kPa.
Solution:
Basis: Air-water vapour mixture of RH= 80%at 293 K and 100kPa.
Vapour pressure of water at 293 K= 2.40 kPa
P8=2.40 kPa
PA= partial pressure of benzene
P8 = vapour pressure of water in air
PA
%RH=  100
P8
pA
80   100
2.40
pA = 1.92 kPa
PA
Initial molal humidity Hm 
P  PA
7.32
Hm =
100-7.32
kmol water vapour
=0.01958 ....Ans(a)
Kmol dry air
Final partial pressure of water vapour (i.e. at 293 K) is equal to the vapour pressure of water
at 283 K (10oC) as air becomes saturated at that stage.
PA at 283K=1.266 kPa
P at 283K = 174.65 kPa
Final molal humidity (i.e. at 283 K and 174.65 kPa).
Dr.K.P.GOPINATH
64
CH 2254
PA

P  PA
1.266
=
174.65-1.266
kmol water vapour
Final molal humidity =0.0073 ....Ans(b)
Kmol dry air
Molal humidity at 293 K=0.01958
Humidity at 293 K (20oC)
18
on weight basis =0.01958 
29
kg water
=0.0122
kg dry air
Humidity at 283 K(10oC)
18
on weight basis =0.0073 
29
kg water
=0.00453
kg dry air
At 293 K(20oC), air water vapour mixture contains 0.0122 kg water vapour (moisture) per kg
dry air i.e. per 1.0122 kg of wet air.
Consider 500 kg of wet air,
Water present at 293 K in wet air (i.e. initial)
0.0122
  500
1.0122
=6.026 kg
Dry air in wet air = 500-6.026
=493.974 kg
0.00453
water present at 283K (i.e. final)=  493.974
1
=2.238.kg
Dr.K.P.GOPINATH
65
CH 2254
Water condensed from 500 kg wet air.
=Water present at 293K-Water present at 288K
=6.026 – 2.238
=3.788kg
Total amount of wet air at 283K(10oC)
=493.974 +2.238
=496.212kg
2.238
Water in wet air at 283 K=
18
=0.1243 kmol
493.974
Dry air in wet air at 283 K=
29
=17.033 kmol
Amount of wet air at 283 K=17.033 kmol
=17.1573 kmol
PV=nRT
nRT
V
P
Where n= 17.1573 kmol, T= 283 K
m3 .kPa
P=174.65 kPa, R= 8.13451
kmol.K
17.1573  8.13451 283

Volume of wet air at 283 K(10oC)=V=
174.65
=231.2m3 …..Ans. (d)
Dr.K.P.GOPINATH
66
CH 2254
9. Carbon dioxide contains 0.053 kmol of water vapour per kmol of dry CO2 gas at
temperature of 308 K(35oC) and a total pressure of 100 kPa.
Calculate: (a) Relative saturation of the mixture, (b) Percentage saturation of the
mixture, and (c) The temperature at which the mixture must be heated in order to
achieve the relative saturation of 30%.
Data: Vapour pressure of waer at 308 K= 5.60 kPa
Vapour pressure of water at 330 K(57oC) = 16.745 kPa
Solution:
Basis: 1 kmol of dry CO2 in the mixture.
Water vapour associated with CO2 in the mixture.
Amount of CO2 water mixture = 1+0.053
= 1.053 kmol
0.053
Molfraction of water vapour in gas mixture = y=
1.053
=0.0503
P= total pressure = 100 kPa
Partial pressure of water vapour = pA =y.P
=0.0503  100
=5.03 kPa
P8 = Vapour pressure of water at 308 K=5.60 kPa
PA
Relative saturation at 308 K(35oC)=  100
P8
5.03
  100
5.60
=89.82 ….Ans(a)
Hm = kmol water vapour per kmol CO2 at 308 K(35oC)
0.0503
  0.0503
1
Consider one kmol of saturated mixture at 308 K(35oC) and 100 kPa.
Volume % of water = pressure % of water
Dr.K.P.GOPINATH
67
CH 2254
5.6
=  100
100
=5.6
(Partial pressure = vapour pressure for saturated gas)
5.6
Water vapour in mixture = 1
100
=0.056 kmol
CO2 in gas mixture =1-0.056
=0.944 kmol
HmS  k mol water vapour per kmol CO2 in saturated mixture
0.056

0.944
=0.0593
Hm
Hms
0.053
=  100
0.0593
=89.37 ...Ans(b)
Relative saturation 30%
PA
Relative saturation   100
P8
Where PA = partial pressure of water vapour
Ps = Vapour pressure of water
5.03
30  100
P8
Solving P8 = 16.767 kPa
Water exerts a vapour pressure of 16.767 kPa (approximately equal to at 330 K(57oC) as
per the data supplied.
Hence, the mixture should be heated to 330 K(57oC) to get the desired relative saturation as
vapour pressure at 330K (57oC).
Given (data) is approximately matching the calculated value.
Temperature two which gas should be heated = 330K(57oC) …Ans.
Dr.K.P.GOPINATH
68
CH 2254
10. A gas mixture containing carbon disulphide vapour [CS2] at a temperature of 300K
(27oC) and a pressure of 100 kPa has the percentage saturation of 70. Calculate the
temperature to which gas must be cooled at constant pressure so as to condense
40% of CS2 present.
Data: Vapour pressure of CS2 at 300 K(27oC)=52.662 kPa
Vapour pressure of CS2 at 287 K (14oC) = 31.997 kPa
Vapour pressure of CS2 at 288 K(15oC) = 33.33kPa
Solution:
Basis: A gas mixture with percentage saturation of 70 at 300 K(27oC).
Vapour pressure of CS2 at 300K=52.662 kPa
P8=52.662 kpa
P=100 kpa
% saturation =70
% saturation =
pA / P  pA   100
P8 / P  Ps 
70=
pA /100  pA   100
52.662 /100  52.662
Solving we get,
PA=43.778kPa
Partial pressure of CS2=43.778 kPa
Consider 1 kmol of mixture
43.778
CS2 in the mixture  1
100
=0.43778
=0.4378 kmol
Other gas component in mixture = 1-0.4378
=0.5622
Amount of CS2 condensed = 0.40  0.4378
=0.1751 kmol
CS2 present finally in the mixture = 0.4378-0.1751
= 0.2627 kmol
Dr.K.P.GOPINATH
69
CH 2254
Amount of gas mixture (final) = 0.5622+0.2627
=0.8249 kmol
0.2627
Mol % CS2 =  100
0.8249
=31.85
Pressure % CS2 = Mole % CS2 = 31.85
pA
 100  31.85
P
pA
 100  31.85
100
 p A  31.85kPa.
As the mixture is saturated, the partial pressure of CS2 is equal to vapour pressure at final
temperature, the vapour pressure of CS2=31.85 kPa.
From the data cited the temperature at which the vapour pressure of CS2 is approximately
31.85 kPa is 287 K(14oC).
Therefore, the gas must be cooled to a temperature of 287 K(14oC).
Temperature to which gas must be cooled = 287 K(14oC)
11. Air has a percentage humidity of 60 at a temperature of 300 K(27oC) and a

pressure of 100kPa. Calculate the pressure to which air must be compressed at a
constant temperature so as to remove 90% of the water present.
Data: Vapour pressure of water at 300 K(27oC) = 3.565 kPa
Solution:
Basis: Air of percentage humidity 60 at 300 K and 100 KPa pressure.
P8 = Vapour pressure of water = 3.565 kPa
P = 100kPa
pA / P  pA
% humidity =  100
P8 / P  Ps
60=
pA /100  pA   100
3.565 /100  3 / 565
Solving Pa = 2.170 kPa
Consider 1 kmol of gas mixture
2.170
Amount of water vapour in mixture  1
100
Dr.K.P.GOPINATH
70
CH 2254
Amount of air in the mixture =0.0217
=0.9783 kmol
(as mole % = pressure %)
Amount of water removed = 0.9  0.0217
=0.01953 kmol
Amount of water remained in gas mixture = 0.0217-0.01953
=2.17  10-3 kmol
Amount of gas mixture (finally) =0.9783+2.17  10-3
=0.98047 kmol
2.17  103
  100
Mole % water vapour in the mixture = 0.98047
 0.2213
Let PT be the final pressure to which air must be compressed.
The partial pressure of water vapour is equal to the vapour pressure at 300 K(27oC) as the
mixture is saturated at PT.
PA=3.565 kPa
Mole% = pressure %
pA
0.2213   100
PT
3.565
0.2213   100
PT
 pT  1610.9kPa(15.90atm). .....Ans.
Dr.K.P.GOPINATH
71
CH 2254
UNIT – V
FUELS AND COMBUSTION
Total heating value:
Dr.K.P.GOPINATH
72
CH 2254
A fuel is heat evolved in its complete combustion under constant pressure at a temperature of 25C.
Net heating value:
It is defined as final state of the water in the system after combustion is taken as vapour at 25C.
Coke and Carbon:
The heat of formation of carbon is the form of the diamond in accurately known and is equal to 0.45
32 Kcal per g-atom.
Coal analysis:
It is addition to organic matter it contain minerals constituent of the plants from which it was
formed and inclusion.
Incomplete combustion of fuels:
The standard heating values at fuel correspond to conditions at complete combustion of all carbon
to carbon dioxide gas.
Enthalpy of water vapour:
The enthalpy of superheated water vapour referred to the liquid at 25C
Heating values of fuel:
The total heating value of a fuel is the heat evolved in its complete combustion under constant
pressure at a temperature of 250C when all the water initially present as liquid in the fuel and
present in the combustion products are condensed to the liquid state.
The net heating value is defined except that the final state of the water in the system after
combustion is taken as vapor at 250C.The total heating value is also termed the `gross` heating value.
The net heating value is also termed as the lower heating value.
Rank of Coal:
Fuel ratio of a coal is defined as the ratio of percentage of fixed carbon to that of volatile matter.
The rank of the coal whether bituminous or anthracite, may be estimated from its fuel ratio.
Heating value of coal:
The total heating value of a coal may be determined by direct calorimetric measurement and
expressed as Btu/lb. The net heating value is obtained by subtracting from the total heating value
the heat of vaporization at 250C of the water present in the coal and that formed by the oxidation of
the available hydrogen.
Net H.V. = total H.V. – 8.94 * H * 1050
Where H.V. = heating value, H wt. Fr. Of total hydrogen including available H2, H2 in moisture and H2
in combined H2O
Dr.K.P.GOPINATH
73
CH 2254
Orsat analysis:
The analysis of flue gases is ordinarily determined by the orsat type of apparatus, yielding the
percentages of carbon dioxide, carbon monoxide, oxygen and nitrogen in the moisture free gases.
Ultimate analysis:
It is a method of analysis of a fuel which gives the complete composition of i) C ii) H 2 iii) N2
iv) S v) Ash
Proximate analysis:
It is determination is made of each of the proximate analysis defined groups of moisture, volatile
matter, ash and fixed carbon (obtained by deducting %moisture, %volatile matter, % ash from 100).
Problem1. The waste acid containing 25% HNO3, 50% H2SO4 and 25% H2O by weight .This acid is
to be concentrated to contain 30% HNO3 and 60% H2SO4, by the addition of concentrated H2SO4
containing 95% H2SO4 by weight and concentrated HNO3 containing 90% HNO3 by weight.
Calculate the weights of waste acid and concentrated acids to obtain 10,000 kg of mixture of desired
composition.
Basis: 10,000 kg of Product Mixture
Let ‘x’ be the amount of waste acid Let ‘y’ be the amount of concentrated H2SO4acid
Let ‘z’ be the amount of conc. HNO3 acid
Overall Material Balance
x + y + z =10000 Kg
H2SO4 Material Balance
0.5x + 0.95y = 0.6*10000=6000
0.5x + 0.95y = 6000
0.95y = 6000 - 0.5x
y=6000-0.5x/0.95=6315.79-0.526x
HNO3 Material Balance
0.25x + 0.9z = 1000x0.3=3000
0.9z = 3000 – 0.25x
z = 3000 – 0.25x/0.9 =3333.33-0.278x
Dr.K.P.GOPINATH
74
CH 2254
x+6315.79-0.526x+3333.33-0.278=10000
x(1-0.526-0.278)=350.88 x=1790.20 kg
x = 1790.20 Kg y = 5374.15 Kg z = 2835.65 Kg
Problem 2: 1000 kg of sodium carbonate solution containing 23% Na2CO3 is subjected to evaporative
cooling. During which 15% of the water present in the solution is evaporated. From the concentrated
solution Na2CO3 .10H2O crystallizes out. Calculate how much crystals would be produced if the
solubility Na2CO3 .10H2O be 21.5grams per 100 grams water.
Basis: 1000 Kg of sodium carbonate solution
Let ‘x’ be the amount of Na2CO3 .10H2O crystallized out
Amount of water fraction evaporated = 800(0.15)=120 kg
Weight fraction in the initial Na2CO3 = 0.2
Weight fraction in the final Na2CO3 = 21.5/121.5=.0177
Weight fraction in the crystal = 106/286 =0.371
1000(0.2)= x(0.371) + (880-x) * 0.177
200 = x(0.371) + 155.76 - 0.177x
44.24 = 0.194x x = 228.04 Kg
Problem.3:1:3 nitrogen hydrogen mixtures are fed to an ammonia converter resulting in 25%
conversion to ammonia. The unconverted gases are recycled to the reactor. The initial mixture
contains 0.2 parts argon per 100 parts of the nitrogen hydrogen mixture. The toleration limit for argon
is 5 parts per 100 parts by volume. Estimate the fraction of the recycle that must be purged
continuously. Find the recycle and purge ratio
Basis: 100 Kgmoles of of H2- N2 mixture
1N2 + 3H2 2NH3
let ‘x’ be the Kg moles of N2 ,H2 ,mixture recycled.
Let ‘y’ be the Kg moles of N2 ,H2 ,mixture purged.
Amount of H2 ,N2 mixture entering the reactor = ( 100 + x ) Kg moles
Amount of H2 , N2 mixture leaving the reactor = 0.75 (100+x)Kg moles 2
Amount of the NH3 formed =(100+x)* 25/100 * 1/ 2
Dr.K.P.GOPINATH
75
CH 2254
Tolerance limit = moles of Ar / moles of N2 ,H2
Tolerance limit = 0.05(100+x)/(1-0.25)(100+x) = 0.05/0.75 = 0.0667
Moles of Ar present in the fresh feed = 0.2 moles
Moles of Ar present in the purge stream = 0.0667 moles
When a steady state operation is obtained for Ar purged is = Argon in the fresh feed supplied
0.2 =0.0667y y=2.99 Kg moles
Material Balance at purge point (b)x + y=0.75(100+x)
x – 0.754x=72.01
0.25x = 72.01 x =288.04 Kg moles
(a) Fraction of recycle =y/x= 2.99/288.04 =0.01038

(b) 0.25(100+x)/2=0.25(100 +288.04)/2= 48.505
(c) Recycle ratio =288.04/100=2.88
(d) Purge ratio =2.99/100=0.0299=0.03
Problem.4:
10,000 kg of an aqueous solution containing 29.6% Na 2SO4 is cooled. During cooling 5% water in
the solution is lost by evaporation. As a result crystals of Na 2SO4 .10H2O crystallize out. If the
mother liquor is found to contain 18.3% Na 2SO4 .Calculate the weight and percent yield of crystals
and the quantity of mother liquor obtained. All percentages are by weight
Basis: 10,000 kg of Na2SO4 solution.
Finding Weight fraction
Na2SO4 balance:
10000X0.296 =0.441x + (10000-352-x) X 0.183
Amount of yield of crystals x=4629.53 Kg.
i) Quantity of mother liquor =10000-352-4629.53 = 5018.47 Kg.
ii)% Yield=2041.62/2960 X100=68.97
Dr.K.P.GOPINATH
76
CH 2254
Problem.5
Air at a temperature of 200 C and a pressure of 750 mmHg has a relative humidity of 80%. (i)
Calculate the molal humidity of the air.
(ii)Calculate the molal humidity of this air if its temperature is reduced to 100 C and its pressure is
increased to 1810 mm Hg condensing out some of the water.
(iii) Calculate the weight of water condensed from 28,000 Liters of the original wet air in cooling
and compressing to conditions of Part (ii)
(iv) Calculate the final volume of the wet air of Part (iii)
V.P. of water 17.5 mmHg at 200 C
9.2 mmHg at 100 C
T=temperature = 200 C =20+273=2930K,Pressure = 750 mmHg ,
Relative humidity=80% ,PAS= V.P. of water =17.5 mmHg at 200 C
PAS= V.P. of water = 9.2 mmHg at 100 C
(i) %RH=PA x100/PAS ,PA=14 mmHg 4
The molal humidity of the air=14 / (750-14)=0.01902
ii) The molal humidity of the final air =9.2 /(1810-9.2)=0.0051
iii) The weight of water condensed = n(H m initial –Hm final ) x18
n=(750-14)x28000 /(62.36x293)=1127.88 gm moles
Weight of water condensed =1127.88(0.01902-0.0051)x18=303.31gm
iv) Final volume of the wet air : (750-14)x28000/293
= (1810-7.36) V2 /283
V2 =11041.95 lits. 4X4=16
Problem.6:
Chlorobenzene is nitrated using mixture of nitric acid and sulphuric acid. The reaction is
C6H5 CI +HNO3  CIC6H4 NO2 +H2O
A charge consisted of 100 Kg of chlorobenzene, 106.5 Kg of 65.5% nitric acid and 108
Kg of 93.6 % Sulphuric acid (by weight). After 2 hrs. of operation the final mixture was
analyzed. It was found that the final product contain 2% unreacted chlorobenzene. Also
Dr.K.P.GOPINATH
77
CH 2254
the product distribution was found to be 66% P-nitrochlorobenzene and

34% O-nitrochlorobenzene. Calculate (i) The analysis of charge
(ii) The percentage conversion of chlorobenzene.
(iii) The Composition of the product mixture.
Molecular weight: Chlorobenzene -112.5 Nitrochlorobenzene -157.5
Basis: 100 Kg of chlorobenzene+106.5 Kg of HNO3 + 108 kg H2SO4 =314.5 Kg of

mixture
(a) Analysis of charge.

Weight of the nitric acid =106.5x0.655 =69.76 Kg
Weight of the sulphuric acid =108x0.936=101.09 Kg
Weight of H2O =(106.5-69.76)+(108-101.09) =36.74+6.91= 43.65 Kg
Compts Kg wt%
Chlorobenzene 100 31.80%
HNO3 69.76 22.18
H2SO4 101.09 32.14
H2O 43.65 13.88

-------------- --------------
314.50 100%
-------------- ---------------
ii)% Conversion of chlorobenzene
100Kg 2Kg% of chlorobenzene unreacted
314.5 Kg charge314.5x2/100=6.29 Kg
Chlorobenzene unreacted =6.29 Kg
Remaining Chlorobenzene =100-6.29 =93.71 Kg
100 Kg  100%
93.71 Kg % conversion =100%93 Kg/100 Kg=93.71%

C6H5Cl + HNO3  ClC3H4NO2 + H2O
112.5 63 157.5 18
93.71 Kg ? ? ?
HNO3 required =93.71x63/112.5=52.48 Kg
Dr.K.P.GOPINATH
78
CH 2254
Nitrobenzene formed =157.5x93.71/112.5=131.19 Kg
In the product distribution,66% P-nitrochlorobenzene 34% O-nitrochlorobenzene
Weight of P-nitrochlorobenzene=131.19x0.66=86.59 Kg
Weight of the O-nitrochlorobenzene=131.19x0.34=44.60 Kg
Weight of H2O formed=93.71x18/112.5 =14.99 Kg
Total H2O produced =14.99 + 43.65 = 58.64 Kg
HNO3 unreacted =69.76-52.48=17.28 Kg
Composition of pdt mixture
Compts Kg Wt%
Unreacted C6H5Cl 6.29 2.0
Unreacted HNO3 17.28 5.49
H2SO4 101.09 32.14
H2O 58.64 18.65
O-N-C-B 44.60 14.18
P-N-C-B 86.59 27.53
____________________
314.50 100%
Problem .7:
Lignite pitch containing 80% carbon, 10% hydrogen, 3% oxygen and 1% nitrogen and remaining
sulphur by weight is completely burnt with 40% excess air. Determine the products of combustion.
Basis: 100 kg of Lignite pitch
Products of combustion: CO2=293.33kg H2O=90 kg SO2=12kg
O2=118.53 kg N2=1388.80 kg
ii) i)Air-fuel ratio by weight=16.66 ii) Air-fuel ratio by volume=8998.5
Weight of dry exhaust gas formed per unit weight of fuel=16.14
Dr.K.P.GOPINATH
79
CH 2254
Problem.8:
A combustible gas with a composition by volume of H2= 45%,CH4=30 %, C2H6 = 15%, N2 = 10 % is

burnt in air. The composition of the dry products of combustion is CO2 = 7.18 %, CO = 0.16%, O2 =
5.89 %, and N2 = 86.77 % by volume. Find i) the air- fuel ratio on the volume basis. ii) Also find the
percentage of excess air.
Basis : 100 Kg mole of combustible gas
Compts Kgmoles Atoms of C
H2 45 -----
CH4 30 30
C2H6 15 30
N2 10 -----
60
Basis: 100 Kgmol of dry combustion gas
Compts Kgmoles Atoms of C
CO2 7.18 7.18
CO 0.16 0.16
O2 5.89 ------
N2 86.77 -----
7.34
For 100 Kg mole of dry combustion gas
Let x= Kgmole of combustible gas
Y=Kgmol of the air used
Carbon Balance
0.690 x = 7.34
x =12.23 kg mol
N2 balance
0.10x= 0.79y = 865.77
y= 86.77-0.10*12.23/0.79 =108.29 Kg mol
(a) Air-Fuel ratio on volume basis=108.29/12.23=8.854.
Dr.K.P.GOPINATH
80
CH 2254
(b) O2 supplied bu air =1087.29*0.21=22.74 kgmol

Excess O2 = O2 in the dry combustion gas- O2 required for CO
=5.89-0.16*1/2=5.81 Kg mole
Theoretical O2= Total O2 – Excess O2
= 22.74 –5.4 =16.93 Kg mol
% Excess Air =5.81/16.93*100 =34.32%
Problem.9:
A Producer gas made from coke has the following composition by volume. CO= 28% , CO2 = 3.5% ,
O2 = 0.5% , and N2 = 68%. The gas is burnt with such a quantity of air that the oxygen from the air is
20% in excess of the net oxygen required for complete combustion if the combustion is 98 %
complete. Calculate the composition in volumetric % of the gaseous products formed per 100 Kg of
gas burned.
Basis: 100 Kgmoles of producer gas
Stoichiometric O2 reqd = 0.5X28/1 = 14 kg mole
Theo. O2 = Stoichiometric O2 - O2 in fuel = 14-0.5=13.5 kgmoles
Total O2= 13.5X1.2=16.2 Kgmoles.
Total Air supplied=16.2/ 0.21 =77.14kgmoles 3
N2 supplied from air=60.94 kgmoles.
N2 coming out =68+60.94= 128.94 kgmoles.
CO in flue gas=28-27.44=0.56 kgmoles 2
Composition of products
Kgmole Mol.wt Kg Vol%
Co 0.56 28 15.68 0.342
Co2 30.94 44 1361.36 18.93
O2 2.98 32 95.36 1.82
N2 128.94 28 3610.32 78.90
_____________
Total 5082.72kg 5
Dr.K.P.GOPINATH
81
CH 2254
Composition of reactants:
Kgmole Mol.wt Kg
CO 28 28 784
CO2 3.5 44 154
O2 0.5 32 16
N2 68 28 1904
____________
Total 100kgmoles 2858kg 4
Problem 10:
The exhaust from the diesel engine shows 10.2 % CO2 , 7.9 % O2, and the rest nitrogen. The analysis
was made in Orsat apparatus. Calculate (i) C / H ratio in fuel
(ii) Percentage by weight of Carbon in fuel
(iii) Air -fuel ratio by weight.
(iv) Percentage excess air.
(v) Moles of exhaust gas per Kg of fuel.
Basis: 100 Kgmoles of exhaust gas
Theo. O2 = Stoichio. O2 - O2 present in fuel
Total O2= (1+ Excess air /100) Theo.O2
Carbon balance
O2 Balance
i) C/H2 ratio in fuel= 10.2X12/7.34X2 = 8.34

ii) % Wt. Of carbon in fuel =122.4/137.08=89.29%
iii) Air –fuel ratio by weight = 2989.84/137.08=21.81
iv) % Excess air= 7.9/13.69 X100=56.96%
v) Moles of exhaust gas per kg of fuel=100/137.08= 0.7295 kgmoles
Dr.K.P.GOPINATH
82
CH 2254
UNIT – VI
THERMO PHYSICS
Dr.K.P.GOPINATH
83
CH 2254
Conservation of energy:
According to law of conservation of energy, energy can neither be created nor be destroyed, but it
can be transferred from one form to another form
Mean gram calorie:
1/100 of the energy required to heat one gram of water from 0 to 100 ºC at a pressure of 1 atm is
called mean gram calorie.
Characterization factor:
When a crude oil of supposedly uniform character is fractioned into narrow cuts, the specific gravity
of each cut is approximately proportional to the cube roots of its absolute boiling point at 1 atm
pressure. The proportionality factor is taken as an index of the paraffinicity of the stock. Thus
K=3√TB/G Where K is the characterization factor, TB- average boiling poin, degress rankine at 1 atm
pressure, G-specific gravity at 60ºF
Kopp’s rule: “The standard heat of capacity of a solid compound is approximately equal to the
sum of the heat capacities of its constituent elements.” This generalization is termed as Kopp’s rule.
The Hess’s law:
Hess’s law of heat summation states that the net heat evolved or absorbed in the chemical process
is the same whether the reaction takes place in one or more steps. (i.e.)H0533 (or) (H0
0 0
R+H 298+H P)
Consider the reaction CH4 (g) + 2O2(g)CO2 (g) + 2H2O(g)
Trouton’s rule:
Trouton’s rule state’s that the ratio of the molal heat of vaporisation bof a substance at its
normal boiling point to the absolute temperature .Tb is a constant.b/Tb=K
where k= Trouton’s ratio21 for many substances.
Flame temperature:
When a fuel is burnt, lot of heat is generated since the reaction is exothermic. If the combustion
chamber is sealed from surroundings, the heat produced is utilized to heat the produce (flue gases).
Hence the flue gas comes out at a higher temperature which is called Flame temperature or
Theoretical Flame Temperature.
Dr.K.P.GOPINATH
84
CH 2254
1. A stream of nitrogen flowing at a rate of 100 kmol/h is heated from 303 K (30 oC) to
373 K (100 oC). Calculate the heat that must be transferred.
o
Data: Cp for nitrogen = 29.5909-5.141x10-3 + 11.1829 x 10-4 T2 – 4.968 x 10-9 T3.
Solution:
Basis : 100 kmol/h of nitrogen gas
T2
Q  n  Cpo dT
T1
T2
 
Q  n  29.5909  5.141 10 3 T  11.1829  10 6 T 2  4.968  10 9 T 3 dT
T1
 5.141 10 3 2 11.1829  10 6 3 4.968  10 9 4 

 n 29.5909  T2  T1    T2  T13  T2  T12    
T2  T14 
 2 3 4 
where n = 100 kmol/h
T2 = 373 K
T1 = 303 K
 5.141 103 11.1829  10 6 

Q  100 29.5909  373  303  
(373)2  (303)2   
(373)3  (303)3  
 2 3 
9
4.968  10

4

(373)4  (303)4 ] 
= 202587.2 kJ/h
= 56.274 kJ/s = 56.274 kW
(As 1 J/s = 1 W)
Dr.K.P.GOPINATH
85
CH 2254
2. A stream of carbon dioxide flowing at a rate of 100 kmol/min is heated from 298 K
o
(25 oC) to 383 K (110 oC). Calculate the heat that must be transferred using Cp .
Data: Cp  a  bT  cT  dT
o 2 3
Gas a b x 103 c x 106 d x 109
CO2 21.3655 64.2841 -41.0506 9.7999
Solution:
Basis : 100 kmol/min of CO2.
Q = Heat that must be transferred

T2
 n  Cpo dT
T1
T2
 
Q  n  21.3655  64.2841 103 T  41.0506  106 T 2  9.7999  109 T 3 dT
T1
 64.2841 103 4 41.0506  106 

 n 21.3655  T2  T1   T2  T1 
4
  
 2 3 
9
9.7999  10
T23  T13  4
T24  T14 
where n = 100 kmo1/min
T2 = 383 K
T1 = 298 K
 64.2841 103
Q  100 21.3655  383  298   (383)4  (298)4 
 2
41.0506  10-6 9.7999  109
-
3

(383)3  (298)3 
4
  
(383)4  (298)4 
= 330335.5 kJ/min
= 5505.6 kJ/s = 5505.6 kW
Dr.K.P.GOPINATH
86
CH 2254
3. Methane gas in heated from 303 K (30o C) to 523 K (250o C) at atmospheric

o
pressure. Calculate the heat added per kmol methane using Cp data given below
Data:
Gas a b x 103 c x 106 d x 109
Methane 19.2494 52.1135 11.973 -11.3173
Solution:
Basis: 1 kmol of methane gas.
Q = Heat added
T2
 n  Cpo dT
T1
T2

Q  n  19.2494  52.1135  103 T  11.973  106 T 2  11.3173  109 T 3 dT 
T1
 52.1135  103 2
 n 19.2494  T2  T1   
T2  T12 
 2
11.973  106 3 11.3173  109 4

3
 
T2  T13 
4

T2  T14  
where n = 1 kmo1
T2 = 523K
T1 = 303 K
 52.1135  103
Q  119.2494  523  303   
(523)2  (303)2 
 2
11.973  106 11.3173  109

3

(523)3  (303)3  4

(523)4  (303)4  
= 4234.9 + 4735 + 459.9 – 187.8
= 9242 kJ
Dr.K.P.GOPINATH
87
CH 2254
4. Temperature of pure oxygen is raised from 350 K (77 oC) to 1500 K (1227 oC).
Calculate the amount of heat to be supplied for raising the temperature of 1 kmol
o
oxygen using the following Cp data given below:
Gas a b x 103 c x 106 d x 109
O2 6.0257 11.7551 -2.3426 -0.5623
Solution:
Basis: 1 kmol of oxygen.
Q = I eat to be supplied
T2
 n  Cpo dT
T1
T2

Q  n  26.0257  11.7551 103 T  2.3426  106 T2  0.5623  109 T3 dT 
T1
3

 n 26.0257  T2  T1  

11.7551 10
2
 T 2
2  T12 
2.3426  106 3 0.5623109 4

3

T2  T13   4

T2  T14  
where n = 1 kmol
T1 = 350 K
T2 = 1500 K
 11.7551 103 
Q  126.0257 1500  350   
(1500)2  (350)2  
 2 
6 9
2.3426  10 0.5623  10

3

(1500)4  (350)4   4

(1500)4  (350)4  
 129929.6  12504.5  2601.94  709.55

 39122.61 kJ
Dr.K.P.GOPINATH
88
CH 2254
5. Pure ethylene is heated from 303 K (30 oC) to 523 K (250 oC) at atmospheric
pressure. Calculate the heat added per kmol ethylene using data given below:
Cpo  4.1261 155.0213  103 T  81.5455  106 T2  16.9755  109 T3
Solution:
Basis : 1 kmol of pure ethylene gas.
Q = Heat added
T2
 n  Cpo dT
T1
T2
 
 n  4.1261  155.0213  103 T  81.5455  106 T 2  16.9755  109 T 3 dT
T1
 155.0213  103 2
 n  4.1261 T2  T1   
T2  T12 
 2
81.5455  106 3 16.9755  109 4

3

T2  T13   4

T2  T14  
where n = 1 kmol
T1 = 303 K
T2 = 523 K
 155.0213  103
Q  1 4.1261 523  303   
(523)2  (303)2 
 2
81.5455  106 16.9755  109

3

523)3  (303)3   4

523)4  (303)4  
 1907.74  14085.23  3132.37  281.75

 12142.35kJ/ kmol
Dr.K.P.GOPINATH
89
CH 2254
6. Heat capacity data for gaseous SO2 is given by following equation:
3 105
C  43.458  10.634  10 T  5.945  2
o
p
T
Calculate the heat required to raise the temperature of 1 kmol pure sulphur dioxide
from 300 K (27 oC) to 1000 K (727 oC).
Solution:
Basis: 1 kmol pure SO2 gas.
Q = Heat required
T2
 n  Cpo dT
T1
 5.945  105 
T2
Q  n   43.458  10.634  10 3 T  2  dT
T1  T 
 10.634  10 3 2  1 1 
 n  43.458  T2  T1    
T2  T12  5.945  105    
 2  T2 T1  
 10.634  103 2  1 1 
 n  43458  T2  T1    
T2  T12  5.94  105    
 2  T1 T2  
where n = 1 kmol
T1 = 300 K
T2 = 1000 K
 10.634  103    1 1 
Q  1 43.458 1000  300    2 2   5.94  105  
 2  1000 300   300 1000  
 130420.6  4838.47  1386

 33873.07 kJ/ kmol
Dr.K.P.GOPINATH
90
CH 2254
UNIT – VII
THERMO CHEMISTRY
Dr.K.P.GOPINATH
91
CH 2254
Heat capacity of a substance:
Heat capacity of a substance is defined as the amount of heat required to raise the
temperature of 1 Kg of a substance by 1 Kelvin.
For pure water, heat capacity at 150C =4.1855kJ/Kg.k
Heat capacity can be expressed in kJ/Kg.k (or) cal/g.c
Hess’s law:
Hess’s law of heat summation states that the net heat evolved or absorbed in the chemical
process is the same whether the reaction takes place in one or more steps. (i.e.)H0533 (or)
(H0 R+H0298+H0P)
Consider the reaction CH4 (g) + 2O2(g)CO2 (g) + 2H2O(g)
Effect of pressure on heat capacity of a gas:
Heat capacities for the ideal gas state are independent of pressure. However, they are
functions of temperature.
Standard heat of reaction:
The standard heat of reaction is the change in the enthalpy of a system as a result of the
chemical reaction-taking place at 1 atm and starting and ending with all the components
(reactants & products) at constant temperature of 250C.If stoichiometric number is doubled,
the standard heat of reaction is doubled.
The standard heat of reaction for any reaction can be calculated if the heat of formation (or
heat of combustion) of the compounds taking part in the reaction is known as follows:
H0298= Hf, products -Hf reactants
H0298= Hc reactants -Hc products
Heat of formation:
A formation reaction is defined as s reaction, which forms a single compound form the
elements contained in it.
e.g. C + ½ O2 +2H2CH3OH
The heat of formation is based on 1 mol of the compound formed. The equations should
indicate the physical state of each reactant and product whether it is gas, liquid or solid. The
heat of formation of a chemical compound is the standard heat of reaction where the
reactants are the necessary elements for the formation of compound which is the only
product formed.
Eg. C(s) + +O2 (g)CO2 Hf =94051 cal/g mol
For all the elements, the heat of formation is zero.
Heat of mixing:
When two liquids are mixed, the enthalpy change or heat effect is called the heat of mixing
measured at constant temperature. Usually at 180C or 250C and at the atmospheric
pressure. It is expressed in kJ/kg mol of solution, kJ/kg mol of solute, kJ/kg of solute, kJ/kg
of solution.
Dr.K.P.GOPINATH
92
CH 2254
Sensible heat and latent heat:
When a liquid is heated from room temperature (say 250C) to a higher temperature (say
600C) and it remains as a liquid at 600C, then the sensible heat absorbed =q= m Cp (60-25)
Where m = mass of liquid Cp= specific heat of liquid.
If the liquid is further heated to 1000C, and it vaporizes, then
Heat absorbed =q= sensible heat + latent heat
= m Cp (100-25) + m  Where = latent heat of vaporization.
The enthalpy –concentration chart:
Enthalpy –concentration diagram is useful for binary solutions. The enthalpy per unit solution
is plotted against concentration for a series of constant temperature and constant pressure
lines. With these charts, calculation effects in involved in changing the concentration and
temperature of the solution become simple and rapid.
*What do you understand by exothermic and endothermic reactions? Give one example in
each.
When heat is evolved in a chemical reaction, the reaction s called exothermic reaction.
For e.g. C(s) + O2(g)CO2 Hf =-94051 cal
When the heat is absorbed in a chemical reaction, the reaction is called endothermic
reaction
For e.g. C2H2OH(l) + CH3COOH(l)C2H5OOCH3(l) + H2O (l) H0298 =3720 cal
* What is Flame temperature?

When a fuel is burnt, lot of heat is generated since the reaction is exothermic. If the
combustion chamber is sealed from surroundings, the heat produced is utilized to heat the
produce (flue gases). Hence the flue gases comes out at a higher temperature which is
called Flame temperature or T.F.T
* Define latent heat of Fusion

The latent heat of fusion is the amount heat required when unit qty of a solid is conducted to
liquid at its melting point.
* Define latent heat of vaporisation

The latent heat of vaporisation is the amount of heat required per unit qty of liquid when it is
changed from liquid to vapour at its boiling point.
* Define standard heat of combustion

It is that resulting from the combustion of a substance, in the state that is normal at 250C and
atm. Pressure with the combustion beginning and ending at a temperature of 250C. It is
dependent on the extent to which oxidation is carried.
* Define heat of combustion

The heat of combustion of a substance is the heat of reaction resulting from the oxidation of
the substance with molecular oxygen.
The assignment of negative values to heat of combustion is consistent with the use of
changes of enthalpy as synonymous with heats of formation and heats of vapour since
combustion the value of SH must be negative and hence the heat of combustion is also
negative.
HR = -HC.
Dr.K.P.GOPINATH
93
CH 2254
* Define heat of reaction

Heat of reaction is the amount of heat to be supplied when a reaction is occurring at
constant pressure (one atom)
* Define heat of sublimation

For solids the heat required to convert one mole of the vapour is more aptly called the heat
of sublimation.
* Define heat of absorption

When the solvent and solute form an ideal system, the heat liberated during the absorption
system is equal to the latent heat of condensation of the solute. The mixing of non-ideal
liquids is accompanied by the evolution of heat and the heat of absorption is equal to the
algebraic sum of the heats of condensation and mixing.
* Define heat of mixing

Heat of solution in a system in which both solute and solvent are liquids termed as heats of
mixing. Heats of mixing are frequently expressed on a unit weight rather than a molal basis.
* Define Heating values of fuel

The total heating value of a fuel is the heat evolved in its complete combustion under
constant pressure at a temperature of 250C when all the water initially present as liquid in
the fuel and present in the combustion products are condensed to the liquid state.
The net heating value is defined except that the final state of the water in the system after
combustion is taken as vapor at 250C.The total heating value is also termed the `gross`
heating value. The net heating value is also termed as the lower heating value.
* Define Rank of Coal

Fuel ratio of a coal is defined as the ratio of percentage of fixed carbon to that of volatile
matter. The rank of the coal whether bituminous or anthracite, may be estimated from its
fuel ratio.
* Define Heating value of coal

The total heating value of a coal may be determined by direct calorimetric measurement and
expressed as Btu/lb. The net heating value is obtained by subtracting from the total heating
value the heat of vaporization at 250C of the water present in the coal and that formed by the
oxidation of the available hydrogen.
Net H.V. = total H.V. – 8.94 * H * 1050
Where H.V. = heating value, H wt. Fr. Of total hydrogen including available H2, H2 in
moisture and H2 in combined H2O
* Define Thermal efficiency

The thermal efficiency of a process may be defined as the percentage of the heat input that
is effectively utilized in a desired manner.
* Define Kopp’s Rule

Kopp’s rule: “The standard heat of capacity of a solid compound is approximately equal to
the sum of the heat capacities of its constituent elements.” This generalization is termed as
Kopp’s rule.
* Define heat of Condensation

Heat of condensation: The amount of heat required to convert from vapour to liquid.
Dr.K.P.GOPINATH
94
CH 2254
1) Calculate the Enthalpy of one Kg Zinc Vapour at 950oC and atmospheric pressure, relative
to the solid at 30 oC
Data: Cp solid = 0.105 cal./gm.oC
Melting Point = 419 oC
Cp liquid = 0.109 cal./gm.oC
Boiling Point = 907 oC
Latent Heat of Vaporization = 26900 cal/gm.atom
Latent Heat of Fusion = 1660 cal/gm.atom
Cp vapor = 4.97 cal/gm atom oC
Atomic Weight of Zinc = 65.38
Q1=Q3=Q5=m Cp dt Q2=Q4=m λ
Q=Q1+Q2+Q3+Q4+Q5=533.987 Kcal.
Enthalpy of Zinc Vapor=533.987 Kcal.
2) Dry methane is burnt with dry air both being initially at 25oC. The flame temperature is
15700k. If complete combustion is assumed, how much excess air is to be used?
Data Standard heat of reaction = - 801556 J/gmmoles.
Cp data: Mean values:
CO2 51.79 J/gmmoles ok
H2O 40.19 "
N2 32.15 "
O2 32.40 "
Basis: 1 gmmole of CH4
CH4+2O2CO2+2H2O
Products: CO2=1gmmole
H2O=2gmmole
O2=x gmmole
N2=(7.52+3.76x) gmmole
Hr=∆Hr+ ∫∑nCppdT- ∫∑nCprdT Assuming, Hr=0 (AFT)
X=1.668 gmmole % Excess air=1.668/2=83.4%
3) Calculate the heat of the gas phase reaction.

C2H2(g) + H2O (g) -------> C2H5OH
At 300 oC . The standard heat of reaction is -10135 J
Heat Capacity Data.
----------------------------
C2H2 = 2.830 + 28.601x10-3T-8.726x10-6T2
H2O = 7.256 + 20.298x10-3T+0.283x10-6T2
C2H5OH = 6.990 + 39.741x10-3T-11.926x10-6 T2
Basis: 1kgmole of Ethyl alcohol.
C2H4 +H2O C2H5OH Cp: J/Kgmole 0K .
Heat of gas phase reaction Hr = -10135 - 2160.13= -12295.13 J
Dr.K.P.GOPINATH
95
CH 2254
4) Distinguish between unsteady state and steady state

Steady state : The process conditions like pressure, concentration , temperature, flow rates
do not change with time at any given point in the process.
Unsteady state : The process conditions like pressure, concentration , temperature, flow rates
within the system changes with time in the process.
(ii) Basis: 100lits of water solution.
Dependent variable either salt quantity or conc.in the tank
Independent variable time
At, t=0,x=4 kg t=50min. x=?
OMB Input=output accumulation
0=5/100x+dx/dt (1)
Solving equation (1) by applying boundary condition, x=0.328 kg.
5) Calculate the theoretical flame temperature of a gaseous fuel containing 20 % CO and 80

% N2 when burnt with 100 % air, both air and gas initially being at 25°C.
Heat of combustion of CO is 67,636 Kcal/ Kg mole.
Data: Specific hats of products of combustion. Kcal/Kg mole °K
Carbondioxide Cp = 6.339 + 10.14 x 10-3T
Oxygen Cp = 6.117 + 3.167x 10-3T
Nitrogen Cp = 6.457 + 1.389 x 10-3T
Where T is temperature in °K Basis: 1 Kgmole of CO
burnt. CO=1 Kgmole N2= 4 kgmole
Products: CO2=1 Kgmole O2=0.5 kgmole N2=4+3.76=7.76 kgmole
∆Hr = -ΔHc =-67,636 kcal/kgmole Theoretical flame temperature=11970K
Dr.K.P.GOPINATH
96

Course Notes PDF

Caricato da

Informazioni sul documento

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Course Notes PDF

Caricato da

Copyright:

Formati disponibili

CH 2254

CHEMICAL PROCESS CALCULATIONS

CH2254 CHEMICAL PROCESS CALCULATIONS

UNIT I UNITS AND DIMENSIONS 5

UNIT II GAS CALCULATIONS 7

UNIT III MATERIAL BALANCE 7

UNIT IV HUMIDITY AND SATURATION 7

UNIT V FUELS AND COMBUSTION 6

UNIT VI THERMO PHYSICS 6

UNIT VII THERMOCHEMISTRY 7

UNITS AND DIMENSIONS

A unit of measurement is a definite magnitude of a physical quantity, defined and

Chlorine 100 71 1.41 0.219

3) Prove 1 W = 0.7376 ft lbf / sec .

5) Convert the diffusion coefficient of 0.5 lb /ft^3.

6) What is the density of air at 40 degree Celsius and 760 mmHg?

Specific gravity of a liquid:

Volume percentage of a component in a mixture is defined as the ratio of volume

Molecular weight and equivalent weight:

Ans. Basis: 100g of caustic soda solution.

Gram equivalents of NaOH 40

Concept of MOLARITY and MOLALITY:

ABSOLUTE temperature and RELATIVE temperature:

COMPONENT VOLUME DENSITY WEIGHT WEIGHT %

a) For liquids lighter than water

Molecular weight of urea: (2*14) + (4*1) + 12 + 16 = 60

Ans. Basis: 100 kg of limestone.

Molecular weights of (i) CaO : 40 + 16 = 56 MgO=40

2) Cracked gas from a petroleum refinery has he following composition by volume :

Methane 40 16 640 24.81

3) An aqueous solution of NaCl in water contains 28 g of NaCl per 100cc of solution at

COMPONENT WEIGHT MOL.WT. Moles Mole fract.. Wt.%

NaCl 28 58.5 0.479 0.087 23.73

Ans. Basis : 100 kg moles of flue gas sample.

(2) – (3)  14x = 1134 Therefore x = 81%

(1) * 44  44x + 44y +44z = 4400 ---- (4)

(2) * 1  28x + 44y + 32 z = 3008 ----(5)

(4) – (5)  16x – 12z = 1392

(1) - y = 100 – 81 –8 y=11%

N2=81% CO2=11% O2=8%

4) The composition of a gas mixture ( on volume basis) is : N2 –70.5% , O2 – 18.8% ,

Ans. For gases , VOLUME% = MOLE%.

Basis: 100 kg mole of gas mixture.

ii) Average molecular weight = Total weight / Total no. of moles

= 2758.7 / 100 = 27.59 kg / kg mol.

Moles of H2O = 1.88  359 = 0.00523 lb – Mole

Weight of H2O = 0.00523  18 = 0.0942 lb.

Moles of H2O = 1.88  359 = 0.00523 lb mole

Weight of H2O = 0.00523  18 = 0.0942 lb

It is desired to compress 10 lb of carbon dioxide to a volume of 20 cu.ft. Calculate the

Volume of S.C. = 0.228  359  81.7 cu.ft.

Temperature at 30 Cu.ft. = 652K (or) 379C

Define Partial Pressure.

Ideal gas law is :

where, n = moles of moist air

Let n1 be the kmol of air

n2 be the kmol of moisture/water vapour.

p1 = Partial pressure of air at 303K

p2 = Partial pressure of moisture at 303K

For ideal gas,

 Pressure fraction = mole fraction

= 1.172 kmol at 303K

For water vapour/moisture.

Molecular weight of urea: (214) + (41) + 12 + 16 = 60