Solutionmanual For Stoichiometry Bhatt and Thakore

Dimensions and Units

EXERCISE 1.1
1 m 10 +9 nm
(a) Wave length 5500 Å = 5500 ´ 108 cm ´
10 +2 cm 1 m
= 550 nm Ans.
(b) Moisture content of humid air
175 grain
=
1 lb dry air
175 grain 1 lb
= ´
1 lb dry air 7000 grains
1 lb moisture kg moisture
= or
40 lb dry air kg dry air
1 kg moisture 1000 g
= ´
40 kg dry air 1 kg
= 25 g moisture/kg dry air Ans.
EXERCISE 1.2
Vacuum = 475 Torr
Absolute pressure = 760 475 = 285 Torr
º 285 ´ 101.325/760
º 38 kPa or 0.38 bar
1 Pa = 1.450 377 ´ 104 psi
Pressure = 38 000 ´ 1.450 377 ´ 104
= 5.511 psia Ans.
EXERCISE 1.3
F
Cross sectional area of piston = (5)2
4
= 19.635 cm2
Pressure = Force/Area = 192.6 ´ 104/(19.635 ´ 106)
= 0.0981 MPa º 0.981 bar
2 Solutions ManualStoichiometry
In FPS units, pressure = 0.0981 ´ 106 ´ (1.450 377 ´ 104)

= 14.228 psi Ans.
EXERCISE 1.4
Weight = 500 lb º 500 ´ 0.4536 º 226.8 kg
Volume = 29.25 L = 0.029 25 m3
Density of Fe, r = 226.8/0.029 25
= 7753.85 kg/m3 º 7.754 t/m3 Ans.
EXERCISE 1.5
Diameter = 5 ft = 1.524 m
Height of tank = 6 ft 6 inch = 1.981 m
Volume of tank = (p/4)(Dia)2(Height)
= (3.1416/4)(1.524)2(1.981)
= 3.614 m3
Volume of CCl4 liquid in the tank
= 3.614 ´ 0.75
= 2.71 m3
Density, r = 1600 kg/m3
Mass of CCl4 in the tank = 2.71 ´ 1600 = 4336 kg Ans.
EXERCISE 1.6
lbf × min (Pa. in 2 )
Pressure drop = 0.05 ´ 6894.759
(in 2 × US gal) lbf
1 US gal 1 h m3
´ 3 3 ´ ´ 10
3.785 412 ´ 10 m 60 min h
1 kPa
´
1000 Pa
= 15.178 kPa Ans.
EXERCISE 1.7
Total exposed area = 2 ´ 7.595 ´ 1.276 + 2 ´ 7.595 ´ 0.1535
+ 2 ´ 1.276 ´ 0.1535
= 22.106 cm2
Weight loss = 14.9412 14.6254 = 0.3158 g
Density = 7753.85 kg/m3
0.3158 1 10 6 365 1
Corrosion rate = ´ ´ ´ ´
1000 7753.85 1 50 22.106
= 0.0134 cm/a
º 0.0053 in/year º 5.3 mpy Ans.
Dimensions and Units 3
EXERCISE 1.8
Let p¢ be the vapour pressure in kPa and T be the temperature in K
101 325kPa = 760 Torr
or 1 kPa = 7.500 62 Torr
p = 7.500 62 p¢
T = t + 273.15
or t = T 273.15
Substitute the values in the equation,
1211.0
log10 (7.500 62 p¢) = 6.9057
(T - 27315
. + 220.8)
1211.0
log10 p¢ + 0.8751 = 6.9057
(T - 52.35)
1211.0
log10 p¢ = 6.0306 Ans.
(T - 52.35)
EXERCISE 1.9
Let Cmo p¢ be the heat capacity of n-butane in SI units.
1 Btu/(lb mole × °R) = 1 kcal/(kmol × K)
= 4.1868 kJ/(kmol × K)
Cmo p¢ /4.1868 = Cmo p
T = 1.8 T ¢
Substituting the values in the equation,
( Cmo p¢ /4.1868) = 4.429 + 40.159 ´ 103 ´ 1.8 T ¢
68.562 ´ 107 (1.8 T¢)2
Simplifying,
Cmo p¢ = 18.5433 + 302.6479 ´ 103 T ¢ 93.006 ´ 106 T ¢2
Ans.
EXERCISE 1.10
Let Dp¢, v¢ and L¢ be pressure drop in cm WC, gas velocity is m/s and liquid
flow rate in m3/m3 gas flow.
Dp¢ = Dp ´ 2.54
v = v¢ ´ 3.281
L¢ = (L/264.172) 35.314 67
= 0.133 68 L
Substitute above values in the Calvert equation.
Dp ¢ L¢
= 5 ´ 105 ´ (v¢ ´ 3.281)2 ´
2.54 0.133 68
Dp¢ = 1.0227 ´ 102 v¢2 L¢ Ans.
EXERCISE 1.11
Let h¢ = heat transfer coefficient, kW/(m2 × K)
G¢ = mass velocity of fluid, kg/(m2 × s)
Cp¢ = specific heat, kJ/(kg × K)
k¢ = thermal conductivity of fluid, kW/(m × K)
D¢ = diameter of tube, m
m¢ = viscosity of fluid, kg/(m × s)
3412.142 ´ 10-3
h= h¢ = 0.1761 h¢
10.7639 ´ 1.8
2.204 62 ´ 3600
G= G¢ = 737.28 G¢
10.7639
9.478 172 ´ 10 -4
Cp = = 2.2885 ´ 104 Cp¢
2.204 62 ´ 1.8
3412.142 ´ 10-3
k= k¢ = 0.5778 k¢
3.2808 ´ 1.8
D = 3.2808 D¢
2.204 62 ´ 3600
m¢ = m¢ = 2419.11 m¢
3.2808
Substituting the values,
0.023( 737.28G ¢ )0.8 (0.5778k ¢ )0.67 (2.3885 ´ 10 -4 C p¢ )0.33

0.1761 h¢ =
(3.2808 D¢ )0.2 (2419.11m ¢ )0.47
or h¢ = 0.023 G¢0.8 k¢0.67 Cl¢0.33 / (D¢0.2 m¢0.47)
Thus the equation does not change when consistent SI units are used. This is
because the equation is a simplified form of Sieder-Tate equation which is made-
up of three dimensionless numbers. Ans.
Basic Chemical
Calculations
EXERCISE 2.1
Molar mass of oxygen = 2 ´ 16 = 32 g/mol
Amount of oxygen = 500/32
= 15.625 mol Ans.
EXERCISE 2.2
1 mol C is present in 1 mol CO2.
12 g C º 44 g CO2
Carbon content in 264 g CO2 = (12 ´ 264/44)
= 72 g Ans.
EXERCISE 2.3
Molar mass of KMnO4 = 39 + 55 + 4 ´ 16 = 158 Ans.
EXERCISE 2.4
Molar mass of HNO3 = 63
Molar mass of H2SO4 = 98
100 g HNO3 = 100/63 = 1.5873 mol
100 g H2SO4 = 100/98 = 1.0204 mol
Excess = 1.5873 1.0204
= 0.5669 mol HNO3
Excess atoms = 0.5669 ´ 6.022 142 ´ 1023
= 3.414 ´ 1023 atoms of HNO3 Ans.
EXERCISE 2.5
Molar mass of CS2 = 12 + 2 ´ 32
= 76
76 g CS2 º 12 g C
1 mol CS2 = 1 mol C

3.5 kmol C = 3.5 kmol CS2
º 3.5 ´ 76 º 266 kg CS2 Ans.
EXERCISE 2.6
Molar mass of Al2(SO4)3 = 2 ´ 27 + 3(32 + 4 ´ 16) = 342
Valence of Al2(SO4)3 = 6
Equivalent mass of Al2(SO4)3 = 342/6 = 57 Ans.
EXERCISE 2.7
Molar mass of KMnO4 = 158
Valence of KMnO4 = 5 (based on oxidation number)
Equivalent mass of KMnO4 = 158/5 = 31.6
500 g KMnO4 = 500/31.6 = 15.82 g eq Ans.
EXERCISE 2.8
Basis: 100 kg magnesite ore
Compound Molar mass kg kmol mole %
MgCO3 84.3 81 0.961 65.28
SiO2 60 14 0.233 15.83
H2O 18 5 0.278 18.89
Total 100 1.472 100.00
Ans.
EXERCISE 2.9
Basis: 100 kg glass
Compound Molar mass kg kmol mole %
Na2O 62 7.8 0.1258 7.65
MgO 40.3 7.0 0.1737 10.57
ZnO 81.4 9.7 0.1192 7.25
Al2O3 102.0 2.0 0.0196 1.19
B2O3 69.6 8.5 0.1221 7.43
SiO2 60.0 65.0 1.0833 65.91
Total 100 1.6437 100.00
Ans.
Basic Chemical Calculations 7
EXERCISE 2.10
Concentration of solids = 35 000 ppm or mg /L
º (35 000 ´ 100)/106 º 3.5% Ans.
For watery solutions, 10 000 ppm = 1% by mass
EXERCISE 2.11
Basis: 100 kg limestone
1 kmol CaO = 1 kmol CaCO3
Molar mass of CaCO 3 ´ 54.5
CaCO3 in limestone =
Molar mass of CaO
= 100 ´ 54.5/56
= 97.32% (by mass) Ans.
EXERCISE 2.12
(a) In one mole of ammonium sulphate, two atoms (or one mole) nitrogen
are present.
Nitrogen content of commercial ammonium sulphate =
Molar mass of N 2 ´ 96 28 ´ 96
=
Molar mass of (NH 4 ) 2 SO 4 132
= 20.36% Ans.
(b) One mole of sodium nitrate contains half mole of nitrogen.
Nitrogen content of pure sodium nitrate =
0.5 ´ Molar mass of N 2 ´ 100 0.5 ´ 28 ´ 100
=
Molar mass of NaNO 3 85
= 16.47% Ans.
EXERCISE 2.13
Chemical equation: 2 NaOH ¾ ¾¾® Na2O + H2O
2 ´ Molar mass of NaOH ´ 74.6
NaOH content of flakes =
Molar mass of Na 2 O
2 ´ 40 ´ 74.6
=
62
= 96.26% Ans.
EXERCISE 2.14
Basis: 1 kmol azeotropic mixture
Compound kmol Molar mass kg % by mass
H2O 0.622 18 11.196 31.98
HNO3 0.378 63 23.814 68.02
Total 1.000 35.010 100.00
Ans.
EXERCISE 2.15
Basis: 100 kg saline solution
Compound kg Molar mass kmol mole %
NaCl 25 58.5 0.4274 9.3
H2O 75 18 4.1667 90.7
Total 100 4.5941 100.0
Ans.
EXERCISE 2.16
Basis: 100 g water
Component mass, g mass % Molar mass mole mole %
HCl 4.00 3.24 36.4609 0.1097 1.85
KCl 19.61 15.86 74.5513 0.2630 4.44
H2O 100.0 80.90 18.0153 5.5508 93.71
Total 123.61 100.00 5.9235 100.00
Ans.
EXERCISE 2.17
Basis: 100 kg solution
Compound kg Nitrogen content Molar mass Nitrogen
kg/kmol comp. Content kg
NH3 19 14 17 15.647
NH4NO3 65.6 28 80 22.960
NH2CONH2 6 28 60 2.800
Total 90.6 41.407
Nitrogen content of the solution = 41.41% Ans.
EXERCISE 2.18
In one mole of ethanol, 2 moles of carbon are present.
TOC of the solution = 2 ´ 12 ´ 1000/46
= 522 mg/L
Oxidation (combustion) reaction:
C2H5OH + 3 O2 ¾ ¾¾® 2 CO2 + 3 H2O
46 3 ´ 32 2 ´ 44 3 ´ 18
ThOD of the solution = 3 ´ 32 ´ 1000/46
= 2087 mg/L Ans.
EXERCISE 2.19
Basis: 100 kg Phosphoric acid of 35% P2O5 strength
2 H3PO4 ¾ ¾¾® P2O5 + 3 H2O
2 ´ 98 142 3 ´ 18
H3PO4 content of the acid = 2 ´ 98 ´ 35/142
= 48.31% Ans.
EXERCISE 2.20
Basis: 100 kg spent acid
Free acid (H2SO4) content = 20 kg
NH4HSO4 content = 45 kg
+
H ¾® H SO + NH +
NH4HSO4 ¾ ¾¾® NH4+ + HSO4 ¾ ¾¾ 2 4 4
115 18 97 98 18
Chemically bound acid = 98 ´ 45/115
= 38.35 kg
Total acid content = 20 + 38.35 = 58.35 kg
or 58.35% Ans.
EXERCISE 2.21
Basis: 1 m3 of aqueous TEA solution
Mass of TEA = 0.47 ´ 1.00 ´ 1125 = 528.75 kg
Mass of water = 0.53 ´ 1.00 ´ 1000 = 530 kg
mass % TEA = 528.75 ´ 100/(528.75 + 530)
= 49.94% Ans.
Note: Volumes are strictly not additive but for an ideal solution, they can be
considered additive.
EXERCISE 2.22
Basis: 100 L wine
Mass of alcohol = 20 ´ 0.79 = 15.80 kg
Mass of alcohol-free liquid = (100 20) ´ 1.0
= 80 kg
15.80 ´ 100
mass % alcohol = = 16.49 Ans.
(15.80 + 80)
EXERCISE 2.23
Component Equivalent mass
CaCO3 100/2 = 50
Na2CO3 106/2 = 53
MgSO4 120.3/2 = 60.15
(a) Concentration of Na2CO3 = 50 ´ 800/53
= 754.7 ppm or mg/L as CaCO3
(b) Concentration of MgSO4 = 50 ´ 85/60.15
= 70.7 ppm or mg/L as CaCO3 Ans.
EXERCISE 2.24
(a) Equivalent mass of H2SO4 = 98/2 = 49
Concn. of H2SO4 in solution = 294/49
= 6 mol/L
º6N Ans.
(b) Equivalent mass of CaCl2 = 112/2 = 55.5
Concn. of CaCl2 in solution = 4.8 ´ 1000/(1000 ´ 55.5)
= 0.0865 mol/L
º 0.0865 N
(c) Equivalent mass of H3PO4 = 98/3 = 32.67
Concn. of H3PO4 in solution = 5 N
º 5 ´ 32.67
º 163.35 g/L Ans.
(d) Equivalent mass of HCl = 36.5
Concn. of HCl in solution = 54.75/36.5 = 1.5 g/L
º 1.5 N º 1.5 M Ans.
(e) Molar mass of K2SO4 = 174
Concn. of K2SO4 in solution = 174 ´ 3
= 522 g/L Ans.
EXERCISE 2.25
Basis: 100 kg aqueous acetic acid solution
Molar mass of acetic acid = 60
Acetic acid content = 35/60 = 0.5833 kmol
Volume of 100 kg solution = 100/1.04 = 96.15 L
Molarity = 0.5833 ´ 1000/96.15
= 6.066 M
Since acetic acid is monovalent.
Normality of the solution = 6.066 N
Molality = 0.5833 ´ 1000/65 = 8.974 Ans.
EXERCISEE 2.26
Basis: 1 litre solution
CO2 dissolved (in gas form) = 40 L at NTP
= 40/22.414 = 1.785 mol
MEA content = 1 ´ 1.011 ´ 0.2 = 0.2022 kg
º 202.2 g
Molar mass of MEA = 61
Moles of MEA in solution = 202.2/61 = 3.315 mol
CO2 concentration = 1.785/3.315
= 0.5385 mol/mol MEA Ans.
EXERCISE 2.27
Basis: 100 L of 60 volume H2O2 solution
O2 liberated in total = 60 ´ 100 = 6000 L
Sp. volume of ideal gas at STP = 23.69 L/mol
O2 liberated = 6000/23.69 = 253.27 mol
H2O2 ¾ ¾¾® H2O + 1/2 O2
H2O2 decomposed = 2 ´ 253.27 = 506.54 mol
Mass of H2O2 decomposed = 506.54 ´ 34 = 17 222.36 g
Mass of H2O2 solution = 100 ´ 1.075 = 107.5 kg
mass % H2O2 in solution = (17 222.36 ´ 100)/(107.5 ´ 1000)
= 16.02 Ans.
EXERCISE 2.28
Boiling point of 40% solution = 402.2 K(129.2°C). (Ref. Fig. 2.3)
Boiling point of pure water at atm. pressure = 100°C (373.15 K)
Boiling point elevation = 402.2 373.2
= 29 K or 29°C Ans.
EXERCISE 2.29
Since solution is an ideal solution, it follows Raoult's law.
Vapour pressure of solution, pvs = 0.5 ´ 37.2 + 0.5 ´ 12.3
= 24.75 kPa Ans.
EXERCISE 2.30
Basis: 100 kg urea solution containing 25 % urea
25
Urea present in solution = = 0.4167 kmol
60
75
Water present in solution = = 4.1667 kmol
18
Quantum of solution = 0.4167 + 4.1667 = 4.5834 kmol
4.1667
Mole fraction of water in solution =
4.5834
= 0.9091
Since vapour pressure of urea at 60°C (333.15 K) is negligible,
Vapour pressure of solution = 0.9091 ´ 19.92
= 18.11 kPa Ans.
EXERCISE 2.31
1 bar = 10.1972 m H2O
1000 m H2O = 98.066 bar
According to Henry's law,
Partial pressure of solvent
mole fraction of solute =
Henry's constant
Assuming partial pressure of solvent (water) to be vapour pressure (as its mole
fraction is near unity),
mole fraction of nitrogen in water at 1000 m depth
98.066
= = 1.119 ´ 103
87 650
mole fraction of helium in water at 1000 m depth
98.066
= = 0.775 ´ 103
126 600
Since helium is much less dissolved in water, it is preferred as a mixture with
oxygen. Ans.
EXERCISE 2.32
Mole fraction of NH3 in solution = 0.02
Roult's law:
yi p = xi pi [Ref. Eq. (2.18)]
xi pi
yi =
p
11.58 ´ 0.02
=
1.01 325
= 0.2286
Henry's law:
pi = Hi xi [Ref. Eq. (2.44)]
= 0.861 ´ 0.02
= 0.01722 bar
= 1.722 kPa
pi 0.01722
yi = =
p 1.013 25
= 0.017 Ans.
EXERCISE 2.33
Basis: 100 kmol gas
Gas Formula Molar mass kmol kg mass %
Ethylene C2H4 28 30.6 856.8 22.00
Benzene C6H6 78 24.5 1911.0 49.07
Oxygen O2 32 1.3 41.6 1.07
Methane CH4 16 15.5 248.0 6.37
Ethane C2H6 30 25.0 750.0 19.26
Nitrogen N2 28 3.1 86.8 2.23
Total 100.00 3894.2 100.00
Average molar mass = 3894.2/100 = 38.942
Ideal gas occupies 22.414 m3/kmol at NTP.
Density of gas mixture = 38.942/22.414
= 1.737 kg/m3 Ans.
EXERCISE 2.34
Basis: 100 kmol sewage gas
Gas Formula Molar mass kmol kg mass %
Methane CH4 16 68 1088 44.55
Carbon CO2 44 30 1320 54.05
dioxide
Ammonia NH3 17 2 34 1.40
Total 100 2442 100.00
Average molar mass = 2442/100 = 24.42
Density of sewage gas = 24.42/22.414
= 1.09 kg/m3 Ans.
EXERCISE 2.35
Basis: 1.10 kg CO2
Moles of CO2 = 1.10/44 = 0.025 kmol
Volume occupied = 33 L = 0.033 m3
V = 0.033/0.025 = 1.32 m3/kmol
T = 300 K
van der Waals equation:
F p + a I (V b) = RT
H VK 2
F p + 3.6 I (1.32 0.043) = 0.008 314 ´ 300 ´ 1000

H 1.32 K 2
Solving the equation, p = 1951.104 kPa

º 19.51 bar Ans.
EXERCISE 2.36
For chlorine gas:
(a) Ideal gas law:
p = 15.2 MPa a, T = 503.15 K (230°C)
V = RT/p = 0.008 314 ´ 503.15/15.2
= 0.2752 m3/kmol
Molar mass 71
Density = = = 258.0 kg/m3 Ans.
V 0.2752
(b) van der Waals equation: For chlorine,
pc = 79.77 bar a and Tc = 416.90 K
a = 27 R2 T2/64 pc
= 27(0.083 14)2(416.90)2/(64 ´ 79.77)

= 6.353 72 (m3 )2× bar/(kmol)2
b = RTc/8pc = 0.083 14 ´ 416.9/(8 ´ 79.77)
= 0.054 314 m3/kmol
Substituting in the van der waals equation
FG 6.353 72 I
H
152 +
V2 K
(V 0.054 314) = 0.083 14 ´ 503.15 = 41.831 89
Simplifying,
152 V3 5.0075 V2 + 0.6354 V 0.03451 = 0
Solving the equation by Newton-Raphson method.
V = 0.152 m3/kmol
Density = 71/0.152 = 467.1 kg/m3
Mathcad Solution:

Density = 71/0.1536 = 462.24 kg/m3 Ans.
EXERCISE 2.37
Pressure p = 73 bar, Temperature T = 423.15 K
Equation: p = [RT(1 e)/ v2] [V + b] A/v2
F
a I
A = A0 1 -
H
V K
= (5.88) [1 (0.058 61/V)]
F
b I
B = B0 1 -
H
V K
= 0.094 [1 (0.019 15/V)]
90 ´ 104
e = c/VT3 =
V (423.15)9
0.9 0.011 89
= =
75.687V V
Substituting the values.
é æ 0.011 89 ö 2 ù
73 = ê0.08314 ´ 423.15 ç1 - /V ú
ë è V ø÷ û
[V + 0.094 (0.0018/V)] [5.88 (0.344 63/V)]/V2
Simplifying and solving the equation by Newton-Raphson method,

V = 0.4 m3/kmol
Molar mass of ethane = 30.0704
Density of ethane = 30.0704/0.4 = 75.176 kg/m3 Ans.
Mathcad Solution:
Density = 30.0704/0.40045 = 75.092 kg/m3 Ans.
EXERCISE 2.38
For dimethyl ether (DME):
p = 15 bar a T = 353.15 K
pc = 53.4 bar a Tc = 400.2 K
Acentric factor w = 0.192
T 353.15
Tr = = = 0.8824
Tc 400.2
0.330 0.1385 0.0121 0.607 ´ 10 3

f ° = 0.1445
0.8824 (0.8824) 2 (0.8824)3 (0.8824)8
= 0.4262
0.331 0.423 0.8 ´ 10 2

f 1 = 0.0637 +
(0.8824) 2 (0.8824)3 (0.8824)8
= 0.148
0.08314 ´ 400.2
B= [ 0.4262 + 0.192 ( 0.148)]
53.4
= 0.283 26
( - 0.283 26)15
Z=1
0.08314 ´ 353.15
= 1.1447
ZRT 1.1447 ´ 0.08314 ´ 353.15
V= =
p 15
= 2.241 m3/kmol Ans.
EXERCISE 2.39
(a) Ideal gas law:
p = 7.09 + 1.013 25 = 8.103 25
T = 923.15 K (650 °C)
RT 0.08314 ´ 923.15
V= =
p 8.103 25
= 9.472 m3/kmol
Density = 27.587/9.472 = 2.912 kg/m3
(b) van der Waals equation:
27 R 2Tc2
a= and b = RTc / 8pc
64 pc
where pc and Tc are pseudo critical properties.
Gas Mole Molar Mass Critical temp Critical

fraction mass kg Tc, K pressure
ni Mi n × Mi pc, bar
Tc ni × Tc pc ni × pc
N2 0.705 28 19.740 126.09 88.893 33.94 23.93
O2 0.188 32 6.016 154.58 29.061 50.42 9.48
H2O 0.012 18 0.216 643.30 7.718 221.2 2.65
NH3 0.095 17 1.615 405.50 38.523 113.50 10.78
Total 1.000 27.587 164.195 46.84
Pseudo critical temperature, Tc = 164.195 K

Pseudo critical pressure, pc = 46.84 bar
a = [27(0.083 14)2(164.195)2]/(64 ´ 46.84)
= 1.678 (m3)2× bar/(kmol)2
b = (0.083 14 ´ 164.195)/(8 ´ 46.84)
= 0.036 42 m3/kmol

F 1.679I
H8.1 +
V2 K (V 0.036 43) = 0.083 14 ´ 923.15 = 75.7507
Mathcad Solution:
Average molar mass = 27.587

Density = 27.587/9.3626 = 2.9465 kg/m3
Specific gravity of the gas mixture = 27.587/28.96 = 0.952 Ans.
EXERCISE 2.40
Concentration of water vapours = 0.216 kg/kmol
º (0.216/9.3626)106 º 23 071 mg/m3
23.071 ´ 27.587
In terms of ppm concentration =
2.9465 ´ 18
= 12000 ppm Ans.
EXERCISE 2.41
Basis: 9.082 g furfural-n-butane mixture
Partial pressure of water = 12.5 Torr at 295.2 K
Partial content of n-butane = 763.2 12.5 = 750.7 torr
n-butane content of vapours = pV/RT
750.7 ´ 105.7
=
760 ´ 1000 ´ 0.082 06 ´ 295.2
= 0.004 314 mol
Mass of n-butane = 0.004 314 ´ 58 = 0.2501 g
Mass of furfural = 9.082 0.2501 = 8.8319 g
mass % n-butane = 0.2501 ´ 100/9.082 = 2.75%
Moles of furfural = 8.8319/96 = 0.092 mol
Total moles = 0.092 + 0.004 314 = 0.096 314 mol
mole % n-butane = 0.004 314 ´ 100/0.096 314
= 4.48 Ans.
EXERCISE 2.42
Basis: 100 kmol flue gases
Gas Molar mass kmol kg
CO2 44 10.00 440.00
O2 32 7.96 254.72
N2 28 82.00 2296.00
SO2 64 0.04 2.56
Total — 100.00 2993.28
Avg. molar mass = 29.933 (of dry gas)
Partial pressure of water = Vapour pressure of water at DP
= 10.612 kPa (ref. Chapter 6)
Absolute humidity = [10.612 ´ 18]/[(100 10.612) 29.933]
= 0.071 39 kg/kg º 71.39 g/kg Ans.
EXERCISE 2.43
Concentration of SO2 in flue gases = (0.04/100) ´ 106 = 400 ppm (v/v)
= 2.56/2993.28
= 0.8552 ´ 103 kg/kg
º 855.2 mg/kg or ppm (by mass)
Volume of gas = 0.082 06 ´ 463.15 ´ 760/750
= 38.513 m3/kmol
2.56 kg mg 1 kmol
Concentration of SO2 = ´ 106 ´
100 kmol kg 38.513 m 3
3
= 664.7 mg/m Ans.
EXERCISE 2.44
Basis: 733 kg mixture
Component kg Molar mass kmol
CH3CH 200 32 6.25
Steam 133 18 7.39
Oxygen (from air) 0.21 ´ 400/29 = 2.897
Nitrogen (from air) 0.79 ´ 400/29 = 10.897
Total pressure = 68.6 kPa g
Absolute Pressure = 68.6 + 101.325 = 169.925 kPa
Component kmol mole % Partial pressures,
kPa
O2 2.897 10.56 17.94
N2 10.897 39.72 67.49
CH3OH 6.250 22.78 38.71
H2O 7.390 26.94 45.78
Total 27.434 100.00 169.92
Ans.
EXERCISE 2.45
Basis: 1 kmol LPG mixture at 313.15 K (40 °C).
Gas kmol Molar mass kg
C3H8 0.30 44.0956 13.229
n-C4H10 0.45 58.1222 26.155
i-C4H10 0.25 58.1222 14.531
Total 1.00 53.915
Average molar mass = 53.915 Ans. (a)
53.915
Specific gravity = = 1.861 Ans. (b)
28.97
Gas kmol Vapour pressure Partial pressure

bar bar
C3H8 0.30 13.975 4.1925
n-C4H10 0.45 3.773 1.6979
i-C4H10 0.25 5.290 1.3225
Total 1.00 7.2129
Pressure in LPG cylinder = 7.2129 bar Ans. (c)
EXERCISE 2.46
Basis: 5 m3 solution
Total pressure = 6.77 MPa g
= 6.77 + 0.1013 = 6.8713 MPa a
Solubility of N2 at 0.1013 MPa and 305.75 K
= 1.35 ´ 5/100 = 0.0675 Nm3/5 m3 soln.
Partial pressure of N2 at 6.77 MPa g total pressure
= (6.8713 ´ 0.206)/(1 0.022)
= 1.4473 MPa (on ammonia-free basis)
Solubility of N2 at 6.77 MPa g and 305.75 K
= 0.0675 ´ 1.4473/0.1013
= 0.9644 Nm3/5 m3 solution
In a similar manner, solubility can be calculated for all the gases as shown in the
following, table,
Gas Solubility at Partial pr. Solubility at

0.1013 MPa a and at 6.77 MPa g 305.75 K and
305.75 K/5 m3 soln. 6.77 MPa g/5 m3
solution
N2 0.0675 1.4473 0.964
H2 0.0800 4.3560 3.440
Ar 0.1375 0.2881 0.391
CH4 0.1400 0.7800 1.078
Total 0.4250 m3 6.8714 MPa a 5.873 Nm3
Ans.
EXERCISE 2.47
Refer Example 2.25
pi = 7 bar g = 8.013 bar a , pf = 1.013 bar a
T f = Ti m (pi pf)
= 313.15 0.21 (8.013 1.013)
= 311.68 K or 38.53°C Ans.
EXERCISE 2.48
p1 = 101 atm a p2 = 1 atm a Ti = 308.15 K
T f = 308.15 0.169 (101 1)
= 291.25 K or 18.1°C Ans.
EXERCISE 2.49
Assume ideal gas law.
Basis: Receiver of 2 m3 capacity
Volume of air in the receiver at 7.5 bar g and 313.15 K,
8.513 25 ´ 2 ´ 27315
.
v1 =
. ´ 1.013 25
31315
= 14.657 Nm3
Volume of air in the receiver at 1 bar g and 313.15 K,
2.013 25 ´ 2 ´ 27315
.
v2 =
31315
. ´ 1.013 25
= 3.466 Nm3
Volume of air pressurized = 14.657 3.466
= 11.191 Nm3 in 4 min
11191
. ´ 60
Capacity of air compressor =
4
= 167.9 Nm3/h Ans.
EXERCISE 2.50
(1 ´ 10-3 - 2 ´ 10-4 )25

qL =
7.5 ´ 60
= 4.444 ´ 105 (mbar × L)/s Ans.
3
Material Balances
without Chemical
Reaction
EXERCISE 3.1
Basis: 4 kg feed water
Product water quantity = 3 kg
Material balance of dissolved solids (DS):
Feed water quantity ´ concentration of DS in feed water
= product water quantity ´ concentration of DS in product water +
concentrated stream quantity ´ concentration of DS in concentrated
stream
Let concentration of DS in concentrated stream = x
4 ´ 500 = 3 ´ 600 + 1 ´ x
x = 18 200 ppm Ans.
EXERCISE 3.2
Basis: Feed rate of 20 000 kg/h solution containing 91% ethanol by mass
Non-permeate from pervaporation unit contains all ethanol of the feed.
Ehanol in non-permeate = 20 000 ´ 0.91
= 18 200 kg/h
Purity of non-permeate stream = 99.7%
18 200
Flow rate of non-permeate stream =
0.997
= 18 254.8 kg/h
Let flow rate of vapour entering pervaporation unit = x kg/h and
flow rate of permeate = y kg/h
x = y + 18 254.8 (1)
Ethanol balance:
x ´ 0.78 = y ´ 0.029 + 18 200 (2)
Solving both equations,
y = 5274.7 kg/h Ans.
EXERCISE 3.3
Basis: 1000 kg solid caustic soda to be processed/d.
When the evaporator system concentrates 4% solution to 25% concentration,
evaporation = 100 (4/0.25)
= 84 kg/100 kg original solution
However, the capacity of the evaporation system is 4 kg solid caustic soda per
100 kg original solution. Consider another case in which 5% solution is
concentrated to 50% concentration the
evaporation = 100 (5/0.5)
= 90 kg/100 kg original solution
The plant capacity is thus 5 kg caustic soda. It may be noted that the plant
capacity in terms of evaporation remains constant, i.e. the plant has actual capacity
of 84 kg evaporation per 100 kg solution.
In second case, for 84 kg evaporation,
Caustic soda processed = 5´ 84/90 = 4.667 kg.
Plant Capacity is terms of solid caustic soda
= 4.667 ´ 1000/4
= 1166.7 kg/d Ans.
EXERCISE 3.4
Basis: 100 kg coal
Carbon content of coal = 67.2 kg
Ash, present in coal = 22.3 kg
Ash does not take part in combustion.
Ash content of refuse = 92.9%
Quantity of refuse = 22.3/0.929 = 24.0 kg
Carbon content of refuse = 24.0 22.3 = 1.7 kg
% carbon, unburnt = 1.7 ´ 100/67.2 = 2.53 Ans.
EXERCISE 3.5
Basis: 100 kg flaked soybean seeds
Solids (unextractable, i.e. inerts) = 69 kg
Final deoiled cake after extraction (meal) = 69/0.877 = 78.68 kg
Oil retained in DOC = 78.68 ´ 0.008 = 0.63 kg
Oil recovery = (18.6 0.63)100/18.6 = 96.6%
Ans.
EXERCISE 3.6
Basis: 100 kmol feed gas (vent stream)
H2 in vent stream = 66 kmol
Material Balances without Chemical Reaction 25
Recovery of hydrogen = 66 ´ 0.85 = 56.1 kmol

Purity of hydrogen stream = 98%
Quantity of hydrogen stream = 56.1/0.98
= 57.24 kmol
CH4 in hydrogen stream = 57.24 56.1
= 1.14 kmol
Composition of Reject Stream
Component kmol mole %
H2 66 56.1 = 9.9 23.15
CH4 33 1.14 = 31.86 74.51
Other components 1.00 2.34
Total 42.76 100.00
Ans.
EXERCISE 3.7
Basis: 100 kg deodorizer distillate
Fatty acids content = 19.8 + 56.1 = 75.9 kg
Let O be kmol of distillate from SPU and R be kmol of residue from SPU.
O + R = 100 (1)
0.95O + 0.1R = 75.9 (2)
Solving two simultaneous equations,
O = 77.53 kg and R = 22.47 kg
Ratio O : R = 77.53 : 22.47
= 3.45 : 1 by mass Ans.
EXERCISE 3.8
Basis: 1000 kg saturated solution of magnesium chloride in ethanol at 298.15 K
(25 ºC)
Let x = mass of crystals of MgCl2 6H2O, kg
y = mass of ethanol, kg
x + y = 1000 (1)
Crystal/solvent = 190/100 = 1.9 = x/y
or x = 1.9y (2)
solving the equations, x = 655.5 kg and y = 344.5 kg
MgCl2 present in solution = 95.32 ´ 655.5/203.32
= 307.3 kg
Water present in solution = 655.5 307.3
= 348.2 kg
Compound Formula molar mass, mass % kmol mole %

mass kg
Magnesium
chloride MgCl2 95.32 307.3 30.73 3.224 10.72
Water H2O 18 348.2 34.82 19.344 64.36
Ethanol C2H5OH 46 344.5 34.45 7.490 24.92
Total 1000.0 100.00 30.057 100.00
Ans.
EXERCISE 3.9
Basis: 1 kmol initial solution at 298.15 K (25 ºC)
Compound Formula molar kmol mass mass %
mass
Chloroacetic
acid (CAA) ClCH2COOH 94.5 0.2 18.9 24.2
Ether (E) (CH3CH2)2O 74.0 0.8 59.2 75.8
Total 1.0 78.1 100.0
New Basis: 290 kg final solution, saturated at 298.15 K (25 ºC)

Compound Mass mass % kmol mole %
kg
CAA 190 65.52 2.01 59.82
E 100 34.48 1.35 40.18
Total 290 100.00 3.36 100.00
Let quantity of spent solution = x kg
and quantity of make-up CAA = y kg
x + y = 500 (1)
Balance of CAA:
0.242 x + y = 0.6552 ´ 500 = 327.6 (2)
Solving the equations, x = 227.44 kg
y = 272.56 kg Ans.
EXERCISE 3.10
Let x = mass of CuSO4 × 5H2O in the mixture, kg
y = mass of FeSO4 × 7H2O in the mixture, kg
x + y = 100 (1)
After dehydration, the mixture will contain CuSO4 and FeSO4 alone.
Molar Mass of CuSO 4 Molar Mass of FeSO 4
+ = 59.78
Molar mass of CuSO 4 × 5H 2 O Molar mass of FeSO 4 × 7H 2 O
(159.5/249.5) ´ x + (152/278) ´ y = 59.78

0.6393 x + 0.5468 y = 59.78 (2)
Solving the equation, x = 55.15 kg
y = 44.85 kg
Ratio, CuSO4/FeSO4 = x/y = 1.23 : 1 by mass Ans.
EXERCISE 3.11
Basis: 100 kmol flue gases
Let x = amount of N2 in gas mixture, kmol
and y = average molar mass of nitrogen-free flue gas
Amount of nitrogen-free gases = 100 x kmol
If correct molar mass of nitrogen is considered,
28 ´ x (100 - x ) y
+ = 30.08 (1)
100 100
If incorrect molar mass (14) of nitrogen is considered,
14 ´ x (100 - x ) y
+ = 18.74 (2)
100 100
Solving two equations, x = 81 kmol
or 81% nitrogen Ans. (a)
Substitute the value of x in Eq. (1),
(100 - 81)
y = 30.08 (28 ´ 81)/100
100
= 7.4
y = 7.4/0.19 = 38.95
Let m and n be the amounts of CO2 and O2, respectively.
m + n = 100 81 = 19 (3)
44 m + 32 n = 38.95 ´ 19 = 740.05 (4)
Solving Eqs. (3) and (4), m = 11 kmol or 11% CO2
n = 8 kmol or 8% O2 Ans. (b)
EXERCISE 3.12
Basis: 100 kg vapour mixture, entering overhead condenser
Let top layer = x kg
bottom layer = y kg
x + y = 100 (1)
Benzene balance:
0.81 x + 0.1 y = 74 (2)
Solving two equations, x = 90.14 kg
y = 9.86 kg
Ratio, x/y = 9.142:1 (by mass) Ans.
EXERCISE 3.13
Basis: 100 kg complex of acetic acid and oil
Let x = quantity of upper layer, kg
y = quantity of lower layer, kg
x + y = 100 (1)
Acetic acid balance:
0.0962 x + 0.9303 y = 0.634 ´ 100 = 63.4 (2)
Solving the equation, x = 35.5 kg and y = 64.5 kg
Ratio x/y = 35.5/64.5 = 0.5504 (by mass) Ans. (a)
The new complex with solvent (chloroform) contains 57.8% acetic acid.
Quantity of new complex = 63.4/0.578
= 109.7 kg
Mass of chloroform added = 109.7 100 = 9.7 kg Ans. (c)
Let m = quantity of upper layer in new complex, kg
n = quantity of lower layer in new complex, kg
m + n = 109.7 (3)
Balance of acetic acid:
0.145 m + 0.875 n = 63.4 (4)
Solving the equations, m = 44.64 kg and n = 65.06 kg
Ratio, m/n = 44.64/65.06 = 0.686 (by mass) Ans. (b)
For solving the example with the help of coordinate plots, following values are
tabulated.
Eq. (1) x 30 32 34 36 38 40
y 70 68 66 64 62 60
Eq. (2) x 30 32 34 36 38 40
y 65.05 64.84 64.63 64.43 64.22 64.01

Eq. (3) m 40 42 44 46 48 50
n 69.7 67.7 65.7 63.7 61.7 59.7

Eq. (4) m 40 42 44 46 48 50
n 65.83 65.5 65.17 64.83 64.50 64.17
Plot of first two equations are given in Fig. E3.1. Similar plot for Eq. (3) and
Eq. (4) can be drawn.
x = 35.52, y = 84.48, m = 44.64 and n = 65.06, all in kg Ans.
700
68
66
(35.52, 64.48)
64
62
60
30 32 34 36 38 40
Fig. E3.1 Solution of Exercise 3.13
EXERCISE 3.14
Basis: 100 kg spent lye
Glycerol content of lye = 9.6 kg
Loss of glycerol by entertainment = 9.6 ´ 0.045 = 0.432 kg
Glycerol content of final solution = 9.6 0.432
= 9.168 kg
Quantity of final solution = 9.168/0.8 = 11.46 kg
Salt content of final solution = 11.46 ´ 0.06 = 0.69 kg

Salt crystallized in salt box = 10.30 0.69 = 9.61 kg
Evaporation = 100 11.46 9.61 = 78.93 kg
For the feed rate of 5000 kg/h,
Rate of crystallization = 5000 ´ 0.0961 = 480.5 kg/h Ans. (b)
Rate of evaporation = 5000 ´ 0.7893 = 3946.5 kg/h Ans. (a)
EXERCISE 3.15
Basis: 100 kg mixed fertiliser of grade 10 : 26 : 26
Nitrogen content of fertilizer = 10 kg as N
Phosphorous content of fertilizer = 26 kg as P2O5
Potassium content of fertilizer = 26 kg as K2O
Element/compound Atomic mass/molar mass
N 14
P2O5 142
K2O 94.2
H3PO4 98
HCl 74.6
NH3 17
Urea 60
(a) Anhydrous NH3 requirement = 17 ´ 10/14 = 12.14 kg
2 kmol H3 PO4 º 1 kmol P2O5
Anhydrous H3PO4 requirement = 98 ´ 2 ´ 26/142 = 35.89 kg
2 kmol KCl º 1 kmol K2O
100% pure KCl requirement = 74.6 ´ 2 ´ 26/94.2
= 41.18 kg Ans.
Total of three is 89.21 kg/h.
Balance is called 'filler'.
(b) Urea requirement = (60/28) ´ 10 = 21.43 kg Ans.
(c) 98% KCl requirement = 41.18/0.98 = 42.02 kg
Aqueous H3PO4 requirement = 100 12.14 42.02 = 45.84 kg
Concentration of H3PO4 in aqueous acid
= 35.89 ´ 100/45.84 = 78.09% Ans.
EXERCISE 3.16
Basis: 100 kg mixed acid
Quantity of 68.3% HNO3 required = 39/0.683 = 57.1 kg
Sulphuric acid requirement = 100 57.1 = 42.9 kg
Water in 68% HNO3 = 57.1 (1.000 0.683) = 18.1 kg
Water content of mixed acid = 19 kg
Water from H2SO4 = 19 18.1 = 0.9 kg

H2SO4 content of the acid = 42.9 0.9 = 42.0 kg
Strength of the acid required = 42.0 ´ 100/42.9
= 97.9% Ans. (a)
Mass ratio of the acids = 57.1/42.9 = 1.33 : 1 Ans. (b)
This problem can be conveniently solved on a triangular plot. Refer Fig. E3.2.
Point A represents 68.3% HNO3. Point B represents the desired mixed acid
containing 39% HNO3 and 42% H2SO4. Join AB which intersects the axis at
point C, representing 97.9% H2SO4.
100% H2O
90 10
80 20
70 30
2O
H
60 40
50 50
40 60
A H2
30 70
SO 4
20 80
10 90
C
100% 90 80 70 60 50 40 30 20 10 100%
HNO3 HNO3 H2SO4
Fig. E3.2 Preparation of Mixed Acid

Mass ratio = BC/AC = 7.9 units/6.0 units = 1.32:1
EXERCISE 3.17
Basis: 100 kg oleum
Oleum contains 10% SO3. This means 110 kg oleum contains 100 kg 100%
H2SO4 and 10 kg SO3.
H2SO4 content of 100 kg oleum = 90.91 kg
SO3 content of 100 kg oleum = 100 90.91 = 9.09 kg
SO3 will combine with H2O to form H2SO4 when mixed with spent acid and
aqueous HNO3.
Let m = quantity of oleum used, kg

n = quantity of spent acid, kg
p = quantity of aqueous 90% HNO3, kg
m + n + p = 1000 (1)
Total H2SO4 available after blending
= 0.0091 m + [0.09 + 98/(80 ´ 100)] m
= 1.0205 m
H2SO4 balance:
1.0205 m + 0.444 n = 600 (2)
HNO3 balance
0.113 n + 0.9 p = 320 (3)
Mathcad Solution:
LM1 1 1 O
M := 1.0205 0.444 0 P
MM0 P
0.113 0.9 PQ
N
LM1000OP
v := 600
MM 320 PP
N Q
LMmOP
MM np PP := M × v
1
NQ
LMmOP LM532 OP
MM np PP := MM339 P
128.589 all in kg
N Q N .41 PQ
m = 532.0 kg, n = 128.6 kg and p = 339.4 kg Ans.
This problem cannot be solved directly on a triangular chart. This is because
total H2SO4 content on equivalent basis is 102.05% and the property of the
triangular chart is that each component can be represented upto 100% on each
axis. However, it is possible to express H2SO4 concentration in equivalent SO3
concentration and then the triangular chart can be used. Since conversion of
H2SO4 concn. to SO3 concn. is required for use of the chart, it is recommended
that the algebraic method be preferred.
EXERCISE 3.18
Refer the triangular chart Fig. E 3.3.
Points A, B and C represent 99% H2SO4, pure water and 95% HNO3 respectively.
Point F1 represents original spent acid. Point F4 represents the final fortified
mixed acid (containing 50% H2SO4, 40% HNO3 and 10% H2O). Join AC. Join F1
and F4 and extend F1 F4 to meet at F3 on AC.
Fig. E3.3 Fortifying of Spent Acid

Basis: 1000 kg original spent acid
Blend F3 5.35 units
=
Blend F1 1.25 units
Blend F3 = (5.35/1.25)1000 = 4280 kg
99% H 2SO 4 10.25 units
=
95% HNO3 9.1 units
Thus (10.25 + 9.1 =) 19.35 kg blend F3 will contain 10.25 kg 99% H2SO4 and
9.1 kg 95% HNO3.
Hence 4280 kg blend F3 will contain 10.25 ´ 4280/19.35 = 2267 kg
99% H2SO4 and 4280 2267 = 2013 kg 95% HNO3. Ans. (a)
Final acid after evaporation 10.75 units
=
original spent acid 17.75 units
Therefore final fortified acid = 10.75 ´ 1000/17.75
= 605.6 kg
Water can be evaporated = 1000 605.6 = 393.4 kg Ans. (b)
EXERCISE 3.19
Basis: 100 kg feed containing 38.2 mass % benzene
Component kg Molar mass kmol mole %
Benzene 38.2 78 0.4897 40.0
Cyclohexane 61.8 84 0.7357 60.0
Total 100.0 1.2254 100.0
Refer Fig. E3.4 which is a triangular chart. Points A, B and C represent 100%
cyclohexane, benzene and acetone each. Point D represents the feed mixture
containing 40 mole % benzene while point E represents the azeotropic mixture
containing 74.6 mole % acetone. Join CD which intersects BE at M which
represents mixture after adding acetone to the feed.
CYCLOHEXANE
A
90 10
80 20
70 30
D 60 40
50 50
40 60
A
30 70
M E
20 80
10 90
B C
BENZENE 90 80 70 60 50 40 30 20 10 ACETONE
Note : All Percentages Are Mole %.
Fig. E3.4 Mixing of Benzene-Acetone-Cyclohexane

Acetone to be added 9 units
=
Feed (Point D) 5 units
Acetone to be added = (9/5)1.2254 = 2.2057 kmol
Molar mass of acetone = 58
Mass of acetone = 127.9 kg Ans.

Note: It may be noted that the triangular chart is plotted with mole %
compositions.
EXERCISE 3.20
Basis: 1000 kg dry building boards
Mass of moist boards = 1000/0.84 = 1190.5 kg
Final mass of boards after drying = 1000/0.995 = 1005 kg
Evaporation = 1190.5 1005 = 185.5 kg
Humidity difference in outgoing and incoming air
= 0.09 0.02 = 0.07 kg/kg dry air
Air required for drying = 185.5/0.07 = 2650 kg/h (dry air)
Specific volume of air at 301 K (28 °C) and 0.02 kg/kg dry air
= 0.882 m3/kg dry air (ref. Fig. 6.14)
Volumetric flow rate of incoming air = 2650.0 ´ 0.882
= 2337.3 m3/h Ans.
EXERCISE 3.21
Basis: 100 kg lard
Molar mass of all the components are listed below.
Component Molar mass Mass, kg
(rounded off values)
Palmitodistearin 862 3
Stearodipalmitin 834 2
Oleodistearin 888 2
Oleopalmitostearin 860 11
Palmirodiolein 858 82
Palmitic acid (C15H31COOH) 256 ?
Stearic acid (C17H35COOH) 284 ?
Oleic acid (C17H33COOH) 282 ?
Consider palmitodistearin (a tri-glyceride):
862 kg palmitodistearin liberates 256 kg plamitic acid.
3 kg palmitodistearin will therefore liberate 256 ´ 3/862 = 0.891 kg palmitic acid.
Similarly, 862 kg palmitodistearin liberates (284 ´ 2) = 568 kg stearic acid.
3 kg palmitodistearin will therefore liberate 568 ´ 3/862
= 1.977 kg stearic acid.
In this manner, the fatty acids present in each tri-glyceride can be calculated
which are summerised follows.
Tri-glyceride Fatty acid content, kg

palmitic stearic oleic Total
Palimitodistearin 0.891 1.977 2.867
Steorodipalmitin 1.228 0.681 1.909
Oleodistearin 1.279 0.635 1.914
Oleopalmitostearin 3.274 3.633 3.607 10.514
Palmitodiolein 24.466 53.902 78.368
Total 29.859 7.570 58.144 95.573
% palmitic acid = 29.859 ´ 100/95.573 = 31.24
% stearic acid = 7.570 ´ 100/95.573 = 7.92
% cleic acid = 100 31.24 7.92 = 60.84 Ans.
EXERCISE 3.22
Basis: 1 litre water
NaCl in water = 58.5 ´ 775.6/35.5 = 1278.1 mg/L
Na2SO4 in water = 142 ´ 230.4/96 = 340.8 mg/L
Na2CO3 in water = 53 ´ 80.5/50 = 85.3 mg/L
NaHCO3 in water = 84 ´ 208.1/50 = 349.6 mg/L
Mg (HCO3) in water = 73.14 ´ 194/50
= 283.8 mg/L
Calcium hardness in water = 284 194 = 90 mg/L as CaCO3
Ca(HCO3)2 in water = 81 ´ 90/50 = 145.8 mg/L
Dissolved solids in water = 1278.1 + 340.8 + 85.3 + 349.6 + 283.8 + 145.8
= 2483.4 mg/L
Na in NaCl = 1278.1 775.6 = 502.5 mg/L
Na in Na2SO4 = 340.8 230.4 = 110.4 mg/L
Na in Na2CO3 = 46 ´ 85.30/106 = 37.0 mg/L
Na in NaHCO3 = 23 ´ 349.6/84 = 95.7 mg/L
Total sodium (Na) content = 110.4 + 502.5 + 37.0 + 95.7
= 745.6 mg/L
º 32.41 meq/L
Equivalent of calcium (Ca) = 90/50 = 1.8 meq/L
Equivalent of magnesium (Mg) = 194/50 = 3.88 meq/L
Total cations = 32.41 + 1.8 + 3.88 = 38.09 meq/L
% sodium (Na) = 32.41 ´ 100/38.09 = 85.09 Ans.
EXERCISE 3.23
Basis: 1 litre dyehouse effluent
Na in effluents = 245.7/23 = 10.68 meq/L
Ca in effluents = 37.5 ´ 2/40 = 1.88 meq/L

% Na in effluents = 10.68 ´ 100/(10.68 + 1.88)
= 85.04
If sodium content is to be brought down to 60%, total cations should equal to
10.68/0.6 = 17.80 meq/L
Additional Ca to be added = 17.80 10.68 1.88
= 5.24 meq/L
º 104.8 mg/L as Ca
CaSO4 to be dissolved = 136 ´ 104.8/40
= 356.3 mg/L Ans.
EXERCISE 3.24
A graph (/Fig. E3.5) is plotted of time (in s on x-axis) vs oxygen concentration
(in volume % on y-axis).
25
N2 Air in N2 Air
21
20
Oxygen consumed
Oxygen Concentration, vol. %
from air
15
Effluent
oxygen
concentration
10
Oxygen consumed from
5 % mixture Start 100 %
air feed
5
Start 5 % Stop
O2 in feed air
feed
0
0 600 1200 1800 2400 3000
Decoking Time, s
Fig. E3.5 Decoking of catalyst
Area under the diagonal lines are as follows:

x-axis coverage Area, square units
0 1800 s 0.6619
Considering 5% concentration of O2 in the feed stream, area upto nitrogen
introduction = 1044 square units
Area for air introduction (i.e. from 1800 to 3600 s)

= 2.099 square units
Basis: Nitrogen supply @ 0.025 L/s at NTP.
0.025 ´ 10-3
Molar flow of nitrogen =
22.414
= 0.1115 ´ 105 kmol/s
Air with 21% O2 is mixed with N2. Let the flowrate of air be x kmol/s.
x ´ 0.21 = (x + 0.1115 ´ 105) 0.05
x = 0.3484 ´ 106 kmol/s
In 1800 s, O2 supply = 0.3484 ´ 106 ´ 0.21 ´ 1800
= 0.132 ´ 103 kmol
º 0.7496 square units
0.6619 ´ 0.132 ´ 10-3

O2 consumed =
0.7496
= 0.117 ´ 103 kmol
º 0.117 mol
After stoppage of N2 supply,
air flow = 0.025 L/s at NTP
= 0.1115 ´ 105 kmol/s
O2 supply during the period 1800 s to 3600 s,
= 0.1115 ´ 105 ´ 1800 ´ 0.21
= 0.42 ´ 103 kmol
º 2.099 square units
0.5495 ´ 0.42 ´ 10-3

O2 consumed =
4384.8
= 0.11 ´ 105 kmol
º 0.011 mol
Total oxygen consumed = 0.117 + 0.011
= 0.128 mol
º 4.096 g or 4.096 ´ 103 kg Ans.
EXERCISE 3.25
Basis: 1000 kg/h feed rate
Material balance across mixer:
Let recycle and mixed feed be R and M kg/h, respectively.
Overall balance:
M = 1000 + R (1)
Balance of solids:
0.15 M = 300 + 0.03 R
M = 2000 + 0.2 R (2)
Equating Eq. (1) and (2);
1000 + R = 2000 + 0.2 R
0.8 R = 1000
or R = 1250 kg/h and M = 2250 kg/h
Balance across calciner:
Let the evaporation in calciner be W kg/h and product from the divider by P kg/h.
M=W+P+R
But P = 700/0.97 = 721.65 kg/h
W = M P R = 2250 721.65 1250
= 278.35 kg/h
Total dry product from the calciner = P + R
= 1250 + 721.65
= 1971.65 kg/h
Recycle fraction = 1250 ´ 100/1971.65 = 63.4% Ans.
EXERCISE 3.26
Basis: Cloth speed = 1 m/s
Production of dry cloth = 1 ´ 3600 ´ 90 ´ 90/(100 ´ 1000)
= 291.6 kg/h
Evaporation in the stenter = 291.6(0.80 0.08)
= 210 kg/h Ans. (a)
Fresh air required = 210/(0.1 0.015)
= 2470.6 kg dry air/h Ans. (b)
Specific volume of air = 8.314 ´ 303/(100 ´ 29)
= 0.8687 m3/kg dry air
Volumetric flow rate of dry air = 2470.6 ´ 0.8687
= 2146.2 m3/h Ans. (c)
Material balance of moisture across points 1 and 3:
R ´ 0.1 + 0.015 ´ 2470.6 = (R + 2470.6) 0.095
R = 39 530 kg dry air/h Ans.(d)
EXERCISE 3.27
Basis: 10 m3/L product water, nett of regeneration
System-I: Ion Exchange based demineralization
Effluent generation = 10 ´ 0.2
= 2 m3/h
Feed (raw) water requirement = 10 + 2 = 12 m3/h Ans. (a)
System-II: RO + Ion Exchange
Effluent generation from ion-exchange system
= 10 ´ 0.1 = 1 m3/h
Feed to ion-exchange system = 10 + 1 = 11 m3/h
In RO module, permeate recovery is 80% and DS rejection is 95%. Thus for
10 m3 input raw water with 2500 mg/h DS, 8 m3 permeate is produced.
8 ´ xDS = 10 ´ 2500 (1 0.95) = 1250
xDS = 156.25 mg/L in permeate
In reject water, DS concentration can be calculated.
2 ´ zDS = 10 ´ 2500 ´ 0.95 = 23 750
zDS = 11 875 mg/L Ans. (d)
Let P1 be flow of permeate water from RO module which is mixed with bypass
flow to achieve 11 m3/h feed rate to ion-exchange column.
P1 ´ 156.25 + (11 P1) 2500 = 11 ´ 500
P 1 = 9.387 m3/h
Bypass flow = 11 9.387 = 1.613 m3/h
Ratio of permeate/bypass = 9.387/1.613 = 5.82 m3/m3 Ans. (c)
Raw water input to RO module = 9.387/0.80
= 11.734 m3/h
Total raw water feed rate = 11.734 + 1.613
= 13.347 m3/h Ans. (b)
EXERCISE 3.28
Refer Example 3.18.
Calculations upto R2 = 1.25 m3/h are common.
Recovery from RO Module I = 60%:
P1 6.25
= 0.6 or = 0.6
F + R2 F + 1.25
F= 9.17 m3/h
R2/F = 1.25/9.17 = 0.136 m3/m3
R1 = F P2 = 9.17 5 = 4.17 m3/h
Fx F = R1 xR + P2 xP
1 2
9.17 ´ 4200 = 4.17 ´ xR + 5 ´ 5
1
xR = 9230 mg /L or g/m3
1
5´5
DS in P1, xP = = 267 g/m3 or mg/L
1 0.015 ´ 6.25
P1 xP = P2 xP + R2 xR
1 2 2
6.25 ´ 267 = 5 ´ 5 + 1.25 ´ xR
2
xR = 1315 g/m3 or mg/L (unchanged)
2
DS in mixed feed = F xF + R2 xR
2
= 9.17 ´ 4200 + 1.25 ´ 1315
= 40 158 g
Total mixed feed (MF) to RO module I = 9.17 + 1.25
= 10.42 m3/h
40 158
Concentration DS in MF =
10.42
= 3854 g/m3 or mg/L
DS in R1 = 4.17 ´ 9230
= 38 489 g
38 489
Rejection RO Module I = ´ 100
40 158
= 95.84% Ans. (a)
Rejection from Module I = 70%
6.25
= 0.7
F + 1.25
F = 7.68 m3/h
R2/F = 1.25/7.68 = 0.163 m3/m3
R 1 = F P2 = 7.68 5 = 2.68 m3/h
F xF = R1 xR + P2 xP
1 2
7.68 ´ 4200 = 2.68 ´ xR + 5 ´ 5
1
xR = 12 026 mg/L or g/m3
1
DS is mixed feed = F xF + R2 xR
2
= 7.68 ´ 4200 + 1.25 ´ 1315
= 33 900 g
33 900
Concentration of DS in MF =
(7.68 + 1.25)
= 3796 g/m3 or mg/L

DS in R1 = R1 xR = 2.68 ´ 12 026
1
= 32 230 g
32 230
Rejection in RO Module I = ´ 100
33 900
= 95.07% Ans.
Note: Recovery from RO Module I can be varied by varying feed pressure (PI1)
and selecting right RO memberane. It can be seen that this does not affect % DS
rejection significantly. However, it makes significant changes in other parameters
(F and R1).
EXERCISE 3.29
Basis: 100 kg final 24% NaOH solution
Let mass of solution in the dissolution tank = W3 kg
Balance of NaOH:
W3 ´ 0.5 + W2 ´ 0 = 100 ´ 0.24
W3 = 48 kg of 60% solution
Overall material balance across the dilution tank:
W2 + W3 = 100
or W2 = 100 48 = 52 kg water
Balance of NaOH across the dissolution tank:
W1 = W3 ´ 0.5 = 48 ´ 0.5 = 24 kg water
W3 /W2 = 24/52 = 0.462:1
EXERCISE 3.30
Basis: 3000 Nm3/h fresh feed
Overall material balance:
.
Let enriched CH4 stream from M-2 = n1 Nm3/h
.
and reject stream from M-3 = n2 Nm3/h
. .
n1 + n2 = 3000 (1)
CH4 balance:
. .
0.985 n1 + 0.04 n2 = 3000 ´ 0.88 (2)
.
Solving two equations, n1 = 2666.67 Nm3/h
.
n2 = 333.33 Nm3/h
Module-2:
Permeate from module = 12 %
Non-permeate from module = 100 12 = 88 %
Non-permeate from M-2 is the enriched CH4 stream.
. 2666.67
Feed rate to M-2, n3 = = 3030.31 Nm3/h
0.88
. .
R 1 = n3 n1 = 3030.31 2666.67 = 363.64 Nm3/h
Module-3:
Permeate from module-1 = 44 %
Permeate from M-3 is the rejedct stream.
. 333.33
Feed rate to M-3, n4 = = 757.568 Nm3/h
0.44
. .
R 2 = n4 n2 = 757.568 333.33 = 424.238 Nm3/h
Mixed feed (MF) to M-1 = F + R1 + R2
= 3000 + 363.64 + 424.238
= 3787.878 Nm3/h
. .
CO2 contents of n4 and n3 streams are 60.2 % and 4.25 % by mole, respectively
CO2 content of MF = x1 (mole fraction)
x1 ´ 3787.878 = 757.568 ´ 0.602 + 3030.31 ´ 0.0425
x1 = 0.1544
Mole fraction of CH4 in MF = 1 0.1544 = 0.8456
.
CH4 in n3 = 3030.31 (1 0.0425) = 2901.522 Nm3/h
CH4 in R1 = 2901.522 2666.67 ´ 0.985
= 274.852 Nm3/h
274.852 ´ 100
CH4 concentration of R1 = = 75.58 %
363.64
.
CH4 in n4 = 757.568 (1 0.602) = 301.512 Nm3/h
CH4 in R2 = 301.512 333.33 ´ 0.04
= 288.179 Nm3/h
288.179 ´ 100
CH4 content of R2 = = 67.93 % Ans.
424.238
EXERCISE 3.31
Basis: 20 L/s weak liquor
Mass flow rate wate = 20 ´ 3600 = 72 000 kg/h (SG = 1.0)
SO2 present in the weak liquor = 72 000 ´ 0.005 = 360 kg/h
SO2 present in the rich liquor = 72 000 ´ 0.01 = 720 kg/h
SO2 absorbed in the absorber = 720 360 = 360 kg/h
Now in the incoming 100 kmol gas, 17 kmol SO2 are present. Out of 17 kmol,
75% SO2 is absorbed.
SO2 absorbed = 17 ´ 0.75 = 12.75 kmol º 816 kg

Outgoing gas mixture = (100 17) + (17 12.75) = 87.25 kmol
SO2 content of outgoing gas mixture = 4.25 ´ 100/87.25
= 4.87%
Gas flow rate = 100 ´ 360/816 = 44.12 kmol/h
º 12.26 ´ 103 kmol/s Ans. (a)
Specific volume of gas mixture,
V = 8.314 ´ 308.15/(101.3 + 50) = 16.925 m3/kmol
Volumetric flow rate = 44.12 ´ 16.925 = 746.73 m3/h
º 207.43 dm3/s Ans. (b)
EXERCISE 3.32
Basis: 1 litre effluent sample
Let x = content of methanol, mg/L
y = content of formaldehyde, mg/L
Carbon content of methanol = 12/32 = 0.375 mg/mg
Carbon content of formaldehyde = 12/30 = 0.4 mg/mg
TOC of the sample = 0.375 x + 0.4 y = 258.3 (1)
Oxidation reactions:
CH3OH + 1.5 O2 ¾ ¾¾® CO2 + H2O
32 1.5 ´ 32 44 18
HCHO + O2 ¾ ¾¾® CO2 + H2O
30 32 44 18
Oxygen demand of methanol = 48/32 = 1.5 mg/mg
Oxygen demand of formaldehyde = 32/30 = 1.068 mg/mg
ThOD of sample = 1.5 x + 1.068y = 956.3 (2)
Solving the equations, x = 535 mg/L
y = 144 mg/L Ans.
EXERCISE 3.33
Basis: 16.5 Nm3/s of moist gas flow rate
Molar flow rate = 16.5/22.414
= 0.736 kmol/s º 2650 kmol/h
Water vapours, present in moist gas = 4.2 Nm3/s
= 0.1874 kmol/s º 674.6 kmol/h
Solids, present in the gas mixture = (16.5 4.2) ´ 9000/106
= 0.1107 kg/s º 398.5 kg/h
Chlorides in gas mixture = 1.5 g/s = 5.4 kg/h
Dry gas flow rate = 2650 674.6 = 1975.4 kg/h
Solids in outgoing gas mixture = 120 ´ (16.5 4.2)/106

= 1.476 ´ 103 kg/s º 5.314 kg/h
Solids scrubbed = 398.5 5.314 = 393.186 kg/h
Vapour pressure of water at 348 K (75 ºC) = 38.549 kPa (ref. Chapter 6)
Humidity = 38.549/(101.325 38.549)
= 0.614 kmol/kmol dry gas
Moisture in outgoing gas mixture = 0.614 ´ 1975.4
= 1213 kmol/h
Moisture added in gas mixture = 1213 674.6 = 538.4 kmol/h
º 9691.2 kg/h
Let x be purge rate (bleed) in kg/h. It will purge solids, equal to the amount
scrubbed (i.e. 393.186 kg/h).
Chlororides in purge = 200 ppm
= 200 mg/kg as Cl
Balance of chlorides:
Chlorides in purge = chlorides from incoming gas mixture + chlorides from
make-up water chlorides loss in evapn.
x ´ 200/106 = 5.4 + (x + 9691.2) 50/106 0
x = 39 230 kg/h
º 10.9 kg/s
Solids concn. in circulating solution = 393.186 ´ 100/39 230
= 1.00%
SO3 in incoming gas mixture = 1600 ´ (16.5 4.2) ´ 3600/106
= 70.85 kg/h
SO3 scrubbed = 70.85 ´ 0.8 = 56.68 kg/h
H2SO4 produced = 98 ´ 56.68/80
= 69.43 kg/h which is purged out in the
bleed.
69.43 ´ 100
H2SO4 concentration = = 0.18%
39 230
Make-up water = 9691 + 39 230 = 48 921
º 13.59 kg/s Ans.
EXERCISE 3.34
Let the baterial suspended in total combined feed = xR mg/L
Bacterial suspended solids in total combined feed = x0 mg/L
For minimum recycle ratio, xR = 5x0 (1)
Bacterial suspended solids in fresh feed =0
Concentration of solids in clarifier overflow =0
Concentration of solids (bacterial and non-bacterial) in the total combined feed =

2% = 20 000 mg/L
Balance of total solids at the entrance of aeration tank:
Total solids in fresh feed + total solids in recycle stream
= total solids in combined feed
485 QF + QR xR = (QF + QR) 20 000
Dividing by QF and substituting the recycle ratio,
r = QR/QF
485 + r xR = (1 + r)20 000
20 000 (1 + r ) - 485
xR = (2)
r
Balance of bacterial suspended solids at the entrance of aeration tank:
Total solids in combined feed fresh feed solids (non-bacterial)
= total bacterial suspended solids
20 000(QR + QF) 485 QF = (QF + QR) x0
20 000(1 + r) 485 = (1 + r) x0
x0 = 20 000 [485/(1 + r)] (3)
Substitute Eqs. (2) and (3) in Eq. (1).
20 000 (1 + r ) + 485
= 5[20 000 (485/(1 + r)}]
r
Simplifying, 80 000 r2 + 58 060 r 19 515 = 0
r = 1/4 or 0.975 75
Discarding negative solution, minimum recycle ratio = 1/4 Ans.
EXERCISE 3.35
At constant temperature T:
(a) Let initial quantum of the component in vessel = x kmol
Total quantum of gas in vessel = n1 kmol
Concentration of component at p1 pressure, c1 = x/n1 kmol/kmol
At an absolute pressure p1, n1 = p1 × V/RT where V = vessel volume
When the vessel is pressurised to absolute pressure p2 with inert gas,
quantum of gas in the vessel will be n2 = p2 × V/RT
Concentration of component at p2 pressure, c2 = x/n2 kmol/kmol
During depressurisation of the vessel there will be no change in
concentration c2.
Ratio, c2/c1 = n1/n2

= p1 × RT/(p2 × RT )
= p1/p2
Thus final concentration of the component will be (p1/p2) times the initial
concentration. This is for one cycle of pressurisation/depressurisation. If
this cyclic process is carried out k times, concentration of the component
after k cycles (ck) will be (p1/p2)k times the original concentration (c1).
Quantum of inert gas required = n2 n1 kmol for one pressurization
Ratio of inert gas required to initial gas quantum = [(n2 n1)/n1]V
= [(p2 p1)/p1] V per cycle Ans.
(b) At sub-atmospheric absolute pressure p (in kPa), quantum of gas in vessel,
n1 = pV/RT kmol. Note that R will have consistent units.
Concentration of component at p pressure, c1 = x/n1 kmol/kmol
During evacuation, there will be no change in concentration c1. Now the
vessel is pressurised with inert gas to atmospheric pressure.
At atmospheric pressure, total gas = n2 = 101.3 × V/RT kmol
Concentration of component at atmospheric pressure, c2 = x/n2 kmol/
kmol
Ratio, c2/c1 = n1/n2 = p/101.3 per cycle of evacuation/pressurisation
If k cycles are carried out, final concentration will be (p/101.3)k times c1.
Ratio of inert gas required to bring the vessel to atmospheric pressure
= [(n2 n1)/n1]V = [(101.3 p)/101.3]V per cycle
Ans.
If pressure p is expressed in atmospheres, c2/c1 = p and inert gas
requirement = (1 p)V per cycle
Note: In industrial practice, pressure cycle method is more common in
use as compared to vacuum cycle method or the atmospheric method
(i.e. Example 3.20 in the text). Why?
EXERCISE 3.36
Empty height of isotank, h1 = 2.5 ´ 0.15 = 0.375 m
2.5
Radius of isotank, R = = 1.25 m
2
h1 0.375
= = 0.3
R 1.25
From Chemical Engineers' Handbook, Ed. R.H. Perry, 5th Ed., p, 1-22, 1973,
cross -sectional area of empty segment, A

= 0.2955
R2
A = 0.2955 (1.25)2 = 0.461 72 m2
Volume of air before purging = 0.461 72 ´ 6
= 2.7703 m3
Based on Exercise 3.35 (a), p1 = 1 atm
p2 = 2 bar g = 1.973 85 atm g
= 2.973 85 atm a
Before pressure purging, c1 = 20.946 vol.% (O2 in air)
20.946
After first cycle of purging, c2 =
2.973 85
= 7.043 vol.%
7.043
After second cycle of purging, c3 =
2.973 85
= 2.368 vol.%
2.368
After third cycle of purging, c3 =
2.973 85
= 0.796 vol.% (i.e. < 1%)
Thus 3 cycles of purging are required.
No. of empty vessel volumes, required for purging
= (p2 p1)/p1 = 1.973 85 times per cycle
Total nitrogen required for purging
= 1.973 85 ´ 3 ´ 2.7703
= 16.404 m3 at 1 atm and 308.15 K (35°C)
At NTP, nitrogen requirement = 16.404 ´ 273.15/308.15
= 14.541 Nm3 Ans.
EXERCISE 3.37
Basis: 100 kmol dry gas mixture at time of shutdown.
Steam present = 100 ´ 1.2 = 120 kmol
Component kmol mole % on wet basis

H2 56.0 25.45
CO 15.0 6.82
CO2 7.0 3.18
N2 21.7 9.86
Ar 0.3 0.14
H2O 120.0 54.55
Total 220.0 100.00
Initially when HT Shift Converter is pressure reduced to 0.25 bar g, there will be
no change in concentrations. Since presence of H 2O is objectional, its
concentration will be considered for calculations.
c1 = 0.5455 mole fraction
p1 = 0.25 bar g = 0.246 73 atm g = 1.246 73 atm a
p2 = 5 bar g = 4.934 62 atm g = 5.934 62 atm a
1.246 73
p1/p2 = = 0.210 08
5.934 62
c2 = (p1/p2) c1 = 0.210 08 ´ 0.5455 = 0.1146 mole fraction
c3 = 0.210 08 ´ 0.1146 = 0.024 07
c4 = 0.210 08 ´ 0.024 07 = 0.005 06 (i.e. < 0.01)
Thus 3 cycles of purging are required.
Final concentration of water = c4 = 0.5% (by volume)
Final concentration of carbon monoxide
= (0.210 08)3 0.0682 = 0.0006 mole fraction
or 0.06% by volume
Number of (empty) void volumes required for purging
= (p2 p1)/p1 = (5.934 62 1.246 73)/1.246 73
= 3.76 times
Nitrogen requirement = 3.76 ´ 3 ´ 40
= 451.2 m3 at
1.246 73 atm a and 308.15 K (35 °C)
451.2 ´ 1.246 73 ´ 27315
.
At NTP, nitrogen requirement =
308.15
= 498.63 Nm3 Ans.
EXERCISE 3.38
Alternate 1: Methane addition
Basis: 200 kmol mixture
H2 present = 100 kmol or 50%
Air present = 100 kmol
Since H2 is 50% in the mixture, it is within the flammability envelope.

Let x kmol CH4 are to be added to raise the upper limit of flammability.
LM 100 OP 100 LM x OP 100
N 200 + x Q + N 200 + x Q = 1
75 14
LM 100 OP + 7500LM x OP = 14 ´ 75 = 1050
1400
N 200 + x Q N 200 + x Q
14 ´ 100 + 75 ´ x = 10.50 (200 + x)
1400 + 75 x = 2100 + 10.5 x
x = 10.85 kmol Ans. (b)
Alternate 2:
Oxygen present = 100 ´ 0.2095
= 20.95 kmol
Let y be kmol of the total mixture.
0.05 y = 20.95
y = 419 kmol
N2 to be added = 419 200 = 219 kmol Ans. (a)
EXERCISE 3.39
At any time G (h) the concentration of oxygen in the chamber is y mol/mol of
mixture.
Total air present initially = pV/RT
p = (53.3 + 101.3)
= 154.6 kPa
Air present = 154.6 ´ 4500/(8.314 ´ 293 ´ 1000)
= 0.2856 kmol
Astronaut inhales 123 kg air and exhales 112 kg air. The difference between
two is the oxygen consumption by the astronaut.
Oxygen consumed from the chamber
= (123 112)/24
= 0.4583 kg/h º 0.0143 kmol/h
CO2 coming to the chamber = 8.8/(44 ´ 24)
= 0.0083 kmol/h
At time G, total moles of dry gas, present in the chamber (N)
= 0.2856 0.0143 G + 0.0083 G
= 0.2856 0.006 G kmol
Oxygen balance at time G:
Consumption of oxygen = input oxygen output oxygen
Since mole fraction of oxygen is y in the chamber at time G, average molar mass
of gas mixture in the chamber, excluding nitrogen
= 32 y + (1 y)44 = 44 12y
Air output (inhalation) from the chamber = 123 kg/d
= 5.125 kg/h
Equivalent oxygen output = 5.125y/(44 12y) kmol/h
Air input (exhalation) to the chamber = 112 kg/d = 4.667 kg/h
Equivalent oxygen input = 4.667y/(44 12y) kmol/h
Input output = 0.458y/(44 12y) kmol/h
dy
But consumption of oxygen = N
dG
dy 0.458 y
(0.2856 0.006 q) =
dG ( 44 - 12 y)
dG -dy( 44 - 12 y)
Rearranging, =
(0.2856 - 0.006 G ) 0.45 y
When G = 0, i.e. start of the mission, y = 1.0, i.e. pure oxygen.
At the end of mission, i.e. G = G, y = 0.2.
z
G 0.2
dG ( 44 - 12 y)dy
ò (0.2856 - 0.006G ) = 0.458 y
0 1
(1/0.006) ln (1 0.021 G ) = 133.655

ln (1 0.021 G ) = 133.655 ´ 0.006 = 0.801 93
1 0.021 G = 0.4485
0.021 G = 0.5515
G = 26.264 h º 26 h 16 min Ans. (a)
This means the mission will last for 1 day 2 hours and 16 minutes before O2
concentration will reduce to 20% (v/v).
At the end of 26.264 h,
CO2 accumulated = 26.264 ´ 0.0083 = 0.218 kmol
Oxygen present = 20%
Total gas mixture = 0.218/0.8 = 0.2725 kmol
nRT 0.2725 ´ 8.314 ´ 293 ´ 100
Pressure in the system = =
V 4500
= 147.5 kPa Ans. (b)
Partial pressure of O2 = 147.5 ´ 0.2 = 29.5 kPa
Partial pressure of CO2 = 147.5 29.5 = 118 kPa Ans. (c)
EXERCISE 3.40
Basis: 1.65 kg/s 10% NaOH solution
The solution contains 0.165 kg/s NaOH. This solution is prepared by mixing
(0.165/0.5 =) 0.33 kg/s 50% lye and (1.65 0.33 =) 1.32 kg/s water.
Hold-up in the tank = 1900 ´ 1.1 = 2090 kg
NaOH balance of unsteady-state process when the flow of 50% lye will stop:
Let c = concentration of NaOH by mass in the tank at any time G (in seconds)
and dG = time interval in seconds
1.32 ´ 0 c ´ dG = 2090 dc
z z
G c2
dG = (2090/0.165) dc/c = 12 667 ln (c1/c2)

0 c1
G = 12 667 ln (0.1/0.08)
= 2827 s Ans.
EXERCISE 3.41
Basis: 150 Sm3/h air at 101.325 kPa and 288.7 K (15 °C)
Specific volume,
V = RT/p = 8.314 ´ 288.7/101.325 = 23.689 m3/kmol
Molar flow rate of moist air = 150/23.689 = 6.332 kmol/h
Inlet pressure = 710 kPa g = 811.325 kPa a
Vapour pressure of water at 318 K (45 °C) = 9.582 kPa (ref. Chapter 6)
Humidity of inlet air = 9.582/(811.325 9.582)
= 0.011 95 kmol/kmol dry air
º 0.0118 kmol/kmol moist air
Total moisture in the inlet air = 6.332 ´ 0.0118
= 0.0747 kmol/h
º 1.345 kg/h
Dry air flow rate = 6.332 0.075 = 6.257 kmol/h
º 181.45 kg/h
Step-I: Increase of moisture content of silica gel from 2.5 to 3.75 kg per 100 kg
desiccant
Mixture picked-up by silica gel = (3.75 2.5) 220/100
= 2.75 kg
Average moisture content of outlet air
= (5 + 10)/2 = 7.5 mg/Sm3
Moisture, removed from air in
G1 h = [1.345 (7.5 ´ 150)/106] G1
= 1.3439 G1 kg
1.3439 G1 = 2.75
G1 = 2.046 h
Similar iterations can be performed.

Step II: Increase in moisture content of silica gel l from 3.75 kg to 5.625 kg
per 100 kg desiccant
G2 = 3.071 h
G3 = 1.537 h
G4 = 1.281 h
Total duration = å G i
= 2.046 + 3.071 + 1.537 + 1.281
= 7.935 h Ans.
EXERCISE 3.42
Basis: Cooling water (CW) hold-up in system = 3000 m3
Consider a small time interval DG = 1 h
G1 = 1 h
Initial total suspended solids in cooling water
= 3000 ´ 50 ´ 103 mg
= 15 ´ 107 mg
Suspended solids removed = 100 (50 10)103 = 0.4 ´ 107 mg
Suspended solids after one hour = (15 ´ 107 0.4 ´ 107) mg
Concentration of suspended solids
= (15 ´ 107 0.4 ´ 107)/(3000 ´ 103)
= 48.667 mg/L
Similar iterations can be performed, which are tabulated below.
Time suspended suspended Time suspended suspended

G h solids in solids in G h solids in solids in
outlet CW at the outlet CW at the
water from end of water from end of
filter, mg/L G h, mg/L filter, mg/L G h, mg/L
0 10 50.0 12 9 36.503
1 10 48.667 13 9 35.587
2 10 47.378 14 9 34.700
3 10 46.131 15 9 33.844
4 10 44.927 16 9 33.016
5 10 43.763 17 9 32.215
6 10 42.637 18 9 31.441
7 10 41.549 19 9 30.693
8 10 40.598 20 8 29.927
9 9 39.448 21 8 29.206
10 9 38.433 22 8 28.499
11 9 37.452 23 8 27.815
24 8 27.155 47 5 15.113
25 7 26.483 48 5 14.776
26 7 25.833 49 5 14.450
27 7 25.205 50 5 14.135
28 6 24.565 51 5 13.831
29 6 23.946 52 5 13.536
30 6 23.348 53 5 13.231
31 6 22.770 54 5 13.143
32 6 22.211 55 5 12.710
33 6 21.671 56 5 12.453
34 6 21.148 57 5 12.205
35 6 20.643 58 5 11.965
36 6 20.155 59 5 11.733
37 5 19.683 60 5 11.508
38 5 19.194 61 5 11.291
39 5 18.721 62 5 11.082
40 5 18.263 63 5 10.879
41 5 17.821 64 5 10.683
42 5 17.394 65 5 10.493
43 5 16.981 66 5 10.310
44 5 16.582 67 5 10.133
45 5 15.822 68 5 9.962
46 5 15.462
Thus time required for bringing down the suspended solids to 10 mg/L level
= 68 h Ans
EXERCISE 3.43
Basis: 3000 m3 hold-up
DG = 1 h
Suspended solids at G = 0 h = 3000 ´ 50 ´ 107 = 15 ´ 107 mg
Suspended solids removed in the filter = 4 ´ 106 mg/h (from Exercise 3.42
after first hour of filtration.)
Dust (turbidity) added in the basin = 16 ´ 109 ´ 106 ´ 106 kg/h
º 1.696 ´ 106 mg/h
Net suspended solids after 1 h = 15 ´ 107 4 ´ 106 + 1.696 ´ 106
= 147.696 ´ 106 mg/h
Suspended solid in CW = 147.696 ´ 106/(3000 ´ 103)
= 49.232 mg/L
Time suspended suspended Time suspended suspended

G h solids in solids in G h solids in solids in
outlet CW at the outlet CW at the
water from end of water from end of
filter, mg/L G h, mg/L filter, mg/L G h, mg/L
0 – 50.0
1 10 49.232 38 9 32.567
2 10 48.490 39 9 32.347
3 10 47.772 40 9 32.134
4 10 47.078 41 9 31.929
5 10 46.407 42 9 31.730
6 10 45.759 43 9 31.537
7 10 45.132 44 9 31.352
8 10 44.526 45 9 31.172
9 10 43.941 46 9 30.998
10 10 42.810 47 9 30.831
11 10 42.282 48 9 30.668
12 10 41.771 49 9 30.511
13 10 41.277 50 9 30.359
14 10 40.800 51 9 30.213
15 10 40.339 52 9 30.071
16 10 39.891 53 8 29.900
17 9 39.427 54 8 29.736
18 9 38.978 55 8 29.577
19 9 38.544 56 8 29.423
20 9 38.124 57 8 29.274
21 9 37.718 58 8 29.130
22 9 37.326 59 8 28.991
23 9 36.947 60 8 28.857
24 8 36.581 61 8 28.727
25 9 36.227 62 8 28.601
26 9 35.885 63 8 28.480
27 9 35.554 64 8 28.363
28 9 35.234 65 8 28.249
29 9 34.925 66 8 28.140
30 9 34.626 67 8 28.034
31 9 34.337 68 8 27.931
32 9 34.058 69 8 27.832
33 9 33.788 70 8 27.737
34 9 33.527 71 8 27.644
35 9 33.275 72 8 27.555
36 9 33.031 73 8 27.468
37 9 32.795 74 7 27.351
(Contd.)
(Contd.)
75 7 27.238 93 7 25.741
76 7 27.129 94 7 25.682
77 7 27.023 95 7 25.624
78 7 26.921 96 7 25.569
79 7 26.822 97 7 25.515
80 7 26.722 98 7 25.464
81 7 26.635 99 7 25.413
82 7 26.546 100 7 25.335
83 7 26.460 101 7 25.318
84 7 26.380 102 7 25.273
85 7 26.296 103 7 25.229
86 7 26.218 104 7 25.187
87 7 26.149 105 7 25.146
88 7 26.070 106 7 25.106
89 7 26.000 107 7 25.068
90 7 25.932 108 7 25.031
91 7 25.866 109 7 24.999
92 7 25.803
Time, required to bring down the turbidity level to 25 mg/L = 109 hAns.
EXERCISE 3.44
Material balance of components A after time G:
Input output = accumulation
DC
0 F × CAG = V ×
DG
dCA F
When DG ® 0, = dG
dCAG V
Integrating on both the sides,
z
CAG
dCA F
= dG
dCAG V
CA 0
F
ln CAG ln CAO = q
V
or CAG = CA0 e(FG/V) Ans.
EXERCISE 3.45
Basis: V m3 volume of the receiver
Input output = accumulation
Output = 0
Actual volume swept = v = v0 × Dv
LM p p FG IJ OP 1/ C
v = v0 1 + c -
MN 100 p0
-c
p0 H K PQ
3600 s v0 p0
Swept volumetric flow rate = kmol/h
ZRT
Input =
3600 s v0 p0
1+ c-
LM
p
-c
p RS UV OP in 1 h
1/ C
ZRT MN
100 p0 p0 T W PQ
After time G,
dn
Accumulation in the receiver =
dG
where n = no. of kmol present at time G
V dp
= ×
ZRT dG
Therefore,
V
×
dp
=
3600 s v0 p0
1+ c-
LM
p
-c
p RS UV 1/ C
OP
ZRT dG ZRT MN
100 p0 p0 T W PQ
3600 s v p L RpU OP
1/ C
dp
dG
=
V
M
MN
0
1+ c-
p 0
100 p
- cS V
Tp W PQ
0 0
or
3600 s v0 p0 L
dq = dp/ M1 + c -
p RpU
- cS V
1/ C
OP
V MN 100 p Tp W 0 0 PQ
Integrating on both the sides,
z z LM p LM1 + c - p RS p UV OP O
G p1 1/ C
PQ PPQ
3600 s v0
dG = dp -c
V
0 p0 MN MN
0
100 p 0 Tp W0
Substitute r = p/p0 and R1 = p1/p0
z LM OP
R1
3600 s v0 r
ZRT
q =
1
N
dr / 1 + c -
100
- c(r )1 / C
Q
z
R1
V dr
or q =
3600 s v0 1 + c - (r /100) - c(r )1/ C
1
Note: For a double acting compressor,
z
R1
V dr
q =
7200 s v0 1 + c - (r /100) - c(r )1/ C
1
EXERCISE 3.46
Basis: Air receiver having 60 m3 capacity is to be from 101.325 kPa a
to 0.7 MPa g
Geometric volume of cylinder v0 = (p/4) (0.312) (0.15)
= 1.132 ´ 102 m3
3
V = 60 m , C = 1.4, c = 0.07, R1 = ?
Each stage has equal compression ratio.
Overall compression ratio = (700 + 101.325)/101.325 = 7.9085
R 1 = R2 = 7.9085
= 2.8122
L OP of Exercise 3.45 can be solved by

z
R1
The integral M
dr
MN 1
1 + c - (r /100) - c(r )1 / C PQ
Numerical integration using Simpsons rule:
r [1 + c (r/100) c(r)1/C] f = 1/[1 + c (r/100) c(r)1/C]
1.000 00 0.990 00 f1 = 1.010 00
1.181 22 0.979 34 f2 = 1.021 09
1.362 44 0.969 07 f3 = 1.031 92
1.543 66 0.959 11 f4 = 1.042 63
1.724 88 0.949 42 f5 = 1.053 27
1.906 10 0.939 97 f6 = 1.063 86
2.087 32 0.930 72 f7 = 1.074 44
2.268 54 0.921 65 f8 = 1.085 01
2.499 76 0.912 75 f9 = 1.095 59
2.630 98 0.903 99 f10 = 1.106 20
2.812 20 0.895 37 f11 = 1.116 85
Value of the integral = (h/3) [f1 + 4f2 + 2f3 + 4f4 + 2f5 + K + f11]
where h = interval = 0.181 22
Value of the integral = (0.181 22/3) [1.010 00 + 4´ 1.021 09
+ 2 ´ 1.031 92 + 4 ´ 1.042 63
+ 2 ´ 1.053 27 + 4 ´ 1.063 86
+ 2 ´ 1.074 44 + 4 ´ 1.085 01
+ 2 ´ 1.095 59 + 4 ´ 1.106 20
+ 1 ´ 1.116 85]
= 0.060 41(1.010 00 + 4.084 36 + 2.063 84

+ 4.170 52 + 2.106 54 + 4.255 44 + 2.148 88
+ 4.340 04 + 2.191 18 + 4.424 80 + 1.116 85
= 0.060 41 ´ 31.912 55
= 1.927 84
For double acting compressor, stroke s = 2 ´ 9.2 s1 which will replace the term
7200 s in the equation for finding the time in Exercise 3.45.
V
Therefore, q = ´ integral
s v0
60 ´ 10 2
= ´ 1.927 84 = 555.3 s
2 ´ 9.2 ´ 1132
.
The above calculated time refers to (2.8122 ´ 101.325) at the discharge of first
stage or 801.325 kPa a at the discharge of second sage.
time required = 555.3 s
º 0.154 h Ans.
Evaluation of the integral by a numerical method is laborious. Mathcad can be
quite useful in quick evaluation of such an integral.
4
Material Balances
Involving Chemical
Reactions
EXERCISE 4.1
Basis: 1000 kg ammonia production
Molar mass of ammonia = 17.0305
1000
NH3 Production = = 58.7182 kmol
17.0305
3
H2 requirement = ´ 58.7182
2
= 88.0773 kmol
CH4 requirement = 88.0773/4
= 22.0193 kmol
º 493.541 Nm3 Ans. (a)
When air is used, 21% O2 is also fed alongwith 79 % N2. For 58.7182 kmol NH3
production,
N2 requirement = 58.7182/2
= 29.3591 kmol
O2 fed alongwith N2 = (21/79) 29.3591
= 7.9044 kmol
H2 consumed by O2 = 2 ´ 7.9044
= 15.8088 kmol
Total H2 requirement = 88.0773 + 15.8088
= 103.8861 kmol
CH4 requirement = (103.8861/4)
= 25.9715 kmol
º 528.126 Nm3 Ans. (b)
Material Balances Involving Chemical Reactions 61
EXERCISE 4.2
Basis: 1000 kg methanol production
Molar mass of methanol = 32.0419
CH3OH production = 1000/32.0419
= 31.2091 kmol
CO2 requirement = 31.2091 kmol
H2 requirement = 3 ´ 31.2091
= 93.6273 kmol
CO2 and H2 are required in 1 : 3 molar proportions. However, reforming reaction
yields CO2 and H2 in 1 : 4 molar proportions. Hence H2 is in excess and therefore
methane requirement will be fixed by CO2 requirement.
CH4 requirement = 31.2091 kmol
º 699.521 Nm3/t Ans.
EXERCISE 4.3
Basis: N2 flow of 0.025 L/s at NTP. This basis is same as that of Exercise 3.24.
Reaction: CH0.6 + 1.6 O2 = CO2 + 0.6 H2O
12.616 1.6 ´ 31.9988
O2 consumed = 4.096 ´ 103 kg (Refer Exercise 3.24)
12.616 ´ 4.096 ´ 10-3
Coke burnt = = 1.0093 ´ 103 kg/s
1.6 ´ 31.9988
Mass of coke
Coke present in catalyst = ´ 100
Mass of catalyst
1.0093 ´ 10-3 ´ 100
=
0.1
= 1.0093% say 1% (by mass) Ans.
EXERCISE 4.4
Basis : Charge to reactor : 50 kg naphthalene (N)
200 kg 98% H2SO4
C10H8 + H2SO4 = C10H7SO3H + H2O (1)
N MSN
128 98 208 18
C10H8 + 2 H2SO4 = C10H6(SO3H)2 + 2 H2O (2)
N DSN
128 2 ´ 98 288 2 ´ 18
New basis: 100 kg product
The product will contain 18.6 kg MSN and 81.4 kg DSN.
N requirement for 18.6 kg MSN = 128 ´ 18.6/208 = 11.45 kg
N requirement for 81.4 kg DSN = 128 ´ 81.4/288 = 36.18 kg

Total N requirement = 11.45 + 36.18 = 47.63 kg
Original basis assumed the charge of N as 50 kg.
MSN produced = 18.6 ´ 50/47.63 = 19.53 kg
DSN produced = 81.4 ´ 50/47.63 = 85.45 kg
Total H2SO4 consumed = (98 ´ 19.53/208) + (2 ´ 98 ´ 85.45/288)
= 67.36 kg
Unconsumed H2SO4 = 196 67.36 = 128.64 kg
Total water produced = (18 ´ 19.53/208) + (2 ´ 18 ´ 85.45/288)
= 12.371 kg
Component Mass, kg mass %
MSN 19.53 7.94
DSN 85.45 34.74
H2SO4 128.64 52.29
H2O 12.37 5.03
Total 245.99 100.00
Ans.
EXERCISE 4.5
Basis: 100 kg product
Compound mass, kg Molar mass kmol mole %
SBP 65 150 0.4333 57.41
Nitric acid 15 63 0.2381 31.55
DNOSBP 18 240 0.0750 9.94
DNPSBP 2 240 0.0083 1.10
Total 100 0.7547 100.00
Nitric acid being the limiting component, conversion has to be based on nitric
acid consumption.
New basis: 100 kmol product
Nitric acid input = 31.55 + 2(9.94 + 1.10) = 53.63 kmol
Conversion = 2(9.94 + 1.10)100/53.63 = 41.2%
Yield of DNOSBP = 2 ´ 9.94 ´ 100/[2(9.94 + 1.10)]
= 90.04%
Yield of DNPSBP = 100 90.04 = 9.96% Ans.
EXERCISE 4.6
Basis: 1000 kg molasses
Monosaccharides present = 1000 ´ 0.45
= 450 kg
450 ´ 2 ´ 46 ´ 2
Theoretical ethyl alcohol production =
342
= 242.105 kg
º 308.41 L Ans.
EXERCISE 4.7
Basis: 1 kmol fresh i-butane (combined feed)
Recycle hydrogen feed to the reactor = 0.75 kmol H2
0.75 ´ 0.1
Methane recycled with H2 = = 0.083 kmol
0.9
Total recycle = 0.75 + 0.083
= 0.833 kmol
i-butane converted = 0.5 kmol
Yield of i-butylene = 0.5 ´ 0.88 = 0.44 kmol [reaction (1)]
H2 produced = 0.44 kmol
Total H2 in product stream = 0.75 + 0.44
= 1.19 kmol
Yield of propylene = 12% as per reaction (2)
Propylene produced = 0.5 0.44 = 0.06 kmol
Methane produced = 0.06 kmol
Total methane in product stream = 0.083 + 0.06
= 0.143 kmol
Reactor outlet stream
Component kmol vol. %
iC4H10 0.5 21.43
iC4H8 0.44 18.86
C3H6 0.06 2.57
H2 1.19 51.01
CH4 0.143 6.13
Total 2.333 100.00
Ans.
EXERCISE 4.8
Basis: 100 kmol creacked gas
Composition of cracked gas:
Component kmol Carbon Hydrogen Oxygen
kmol kmol
H2 56.5 56.5
CH4 5.2 5.2 10.4
C2H4 0.3 0.6 0.6
C2H2 7.5 15.0 7.5
C3H6 0.5 1.5 1.5
CO 25.8 25.8 12.9

CO2 4.0 4.0 4.0
O2 0.2 0.2
Total 100.0 52.1 76.5 17.1
Entire carbon atom comes from methane.

Methane fed = 52.1 kmol Ans. (a)
Hydrogen from methane = 52.1 ´ 2 = 104.2 kmol
Hydrogen unaccounted = 104.2 76.5
= 27.7 kmol
This hydrogen is burnt with oxygen to produce water.
Water produced = 27.7 kmol Ans. (c)
O2 used for water production = 27.7/2
= 13.85 kmol
O2 consumed = 13.85 + 17.1 = 30.95 kmol Ans. (b)
Conversion of methane = (52.1 5.2) 100/52.1
= 90.02% Ans. (d)
Yield of acetylene = 15 ´ 100 (52.1 5.2) Ans. (c)
= 31.98%
EXERCISE 4.9
Basis: 1 litre mixture of N2 + O2
Mass of water, absorbed on silica gel = 0.0362 g
= 0.002 01 mol
Let P = Phenolphthalein reading, mL,
M = Methylorange reading (i.e. total alkalinity), mL and
N = Normality
M ´ N ´ 50 000
Total alkalinity = mg/L as CaCO3
vol.of sample, mL
P = 35.4 mL and
1
M = 38 mL. Hence P > M
2
Therefore, the solution contains hydroxide and carbonate alkalinies.
Normally of titrating acid, N = 0.012
(2P M) N ´ 50 000
Hydroxide alkalinity = ppm as CaCO3
vol. of sample in mL
(2 ´ 35.4 38)0.012 ´ 50 000
=
10
= 1956 ppm (mg/L) as CaCO3
38 ´ 0.012 ´ 50 000
Total alkalinity =
10
= 2280 ppm (mg/L) as CaCO3

KOH is solution = 1956 ´ 56/50 = 2190.7 ppm or mg/L
K2CO3 in solution = (2280 1956) 69/50
= 447.1 ppm or mg/L
K2CO3 formation takes place due to the reaction of CO2 with KOH.
2 KOH + CO2 = K2CO3 + H2O
2 ´ 56 44 138 18
CO2 absorbed = 44 ´ 447.1/138 = 142.6 mg/L
Since the solutions volume is 1 litre,
CO2 absorbed = 142.6 mg º 0.1426 g º 0.003 24 mol
Water in the flue gas = 0.0362 g
º 0.002 01 mol
Molar volume at 101.325 kPa a and 298.15 K (25 °C),
V = 8.314 ´ 298/101.325 = 24.464 L/mol
Let x = mol of O2 and y = mol of N2 in flask
32x + 28y = 1.16 (1)
24.464 (x + y) = 1 (2)
Solving the equations, x = 0.003 87 mol, y = 0.037 mol
Component mol mole % (dry) Molar mass Mass, g mass %

CO2 0.003 24 7.34 44 0.1426 10.65
O2 0.003 87 8.78 32 0.1238 9.25
N2 0.037 83.88 28 .1.036 77.39
H2O 0.002 01 18 0.0362 2.71
Total 0.046 12 100.00 1.3386 100.00
Ans.
EXERCISE 4.10
Basis: 500 kg limestone
CaCO3 content of limestone = 500 ´ 0.60 = 300 kg
MgCO3 content of limestone = 500 ´ 0.335 = 167.5 kg
Inerts = 500 300 167.5 = 32.5 kg
Reactions are:
CaCO3 + H2SO4 = CaSO4 + H2O + CO2 (1)
100 98 136 18 44
MgCO3 + H2SO4 = MgSO4 + H2O + CO2 (2)
84.3 98 120.3 18 44
Stoichiometric H2SO4 requirement = (98 ´ 300/100) + (167.5 ´ 98/84.3)
= 294 + 194.7 = 488.7 kg
Amount of acid charged = 488.7 ´ 1.15 = 562.0 kg (100%) Ans. (a)
Strength of acid = 12% (by mass)
Quantity of aqueous acid = 562.0/0.12 = 4683.3 kg
Products of reaction (1):

CaSO4 produced = 136 ´ 300/100 = 408 kg
H2O produced = 18 ´ 300/100 = 54 kg
CO2 produced = 44 ´ 300/100 = 132 kg
º 3 kmol
Products of reaction (2):
MgSO4 produced = 120.3 ´ 167.5/84.3 = 239.0 kg
H2O produced = 18 ´ 167.5/84.3 = 35.8 kg
CO2 produced = 44 ´ 167.5/84.3 = 88 kg
º 2 kmol
Total CO2, escaped from reactor = 132 + 88 = 220 kg
º 5 kmol
Ans.(d)
Total H2O at the end of reactions = 4683.3 562 + 54 + 36
= 4219.1 kg
Compound Mass of Mass of mass %
reactants, kg products, kg in product
CaCO3 300.0 Nil
MgCO3 167.5 Nil
Inerts 32.5 32.5 0.65
H2SO4 562.0 73.3 1.48
H2O 4121.3 4211.3 84.84
CaSO4 Nil 408.0 8.21
MgSO4 Nil 239.0 4.82
Total 5183.3 4964.1 100.00
Ans. (b) and (c)
EXERCISE 4.11
Basis: 100 kmol of hydrogen chloride gas
4 HCl + O2 = 2 Cl2 + 2 H2O
Theoretical oxygen requirement = 100/4 = 25 kmol
Actual oxygen supply = 25 ´ 1.3 = 32.5 kmol
This oxygen is supplied in the form of air.
N2, entering with O2 = 79 ´ 32.5/21 = 122.3 kmol
The reaction goes to 80% completion.
HCl reacted = 100 ´ 0.80 = 80 kmol
O2 reacted = 80/4 = 20 kmol
Cl2 produced = 2 ´ 80/4 = 40 kmol
Component kmol mole % (dry basis)

HCl 20.0 10.27
O2 12.5 6.42
Cl2 40.0 20.53

N2 122.3 62.78
Total 194.8 100.00
Ans.
EXERCISE 4.12
Basis: 100 kmol of (A + inerts)
In a constant pressure reactor, the volume doubles by doubling total number of
moles (assuming that Ideal Gas Law holds).
At the end of reaction, total no. of moles = 200 kmol
A in the input mixture = 100 ´ 0.75 = 75 kmol
Let x kmol A are reacted.
Unreacted A = 75 x kmol
Product = 3x kmol
Total gas mixture at the end of reaction = 75 x + 25 + 3x
= 100 + 2x kmol
100 + 2x = 200
x = 50 kmol
Conversion = 50 ´ 100/75 = 66.67% Ans.
EXERCISE 4.13
Basis: 100 kmol dry inlet gas
CO present in ingoing gas mixture = a kmol
Let nCO kmol CO are reacted in the shift converter.
CO in outlet gas mixture = (a nCO) kmol
CO2 and H2 produced = nCO (each)
Total dry gas mixture at the outlet = (100 + nCO) kmol
% CO, present in outcoming gas mixture = b
a - nCO b
=
100 + nCO 100
100( a - b)
Simplifying, nCO = Q.E.S.
100 + b
EXERCISE 4.14
Basis: 100 kmol of gases, entering secondary converter.
The mixture contains 4 kmol SO2, 13 kmol O2 and 83 kmol N2.
Let x kmol SO2 are reacted to SO3 as per reaction:
1
SO2 + O2 = SO3
2
Outgoing gas mixture from the converter will contain (4 x) kmol SO2, (13
0.5x) kmol O2 and 83 kmol N2 on SO3free basis.
( 4 - x )100
= 0.45
( 4 - x ) + (13 - 0.5 x ) + 83
400 - 100 x
= 0.45
100 - 1.5 x
400 100 x = 45 0.675x
99.325 x = 355
x= 3.574 kmol
Conversion = 3.574 ´ 100/4
= 89.35% Ans.
EXERCISE 4.15
Basis: 100 kmol of outgoing gas mixture from reactor
Reactions are: CO2 + 4 H2 = CH4 + 2 H2O (1)
CO2 + H2 = CO + H2O (2)
The outgoing gas mixture (100 kmol) contains 1.68 kmol CH4 and 0.12 kmol CO.
Reaction (1) : CO2 required = 1.68 kmol
H2 required = 4 ´ 1.68 = 6.72 kmol
Reaction (2) : CO2 required = 0.12 kmol
H2 required = 0.12 kmol
Total CO2 required = 1.68 + 0.12 = 1.8 kmol
Total H2 required = 6.72 + 0.12 = 6.84 kmol
Unconverted CO2 = 57.1 kmol
Total CO2, entering the reactor = 57.1 + 1.8 = 58.9 kmol
Conversion of CO2 per gas = 1.8 ´ 100/58.9
= 3.06% Ans. (a)
Yield of CH4 = 1.68 ´ 100/1.8 = 93.33% Ans. (b)
Total H2, entering the reactor = 6.84 + 41.1
= 47.94 kmol
CO2 content in incoming mixture = (58.9 ´ 100) / (58.9 + 47.94)
= 55.13%
H2 content in incoming mixture = 100 55.13 = 44.87% Ans.(c)
EXERCISE 4.16
Basis: 100 kmol dry outgoing gas mixture
N2 content of the mixture = 69.05 kmol
O2 entering with N2 through air = 21 ´ 69.05/79
= 18.36 kmol
Air, entering the system = 69.05 + 18.36 = 87.31 kmol
O2 unreacted = 2.55 kmol
O2 reacted = 18.36 2.55 = 15.8 kmol
Reactions: 2 CH3CHO + O2 = 2 CH3COOH (1)
2 CH3CHO + 5 O2 = 4 CO2 + 4 H2O (2)
CO2 content of exit gas mixture = 4.85 kmol

O2 reacted as per reaction (2) = 5 ´ 4.85/4 = 6.06 kmol
CH3CHO, reacted as per reaction (2) = 2 ´ 4.85/4 = 2.43 kmol
O2 reacted as per reaction (1) = 15.81 6.06 = 9.75 kmol
Acetic acid produced = 2 ´ 9.75 = 19.5 kmol
Acetaldehyde, reacted as per reaction (1) = 19.50 kmol
Total CH3CHO reacted = 2.43 + 19.50
= 21.93 kmol
CH3CHO in exit gases = 8.65 kmol
Total CH3CHO, entering the reactor = 21.93 + 8.65
= 30.58 kmol
Conversion = 21.93 ´ 100/30.58 = 71.7%
Ans. (a)
Yield of acetic acid = 19.50 ´ 100/21.93 = 88.9%
Ans. (b)
air 29 ´ 87.41
Mass ratio, = = 1.884 kg/kg Ans. (c)
acetic acid 30.58 ´ 44
Water, produced as per reaction (2) = 4.85 kmol
CH3CHO in the exit gases = 14.90 kmol
Acetic acid removed with water = 19.50 14.90
= 4.60 kmol
Composition of gas mixture, leaving reactor:

CO2 4.85 4.43
CH3CHO 8.65 7.90
CH3CHOH 19.50 17.82
O2 2.55 2.33
H2O 4.85 4.43
N2 69.05 63.09
Total 109.45 100.00
Ans. (e)
EXERCISE 4.17
Basis: 100 kg CH4, 100 kg O2 and 100 H2O
Moles of methane = 100/16 = 6.25 kmol
Moles of oxygen = 100/32 = 3.125 kmol
Moles of steam = 100/18 = 5.555 kmol
In the reactor, oxygen will be completely consumed. As a result, CO, CO2, H2
and CH4 will appear in the product mixture.
Let a, b, c and d be kmol of CO2 CO, H2O and H2 in the product gas mixture,
respectively.
Carbon balance: a + b = 6.25 (1)

Hydrogen balance: c + d = 2 ´ 6.25 + 5.555
= 18.055 (2)
Oxygen balance: (c/2) + a + (b/2) = 3.125 + (5.556/2)
= 5.903
or 2a + b + c = 11.806 (3)
Eq. (3) Eq. (1): 2a + b + c a b = 11.806 6.25
a + c = 5.556 (4)
Eq. (2) + 2 ´ Eq. (1) Eq. (3): c + d + 2a + 2b 2a b c
= 18.056 + 2 ´ 6.25 11.806
b + d = 18.75 (5)
yCO 2 × yH 2
Based on kinetic considerations for shift reaction, K p =
yCO × yH 2 O
Since there is no change of number of moles during the shift reaction, mole
fraction can be replaced by number of moles in the equilibrium equation.
(ad)/(bc) = 0.7 (6)
From Eq. (5), d = (18.75 b)
From Eq. (1), d = 18.75 6.25 + a = 12.5 + a
From Eq. (1), b = 6.25 a
From Eq. (4), c = 5.556 a
Substituting values of b, c and d in Eq. (6):
a(12.5 + a)
= 0.7
(6.25 - a)(5.556 - a )
Simplifying,
0.3a2 + 20.7642a 24.3075 =0
Solving the quadratic equation, a = 1.151 kmol CO2
b = 6.25 1.151 = 5.099 kmol CO
c = 5.556 1.151 = 4.405 kmol H2O
d = 12.5 + a = 13.651 kmol H2 Ans.
EXERCISE 4.18
Basis: 1 litre water to be treated with lime and soda ash.
In this case, since only temporary hardness is present in water, only burnt lime
(CaO) is required to be added for treatment.
CaO required to be added = 284 ´ 56/100 = 159 mg/L CaO Ans.
EXERCISE 4.19
Basis: 1 litre water
In this case, since water contains temporary and permanent hardness, lime and
soda ash will be required to treat them.
Requirement of CaO = 56 ´ 232.6/100 = 130.3 mg/L
Requirement of Na2CO2 = 106 ´ 623.4/100 = 660.8 mg/L
Permanent hardness can be due to chlorides and sulphates of Ca and Mg. Since
this split-up is not known, it is not possible to give actual concentrations of all
components.
EXERCISE 4.20
Basis: 1 litre water to be softened
In the softener, temporary hardness is removed by passing the water through
sodium based cation exchanger. Raw water contains 275.5 mg/L Ca(HCO3)2
and 329.2 mg/L Mg(HCO3)2.
Equivalent NaCl requirement (theoretical) for regeneration
= 58.5 ´ 2 [(257.5/162) + (329.2/146.3)]
= 449.25 mg/L
Total NaCl consumption (theoretical) = 449.25 ´ 50 ´ 8/1000
= 179.7 kg
Actual consumption of NaCl = 60 ´ 4.24
= 254.4 kg
Excess NaCl = 254.4 179.7 = 74.7 kg
Excess NaCl over theoretical = 74.7 ´ 100/179.7
= 41.5 % Ans.
EXERCISE 4.21
Basis: 100 kg cottonseed oil
Each sponification reaction will be separately dealt.
(i) Saponification of oleodipalmitin:
CH2OOCH33C17
—
CHOOCH31C15 + 3 KOH = C17H33COOK + 2 C15H31COOK

—
+ C3H5(OH)3
CH2OOCCH31C15
832 3 ´ 56 92
Stoichiometric requirement of KOH = 3 ´ 56 ´ 8/832
= 1.615 kg
Gycerine produced = 92 ´ 8/832 = 0.885 kg
(ii) Saponification of Olepalmitostearin:
CH OOCH !!C%
a a
CHOOCH!# C # + 3 KOH = C#H !COOK + C%H !!COOK + C!H#(OH)!

+ C #H !#COOK
CH OOCH ! C#
860 3 ´ 56 92
KOH requirement= 3 ´ 56 ´ 5/860 = 0.977 kg
Gycerine produced= 92 ´ 5/860 = 0.535 kg
(iii) Saponification of palmito-oleolinolein
CH2OOCH33C17

CHOOCH31C15 + 3 KOH = C17H33COOK + C15H31COOK

+ C17H31COOK + C3H5(OH)3
CH2OOCH31C17
856 3 ´ 56 92
KOH required = 8.047 kg and glycerine produced = 4.407 kg
(iv) Saponification of palmitodilinolein:
CH2OOCH31C15

CHOOCH31C17 + 3 KOH = C15H31COOK + 2 C17H31COOK + C3H5(OH)3

CH2OOCH31C17
854 3 ´ 56 92
KOH required = 3.541 kg and glycerine produced = 1.939 kg
(v) Saponification of oleodilinolein:
CH2OOCH33C17

CHOOCH31C17 + 3 KOH = C17H33COOK + C3H5(OH)3 + 2 C17H31COOK

CH2OOCH31C17
880 3 ´ 56 92
KOH requirement = 3 ´ 56 ´ 28/880 = 5.345 kg
Glycerine produced = 92 ´ 28/880 = 2.927 kg
Total theoretical requirement of KOH = 1.615 + 0.977 + 8.047
+ 3.541 + 5.345 = 19.525 kg
Total glycerine produced = 0.885 + 0.535 + 4.407 + 1.939 + 2.927
= 10.693 kg Ans.
EXERCISE 4.22
Basis: 100 kg castor fatty acids
Composition of castor fatty acids:
H2 requirement,
Fatty acid kg Molar mass kmol kmol
Palmitic acid 1.4 256.42 0.0055
Stearic acid 1.2 284.48 0.0042
Oleic acid 4.5 282.46 0.0159 0.0159
Linoleic acid 6.0 280.45 0.0214 0.0428
Linolenic acid 0.5 278.43 0.0018 0.0054
Ricinoleic acid 86.4 298.46 0.2895 0.2895

Total 100.0 0.3383 0.3536
100
Average molar mass of castor fatty acids =
0.3383
= 295.6
Average molar mass of castor oil = 295.6 ´ 3 + 92.09 3 ´ 18.02
= 924.83
924.83 ´ 100
Quantity of castor oil =
295.6 ´ 3
= 104.29 kg
H2 requirement = 0.3536 kmol/100 kg castor fatty acids
= 0.3391 kmol/100 kg castor oil
= 7.601 Nm3/100 kg castor oil Ans.(b)
Iodine value = 0.3536 kmol/100 kg castor fatty acids
= 0.3391 kmol/100 kg castor oil
= 86.07 kg/100 kg castor oil Ans. (a)
EXERCISE 4.23
Basis: 100 kg soybean fatty acids
Fatty acid kg Molar mass kmol
Palmitic acid 46.04 256.42 0.1795
Stearic acid 5.60 284.48 0.0197
Oleic acid 21.94 282.46 0.0777
Linoleic acid 23.22 280.45 0.0828
Linolenic acid 3.20 278.43 0.0115
Total 100.0 0.3712
100
Average molar mass of fatty acids = = 269.4
0.3712
Average molar mass of used soybean oil = 269.4 ´ 3 + 92.09 3 ´ 18.02
= 846.23
846.23 ´ 100
Quantity of used soybean oil =
269.4 ´ 3
= 104.71 kg
º 0.1237 kmol
Reaction :
CH3(CH2)14 COOH + CH3OH = CH3(CH2)14COOCH3 + H2O
Palmitic acid Methanol Methyl ester Water
256.42 32.04 270.44 18.02
Methyl ester produced equivalent to palmitic acid
270.44 ´ 46.04
= = 48.56 kg
256.42
32.04 ´ 46.04
Methanol required = = 5.75 kg
256.42
Water produced = 46.04 + 5.75 48.56 = 3.23 kg
Similar calculations can be made for other fatty acids.
Fatty acid kg Methanol Methyl ester water produced
required, kg produced, kg kg
Palmitic acid 46.04 5.75 48.56 3.23
Stearic acid 5.60 0.62 5.88 0.34
Oleic acid 21.94 2.49 23.03 1.40
Linoleic acid 23.22 2.65 24.38 1.49
Linolenic acid 3.20 0.37 3.36 0.21
Total 100.00 11.88 105.21 6.67
11.88
Specific methanol requirement = = 0.1135 kg/kg soybean oil
104.71
105.21
Specific methyl ester production = = 1.005 kg/kg soybean oil Ans.
104.71
EXERCISE 4.24
Basis: 100 kg soybean fatty acids
Reaction:
CH3(CH2)14COOCH3 + 2 H2 = CH3(CH2)14CH2OH + CH3OH
FAME of Hydrogen FOH of Methanol
Palmitic acid Palmitic acid
Similar reactions can be written for other fatty acids.
FAME of Molar mass kg Molar mass kg kg
of FAME FAME* of corres- FOH CH3OH
ponding
Palmitic acid 270.44 48.56 242.43 43.53 5.75
Stearic acid 298.50 5.88 270.49 5.33 0.63
Oleic acid 296.48 23.03 268.47 20.85 2.49
Linoleic acid 294.83 24.38 266.82 22.06 2.65
Linolenic acid 292.81 3.36 264.80 3.04 0.36
Total 105.21 94.81 11.89
* Reference: Exercise 4.23

FOH produced = 94.81 kg/105.21 kg FAME
= 90.1 kg/100 kg FAME Ans.
Note: Methanol produced = 11.89 kg
= Methanol consumption in Exercise 4.23
EXERCISE 4.25
Basis: Urea feed rate of 350 kg/h
. 350
Molar feed rate of urea, nu = = 5.833 kmol/h
60
H2SO4 required = 5.833 kmol/h º 571.67 kg/h
SO3 required = 5.833 kmol/h º 466.64 kg/h
Actual H2SO4 charged = 1.25 ´ 571.66
= 714.58 kg/h
2
H2O entering with H2SO4 = ´ 714.58
98
= 14.58 kg/h
Actual SO3 charged = 3.5 ´ 466.64
= 1633.24 kg/h
On completion of reaction,
H2SO4 consumed = 571.67 kg/h
SO3 consumed by reaction (1) = 466.64 kg/h
80
SO3 consumed by reaction (2) = ´ 14.58
18
= 64.8 kg/h
H2SO4 produced by reaction (2) = 14.58 + 64.8
= 79.38 kg/h
194
Sulphamic acid produced = ´ 350 = 1131.67 kg/h
60
.
Component mass, mi kg/h mass %
H2SO4 714.58 571.67 + 79.38 = 222.29 9.05
SO3 1633.24 466.64 64.8 = 1101.80 44.87
Sulphamic acid 1131.67 46.08
Total 2455.76 100.00
Ans.
EXERCISE 4.26
Basis: Liquid feed rate = 6.1 kg/h
For 100 kmol liquid feed rate, following calculations are made which are converted
for 6.1 kg/h feed rate in last column.
Liquid Feed
kmol
Component Molar kg mass % kg/h for
kmol feed
mass 6.1 kg/h
feed
C10H20 140 0.8 112.0 0.67 0.040 87

C11H22 154 9.9 1 524.6 9.11 0.555 71
C12H24 168 82.2 13 809.6 82.47 5.030 67
C13H26 182 6.7 1 219.4 7.28 0.444 08
C14H28 196 0.4 78.4 0.47 0.028 67
Total 100.0 16 744.0 100.00 6.100 00
16 744
Average molar mass of liquid =
100
= 167.44
6.1
Tetramer feed rate = ´ 0.822
167.44
= 0.029 95 kmol/h
Gas feed rate = 1 Nm3/h (saturated)
= 0.044 61 kmol/h
Vapour pressure of water at 50°C (323.15 K)
= 12.335 kPa (Ref. Chatper 6)
Feed gas pressure = 0.35 bar-g
= 1.363 25 bar a
0.123 35
Moisture in gas =
(1.363 25 - 0.123 35)
º 0.0905 kmol/kmol wet gas
Dry feed as = 0.04461 (1 0.0905)
= 0.04057 kmol/h
Feed Gas (Dry)
Component mole fraction kmol/h
H2S 0.967 0.039 23
CO2 0.013 0.000 53
HC 0.020 0.000 81
Total 1.000 0.040 57
Moisture in gas = 0.044 61 0.040 57

= 0.004 04 kmol/h
Tetramer (C12H24) consumed = 0.029 95 kmol/h
DDM produced = 0.029 95 kmol/h
Molar mass of DDM = 202
DDM produced = 0.029 95 ´ 202
= 6.0499 kg/h
Liquid Flowing Out of Reactor
Component kg/h mass %
C10H20 0.040 87 0.57
C11H22 0.555 71 7.81
C13H26 0.444 08 6.24
C14 H28 0.028 67 0.40
C12H26S(DDM) 6.049 90 84.98
Total 7.119 23 100.00
Ans.(a)
H2S consumed = 0.029 95 kmol/h
BF3 introduced = 0.35 Nm3/h
= 0.001 56 kmol/h
Gas Stream Exit of Reactor
Component Kmol mole %
H2S 0.039 23 0.029 95 = 0.009 28 76.19
CO2 0.000 53 4.35
HC 0.000 81 6.65
BF3 0.001 56 12.81
Total 0.012 18 100.00
Ans.(b)
Dry gas/liquid feed = 0.040 57/(6.0/167.44)
= 1.114 kmol/kmol Ans. (c)
Conversion of H2S = (0.029 95/0.039 23) 100
= 76.34 % Ans.(d)
EXERCISE 4.27
Basis: 4 kmol FeS2 burnt
Theoretical oxygen requirement = 11 kmol
SO2 produced due to complete combustion (roasting) = 8 kmol
Excess O2 supply = 11 ´ 0.6 = 6.6 kmol
O2 is supplied from air.
N2 entering with O2 = 79 (11 ´ 1.6)/21 = 66.21 kmol
Gas kmol mole %

SO2 8.0 9.90
O2 6.6 8.17
N2 66.21 81.93
Total 80.81 100.00
Ans.
EXERCISE 4.28
Basis: 100 kg ZnS ore
It contains 74 kg ZnS and 26% kg inerts.
ZnS = [74/(65.4 + 32)] = 0.76 kmol
Roasting reaction: 2 ZnS + 3 O2 = 2 ZnO + 2 SO2
Theoretical O2 requirement = 3 ´ 0.76/2 = 1.14 kmol
Actual O2 supply = 1.55 ´ 1.14 = 1.767 kmol
N2 entering with O2 = 79 ´ 1.767/21 = 6.647 kmol
Total air = 1.767 + 6.647 = 8.414 kmol
SO2 produced = 0.76 kmol
Composition of burner gases:
SO2 0.76 9.46
O2 (1.767 1.14) = 0.627 7.80
N2 6.647 82.74
Total 8.034 100.00
Ans. (a)
SO3 produced in converter = 0.76 ´ 0.98 = 0.745 kmol
Unconverted SO2 = 0.76 0.745 = 0.015 kmol
O2 consumed = 0.745/2 = 0.373 kmol
Unused O2 = 0.627 0.373 = 0.254 kmol
Composition of converter exit gas mixture:

SO2 0.015 0.20
O2 0.254 3.32
SO3 0.745 9.72
N2 6.647 86.76
Total 7.661 100.00
Ans. (b)
Assume that all SO3 is absorbed.
SO3 absorbed = 0.745 kmol
H2SO4 produced = 0.745 kmol
= 73.01 kg of 100% strength
= 81.12 kg of 90% strength
For 1000 kg/h 90% acid production, requirement of sulphide ore

= 100 ´ 1000/81.12
= 1232.7 kg/h Ans. (c)
Requirement of dry air = 8.414 ´ 1000/81.12 = 103.72 kmol/h
Specific volume of air at 100 kPa and 300 K
V = RT/p = 8.314 (300)/100
= 24.942 m3/kmol
Volumetric flow rate of air = 103.72 ´ 24.942
= 2587 m3/h Ans. (d)
EXERCISE 4.29
Basis: 100 kg pyrites
FeS2 content = 88 kg
Roasting reaction: 4 FeS2 + 11 O2 = 2 Fe2O3 + 8 SO2
Theoretical O2 requirement = 11 ´ 88/(4 ´ 120)
= 2.02 kmol
Excess air = 150%
Total air supply = 19 + 5.05 = 24.05 kmol
Sp. vol.of dry air to 100 kPa and 300 K = 24.942 m3/kmol
Volumetric air supply = 24.05 ´ 24.942
= 600 m3 Ans. (d)
New basis: 100 kg cinder
Cinder contains 2.6 kg S.
S present in form of FeS2 = 2.6 ´ 0.4 = 1.04 kg
FeS2 content of cinder = 120 ´ 1.04/32 = 3.90 kg
S present in the form of SO2 = 2.6 1.04 = 1.56 kg
SO3 content of cinder = 80 ´ 1.56/32 = 3.90 kg
(Fe2O3 + gangue) in cinder = 100 (3.90 + 3.90)
= 92.20 kg
Let x be the amount of FeS2 roasted.
Unburnt FeS2 = (88 x) kg
Fe2O3 produced = 160 ´ 2 ´ x/(120 ´ 4)
= 0.667 x kg
Sulphur free cinder = 0.667 x + 12 kg
88 x 3.90 FeS2 unburnt
= =
0.667 x + 12 92.20 S- free cinder
x = 85.1 kg
Unburnt FeS2 = 88 85.1 = 2.9 kg

Quantity of cinder = 2.9 ´ 100/3.9 = 74.4 kg Ans. (a)
Sulphur, lost in cinder= 74.4 ´ 0.026 = 1.93 kg
Total sulphur charged = 64 ´ 88/120 = 46.93 kg
% S, lost in the cinder= 1.93 ´ 100/46.93 = 4.11% Ans. (b)
Actual FeS2 roasted = 85.1/120 = 0.709 kmol
FeS2 roasted to SO2 = 0.709 ´ 0.92 = 0.652 kmol
FeS2 roasted to SO3 = 0.709 0.652 = 0.057 kmol
O2 consumed = [11 ´ 0.652/4] + [15 ´ 0.057/4]
= 1.793 + 0.214 = 2.007 kmol
SO2 produced = 8 ´ 0.652/4 = 1.304 kmol
SO3 produced = 8 ´ 0.057/4 = 0.114 kmol
Excess oxygen = 5.05 2.007 = 3.043 kmol
Composition of burner exit gas mixture:
Component kmol mole % mole % on SO3 free basis
SO2 1.304 5.56 5.59
SO3 0.114 0.49
O2 3.043 12.97 13.03
N2 19.000 80.98 81.38
Total 23.461 100.00 100.00
Ans. (c)
EXERCISE 4.30
Basis: 100 kmol fuel gases
CO2 content of fuel gases = 12.8 kmol
Let x kmol CO3 are added in the furnace due to decomposition of MgCO3.
Total CO2 at the exit = 12.8 + x kmol
Total flue gas mixture = 100 + x kmol
The exit gas mixture contains 24% CO2
12.8 + x
= 0.24, or x = 14.74 kmol Ans. (a)
100 + x
Component Molar Incoming gases Outgoing gases
mass kmol kg kmol kg mole %
CO2 44 12.8 563.2 27.54 1211.76 24.00
O2 32 6.1 195.2 6.10 195.20 5.32
N2 28 81.1 2270.8 81.10 2270.80 70.68
Total 100.0 3029.2 114.74 3677.76 100.00
Avg. molar mass of dry incoming gases= 30.29

Avg. molar mass of dry outgoing gases = 3677.79/114.74 = 32.05 Ans. (b)
EXERCISE 4.31
Basis: 100 kmol/h of feed to reactor
There are 4 reactions and 7 reaction components. Hence total 11 equations can
be written.
Component balance equations:
Benzene balance: nB,in = nB,out - A1 + 2A 4
Toluene balance: nT,in = nT,out + A1 - A 2
Xylene balance: nX,in = nX,out + A 2 - A 3
Pseudocumene balance: nP,in = nP,out + A 3
Methane balance: nCH4 , in = nCH4 ,out - A1 - A 2 - A3
Hydrogen balance: nH2 , in = nH2 ,out + A1 + A 2 + A3 - A 4
Diphenyl balance: nDP2 , in = nDP,out - A 4
Reaction performance equations:
nC,B × nB,in = - A1 + 2A 4
nC,T × nT,in = - A1 - A 2
nC,X × nX,in = A 2 - A 3
nC,P × nP,in = A3
These eleven equations can be represented in matrix form as under.
é n ù é nB,in ù
é 1 0 0 0 0 0 0 -1 0 0 2 ù ê nB,0 ú ê nT,in ú
ê 0 1 0 0 0 0 0 1 -1 0 0 ú ê T,0 ú ê n ú
ê 0 0 1 0 0 0 0 0 1 -1 0 ú ê nX,0 ú ê X,in ú
ê 0 0 0 1 0 0 0 0 0 1 0 ú ê nP,0 ú ê nP,in ú
ê 0 0 0 0 1 0 0 -1 -1 -1 0 ú ê nCH ,0 ú ê nCH 4 ,in ú
ê 0 0 0 0 0 1 0 -1 -1 -1 1ú ê n 4 ú = ê nH ,in ú
ê 0 0 0 0 0 0 1 0 0 0 -1ú ê H2 ,0 ú ê n 2 ú
ê 0 0 0 0 0 0 0 -1 0 0 2 ú ê nDP,0 ú ê DP,in ú
ê 0 0 0 0 0 0 0 2 -1 0 0 ú êA1 f n
ú ê C,B× B,in ú
ê 0 0 0 0 0 0 0 0 1 -1 0 ú êA 2 ú ê f C,T × nT,in ú
ê 0 0 0 0 0 0 0 0 0 1 0 ú êA 3
êë úû ú ê f C,X × nX,in ú
ëêA 3 ûú êëê f C,× nP,in úûú
é n ù
é1 0 0 0 0 0 0 -1 0 0 2 ù ê B,0 ú é 1 ù
0 1 -1 0 0 ú ê n
ê0 1 0 0 0 0 T,0
ú ê 3.67 ú
ê0 0 1 0 0 0 0 0 1 -1 0 ú ê nX,0 ú ê 6 ú
ê0 0 0 1 0 0 0 0 0 1 0 ú ê nP,0 ú ê 7.34 ú
ê0 0 0 0 1 0 0 -1 -1 -1 0 ú ê nCH4 ,0 ú ê 0 ú
ê0 0 0 0 0 1 0 1 1 1 -1ú ê nH ,0 ú = ê81.99 ú
ê0 0 0 0 0 0 1 0 0 0 -1ú ê n 2 ú ê 0 ú
ê0 0 0 0 0 0 0 -1 0 0 2 ú ê DP,0 ú ê 0.2 ú
ê0 0 0 0 0 0 0 2 -1 0 0 ú êA1 ú ê 2.5 ú
ê0 0 0 0 0 0 0 0 1 -1 0 ú êA 2 ú ê 1.02 ú
ê0 0 0 0 0 0 0 0 0 1 0 ûú ú ê A ú êëê 5.138úûú
ëê 3
êëA 4 úû
V×0 = I
0 = V1 I
EXERCISE 4.32
Basis: Liberation of 127 g iodine
Electrochemical reactions: KI ¾ ¾¾® K + I -
1
I - - e ¾ ¾¾® I 2
2
Equivalent mass of iodine = 126.9
Let I = current passed through the cell, amperes
Total Faradays passed = (I ´ 3600 ´ 3)/96 485
I ´ 3600 ´ 3 ´ 126.9
Iodine liberated = = 127.0
96 485
I = 8.95 amperes. Ans.
EXERCISE 4.33
Basis: 2 m3 oxygen liberation at NTP
Molar liberation = 2/22.414 = 0.0892 kmol
º 2855.4 g
Electrochemical reactions: AgNO3 ¾ ¾¾® Ag+ + NO 3-
Ag+ + e ¾ ¾¾® Ag
NO 3- e ¾ ¾¾® NO3
NO3 + H2O ¾ ¾¾® HNO3 + OH
2 OH 2e ¾ ¾¾® H2O + 1/2 O2
1 equivalent of oxygen = 2 equivalents of Ag
Ag deposited = 108 ´ 2855.4/8 = 38 548 g
º 38.548 kg Ans. (a)
Total Faradays passed through the solution
= 1130 ´ 3600 ´ 9/96 485
= 379.457
Theoretical Ag liberated = 379.457 ´ 108 = 40 981 g
Current efficiency = 38 548 ´ 100/40 981 = 94.1% Ans. (b)
EXERCISE 4.34
Let m = mass of 0.1 N HCl solution to be added, g
H = density of resulting solution, g/mL
Balance of H+ ion:
m ´ 10 -3 é (1500 ´ 1.25 ´ 103 ) + m ù
´ 10 = ë û ´ 10 -4
9
1500 ´ 10 + -1
1.005 H ´ 103
(1875 000 + m)
1.5 ´ 106 + 9.95 ´ 105 m = ´ 10-7 (1)
H
pH of 0.1 N HCl solution = log (0.1) = 1
1
H =
w
å i
Hi
1
H =
æ 1875 000 ö 1 æ m ö 1
çè 1875 000 + m ÷ø 1.25 + çè 1875 000 + m ÷ø 1.005
1875 000 + m
= (2)
1500 000 + 0.995 m
Solving Eq. (1) and Eq. (2),

m = 1509 g Ans.
EXERCISE 4.35
Basis: 2 kmol of Ca(OH)2 to be recarbonated
Reactions: Ca(OH)2 + CO2 = CaCO3 + H2O (1)
Ca(OH)2 + 2 CO2 = Ca(HCO3)2 (2)
Ca(OH)2 + Ca(HCO3)2 = 2 CaCO3 + 2H2O (3)
Let x be the kmol of Ca(OH)2 bypassed.
Ca(OH)2 reacted as per reaction (2) = (2 x) kmol
CO2 required = 2 (2 x) kmol
Total CO2 required = 2 kmol even after reaction
2 (2 x) = 2 or x = 1 kmol
Bypass total feed = 1 ´ 100/2 = 50% Ans.
EXERCISE 4.36
Basis: 100 kmol/s fresh feed. This is the same basis as that of Example 4.17.
Case (a): Conversion per pass = 24%, ammonia separation = 65%
Case (b): Conversion per pass = 25%, ammonia separation = 70%
Case (a) Case (b)

N2 reacted, kmol/s 0.24 a 0.25 a
H2 reacted, kmol/s 0.72 a 0.75 a
NH3 produced, kmol/s 0.48 a 0.50 a
Total gas mixture, leaving M 0.48 a M 0.5 a
the converter, kmol/s
NH3 in outlet gas 0.9 M 3.52 a 0.9 M 3.5 a
mixture, kmol/s
NH3 separated, kmol/s 0.585 M 2.288 a 0.63 M 2.45 a
NH3 uncondensed, kmol/s 0.315 M 1.232 a 0.27 M 1.05 a
Composition of gas mixture,
leaving separator, kmol/s
Component
N2 0.76 a 0.75 a
H2 2.28 a 2.25 a
NH3 0.315 M 1.232 a 0.27 M 1.05 a
Inerts 0.1 M 0.1 M
Total 0.415 M + 1.808 a 0.37 M + 1.95 a
Case (a):
Purge balance:
0.1 M P
= 1.0 (2)
0.415 M + 1.808 a
Recycle stream = 0.415 M + 1.808 a P
Substituting the value in Eq. (1) of Example 4.15,
100 + 0.415 M + 1.808 a P = M (3)
Nitrogen balance:
0.76 a P
Nitrogen lost in purge = kmol/s
(0.415 M + 1.808 a)
0.76 a P
Nitrogen in recycle stream = 0.76 a kmol/s
(0.415 M + 1.808 a)
0.76 a P
Hence 0.76 a + 24.75 = a (4)
(0.415 M + 1.808 a)
Substitute 0.415 M + 1.808 a = 0.1 MP from Eq. (2)
0.76 a P
0.75 a + 24.75 = 1
0.1 M P
24.75 M
a= (5)
0.24 M + 7.6
4.15 M + 18.08 a
From Eq. (2), P=
M
Substitute values of a and P in Eq. (3) and simplify.
0.1404 M2 63.306 M 280.98 = 0
Mathcad solution:
f (M ) := 0.140 M2 63.306 M 280.98
M := 350
soln := root (f(M), M)
soln = 455.293
or M = 455.293 kmol/s
24.75 ´ 455.293
a=
0.24 ´ 455.293 + 7.6
= 96.419 kmol/s
4.15 ´ 455.293 + 18.08 ´ 96.419
P=
455.293
= 7.971 kmol/s Ans.
Case (b)
Purge balance:
0.1 MP
= 1.0 (2)
0.37 M + 1.95 a
recycle stream = 0.37 M + 1.95 a P

or 100 + 0.37 M + 1.95 a P = M (3)
Nitrogen balance:
0.75 a P
Nitrogen lost in purge = kmol/s
(0.37 M + 1.95 a)
0.75 a P
Nitrogen in recycle stream = 0.75 a kmol/s
(0.37 M + 1.95 a)
Hence,
0.75 a P
0.75 a + 24.75 = a (4)
(0.37 M + 1.95 a)
Substitute 0.37 M + 1.95 a = 0.1 M P from Eq. (2)
0.75 a P
0.75 a + 24.75 = a
0.1 M P
24.75 M
a= unchanged from Example 4.14
0.25 M + 7.5
3.7 M + 19.5 a
From Eq. (2), P=
M
Substitute values of a and P in Eq. (3) and simplifying,
0.1575 M2 67.6125 M 239.625 = 0
Mathcad solution:
f (M) := 0.1575 M2 67.6125 M 239.625
M := 300
soln := root (f(M), M)
soln := 432.801
or M = 432.801 kmol/s
24.75 ´ 432.801
a=
0.25 ´ 432.801 + 7.5
= 92.5826 kmol/s
3.7 ´ 432.801 + 19.5 ´ 92.5826
P=
432.801
= 7.8713 kmol/s Ans.
Note: Exercise 9.3 is Mathcad exercise for this exercise.
EXERCISE 4.37
Since simultaneous equations cannot be easily solved, program, developed in
exercise 9.7 is used. In this program value of i is changed, keeping all other
perameters constant.
(a) For i = 0.09 P = 11.951 kmol/s
(b) For i = 0.11, P = 9.162 kmol/s.
Using values of M, P and a from the program, ammonia productions can be

calculated .
EXERCISE 4.38
Basis: Make-up hydrogen stream = 45 000 Nm3/h
H2 content of make-up stream = 45 000 ´ 0.885
= 39 825 Nm3/h
H2 consumed in hydrocraker unit
= H2 in make-up stream
H2 lost in HP purge
H2 lost in LP purge
HP purge stream = 4500 Nm3/h
H2 lost in HP purge = 4500 ´ 0.745
= 3352.5 Nm3/h
LP purge stream = 12 000 Nm3/h
H2 lost in LP purge = 12 000 ´ 0.517
= 6462.5 Nm3/h
H2 consumed in hydrocracking unit
= 39 825 3352.5 6462.5
= 30 010 Nm3/h Ans.(a)
Membrane System I:
Hydrocarbons (HC) in HP purge = 4500 3352.5
= 1147.5 Nm3/h
Membrane system removes 85% HC in the reject stream I.
HC in Reject I = 1147.5 ´ 0.85
= 975.375 Nm3/h
HC in Permeate I = 1147.5 975.375
= 172.125 Nm3/h
Permeate I constains (1 0.945 =) 0.055 mole fraction HC.
Permeate I flow rate = 172.125/0.055
= 3129.545 Nm3/h
H2 recycled in Parmeate I = 3129.545 172.125
= 2957.42 Nm3/h
2957.42
Since fresh make-up has 88.5 % H2, reduction in make-up stream =
0.885
= 3341.71 Nm3/h
3341.71
% reduction = ´ 100
45 000
= 7.43 Ans.(b)
Membrane System II:
HC in LP purge = 12 500 6462.5
= 6037.5 Nm3/h
Membrane system removes 88% HC.
HC in Reject II = 6037.5 ´ 0.88
= 5313 Nm3/h
HC in Permeate II = 6037.5 5313
= 724.5 Nm3/h
Permeate II contains (1 0.92 = ) 0.08 amole fraction HC.
724.5
Permeate II flow rate = = 9056.25 Nm3/h
0.08
H2 recycled in Permeate II = 9056.25 724.5
= 8331.75 Nm3/h
8331.75
Reduction in make-up stream =
0.88
= 9414.41 Nm3/h
9414.41
% reduction = ´ 100
45 000
= 20.92 Ans.(c)
Note: Reduction in make-up stream will result in same reduction in H 2
consumption.
EXERCISE 4.39
Basis: 1 litre feed water
Water going to C II should be 1 litre, irrespective of the recycled water.
Sodium content also should be equivalent to that of feed water.
Na content of feed water = C H meq
Na recycled in the water from AI = X (C H) meq
where X = litres of water recycled/litre feed
Recycled Na is in the form of bicarbonates which means that alkalinity to the
extent of X (C H) meq is added to feed water.
Total alkalinity in mixed feed to CI = M + X (C H) meq
Total alkalinity should be equal to H to convert all hardness causing cations
(which are strong in nature) to bicarbonates so that the same can be removed in
CI.
M + X (C H) = H
X = (H M)/(C H)
Because of alkalinity recycle, CO2 availability at the exit of CI is H meq. However,
it is desired to convert all the strong anions (such as SO4) to bicarbonates.
Strong anions to be converted to HCO-3 = A H meq
= CO2 requirement from degasser (D)
Now CO2 content of the product water from D should equal to alkalinity in the
feed water, irrespective of recycle.
Recycled CO2 = y × M meq
yM=AH
y = (A H)/M
F H - M I F1 + A - H I
H
(1 + x) (1 + y) = 1 +
C- H KH M K
(C - M )( M + A - H )
=
(C - H ) M
(C - M )(C - H )
= because M + A = C
(C - H ) M
C- M A
= = because C M = A
M M
EXERCISE 4.40
Let R kmol/h of dry tail gas recycled.
Moisture in recycle stream = 0.1146 R kmol/h
Let F kmol/h be the flow of dry ambient air.
Moisture in ambient air = 0.017 72 F kmol/h
Since total molar flow rate of gas mixture to the reactor is unchanged,
1.1146 R + 1.017 72 F = 1363.1 (1)
Let yO2 , yUC and yN 2 be the mole fractions of oxygen, undesired components
(i.e. CO + CO2 + H2 + CH4 + Ether) and nitrogen respectively in the dry recycle
stream.
yO 2 + yUC+ yN 2 = 1 on dry basis (2)
In the total feed to the reactor, oxygen concentration is 10 mole %.
0.21 F + R × yO2 = 1488.1 ´ 0.1
= 148.81 (3)
Nitrogen, entering in air = 0.79 F
N2 in recycle stream = R × yN 2
= R R × yO2 R × yUC
Since reaction pattern is unchanged,

addition of UC = 13.365 kmol/h
UC in tail gas from absorber = R × yUC + 13.365 kmol/h
Total oxygen consumption = 68.559 kmol/h
O2 in tail gas from absorber = 0.21 F + R × yO2 68.559
= 148.81 68.559 [from Eq. (3)]
= 80.251 kmol/h
N2 in tail gas from absorber = R R × yO 2 R × yUC+ 0.79 F
Total tail gas from absorber = R × yUC + 13.365 + 0.21 F + R × yO 2
68.559 + R R × yO2 R × yUC + 0.79 F
= R + F 55.194 kmol/h
Balance of oxygen:
80.251
= yO 2 (4)
R + F - 55194
.
1.017 72
Multiply Eq. (3) by = 4.8463
0.21
1.017 72 F + 4.8463 R × yO2 = 721.78 (5)
Substract Eq. (5) from Eq. (1)
1.1146 R 4.8463 R × yO2 = 641.32
or R 4.348 R × yO2 = 575.381

or R × yO2 = 0.23 R 132.332 (6)
From Eq. (1), F = 1339.37 1.0952 R (7)
Combining Eq. (4) and Eq. (6),
80.251 0.23 R - 132.332
=
R + F - 55194. R
Substitute value of F form Eq. (7) and simplify.
0.0219 R2 227.567 R + 169 937.6 = 0 (8)
Solution of Eq.(8) yields R = 809.9 kmol/h
Substitute value of R in Eq. (6).
R × yO2 = 0.23 ´ 809.9 132.332 = 53.94 kmol/h
yO 2 = 0.0666 or 6.66% O2 in recycle.
Substitute value of R in Eq. (7).
F = 1339.37 1.0952 ´ 809.9 = 452.37 kmol/h
From Eq. (2), yN 2 + yUC = 1.0 yO 2 = 0.9334

UC Balance:
R × yUC + 13.365
= yUC (9)
R + F - 55.194
R + F 55.194 = 809.9 + 452.37 55.194
= 1207.076 kmol/h
809.9 yUC + 13.365 = 1207.076 yUC
yUC = 0.0337 or 3.37% in recycle.
yN 2 = 0.9334 0.0337 = 0.8997
or 89.97% in recycle
Compositions of tail gas and recycle gas will be same.
Composition of Gaseous Mixture, Entering Reactor
(wet basis)
CH3OH 125.00 8.40
O2 148.81 10.00
N2 452.37 ´ 0.79 + 809.9 ´ 0.8997 = 1086.04 72.99
H2O 452.3 ´ 0.017 72 + 809.9 ´ 0.1146 = 100.84 6.78
UC 809.9 ´ 0.0337 = 27.30 1.83
Total 1487.99 100.00
Composition of Gaseous Mixture Leaving Reactor

mole %
Component kmol
Wet Dry tail gas
CH3OH 1.25 0.08 —
HCHO 111.375 7.18 —
UC 27.30 + 13.365 = 40.665 2.62 3.37
O2 80.251 5.18 6.65
N2 1086.04 70.05 89.98
H2O 100.84 + 129.937 = 230.779 14.89 —
Total 1550.358 100.00 100.00
Purge stream must contain 13.365 kmol/h UC.

13.365
Total purge stream = = 396.6 kmol/h (dry)
0.0337
Recycle stream 809.9
=
Purge stream 396.6
= 2.042 kmol/kmol Ans. (a)

Recycle stream 809.9 ´ 1.1146
Recycle ratio = =
Fresh air stream 452.37 ´ 1.017 72
= 1.96 kmol/kmol Ans. (b)
Total dry tail gas stream from absorber = 1550.358 (1.25 + 111.375 + 230.779)
= 1206.954 kmol/h
40.665 ´ 100
Concentration of UC in tail gas =
1206.954
= 3.37% (Check !) Ans. (c)
EXERCISE 4.41
Basis: 100 kmol benzene feed
Let fresh H2 = a kmol
Recycle H2 stream = b kmol
Recycle cyclohexane stream = c kmol
Mixed feed, entering the reactor = 100 + a + b + c kmol
Inerts in the mixed feed = 0.1 (100 + a + b + c)
= 10 + 0.1a + 0.1b + 0.1c kmol
Benzene concentration in mixed feed = 18.5 mole %
100
= 0.185
100 + a + b + c
18.5 + 0.185a + 0.185b + 0.185c = 100
0.185a + 0.185b + 0.185c = 100 18.5 = 81.5
0.9a + 0.9b + 0.9c = 396.486 (1)
Hydrogen in the mixed feed = 100 + a + b + c 10 0.1a
0.1b 0.1c c 100
= 0.9a + 0.9b 0.1c 10 kmol
H2/benzene = 3.3
0.9a + 0.9b + 0.1c 10 = 3.3 ´ 100 = 330
0.9a + 0.9b + 0.1c = 340 (2)
Eq. (1) Eq. (2) yields
c = 56.486 kmol
0.9b = 340 + 0.1c 0.9a
= 345.645 0.9a
or b = 384.054 a (3)
The conversion of benzene is 100%. Therefore 100 kmol benzene and 300 kmol
H2 are consumed.
Cyclohexane produced = 100 kmol

All the cyclohexane is condensed in the cooler.
Cooler exit gas mixture:
H2 = 0.9a + 0.9b 0.1c 10 300
= 0.9a + 0.9b 0.1c 310 kmol
Inerts = 10 + 0.1a 0.1b + 0.1c kmol
Total gas mixture = a + b 300 kmol
Let P be kmol of purge gas mixture. Since the compositions of purge gas mixture
and the recycle gas mixture are same,
(0.1a + 0.1b + 0.1c + 10) P
purge gas will also contain inerts =
( a + b - 300)
This should be equal to the inerts in the fresh hydrogen stream.
(0.1a + 0.1b + 0.1c + 10) P
= 0.025 a
( a + b - 300)
0.025a( a + b - 300)
P= (4)
(0.1a + 0.1b + 0.1c + 10)
Recycle hydrogen stream = a + b 300 P
=b
or a P = 300
or P = a 300
Hydrogen balance:
F 0.9a + 0.9b - 0.1c - 310 I P + 300 = (1 0.025) a
H a + b - 300 K
= 0.975 a
But from Eq. (2),
0.9a + 0.9b 0.1c 310 = 30
( 0.975a - 300)( a + b - 300)
P=
30
= a 300 from Eq. (5)
2
0.975a + 0.975ab 292.5 a 300a 300b + 90 000 = 30a 9000
or a2 + ab 638.46a 307.69b + 101 538 = 0 (6)
Substitute the value of b from Eq. (3) into Eq. (6).
a2 + a(384.054 a) 638.46a 307.69 (384.054 a) + 101 538 = 0
a2 + 383.054a a2 638.46a 118 170 + 307.69a + 101 538 =0
53.284 a = 16 632
a = 312.139 kmol
b = 384.054 312.139
= 71.915 kmol
P = 312.139 300 = 12.139 kmol Ans.
EXERCISE 4.42
Hydrogen in the reactor effluent = 30 kmol
Recovery of H2 = 0.9 ´ 30 = 27 kmol
Inerts in the purge = 0.025 a kmol
Inerts in the cooler exit gas mixture = (0.025a/0.95)
= 0.0263a kmol
Inerts in the recycle stream = (0.0263 0.025) a
= 0.0013a kmol
Recycle hydrogen stream = 27 + 0.0013a
=b
or b 0.0013 a = 27
Make-up hydrogen requirement = 330 27
= 303 kmol
Inerts entering with make-up H2 = 303 ´ 2.5/97.5
= 7.769 kmol
a = 303 + 7.769 = 310.769 kmol
b = 27 + 0.0013 ´ 310.768 = 27.404 kmol
Inerts in the reactor inlet = 0.0263 a = 8.137 kmol
Total mixed feed = 100/0.185 = 540.541 kmol
Recycle cyclohexane = 540.541 330 8.173 100
= 102.367 kmol
Inerts content of mixed feed = 8.173 ´ 100/540.541
= 1.51 mole %
Purge, P = 30 + 8.173 27 0.404
= 10.769 kmol Ans.
EXERCISE 4.43
Basis: 3500 kg/h ethylene oxide (EO) production rate
Only first two reactions are considered.
Compound Molar mass

Ethylene (C2H4) 28.0538
Oxygen (O2) 31.9988
Ethylene oxide (C2H4O) 44.0532
Carbon dioxide (CO2) 44.0098
Water (H2O) 18.0153
Ethylene required for EO production = 28.0538 ´ 3500/44.0532
= 2228.86 kg/h º 79.45 kmol/h
Since the yield of EO is 70%,

total ethylene reacted = 2228.86/0.7
= 3184.08 kg/h
Ethylene converted to CO2 and H2O = 3184.08 2228.86
= 955.22 kg/h
Since the conversion of ethylene is 50% per pass,
ethylene fed to the reactor = 3184.08/0.5
= 6368.16 kg/h
º 227.000 kmol/h
Total mixed feed to the reactor = 227.0/0.1
= 2270 kmol/h
Inerts in the mixed feed = 2270 ´ 0.1
= 227.0 kmol/h
O2 consumed for reaction (1) = 227.0 ´ 0.5 ´ 0.7/2
= 39.725 kmol/h
O2 consumed for reaction (2) = 227.0 ´ 0.5 ´ 0.3 ´ 3
= 102.15 kmol/h
Total O2 consumed = 39.725 + 102.15
= 141.875 kmol/h
O2 concentration of the mixed feed = 141.875 ´ 100/2270
= 6.25% Ans. (d)
2
CO2 produced = ´ 102.15 = 68.1 kmol/h
3
= H2O produced
Inerts (N2 + Ar) entering with O2 = (102.15 + 39.725) ´ 0.03/0.97
= 4.39 kmol/h
Component Mixed feed to reactor Reactor effluent,
(M), kmol/h kmol/h
Ethylene 227.000 113.500
Oxygen 141.875 Nil
Inerts (N2 + Ar) 227.000 227.000
CO2 + H2O 1674.125 1674.125 + 68.10 ´ 2
(by balance) = 1810.325
Ethylene oxide Nil 3500/44.0532 = 79.450
Total 2270.00 2230.275
Let recycle stream R1 contain x kmol/h of (CO2 + H2O). Ethylene and inerts
content are 113.50 and 227.00 kmol/h, respectively. Total stream R1 will amount
to (340.5 + x) kmol/h. Let purge rate be P kmol/h.
x (340.5 + x - P)
CO2 + H2O in stream R2 =
(340.5 + x )
= 1674.125
Simplifying,
x2 1333.625 x x P 570 040 = 0 (1)
227.00 P
Inerts in purge =
(340.5 + x )
= 4.39 kmol/h (2)
or P = 6.585 + 0.019 34x.
Substitute value of P in Eq. (1).
x2 1333.625 x x (6.585 + 0.019 34x) 570 040 = 0
or 0.980 66x2 1340.21 x 570 040 = 0
Solving, x = 1707.14 kmol/h
Streams, kmol/h
Component R1 Purge R2 Fresh feed
(M R2)
Ethylene 113.50 2.194 111.306 115.694
Inerts 227.00 4.392 222.608 4.392
CO2 + H2O 1707.14 33.015 1674.125 Nil
Oxygen Nil Nil Nil 141.875
Total 2047.64 39.601 2008.039 261.961
Recycle ratio = 2008.039/261.961 = 7.665 kmol/kmol Ans. (c)
Ethylene feed rate = 115.694 ´ 28.0538
= 3245.66 kg/h Ans. (a)
Oxygen feed rate = (141.875 + 4.39) 22.414
= 3277.8 Nm3/h Ans. (b)
EXERCISE 4.44
Basis: 100 kmol fresh ethylene feed
Feed consists of 96 kmol of ethylene and 4 kmol of non-reactive gases (NRG).
Let R and C be kmol of (ethylene + NRG) in the recycle stream and combined
feed, respectively.
Overall materials balance at A:
F+R=C (1)
If x is the mole fraction of ethylene in recycle stream, ethylene balance fields:
0.96 ´ 100 + x R = 0.85 C (2)
Reactor inlet stream:
Component kmol
Ethylene 0.85 C
Water 0.85 ´ 0.65 C = 0.5525 C
NRG 0.15 C
Total 1.5525 C
Conversion per pass = 5%, based on ethylene

Ethylene reacted = 0.05 ´ 0.85 C = 0.0425 C kmol
Water reacted = 0.0425 C kmol
Ethanol produced = 0.0425 C kmol
Reactor outlet stream:
Component kmol
Ethylene (0.85 0.0425) C = 0.8075 C
(0.5525 0.0425) C = 0.51 C
NRG 0.15 C
Ethanol 0.0425 C
Total 1.51 C
In the scrubber, it is assumed that all the water and alcohol are removed:
Scrubber outlet off-gases:
Component kmol
Ethylene 0.8075 C
NRG 0.1500 C
Total 0.9575 C
Mole fraction of NRG in off gases = x = 0.15 C/0.9575 C
= 0.1567
Let P be kmol of purge gas.
NRG in purge = NRG in fresh feed
0.1567 P = 4
P = 4/0.1567 = 25.526 kmol
R = 0.9575 C 25.526 kmol
Substitute the value of R in Eq. (2).
96 + (0.9573 C 25.526) (1 0.1567)= 0.85 C
Solving the equation, C = 1752.33 kmol
R = C 100 = 1652.33 kmol
Recycle ratio = R/F = 1652.33/100
= 16.52 kmol/kmol fresh feed Ans. (a)
Ethylene in the purge = 25.526 4.0
= 21.526 kmol
Unreacted ethylene = 0.8075 C = 0.8075 ´ 1752.33
= 1415.00 kmol
% loss of ethylene = 21.526 ´ 100/1415
= 1.52 Ans. (c)
Component Gas mixture, incoming Gas mixture, outgoing

to reactor from reactor
kmol mole % kmol mole %
C2 H 4 1489.41 54.83 1414.94 53.56
H2O 968.12 35.64 893.65 33.82
NRG 258.92 9.53 258.92 9.80
C2H5OH Nil Nil 74.47 2.82
Total 2716.45 100.00 2641.98 100.00
Ans. (d) and (e)
EXERCISE 4.45
Basis: 100 kmol mixed feed
Carbon input to the reactor = 4 ´ 100 = 400 kmol
New basis: 100 kmol reactor effluent gases
Carbon content = 3.25 + 1.16 ´ 2 + 1.08 ´ 2 + 1.32 ´ 3 + 0.64 ´ 3
+ 2.5 ´ 4 + 4.93 ´ 4 + 17.88 ´ 4 + 30.91 ´ 4
+ 8.78 ´ 4 + 0.16 ´ 5 + 5.34 ´ 1
= 279.75 kmol for 100 kmol reactor offluent stream
Therefore for 100 kmol mixed feed (i.e. original basis), reactor effluent
= 400 ´ 100/279.75
= 143 kmol
Hydrogen in reactor effluents = 143 ´ 0.2205
= 31.53 kmol
Hydrogen is present in the fuel gas.
Quantity of fuel gas = 31.53/0.7357
= 42.86 kmol
Balance of butadiene:
Butadiene in the reactor effluent = 143 ´ 0.0878
= 12.56 kmol
Butadiene in the fuel gas = 42.86 ´ 0.0024
= 0.1 kmol
Butadiene in the product mixture = 12.56 0.1 (100 ´ 0.34)/100
= 12.12 kmol
Total quantity of product mixture = 12.12/0.9831
= 12.33 kmol
n-butylene in product mixture = 12.33 12.12

= 0.21 kmol i.e.1.69%
Coke in reactor affluents = 5.34 ´ 143/100
= 7.64 kmol
This coke will deposit on the catalyst and will provide heat to the catalyst bed
during regeneration.
Leftover recycle stream = 143 12.33 7.64 42.86
= 80.17 kmol
Fresh feed = 100 80.17 = 19.83 kmol
Recycle ratio = recycle stream/fresh feed
= 80.17/19.83 = 4.043 kmol/kmol
Ans. (a)
Component Fresh feed Mixed feed Recycle stream
mole % kmol kmol kmol mole %
i-butane 1.5 0.297 3.84 3.543 4.42
i-butylene Nil Nil 6.94 6.940 8.66
n-butylene Nil Nil 25.29 25.290 31.55
n-butane 98.5 19.533 63.59 44.057 54.95
1,3-butadiene Nil Nil 0.34 0.340 0.42
Total 100.0 19.830 100.00 80.17 100.00
Total n-butane consumed = 100 ´ 0.6359 143 ´ 0.3091
= 19.39 kmol
Total butadiene produced = 143 ´ 0.0878 0.34
= 12.215 kmol
º 12.215 kmol n-butane consumed
for butadiene production
Yield of butadiene = 12.215 ´ 100/19.39 = 63.00% Ans. (c)
EXERCISE 4.46
Basis: 265 000 m3/h at 448.15 K (175°C) flue gases
SO2 content of the flue gases = 1160 mg/m3 ´ 265 000 m3/h
1
´
kg/mg
10 6
= 307.4 kg/h
SO2 reacted = 307.4 ´ 0.9 = 276.66 kg/h
Reaction: Na2CO3 + SO2 = Na2SO3 + CO2
Na2CO3 reacted = 106 ´ 276.66/64 = 458.22 kg/h
Na2SO3 formed = 126 ´ 276.66/64 = 544.67 kg/h

CO2 formed = 458.22 + 276.66 544.67 = 190.21 kg/h
Specific volume of ingoing flue gases = RT/p
= 8.314 (448.15)/106.6
= 34.94 m3/kmol
Molar flow rate of flue gases = 265 000/34.94 = 7584.43 kmol/h
Water vapours in flue gases = 7600 kg/h = 422.22 kmol/h
Dry gas mixture flow rate = 7584.43 422.22
= 7162.21 kmol/h
Dry gas mixture flow rates at inlet and outlet remain same as equal moles of CO2
are produced in place SO2.
SO2 in outgoing gases = 307.4 276.66 = 30.74 kg/h
Vapour pressure of water at 323 K (50°C), pw = 12.335 kPa
Water vapours in outgoing gases = 12.335/(106.6 12.335)
Total water vapours in outgoing flue gas = 7162.21 ´ 0.1309
= 937.53 kmol/h
Water, evaporated in absorber = 937.53 422.22
= 515.31 kmol/h
º 9275.6 kg/h
Moist flue gases, leaving the absorber = 7162.21 + 937.53
= 8099.74 kmol/h
Stoichiometric Na2CO3 requirement = 106 ´ 307.4/64
= 509.13 kg/h
Actual Na2CO3 supply = 1.5 ´ 509.13 = 763.7 kg/h
Excess Na2CO3 over actual reacted = 763.7 458.22
= 305.48 kg/h
Total solids in purge stream = 544.67 + 305.48
= 850.15 kg/h
Total solids should be 8% in purge stream.
Flow rate of purge stream = 850.15/0.08 = 10 626.88 kg/h
Water in purge stream = 10 626.88 850.15
= 9776.73 kg/h
Make-up Na2CO3 solution = 763.7/0.3 = 2545.7 kg/h
Water in the make-up solution = 2545.7 763.7 = 1782 kg/h
Dilution water requirement = 9275.6 + 9776.7 1782
= 17 270.3 kg/h Ans.
EXERCISE 4.47
Rock phosphate contains 34.55 kg P2O5.
Ca3(PO4)2 = 3 CaO + P2O5
310 3 ´ 56 142
Equivalent Ca3(PO4)2 in rock = 75.43 kg

HCl fed = 3 ´ 100 = 300 kg of 25% concentration
= 75 kg 100% HCl
Reaction: Ca3(PO4)2 + 6 HCl = H3PO4 + 3 CaCl2
Theoretical HCl requirement = [6 ´ 36.5/310] (75.43)
= 53.29 kg Ans. (a)
Excess acid = (75 53.29) 100/53.29 = 40.74%
Reaction of CaF2 : CaF2 + 2 HCl = CaCl2 + 2 HF
78 2 ´ 36.5 111
HCl required for this reaction = 2 ´ 36.5 ´ 2.5/78 = 2.34 kg
CaCl2 produced = 111 ´ 2.5/78 = 3.558 kg
Actual conversion of the phosphate = 75.43 ´ 0.95
= 71.66 kg Ca3(PO4)2
HCl consumed = 6 ´ 36.5 ´ 71.66/310 = 50.62 kg
CaCl2 produced = 3 ´ 111 ´ 71.66/310 = 76.98 kg
Balance CaO in the rock = 48.62 40.88 = 7.74 kg
CaCl2 produced by the reaction of
CaO and HCl = 7.74 ´ 111/56
= 15.34 kg
Total CaCl2 produced = 76.98 + 3.558 + 15.34
= 95.880 kg
H3PO4 produced = 2 ´ 98 ´ 71.66/310
= 45.31 kg
Recovery of H3PO4 by leaching = 45.31 ´ 0.97 = 43.95 kg
Thus for 43.95 kg H3PO4 production, rock phosphate consumption is 100 kg.
For 2 t/h of 80 % H3PO4 production, rock phosphate requirement
= 2000 ´ 0.8/0.4395 = 3640.5 kg/h
º 3.64 t/h Ans. (b)
CaCl2 produced = 95.88 ´ 2.0 ´ 0.8/0.4395
= 3.491 t/h Ans. (c)
EXERCISE 4.48
Basis: Ammonia flow to burner = 3266 Nm3/h
Molar flow rate = 3266/22.414 = 145.71 kmol/h
Volumetric flow rate of air = 29 394 Nm3/h (dry)
Molar flow rate of dry air = 29 394/22.414 = 1311.41 kmol/h
O2 supply to burner = 1311.41 ´ 0.21
= 275.40 kmol/h
N2 supply to burner = 1311.41 275.4 = 1036.01 kmol/h
Let x be kmol of NH3 reacted as per reaction (1).
NO formed = x kmol/h
O2 consumed = 1.25x kmol/h
H2O produced = 1.5x kmol/h
NH3 reacted as per reaction (2) = (145.71 x) kmol/h
N2 formed = 0.5 (145.71 x) = 72.86 0.5x kmol/h
O2 consumed as per reaction (2) = (3/4) (145.71 x)
= 109.28 0.75x kmol/h
H2O produced = 1.5 (145.71 x)
= 218.57 1.5x kmol/h
Composition of reactor effluent:
Component kmol/h
NO x
O2 275.4 [1.25x + 109.28 0.75 x] =
166.12 0.5x
N2 1036.01 + 72.86 0.5x =
1108.87 0.5x
H2O 218.57 1.5x + 1.5x = 218.57
Total 1493.56
% NO in burner gases = 100 x/1493.56 = 9.27

or x = 138.45 kmol/h
N2 in burner gas = 1108.87 138.45 ´ 0.5
= 1039.65 kmol/h
O2 in burner gas = 166.12 138.45 ´ 0.5
= 96.9 kmol/h
Material balance across absorber:
Air entry to absorber = 8145 Nm3/h
= 363.39 kmol/h (dry)
O2, entering the absorber = 363.39 ´ 0.21 = 76.31 kmol/h
N2, entering the absorber = 363.39 76.31 = 287.08 kmol/h
In the absorber, two reactions are taking place.
Combining both the reactions [i.e. reactions (3) and (4)],
3
2 NO + O2 + H2O = 2 HNO3
2
O2 consumed = (3/4) y = 0.75 y
where y = NO consumed in absorber, kmol/h
Composition of absorber outlet gas:

Component kmol/h
NO 138.45 y
O2 96.9 + 76.31 0.75 y = 173.21 0.75 y
N2 1039.65 + 287.08 = 1326.73
Total 1638.39 1.75 y
(138.45 - y)100
% NO in absorber outlet gases =
1638.39 - 1.75 y
= 0.2
or y = 135.65 kmol/h
NO consumed
Absorber efficiency = ´ 100
NO fed
135.65
= ´ 100 = 98.0% Ans. (b)
138.45
NH 3 converted to NO
Combustion efficiency of reactor = ´ 100
Total NH 3 fed
138.45
= ´ 100
145.71
= 95.02% Ans. (a)
Overall efficiency = Combustion efficiency ´
Absorption efficiency
= 0.98 ´ 0.9502
= 0.9312 or 93.12% Ans. (c)
EXERCISE 4.49
Basis: 1000 kg pig iron
Fe, available per kg ore = 112 ´ 0.9/160 = 0.63 kg
Ore, required to produce 1000 kg pig iron = 950/0.63
= 1508 kg
Slag contains CaO, MgO and SiO2.
Silica balance:
Si presents in pig iron = 0.01 ´ 1000 = 10 kg
Equivalent SiO2 = 60 ´ 10/28 = 21.43 kg
Silica in ore = 0.1 ´ 1508 = 150.8 kg
Silica in coke = 0.1 ´ 1000 = 100 kg
Let x be the amount (in kg) of limestone added to the furnace.
Silica in the slag = 150.8 + 100 + 0.02 x 21.43
= 229.37 + 0.02 x kg
CaO in the slag = 0.95 ´ 56 x/100 = 0.532x kg
MgO in the slag = 0.03 ´ 40.3 x/84.3 = 0.0143x kg
Total mass of the slag = 229.37 + 0.02x + 0.532x + 0.0143x
= 229.37 + 0.5663x kg
CaO in the slag = 0.532x ´ 100/(229.37 + 0.5663 x) %
MgO in the slag = 0.0143x ´ 100/(229.37 + 0.5663 x)
However, (CaO + MgO) in slag = 45%
(0.532x + 0.0143x) 100 = 45(229.37 + 0.5663x)
or x = 354.1 kg/t pig iron Ans.
5
Energy Balances
EXERCISE 5.1
Basis: 10 000 Lph of thermic fluid
Energy balance:
qm æ p1 gö q æp gö
E1 + ç + Z1 ÷ + Q + W = E2 + m ç 2 + Z 2 ÷
J è r gc ø J è r gc ø
Z1 =
Z2
p1 =
101.325 kPa a
p2 =
100 + 101.325 = 201.325 kPa a
p2 p1 =
201.325 101.325 = 100 kPa
º 0.1 MPa
W = pump work = 1.1 ´ 0.5 = 0.55 kW
Q = 232.6 kW
×
qm = m = 10 000 ´ 0.75 = 7500 kg/h
7500 ( -0.1) ´ 1000
E2 E1 = + 0.5 + 232.6
3600 ´ 0.75 ´ 1000
= 0.277 + 0.5 + 232.6
= 232.823 kW
This change in energy is responsible for rise in temperature of the thermic fluid.
Rise in temperature, T = (232.823 ´ 3600)/(7500 ´ 2.68)
= 41.7 K or 41.7°C
Outlet temperature of thermic fluid = 473.15 + 41.7
= 514.85 K (241.7ºC) Ans.
EXERCISE 5.2
Basis: 1 kmol oxygen
T1 = 350 K and T2 = 1500 K
Ref. 7:
z
T2
H1 = (29.8832 11.3842 ´ 108 T + 43.3779 ´ 106 T 2
T1
37.0082 ´ 109 T 3 + 10.1006 ´ 1012 T 4) dT
11.3842
= 29.8832 (1500 350) ´ 103 (15002 3502)
2
43.3779 37.0082
+ ´ 106 (15003 3503) ´ 109 (15004 3504)
3 4
101006
.
+ ´ 1012 (15005 3505)
5
= 34 365.7 12 109.9 + 48 180.2 46 700.0 + 15 330.0
= 39 066 kJ Ans. (ii)
Ref. 5:
z
T2
H2 = (26.0257 + 11.7551 ´ 103 T 2.3426 ´ 106 T 2
T1
0.5623 ´ 109 T 3) dT
117551
.
= 26.0257(1500 350) + ´ 103 (15002 3502)
2
2.3426 0.5623
´ 10 (1500 3503)
6 3
´ 103 (15004 3504)
3 4
= 29 929.6 + 12 504.5 + 2601.9 709.6
= 39 122.6 kJ Ans. (i)
Based on absolute enthalpies (Table 5.22),
H3 = 49 273 [(11 603 8597)(350 298.15)/(400 298.15) + 8597]
= 49 273 (8597 + 1530)
= 39 146 kJ Ans. (iii)
EXERCISE 5.3
Basis: 1 kmol SO2
T1 = 300 K and T2 = 1000 K
Ref. 7:
z
T2
H= (25.7725 + 57.8938 ´ 102 T 38.0844 ´ 106 T 2
T1
+ 8.6063 ´ 109 T 3) dT
Energy Balances 107
57.8938
= 25.7725 (1000 300) + ´ 103 (10002 3002)
2
38.0844 8.6063
+ ´ 106 (10003 3003) ´ 109 (10004 3004)
3 4
= 18 040.8 + 26 341.7 12 352.0 + 2134.1
= 34 164.6 kJ/kmol Ans. (a)
Ref. 9:
z
T2
H= (24.7706 + 62.9481 ´ 103 T 44.2582 ´ 106 T 2
T1
+ 11.122 ´ 109 T3) dT
62.9481
= 24.7726 (1000 300) + ´ 103 (10002 3002)
2
44.2582 11122
.
´ 106 (10003 3003) + ´ 109 (10004 3004)
3 4
= 17 340.8 + 28 641.4 14 354.4 + 2758.0
= 34 385.8 kJ/kmol Ans. (b)
Ref. 61:
z
T2
H= (44.4586 + 10.634 ´ 103 T + 5.945 ´ 105/T 2) dT
T1
10.634
= 43.458 (1000 300) + ´ 103 (10002 3002)
2
+ 5.945 ´ 105 [(1/1000) (1/300)]
= 30 420.6 + 4838.5 1387.2
= 33 871.9 kJ/kmol Ans. (c)
Use of absolute enthalpies (Table 5.22):
H = 314 357 ( 347 921)
= 33 564 kJ/kmol Ans. (d)
EXERCISE 5.4
Basis: 1 kmol dry gas mixture from absorber
T1 = 343 K and T2 = 618 K
Component kmol ° equation constants

Cmp
ni ai × ni bi × ni ´ 103 ci × ni ´ 106 di × ni ´ 109
CH4 0.0025 0.0481 0.1303 0.0299 0.0283
CO 0.0038 0.1103 0.0107 0.0443 0.0179

CO2 0.001 0.0214 0.0643 0.0411 0.0098
H2 0.7462 21.3492 0.7607 0.1101 0.5738
N2 0.2435 7.2054 1.2518 3.2100 1.2097
Ar 0.003 0.0623
H2O 0.0126 0.4094 0.0010 0.1665 0.0573
Total 1.0126 29.2061 0.2840 3.2995 0.7296
For 100 kmol dry gas mixture,

heat exchanged Q = 100 [29.2061 (618.15 343.15)
0.2840 ´ 103 (618.152 343.152)/2
+ 3.2995 ´ 106 (618.153 343.153)/3
0.7296 ´ 109 (618.154 343.154)/4
= 100 [8031.7 37.5 + 215.3 24.1]
= 818 540 kJ Ans. (a)
Use data of Table 5.22.
ni A= B=
Component kmol (Ho H0o + DH fo)1 ni × A (H º H0o + DH of )2 ni × B
CH4 0.0025 55 311 138 42 622 107
CO 0.0038 103 981 395 95 802 364
CO 0.001 382 381 382 307 401 370
CO2 0.7462 + 9 709 + 7245 + 17 722 + 13 224
H2 0.2435 + 9 902 + 2411 + 18 029 + 4 390
Ar 0.003
H2O 0.0126 27 751 2870 218 133 2748
Total 1.0126 + 5871 + 14 025
Enthalpy change for 100 kmol dry gas mixture,

Q = 100 (14 025 5871) + 100 ´ 0.003 ´ 20.7723 (618.15 343.15)
= 815 400 + 1714
= 817 114 kJ (including that of argon) Ans. (b)
At 343.15 K (70ºC), pw = 31.162 kPa (Ref. Table 6.13)
Mole fraction of water vapour in gas mixture = 0.0126/1.0126
= 0.012 44
If total system pressure is p,
31.162 = 0.012 44 p
or p = 2505 kPa a
º 2.505 MPa a or 25.05 bar a Ans. (c)
Energy Balances 109
EXERCISE 5.5
Basis: 5000 kg/h hot oil
Heat load of oil = 5000 ´ 2.51 (423.15 338.15)
= 1066 750 kJ/h º 296.32 kW
Heat gained by water = 10000 ´ 4.1868 (T 294.15)
Where T = outlet temperature of cooling water
Heat loss = Heat gain
10 000 ´ 4.1868 (T 294.15) = 1066 750
T = 319.63 K (46.5ºC) Ans.
EXERCISE 5.6
Basis: 1 kg Diphyl DT
z
T2
Q= (1.436 + 0.002 18 T) dT
T1
= 1.436 (533.15 453.15) + 0.002 18 (533.152 453.152)/2

= 114.9 + 86 = 200.9 kJ/kg Ans. (a)
Mean heat capacity = (2.03 + 2.206)/2 = 2.118 kJ/(kg × K)
Q= 2.118 (533.15 453.15) = 169.4 kJ/kg
Error = (169.4 200.9) 100/200.9
= 15.7% Ans.(b)
EXERCISE 5.7
For benzene: C = a + bT
1.591 = a + 283b (1)
2.018 = 1 + 338b (2)
Solving the equations, a = 0.6051, b = 0.007 76
For toluene: C¢ = a¢ + b¢T
1.524 = a¢ + 283b¢ (3)
2.236 = a¢ + 358b¢ (4)
Solving the equations, a ¢ = 1.1645, b = 0.0095
Basis: 5 kmol benzene toluene mixture
(a) The mixture contains 3 kmol benzene and 2 kmol toluene.
Mass of benzene = 3 ´ 78 = 234 kg
Mass of toluene = 2 ´ 92 = 184 kg
Let T be the temperature of the mixture.
z
T
Heat gained by benzene = m1 × Cl1 × dT
303
0.007 76 2
= 234 [ 0.6051 (T 303)] + (T 3032)
2
= 0.907 92 T 2 141.593 T 40 452
z
373
Heat lost by toluene = m2 × Cl2 × dT

T
= 184 [ 1.1645 (373 T)] + (0.0095/2) (3732 T2)
= 416 77 + 214 268 T 0.874 T2
Heat loss by toluene = heat gain by benzene
0.907 92 T 2 = 141.593 T 40 452 = 41 677 + 214.268 T 0.874 T2
1.781 92 T 2 355.861 T 82 129 = 0
Solving the quadratic equation, T = 336.6 K (63.45ºC) Ans. (a)
(b) Use of data given in Table 5.3 (Ref. 7).
T1 = 303 K (30ºC)
Let the final temperature of the mixture after mixing is T K.
z
T
Heat gained by benzene = 3 ( 7.2733 + 770.541 ´ 103 T
303
1648.18 ´ 106 T2 + 1897.94 ´ 109 T 3)

= 3 [ 7.2733 (T 303)
+ 770.541 ´ 103 (T2 3032)/2
1648.18 ´ 103 (T9 3033)/3
+ 1897.94 ´ 103 (T4 3034)/4]
=1423.47 ´ 109 T 4 1624.17 ´ 106 T 3 + 1.1559 ´ 103 T 2
21.8199 T 65 651.7
T2 = 373 K (100ºC)
z
373
Heat given-up by toluene = 2 (1.8083 + 812.223 ´ 103 T
T
1512.67 ´ 106 T 2+ 1630.01 ´ 109 T 3)

= 2 [1.8083(373 T )
+ 812.223 ´ 103 (3732 T2)/2
1512.67 ´ 106 (3733 T3)/3
+ 1630.01 ´ 109 (3734 T4)/4]
= 815 ´ 109 T 4 + 1008.4 ´ 106 T 3
0.8122 ´ 103 T2 3.6166 T + 77 795.4
Energy Balances 111
Heat gained by benzene = heat given-up by toluene

Equating the two and simplifying,
2238.47 ´ 109 T 4 2362.57 ´ 106 T 3 + 1.9681 T2
18.2033 T = 143 447.1
The equation can be solved by trial and error method or by Mathcad.
Mixing temperature = 334.25 K (61.1ºC) Ans. (b)
EXERCISE 5.8
(a) From Table 5.4 for acetic acid,
1642.540
log p = 4.682 06
(T - 39.764)
T = 316.15 K
1642.540
log p = 4.682 06
(316.15 - 39.764)
= 1.260 86
or p = 0.0548 bar or 5.48 kPa Ans.
(b) From Table 5.4, for sulphur trioxide,
892.175
log p = 4.205 15
T - 103.564
T = 335.15 K
log p = 0.352 69
p = 2.253 bar Ans.
EXERCISE 5.9
(a) From Table 5.5, for acetone,
lv LM
T - To
= c
OP 0.38
lv1 T N
c - TB Q
0.38
lv é 508.1 - 313.15 ù
= ê ú l v = 29.1 kJ/mol
lv1 ë 508.1 - 329.3 û 1
lv = 29.1 ´ 1.0334
= 30.072 kJ/mol
(b) From Table 5.5, for carbon disulphide,
0.38
lv é 552.0 - 413.15 ù
= ê ú
26.74 ë 552.0 - 319.4 û
l v = 26.74 ´ 0.821 97
= 21 98 kJ/mol Ans.
EXERCISE 5.10
From Table 5.4, for chlorobenzene
1435.675
log p = 4.110 83
T - 55.124
p= 1.013 25 bar
T 55.124 = 347.292
T = TB = 402.42 K or tB = 129.27°C
Table 5.5 reports TB = 404.9 K or tB = 131.75ºC
Riedel equation:
lv 1.092(ln pc - 5.6182 )
=
R × TB 0.930 - TBr
Read Tc and pc values from Appendix III.2
TBr = TB /Tc = 404.9/633.0
= 0.6396
pc = 4.53 MPa = 4530 kPa
8.31451 ´ 404.9 ´ 1.092 (ln 4530 - 5.6182)
lv =
(0.930 - 0.6396)
= 35 450 kJ/kmol Ans.
Table 5.5 reports lv = 35 190 kJ/kmol
EXERCISE 5.11
(a) Benzene:
pc = 4.895 MPa, Tc = 562.05 K, TB = 353.3 K
Tr = 353.3/562.05 = 0.6286 at TB
Riediel equation:
é1.092 (ln 4895 - 5.6182) ù

l v1 = 8.314 51 ´ 353.3 ê ú
ë (0.930 - 0.6286) û
= 30 628 kJ/kmol at 353.3 K
NIST equation:
l v1 = 47 410 ´ e(0.1231 ´ 0.6286) ´ (1 0.6286)0.3602
= 30 712 kJ/kmol at 353.3 K
At t/T = 25°C/298.15 K, Tr = 298.15/562.05 = 0.530 47
l v2 = 47 410 ´ e(0.1231 ´ 0.530 47) ´ (1 0.530 47)0.3602
= 47 410 ´ 0.936 79 ´ 0.761 61
= 33 826 kJ/kmol at 298.15 K
Energy Balances 113
Watson equation:
0.38
é ù
lv2 = 29 100 ê 562.05 - 298.15 ú
ë 562.05 - 353.3 û
= 31 811 kJ/kmol at 298.15 K
(b) Acetone:
pc = 4.700 MPa, Tc = 508.1 K, TB = 329.3 K
Tr = 329.3/508.1 = 0.6481 at TB
Riedel equation:
é1.092 (ln 4700 - 5.6182) ù

lv1 = 8.314 51 329.3 ê ú
ë (0.930 - 0.6481) û
= 30 091 kJ/kmol at 329.3 K
NIST equation:
lv1 = 46 950 ´ e(0.2826 ´ 0.6481) ´ (1 0.6481)0.2876
= 29 101 kJ/kmol at 329.3 K
At t/T = 25°C/298.15 K, Tr = 298.15/508.1 = 0.5868
lv2 = 46 950 ´ e(0.2826 ´ 0.5868) ´ (1 0.5868)0.2876
= 30 984 kJ/kmol at 298.15 K
Watson equation:
0.38
é ù
lv2 = 29 100 ê 508.1 - 298.15 ú
-
ë 508.1 329.3 û
= 30 931 kJ/kmol at 298.15 K Ans.
EXERCISE 5.12
Basis: 100 kg naphthalene
Total heat to be supplied consists of sensible heat, supplied to the solid from
303.15 K to its melting point (353.35 K), latent heat of fusion l f at 353.35 K,
sensible heat supply to liquid naphthalene from the melting point (353.35 K) to its
normal boiling point (490 K) and the latent heat of vaporzation at 490 K.
z
Q2 = Cs dT = 100 [ 0.092 (353.35 303.15) + (0.0046/2) (353.352 303.152)]
= 461.8 + 7579.9 = 7118.1 kJ
Q2 = m × lf = 100 ´ 150.7 = 15 070 kJ
For evaluation of Q3, C1 is required to be expressed in the polynomial form of
temperature.
Cl = a + bT
1.738 = a + b ´ 353 (1)
2.135 = a + b ´ 473 (2)
z
Solving the equations, a = 0.57 and b = 0.003 31
Q3 = m Cl dT
= 100 [0.57 (491 353) + (0.003 31/2)
(4912 3532)]
= 7866 + 19 276 = 27 142 kJ
Q4 = m ×lv = 100 ´ 316.1 = 31 610 kJ
Total heat load = S Qi
= 7118.1 + 15 070 + 27 142 + 31 610
= 80 940.1 kJ
Latent heat of vaporisation of the eutectic mixture at 171 kPa a
= 278.0 kJ/kg (Ref. Table 5.6)
Quantity of the eutectic mixture condensed
= 80 940.1/278.0
= 291.15 kg Ans.
EXERCISE 5.13
Basis: 10 000 kg/h superheated stem @ 0.44 MPa a and 543 K (270°C) is
mixed with 7500 kg/h saturated steam at 0.44 MPa a.
From Table AIV.2 enthalpy of saturated steam = 2741.9 kJ/kg
From Table AIV.3 enthalpy of superheated steam = 3004.5 kJ/kg
Total enthalpy of 7500 kg/h saturated steam = 7500 ´ 2741.9
= 20 564 250 kJ/h
º 5712.29 kW
Total enthalpy of 10 000 kg/h superheated steam = 10 000 ´ 3004.5
= 30 045 000 kJ/h
º 8345.83 kW
Total enthalpy of mixed fluids = 5712.29 + 8345.83
= 14 058.12 kW
º 50 609 250 kJ/h
50 609 250
Specific enthalpy of mixture = = 2891.96 kJ/kg
17 500
From steam tables (AIV.3), temperature of mixed steam
= 489.15 K (216.0°C) at 0.44 MPa a which is superheated.
EXERCISE 5.14
Basis: 100 kg superheated steam @ 0.5 MPa a and 523 K (250°C)
From Steam Tables AIV.3, specific enthalpy of superheated steam
= 2961.1 kJ/kg
Energy Balances 115
From Steam Tables AIV.2, specific enthalpy of saturated steam at 0.5 MPa a
= 2747.5 kJ/kg at (TS) saturation temp.
of 425 K (151.85°C).
Enthalpy of steam to be reduced = 2961.1 2747.5 = 213.6 kJ/kg
Enthalpy of water to be sprayed = 125.66 kJ/kg
Let a be the quantity of water to be sprayed.
100 ´ 2961.1 + a ´ 125.66 = 2747.5 (100 + a)
or a = 8.15 kg Ans.
EXERCISE 5.15
Basis: 1 kg condensate
Operating pressure of dryer = 310 kPa a
Operating pressure of flash vessel = 101.325 kPa a
At 310 kPa a, Ts = 407.8 K (134.65°C),
h = 566.23 kJ/kg and l v = 2159.9 kJ/kg
At 101.3 kPa a, Ts = 373.15 K (100°C),
h = 419.06 kJ/kg, l v = 2256.9 kJ/kg and
H = 2676.0 kJ/kg
Let the flash quantity be a kg per kg of condensate at 310 kPa.
(1 a) 419.06 + 2676.0a = 566..23
a = 0.065 kg/kg condensate
Enthalpy of saturated steam at 780 kPa a= 2767.5 kJ/kg
Let y and y¢ be the quantities of water to be sprayed before modification and after
the modification per kg of saturated steam at 310 kPa, respectively.
y ´ 419.06 + (1 y) 2767.5 = (566.23 + 2159.9) = 2726.13
y = 0.0176 kg/kg condensate
After the modification,
y¢ ´ 419.06 + 0.065 ´ 2676.0 + (1 y¢ 0.065) 2767.5
= 2726.13
y¢ = 0.015 kg/kg condensate
Make-up 0.8 MPa a steam = 1 0.065 0.015 = 0.92 kg
Reduction in make-up steam = [(0.9824 - 0.92)/0.9824] 100
= 6.35% Ans.
EXERCISE 5.16
Basis: 1 kmol dry gas mixture. T1 = 1473.15 K, T2 = 573.15 K
Component kmol ° equation constants

Cmp
ni
ai × ni bi × ni ´ 103 ci × ni ´ 103 di × ni ´ 103
H2 0.557 15.936 0.568 0.082 0.428
CO 0.345 10.015 0.972 4.017 1.624
CO2 0.028 0.598 1.800 1.149 0.274
CH4 0.005 0.096 0.261 0.060 0.057
N2 0.065 1.923 0.334 0.857 0.323
H2O 1.850 60.110 0.147 24.440 8.413
Total 2.850 88.678 1.470 28.143 9.715
Heat lost in WHB, DH = 88.678 (1473 573) + 1.470 ´ 103 (14732 5732)/2
+ 28.143 ´ 106 (14733 5733)/3 9.715 ´ 109 (14734 5734)/4
= 79 810.2 + 1353.4 + 28 216.9 11 172.1
= 98 208.4 kJ/kmol dry gas mixture
º 9820 840 kJ/100 kmol dry gas mixture
Steam pressure p = 4.0 MPa g = 4.1013 MPa a
Ts = 524.8 K (251.8°C) (Ref. A IV.2)
Water enters WHB at 504.8 K (231.8°C), 20 K lower than 524.8 K.
Enthalpy of water at 504.8 K, h = 998.7 kJ/kg
Enthalpy of saturated steam at 4.1013 MPa a, Hs = 2800 kJ/kg
Enthalpy supplied to water in WHB
= 2800 998.7
= 1801.3 kJ/kg
Steam generated in WHB = 9820 840/1801.3
= 5452 kg per 100 kmol dry gas Ans.
EXERCISE 5.17
Basis: 100 kg saturated liquid ammonia at 705 kPa a
Let y be the quantity of NH3 vapours flashed.
Liquid NH3 at 101.325 kPa a = 100 y kg
Heat balance:
Enthalpy of liquid NH3 at 705 kPa a
= Enthalpy of liquid NH3 at 101.3 kPa a
+ Enthalpy of flash vapours at 101.3 kPa a
100 ´ 265.56 = (100 y) 49.1 + y ´ 1418.7 kJ/h (º 44.85 kW)
Solving the equation, y = 15.8 kg or 15.8 % flashing Ans.
EXERCISE 5.18
Basis: 100 kg NH3 vapours, entering 1st stage of compressor
Energy Balances 117
Enthalpy H1 = 100 ´ 1632.68 = 163 268 kJ/h (º 45.35 kW) of gas leaving 1st
stage.
Enthalpy of 100 kg liquid NH3 at 276 K = 100 ´ 213.92
= 21 392 kJ/h (º 5.94 kW)
Heat, removed in flash cooler = 163 268 21 392
= 141 876 kJ/h (º 39.41 kW)
Let y be the quantity of liquid NH3, obtained from the condenser and is utilised in
flash cooler. Out of this, a part will be flashed due to pressure reduction.
Another basis: 1 kg liquid NH3 at 1930.3 kPa a and 321 K (48°C)
Enthalpy of saturated liquid at 1930.3 kPa a
= Enthalpy of saturated liquid at 276 K (3°C) + Enthalpy
of saturated vapours at 276 K (3°C)
100 ´ 431.07 = (100 z) 213.92 + z ´ 1464.92
where z = amount of flash vapours, produced due to pressure reduction
z = 17.36 kg
Thus 17.36% liquid, entering the flash cooler (i.e. y kg) will be flashed.
Balance liq. NH3, available for cooling 1st stage vapours
= (1 0.1734) y = 0.8266y kg/h
This ammonia should cater for the heat load of 141 876 kJ/h.
0.8266 y ´ 1251.0 = 141 876
or y = 137.13 kg/h Ans. (a)
Heat load of condenser = 1663.91 431.07
= 169 059 kJ/h º 46.96 kW
Cooling water to condenser = 169 059/[3600 ´ 4.1868 ´ (313 305)]
= 1.402 kg/s Ans. (b)
EXERCISE 5.19
Basis: 65 kW refrigeration load in chiller
From Table 5.7,
Enthalpy of saturated R-134a liquid at 40°C (313.15 K) = 256.35 kJ/kg
Saturation temperature of R-134a at 101.325 kPa = 26°C
Superheat = 10°C
Temperature of R-134a gas, leaving chiller = 26 + 10 = 16°C
Enthalpy of superheated R-134a gas at 101.325 kPa and 16°C = 391.0 kJ/kg
(Ref. Table 5.71)
Heat picked up by R-134a in chiller = 391.0 256.35
= 134.65 kJ/kg
kJ 1 kg
Evaporation rate = 60 ×
s 134.65 kJ
= 0.4456 kg/s Ans.(a)
With the incorporation of the economizer, R-134a gas heats upto 10°C at 101.325
kPa.
Heat picked up in the economizer = 412 391
= 21 kJ/kg
In exchange, R-134a liquid under saturation pressure (10.165 bar) at 40°C (313.15 K)
is cooled.
Enthalpy of sub-cooled R-134a liquid = 256.35 21
= 235.35 kJ/kg
Heat picked up in chiller = 391 235.35
= 155.65 kJ/kg
65
Evaporation rate = = 0.4176 kg/s with
155.65
economizer Ans. (b)
EXERCISE 5.20
(a) Locate a point representing 273 K (0°C) on p-H diagram for CO 2
(Fig. 5.11). Follow constant enthalpy line (i.e. vertical line) which inter-
sects the pressure line representing 1.0 MPa g (= 1.101 MPa a).
Read dryness fraction of 0.277. Thus vapours produced by pressure
reduction is 27.7%. Ans.
(b) Enthalpy of CO2 at 1.101 MPa a and 313 K(40°C) = 811 kJ/kg
Enthalpy of vapour-liquid mixture at 1.101 MPa a = 500 kJ/kg
Enthalpy required to produce CO2 gas at 1.101 MPa a and 313 K
= 811.0 500 = 311 kJ/kg Ans.
EXERCISE 5.21
Basis: 1 kmol dry gas
T1 = 403.15 K and T2 = 313.15 K
Component kmol Molar mass ni × M i Critical Critical
yi Mi pressure temperature
p ci yi ×pci Tci yi ×Tci
MPa K
CO2 0.947 44.01 41.677 7.375 6.983 304.12 288.00
O2 0.008 31.9988 0.256 5.042 0.040 154.59 1.24
N2 0.030 28.0134 0.840 3.394 0.102 126.09 3.78
H2 0.015 2.016 0.030 1.297 0.019 33.2 0.48
Total 1.000 42.803 7.144 293.50
Energy Balances 119
Average molar mass = 42.803 of incoming gas mixture

Pseudo critical pressure pc = 7.144 MPa
Pseudo critical temperature Tc = 293.5 K (20.35°C)
New Basis: 100 kmol dry gas
Component kmol C°
mp equation constants
ni
CO2 94.7 2023.313 6087.704 3887.492 928.051
O2 0.8 20.821 9.404 1.874 0.450
N2 3.0 88.773 15.423 39.549 14.904
H2 1.5 42.916 1.529 0.221 1.154
Total 100.0 2175.823 6083.214 3850.038 913.851
Tr1 = 403.15/293.5 = 1.374, Tr2 = 313.15/293.5 = 1.067

Avg. Tr = (1.374 + 1.067)/2 = 1.220
pr = 20/7.144 = 2.8
Fig. 5.1 does not provide value of C Rmp for the required pr and Tr. From Lee at el
article (ref. 12).
R
Cmp

0 1
R
= Cmp + w CmRp
R
At pr = 2.8 and Tr = 1.22
C
0
R
mp = 5.681
Acentric factor (wi) for each component is to be considered and S (yi × wi) is
required to be calculated for the mixture, However, since CO2 is 94.7% in the
mixture, its wCO value is taken for calculation.
2
w = 0.225 for CO2 (Ref. 3)
C
1
R
mp = 7.222
R
Cmp
= 5.681 + (0.225 ´ 7.222) = 7.306
R
C Rmp = 7.306 ´ 8.314 51 = 60.746
Cmp = C omp + C Rmp = C omp + 60.746 kJ/(kmol × K)
Therefore, corrected heat capacity equation will become
Cmp = (2175.823 + 60.746 ´ 100)
+ 6083.214 ´ 109 T 3850.038 ´ 103 T2 + 913.851 ´ 103 T 3
Heat removed in water cooler
= 8250.423 (403.15 313.15) + 6083.214 ´ 103 (403.152 313.152)/2
3850.038 ´ 106 (403.153 313.153)/3 + 913.851 ´ 109
(403.154 313.154)/4
= 742 538 + 196 087 44 680 + 3838
= 897 783 kJ/h

º 249.38 kW
For p = 4.0 MPa a
pr = 4.0/7.144 = 0.56, Tri = 313.15/293.5 = 1.067
R ö 0
æ Cmp
ç ÷ = 1.2062
è R ø
1
æ Cmp
R ö
ç ÷ = 2.3857
è R ø
æ Cmp
R ö
ç ÷ = 1.2062 + (0.225 ´ 2.3857) = 1.743

è R ø
= 1.743 ´ 8.314 14 = 14.491
R
From Fig. 5.1, C mp = 14.5
Both are closely matching.
Since incoming gas mixture has 5.3 mole % inerts, liquefaction temperature
will have to be found by trails such that at the liquefaction temperature, ratio of
uncondensed CO2 to inerts satisfy the vapour pressure data. At 40 bar a pressure,
saturation temperature of CO2 is +5.32°C (278.47 K). Presence of inerts will
require liquefaction temperature to be lower than 278.47 K.
Trial 1: Assume liquefaction temperature of 273.15 K.
Consider enthalpy of liquid CO2 = 0 kJ/kg at 273.15 K
Heat given-up by gas from 313.15 K to 273.15 K
= (2175.823 +1449.1) (313.15 273.15)
+ 6083.214 ´ 103 (313.152 273.152)/2
3850.038 ´ 106 (313.153 273.153)/3
+ 913.851 ´ 109 (313.154 273.154)/4
= 144 997 + 71 332 13 255 + 925
= 203 999 kJ/h
º 56.666 kW
l v of CO2 at 273.15 K = 231.00 kJ/kg = 10 166 kJ/kmol (Ref. 24)
Let x be the amount of uncondensed CO2 (kmol/h)
(94.7 x) 10 166 = 203 999
94.7 x = 20.067
x = 74.633 kmol/h
CO2 condensed = 20.067 kmol/h
Inerts = 0.8 + 3.0 + 1.5 = 5.3 kmol/h
Energy Balances 121
Uncondense CO 2 74.633
= = 14.083 kmol / kmol
inerts 5.3
At T = 273.15 K, saturation pressure of CO2, pS1 = 3485.9 kPa (Ref. 24)
total pressure = 3000 kPa
Applying Raoult's law,
Moles of CO 2 3485.9
= = 6.781
Moles of inerts (4000 3485.9)
Thus calculated ratios do not match.
Trial 2: Assume liquefaction temperature (T2 ) of 275.15 K.
Enthalpy of gas mixture from 313.15 K to 275.15 K
= 193 955 kJ/h
º 53.876 kW
lv at 275.15 K = 225.05 kJ/kg = 9904.3 kJ/kmol
(94.7 x) 9904.3 = 193 955
94.7 x = 19.532
x = 74.1168 kmol/h
CO 2 74.168
= = 14.183
Inerts 5.3
CO2 condensed = 20.555 kmol/h
At T = 275.15 K pS2 = 3673.3 kPa
Moles of CO 2 3673.3
= = 11.244 no match
Moles of inerts (4000 - 3673.3)
Trial 3: Assume T3 = 276.15 K or t3 = 3°C.
lv = 221.53 kJ/kg = 9749.4 kJ/kmol
Heat given up by gas from 313.15 K
to 276.15 K = 188 926 kJ/h
º 52.479 kW
(94.7 x) 9749.1 = 188 926
x = 75.322 kmol/h
Uncondensed CO 2 = 75.322
= 14.211
Inerts 5.3
Saturation pressure of CO2 at 276.15 K, p53 = 3768.5 kPa
= 16.279
Inerts (4000 - 3768.5)
Since ratio is reversed, the liquefaction temperature is between 275.15 K and
276.15 K.
Trial 4: Assume T4 = (275.15 + 276.15)/2
= 275.65 K or t4 = 2.5°C
lv = (225.05 + 221.53)/2
= 223.29 kJ/kg º 9826.9 kJ/kmol

Heat given-up by gas = (193 955 + 188 926)/2
= 191 441 kJ/h
º 53.178 kW
(94.7 x) 9826.9 = 191 441
x= 75.219 kmol/h
= 192
Inerts 5.3
At T4 = 275.65 K, p54 = 3720.9 kPa
= 13.332
Inerts (4000 - 3720.9)
Further trials are unwarranted as both ratios are close enough.
CO2 condensed = 94.7 75.219 = 19.481 kmol/h
Hence liquefaction temperature = 269.85 K (3.3 °C)
CO2 liquefied = (94.7 75.219) 100/94.7
= 20.57 % Ans. (b)
Enthalpy of saturated liquid CO2 at 37.21 bar a and 2.5°C (275.65)
= 206.13 kJ/kg (Ref. 24)
Liquefied gas is precooled in the revert gas exchanger before dry gas production.
Note that liquid CO2 temperature after the revert gas exchanger but before the
snow tower will be at higher then 11°C.
Refer Example 5.19,
100 ´ 206.13 = (100 y) 422.61 + (148.39 y)
571.0 y = 21 648
y = 37.91 kg dry ice/100 kg liquid CO2
For 100 kmol raw gas input, dry ice production
= 19.481 ´ 0.3791
= 7.385 kmol/h
º 325.2 kg/h
For 100 kg dry ice production, raw gas requirement
= 100 ´ 100 ´ 42.803/325.02
= 1316.93 kg/h Ans. (c)
º 30.767 kmol/h
Duty of water cooler = (30.767 ´ 191.441)/100
= 58 901 kJ/h
º 16.361 kW Ans. (a)
Note: Application of Raoult's law may not be fully justified as pressure of liquid
CO2 is high (40 bar a). Use of modified Raoult's law or pure component pressures
(Sec. 2.6.3) is more appropriate.
Energy Balances 123
EXERCISE 5.22
Basis: 32 000 kg of total ammonia (liquid + vapour) in each tank wagon
Temperature of ammonia in wagon = 29°C (244.15 K)
Let x = quantity of ammonia vapours,
contained in the wagon (in kg)
Liquid ammonia = 32 000 x kg
Total volume of each wagon = 60.663 m3
x (32 000 x )
+ = 60.663
1.0844 676.25
x = 14.49 kg vapours of ammonia
Liquid NH3 = 320 00 14.49 = 31 985.51 kg
Total enthalpy, H1 = 14.49 ´ 1425.06 + 31 985.51 ´ 68.32
= 2205 899.1 kJ
Similar values of liquid ammonia and vapour ammonia at different temperatures
can be calculated.
Temperature, NH3 vapours, liquid NH3, total enthalpy,

°C(K) kg kg kJ
29 (244.15) 14.49 31 985.51 2205 899.1
27 (246.15) 15.62 31 984.38 2493 097.8
25 (248.15) 16.85 31 983.15 2781 056.0
23 (250.15) 18.12 31 981.88 3069 691.4
21 (252.15) 19.44 31 980.56 3359 336.6
19 (254.15) 20.84 31 978.16 3649 276.3
17 (256.15) 22.27 31 377.73 3940 422.8
Temperature change from 244.15 K to 246.15 K
Average temperature, T = 246.15 K
Ambient temperature Ta = 298.15 K
Heat gain, f1 = 1.3 (298.15 245.15) + 3.76 = 72.66 kW
º 261 576 kJ/h
Enthalpy gain between two temperatures,
H1¢ = 2493 097.8 2205 899.1
= 287 198.7 kJ
Time, required for increase in temp. = 287 198.7/261 576 = 1.098 h
Similar calculations are listed below:
Rise in temperature Enthalpy change, Heat transfer Time, h

K kJ rate, f, kJ/h
From to
244.15 246.15 287 198.7 261 576 1.098
246.15 248.15 287 958.2 252 216 1.142
248.15 250.15 288 635.4 242 856 1.189

250.15 252.15 289 645.2 233 496 1.240
252.15 254.15 289 939.7 224 136 1.294
254.15 256.15 291 146.5 214 776 1.356
Total 1734 523.7 7.319
Ans. (a)
244.15 + 256.15
Average T = = 250 K
2
f = 1.3 [298.15 250.15] + 3.76
= 66.16 kW º 238 176 kJ/h
Time q = 1734 523.7/238 176 = 7.283 h Ans. (b)
EXERCISE 5.23
Basis: 1650 Nm3/h air flow rate
Molar flow rate = 1650/22.414 = 73.615 kmol/h
Mass flow rate = 73.615 ´ 28.84 = 2123.06 kg/h
Temperature drop from 463.15 K to 453.15 K:
Heat loss rate at 463.15 K (190°C) = 575.8 W/m [Ref. Fig. (5.35)]
Heat loss rate at 459.15 K (180°C) = 532.3 W/m [Ref. Fig. (5.35)]
Average heat loss rate = (575.8 + 532.3)/2457.5
= 554.05 W/m
Enthalpy to be removed from air = 2123.06 ´ 1.006 ´ 10
= 21 358 kJ/h º 5.9328 kW
Length of pipe, required for cooling, L1 = 5.9328 ´ 1000/554.05
L1 = 10.71 m
Similar calculations are listed below, keeping enthalpy removal quantity as same
(i.e. 5.9328 kW) for 10 K drop.
Temp, Heat loss rate, Avg. heat loss Length of pipe
°C(K) ref. Fig. (5.35), W/m rate, W/m m
190 (463.15) 575.8
180 (453.15) 532.3 554.05 10.71
170 (443.15) 481.1 506.7 11.71
160 (433.15) 434.4 457.75 12.96
150 (423.15) 400.0 417.2 14.22
140 (413.15) 364.8 382.4 15.51
130 (403.15) 324.6 344.7 17.21
120 (393.15) 292.6 308.6 19.22
110 (383.15) 266.4 279.5 21.23
100 (373.15) 244.3 255.35 23.23
Total 146.00
Energy Balances 125
Balance length of pipe = 150 146 = 4 m

Heat loss rate at 363.15 K (90°C) = 216.4 W/m
Avg. heat loss rate between 373.15 K (100°C) and 363 K(90°C)
= (244.3 + 216.4)/2 = 230.35 W/m
Length of pipe, required to cool to 363 K (90 °C)
= 5932.8/230.35
= 25.76 m
However, actual length to be cooled = 4 m
Drop in temperature = (4/25.76) 10
= 1.55 K
Temperature of air at the end of 150 m pipe = 373.15 1.55
= 371.6 K (98.45°C) Ans.
EXERCISE 5.24
Basis: 1 kmol mixture of benzene and toluene containing 0.6 kmol benzene.
Antoine equation:
1203.835
for benzene: log p = 4.018 14
(T 53.226)
1343.943
for toluene: log p = 4.078 27
(T 53.773)
At p = 101.325 kPa, = 1.013 25 bar
Ts1 = 353.25 K, Ts2 = 383.77 K
ts1 = 80.1°C ts2 = 110.62 °C
Initial guess, T1 = 353.60 ´ 0.6 + 383.77 ´ 0.4
= 365.67 K say 366 K
Bubble point: component 1 = benzene and component 2 = toluene. All pressures
are kPa.
Temperature, K
x1 T1 = 366 T2 = 360 T3 = 364 T5 = 362.75
p si yi p si yi p si yi p si yi
0.6 147.653 0.8743 124.155 0.7352 139.468 0.8259 134.533 0.7966
0.4 59.416 0.2346 48.928 0.1932 55.737 0.2200 53.132 0.2121
1.0 1.1089 0.9284 1.0459 1.0087
At Syi = 1.00. Bubble point, TBP = 362.75 K or 89.6°C Ans. (ai)

Dew point:
Temperature, K
y1 T1 = 366 T2 = 368 T3 = 370 T4 = 369
p si xi p si xi p si xi p si xi
0.6 147.653 0.4117 156.206 0.3892 165.137 0.3681 160.62 0.3785
0.4 59.416 0.6821 63.283 0.6405 67.350 0.6018 65.29 0.6208

1.0 1.0938 1.0297 0.9699 0.9993
At Sx i = 1.00 dew point, TDP= 369 K or 95.85 °C Ans. (a ii)

Enthalpy (sensible heat) of liquid mixture at T:
Reference temperature: T0 = 273.15 K (0 °C)
TBP
H1 = ò Cl1 × dT
273.15
= 484.365 (362.75 273.15)
+ 5056.235 ´ 103 (362.752 273.152)/2
14 292.204 ´ 106 (362.753 273.153)/3
+ 14 419.754 ´ 108 (362.754 273.154)/4
= 43 471.8 + 144 250.8 130 473.5 + 42 394.1
= 12 699.6 kJ/kmol benzene
TBP
H2 = ò Cl2 × dT
273.15
= 56.3627 (362.75 273.15)
+ 1768.423 ´ 103 (362.752 273.152)/2
5192.623 ´ 103 (362.753 273.153)/3
+ 5497.39 ´ 104 (362.754 273.154)/4
= 5058.6 + 50 451.8 47 403.5 + 16 162.3
= 14 152.0 kJ/kmol toluene
Hsol = S (Hi × xi)
= 0.6 ´ 12 699.6 + 0.4 ´ 14 152.0
= 7619.8 + 5660.8
= 13 280.6 kJ/kmol liquid mixture
From Fig. 6.2, Hsol = 13 733 kJ/kmol liquid mixture
Enthalpy of vapour mixture at TDP :
0.38
é 562.05 369.0 ù
l v1 = ê ú ´ 30 720
ë 562.05 353.3 û
= 29 820.7 kJ/kmol of benzene at TDP
0.38
é 591.75 369.0 ù
l v2 = ê ú ´ 33 180
ë 591.75 383.8 û
= 34 058.3 kJ/kmol of toluene at TDP
TDP
H1¢ = ò Cl1 × dT
273.15
= 484.365 (369.0 273.15)

Energy Balances 127
+ 5056.235 ´ 103 (369.02 273.152)/2

14 292.204 ´ 106 (369.03 273.153)/3
+ 14 419.754 ´ 109 (369.04 273.154)/4
= 46 547.5 + 155 999.5 142 626.2 + 46 883.5
= + 13 709.3 kJ/kmol benzene
TDP
H 2¢ = ò Cl2 × dT
273.15
= 56.3627 (369.0 273.15)
+ 1768.423 ´ 103 (369.02 273.152)/2
5192.623 ´ 106 (369.03 273.153)/3
+ 5497.39 ´ 109 (369.04 273.154)/4
= 5416.5 + 54 561.0 51 818.7 + 17 873.9
= + 15 199.7 kJ/kmol toluene
Enthalpy of benzene vapour at TDP = 13 709.3 + 29 820.7
= 43 530 kJ/kmol benzene vapour
Enthalpy of toluene vapour at TDP = 15 199.7 + 34 058.3
= 49 258 kJ/kmol toluene vapour
Enthalpy of vapour mixture = S Hi¢ × yib g
= 0.6 ´ 43 530 + 0.4 ´ 49 258
= 45 821 kJ/kmol vapour mixture Ans. (b)
From Fig. 6.2, enthalpy of vapour mixture
= 45 666.7 kJ/kmol vapour mixture
EXERCISE 5.25
Basis: 1 kmol natural gas
Values of Li for trial value of L
Temperature ni Ki
L = 0.5 0.1 0.01 0.041
CH4 0.8957 2.70 0.2421 0.0354 0.0033 0.0140
CO2 0.0112 0.90 0.0059 0.0012 0.0001 0.0005
C2 H 6 0.0526 0.38 0.0381 0.0019 0.0014 0.0053
C3 H 3 0.0197 0.098 0.0179 0.0105 0.0019 0.0060
i-C4H10 0.0068 0.038 0.0065 0.0051 0.0014 0.0036
n-C4H10 0.0047 0.024 0.0046 0.0039 0.0014 0.0030
C5H12 0.0038 0.0075 0.0038 0.0035 0.0022 0.0032
C6H14 0.0031 0.0019 0.0031 0.0030 0.0026 0.0030
C7H18 0.0024 0.0007 0.0024 0.0024 0.0022 0.0024
Total 1.0000 0.3244 0.0769 0.0165 0.041
V = 1 0.041 = 0.959 kmol and L = 0.041 kmol Ans.

EXERCISE 5.26
Basis: 1 kmol crude gas mixture from demethanizing unit
Cryogenic temp. in cold box = 111 K ( 162.15 °C)
Component yi K*i L1 = L2 = L3 = L4 = V
0.5 0.25 0.22 0.215
H2 0.750 49.73 0.0148 0.0050 0.0042 0.0041 0.7459
CH4 0.200 0.057 0.1892 0.1708 0.1664 0.1655 0.0345
C2H6 0.045 9.45 ´ 105 0.0450 0.0450 0.0450 0.0450 Nil
N2 0.005 1.158 0.0022 0.0011 0.0010 0.0010 0.0040
1.000 0.2512 0.2219 0.2166 0.2156 0.7844
*
Ki values are calculated from Table 5.15 of the text at T = 111 K.
New basis: crude gas stream flow = 18 720 Nm3/h
= 835.19 kmol/h
Ingoing gas stream:
components ni Molar ( m i ) Hi , kJ/kg mi × Hi

kmol/h mass kg/h at 2.75 MPa a kW
and 300.15 K
H2 626.4 2 1252.8 3972.1 1382.29
CH4 167.03 16 2672.5 888.43 659.54
C2H6 37.58 30 1127.4 607.82 190.35
N2 4.18 28 117.0 305.67 9.93
Total 835.19 5169.8 2242.11
Product gas stream:

component kmol/h Molar kg/h Hi, kJ/kg mi× Hi
ni mass ( m i ) at 2.75 MPa a, kW
and 297.65 K
H2 622.98 2 1246.0 3935.7 1362.19
CH4 28.81 16 461.0 883.44 113.13
C2H8 Nil 30 Nil 604.90 Nil
N2 3.34 28 93.5 303.17 7.83
Total 655.13 1800.5 1483.19
Tail gas stream:

component ni Molar ( m i ) Hi, kJ/kg mi× Hi
kmol/h mass kg/h at 140 KPa a, kW
and 297.15 K
H2 3.42 2 6.8 3917.6 7.40
Energy Balances 129
CH4 138.22 16 2211.5 907.34 557.38

C2H6 37.58 30 1127.4 665.26 208.34
N2 0.84 28 23.5 308.14 2.01
Total 180.06 3369.3 775.13
Net heat change, f1 = 775.13 + 1483.19 2242.11

= 16.21 kW (endothermic)
Heat infiltration, f2 = 20.9 kW
Refrigeration requirement, f3 = 20.9 16.21 = 4.69 kW
º 1.334 TR
Recovery of hydrogen = (622.98 ´ 100)/626.4 = 99.45%
Purity of product hydrogen stream = 622.98 ´ 100/655.13
= 95.1% Ans.
EXERCISE 5.27
(a) C7H16(g) + 11 O2(g) ¾ ¾¾® 7 CO2(g) + 8 H2O(g)
Heat of combustion of n-heptane (g), DH°c = 4501.46 kJ/kmol
7 C(s) + 7 O2(g) ¾ ¾¾® 7 CO2(g)
Heat of combustion of carbon (s), DH°c = 393.51 kJ/kmol
8 H2(g) + 4 O2(g) ¾ ¾¾® 8 H2O(g)
Heat of combustion of hydrogen (g), DH°c (g) = 241.82 kJ/kmol
Heat of formation of n-heptane (g) = Heat of combustion of carbon +
Heat of combustion of hydrogen Heat of combustion of n-heptane
DH°f = 7 ´ 393.51 8 ´ 241.82 + 4501.46
= 187.67 kJ/kmol Ans.
From Table AV.2 DH°f = 187.78 kJ/kmol
(b) C2H5OH (g) ¾ ¾¾® 2 CO2(g) + 3 H2O(g)
Heat of combustion of ethyl alcohol (g), DH°c = 1277.53 kJ/kmol
2 C(s) + 2 O2(g) ¾ ¾¾® 2 CO2(g)
3 H2(g) + 1.5 O2(g) ¾ ¾¾® 3 H2O(g)
D H°f of C2H5OH (g) = 2 ´ 393.51 3 ´ 241.82 + 1277.53
From Table AV.2, D H°
f = 234.95 kJ/kmol
(c) C4H6(l) + 5.5 O2 (g) ¾ ¾¾® 4 CO2(g) + 3 H2O(g)
Heat of combustion of butadiene (1,3), DH°c = 2386.69 kJ/kmol
4 C(s) + 4 O2(g) ¾ ¾¾® 4 CO2(g)
3 H2(g) + 1.5 O2(g) ¾ ¾¾® 3 H2O(g)
D H°f of C4H6(l) = 4 ´ 393.51 3 ´ 241.82 + 2386.69

From Table AV.2, D H°f = 87.19 kJ/kmol
EXERCISE 5.28
(a) DH°c (g) for hydrogen = 241.82 kJ/kmol
lv at 298.15 for water = 2442.5 kJ/kg
º 44.002 kJ/mol
D H°f (l) = 241.82 44.002
= 285.82 kJ/mol Ans.
(b) D H°f (g) for methanol = 200.94 kJ/mol
Watson equation:
0.38
é 512.5 298.15 ù
lv at 298.15 K for methanol = 35 210 ê ú
ë 512.5 337.7 û
= 38 048 kJ/kmol
D H°f (l) = 200.94 38.05 = 238.99 kJ/mol Ans.
NIST equation:
For methand, pc = 80.84 bar, Tc = 512.5 K
At T = 298.15 K Tr = 0.5818
lv at 298.15 K= 45.3 ´ e(0.31)(0.5818) ´ (1 0.5818)0.4241
= 37.485 kJ/mol
DH°f (l) = 200.94 37.485
= 238.43 kJ/mol Ans.
(c) D H°f (g) for CS2 = 117.36 kJ/mol
Watson equation:
0.38
é 552 298.15 ù
l v = 26 740 ê ú
ë 552 319.04 û
= 27 627 kJ/kmol
D H°f (l) = 117.36 27.64
= 89.72 kJ/mol Ans.
NIST equation:
For CS2, pc = 73.00 bar Tc = 552.0 K
At T = 298.15 K Tr = 298.15/552 = 0.5786
lv at 298.15 K = 37.07 ´ e(0.2264 ´ 0.5786) ´ (1 0.5786)0.2264
= 26.739 kJ/mol
DH°f (l) = +117.36 26.739 = 90.62 kJ/mol Ans.
Energy Balances 131
EXERCISE 5.29
Basis: 1 kg NaHCO3
D H ro = ( 1130.68 393.51 241.82) 2( 950.81)
= + 135.61 kJ/2 mol NaHCO3
º + 67.805 kJ/mol NaHCO3 (endothermic)
Molar mass of NaHCO3 = 84.0066
Moles of NaHCO3 = 1000/84.0066 = 11.904 mol/kg
Heat to be supplied for dissociation = 67.805 ´ 11.904
= 807.15 kJ/kg NaHCO3 Ans.
EXERCISE 5.30
d
D H ro = D Hfo i products
d
D Hfo i reactants
= ( 1412.2 393.51) ( 1130.68 824.2)
= 149.17 kJ/mol Na2CO3 or mol Fe2O3 Ans.
EXERCISE 5.31
Basis: 100 kg CH4 reformed
Input heat balance:
Gas kg Molar kmol Tempera- (H° DH°o + DH°f )i ni × (H° DH°o
mass ni ture K(°C) kJ/kmol + DH°f ), kJ
CH4 100 16 6.250 698 (425) 38 416 240 100
O2 100 32 3.125 698 (425) + 2 102 + 65 691
H2O 100 18 5.55 1253 (980) 192 447 1068 081
Total 300 14.925 1242 490
Outlet Heat balance:
Gas kg Molar kmol Tempera- (H° DH°o DH°f )i ni × (H° DH°o
mass ni ture K(°C) kJ/kmol + DH°f )i, kJ
H2 27.3 2 13.65 1198 (925) + 35 134 + 479 579
H2O 79.2 18 4.40 1198 (925) 194 882 857 481
CO 149.8 28 5.10 1198 (925) 76 942 392 404
CO2 50.7 44 1.15 1198 (925) 339 706 390 662
Total 300.0 24.30 1160 968
Heat of reaction, D H r° = 1160 968 (1242 490)

= 81 522 kJ (endothermic) Ans.
EXERCISE 5.32
Basis: 0.1 kg coke and N2 flow of 0.025 L × s1. These are same bases as those
of Exercises 3.24 and 4.1.
Reaction: CH0.6 + 1.6 O2 = CO2 + 0.6 H2
101.1 1.6 ´ 0 393.51 0.6 ´ ( 241.82) DH°f
D H °r = 393.51 0.6 ´ 241.82 + 101.1
= 393.51 145.09 + 101.1
= 437.5 kJ/1.6 mol oxygen
(exothermic)
Actual oxygen consumed = 0.128 mol
Heat generated = 437.5 ´ 0.128/1.6
= 35 kJ Ans.
EXERCISE 5.33
Many data are taken from Example 4.20.
Heat capacity Data of RII Exit Gas stream
.
Component ni Heat capacity (C°mpr2 ) equation constants
kmol/h . . . .
ai× ni bi× ni ´ 103 ci× ni ´ 106 di× ni ´ 109
CH3OH 1.415 35.2 72.0 83.0 63.9
HCHO 218.267 10 520.5
CO2 16.481 352.1 1059.5 676.6 161.5
CO 1.857 53.9 5.2 21.6 8.7
H2 3.714 106.3 3.8 0.5 2.9
CH4 1.16 22.3 60.5 13.9 13.1
(CH3)2O 1.858 122.3
O2 159.270 4145.1 1872.2 373.1 89.6
N2 1082.930 32 044.9 5567.3 14 276.2 5380.0
H2O 268.04 8709.2 21.3 3541.0 1218.9
Total 1754.852 56 111.8 2483.2 16 885.5 6609.8
In the gas to gas heat exchanger, air is preheated from 308.15 K to 523.15 K. Air
flow rate is 1395.1 kmol/h against 1363.1 kmol/h in Example 4.10.
From Example 5.37 (Table 5.31),
z
523.15
Heat duty of heat exchanger f6 = (1395.1/1363.1) C°mpa
308.15
Energy Balances 133
= 8935 667 kJ/h

º 2482.13 kW
In the static mixer (I), 1395.1 kmol/h of air at 523.15 K is mixed with 93 kmol/
h methanol at 351.47 K (i.e. at the outlet of evaporator).
From Table 5.31,
z z
T1 T1
(93/125) C°mpme dT = (1395.1/1363.1) C°mpa dT

351. 47 523.15
Solving by Mathcad, T1 = 504.9 K or 231.75 °C

Enthalpy of reactor input stream over 298.15 K,
z z
504.9 504.9
f2 = (93/125) C°mpme dT + (1395.1/1363.1) C°mpa
298.15 298.15
= 9546 895 kJ/h

º 2651.92 kW
Heat of reactions at 298.15 K in RI,
D H°rI = 20320 839 ´ 92.07/123.75
= 15118 704 kJ/h
º 4199.64 kW
Heat Capacity Data for RI Exit Gas stream
.
Component ni, kmol/h Heat capacity (Cpmr1
° ) equation constants
. . . .
CH3OH 0.93 23.1 47.3 54.5 42.0
HCHO 92.07 4437.7
CO2 6.537 139.7 420.2 268.3 64.1
CO 0.737 21.4 2.1 8.6 3.5
H2 1.474 43.2 1.5 0.2 1.1
CH4 0.460 8.9 24.0 5.5 5.2
(CH3)2O 0.737 48.5
O2 236.865 6164.6 2784.4 554.9 133.2
N2 1082.930 32 044.9 5567.3 14 276.2 5380.0
H2O 120.974 3930.7 9.6 1598.2 550.1
Total 1543.714 46 861.7 2282.4 15 119.6 6048.8
Enthalpy of RI exit stream, at 613.15 K over 298.15 K,
z
613.15
f ¢3 = Cmpr1
° dT
298.15
= 15 260 251 kJ/h º 4238.96 kW

Heat transfer in RI = 9546 895 + 15 118 704 15 260 251
= 9405 348 kJ/h
º 2612.60 kW
Enthalpy of additional methanol vapours added to RI exit stream
z
351. 47
140.548
f 3¢¢ = Cmpa
° dT
125
298.15
= 344 999 kJ/h

º 95.83 kW
Total enthalpy of gas mixture, entering RII
= 15 260 251 + 344 999
= 15 605 250 kJ/h
Let T2 be the temperature of stream, entering RII.
By Mathcad, T2 = 582.3 K or 309.15 °C
Enthalpy of RII exit gas stream,
z
613.15
f4 = C°mpr2 dT
298.15
= 18 246 584 kJ/h º 5068.50 kW

140.063
Heat of reaction in RII = ´ 20 320 639
123.75
= 22 999 351 kJ/h
º 6388.71 kW
Heat transfer in RII = 15 260 251 + 22 999 351 18 246 584
= 20 013 018 kJ/h
º 5559.17 kW
RII exit gases leave the gas heat exchanger at 383.15 K (110°C).
Heat transfer in BFW heater and heat exchanger
z
613.15
= C°mpr2 = 13 404 122 kJ/h
383.15
Energy Balances 135
Heat transfer in BFW heater,

f5 = 13 404 122 8935 667
= 4468 455 kJ/h
º 1241.24 kW
Total heat transfer taken place for steam generation
= 9405 348 + 20 013 018 + 4468 455
= 33 886 821 kJ/h
º 9413.01 kW
33 886 821
Steam generated =
2629.3
= 12 888.2 kg/h
Total methanol evaporated = 93 + 140.548
= 233.548 kmol/h
233.548 ´ 4551 263
Heat duty of evaporator f1 =
125
= 8503 506 kJ/h
º 2362.01 kW
8503 506
Steam consumption in evaporator, ms =
2119.7
= 4011.7 kg/h Ans.
EXERCISE 5.34
(a) Basis: 1 kmol CH4
Reaction: CH4 + C2H4 = C3H8 (gaseous)
Gas D H°f Constants of C°mp equation
kJ/kmol a b ´ 103 c ´ 106 d ´ 109
CH4 74 520 19.2494 52.1135 11.973 11.3173
C2H4 + 52 550 4.1261 155.0213 81.5455 16.9755
C3H8 104 680 4.2227 306.264 158.6316 32.1455
D H °r r= 104 680 ( 74 520 + 52 550) = 82 710 kJ/kmol

D a = 4.2227 4.1261 19.2494 = 27.5982
Db ´ 103 = 306.264 (155.0213 + 52.1135) = 99.1292
Dc ´ 106 = 158.6316 + 81.5455 11.973 = 89.0591
Dd ´109 = 32.1455 16.9755 + 11.3173 = 26.4873
DH°o = D H°RT DaT (Db/2)T 2 (Dc/3)T 3 (Dd/4)T 4
For T = 298.15 K, D H r°T = D H °r = 82 710 kJ/kmol
D H °0 = 82 710 + 27.5982 ´ 298.15 (99.1297 ´ 103/2) (298.15)2
+ (89.0591 ´ 106/3)(298.15)3
(26.4873 ´ 109/4)(298.15)4
= 82 710 + 8828 4406 + 787 52
= 77 553 kJ/kmol heat of reaction at 0 K
D Hr°T = 78 154 27.598 T + 49.565 ´ 103 T2 29.686 ´ 106 T 3
+ 6.622 ´ 109 T4 Ans.
(b) CO(g) + H2O(g) = CO2(g) + H2(g)
D H°f 110.53 241.82 393.51 0 all in kJ/mol
D Hr° = 393.51 ( 110.53 241.82)
= 41.16 kJ/mol
Gas Constants of C°mp equation

a b ´ 103 c ´ 103 d ´ 103
CO2 21.3655 64.2841 41.0506 9.7999
H2 28.6105 1.0194 0.1476 0.769
CO 29.0277 2.8165 11.6437 4.7063
H2O 32.4921 0.0796 13.2107 4.5474
D a = 21.3655 + 28.6105 29.0277 32.4921 = 11.5438

Db ´ 103 = 64.2841 + 1.0194 ( 2.8165 + 0.0796) = 68.0404
Dc ´ 103 = 41.0506 0.1476 (11.6437 + 13.2107) = 66.0526
Dd ´ 103 = 9.7999 + 0.769 ( 4.7063 4.5474) = 19.8226
D H 0° = 41 160 + 11.5438 (298.15) + 68.0404 ´ 103 (298.15)2/2
+ 66.0526 ´ 106 (298.15)3/3 19.8226 ´ 109 (298.15)4/4
= 41 160 + 3442 3024 + 583 39
= 40 378 kJ/kmol at 0 K
D H °r = 40 378 11.544 T + 34.02 ´ 103 T 2 22.018 ´ 106 T 3
+ 4.956 ´ 109 T 4 Ans.
(c) Basis = 1 kmol CO consumed or CH3OH produced
CO(g) + 2 H2(g) = CH3OH(g)
Energy Balances 137
Gas DHºf Constants of C mp

º equation
kJ/mol a b ´ 103 c ´ 103 d ´ 103
CH3OH 200.94 24.8692 50.8755 58.6278 45.1266
CO 110.53 29.0277 2.8165 11.6437 4.7063
H2 O 28.6105 1.0194 0.1476 0.769
DHºr = 200.94 ( 110.53) = 90.41 kJ/mol CO consumed
Da = 24.8692 (29.0277 + 2 ´ 28.6105) = 61.3795
Db ´ 103 = 50.8755 ( 2.8165 + 2 ´ 1.0194) = 51.6532
Dc ´ 106 = 58.6278 (11.6437 2 ´ 0.1476) = 47.2793
Dd ´ 109 = 45.1266 ( 4.7063 + 2 ´ 0.769) = 41.9583
DHº0 = 90 410 + 61.3795 ´ 298.15 51.6532 ´ 103 (298.15)2/2
47.2793 ´ 106 (298.15)3/3 + 41.9583 ´ 109 (298.15)4/4
= 90 410 + 18 300 2296 418 + 83
= 74 741 kJ/kmol
DHºrT = 74 741 61.38 T + 25.827 ´ 103 T2 + 15.76 ´ 106 T3
10.49 ´ 109 T 4 Ans.
At T = 593.15 K
DHºrT = 78 741 61.38 ´ 593.15 + 25.827 ´ 103 (593.15)2 +
+ 15.76 ´ 106 (593.15)3 10.49 ´ 109 (593.15)4
= 74 748 36 408 + 9087 + 3289 1298
= 100 071 kJ/kmol CH3OH Ans.
EXERCISE 5.35
Let H¢ be enthalpy in kJ/kg, T be temperature in K and p be pressure in bar a
H¢
H=
1.055 056 ´ 2.204 623
H¢
=
2.326
t = 1.8T 459.67
p
and p¢ = or p = 14.503 77 p¢
14.503 77
Substitute these values in equation.
H
= 34.38 + 0.7209 (1.8T 459.67)
2.326
1075
. ´ 105
+ 7.763 ´106 (1.8T 459.67)2 +
14.503 77 p
Simplifying
17.2403 ´ 103
H = 846.934 + 2.9884 T + 58.5038 ´ 106T2 + Ans.
p
EXERCISE 5.36
Basis: 100 kmol outgoing gas mixture
Gas kmol ni Constants of Cºmp equation
incoming outgoing a b ´ 103 c ´ 106 d ´ 109
CO2 58.9 57.10 21.3655 64.2841 41.0506 9.7999
H2 47.94 41.10 28.6105 1.0194 0.1476 0.769
CH4 1.68 19.2494 52.1135 11.973 11.3173
CO 0.12 29.0277 2.8165 11.6437 4.7063
Total 107.84 100.00
T1 = 298.15 K, T2 = 588.15 K
T2
H1 = ò (ni × c pi ) × dT
T1
= (21.3655 ´ 58.9 + 28.6105 ´ 47.94) (588.15 298.15)

+ (64.2841 ´ 58.9 + 1.0194 ´ 47.94) 103 (588.152 298.152)/2
(41.0506 ´ 58.9 + 0.1476 ´ 47.94) 106 (588.153 298.153)/3
+ (9.7999 ´ 58.9 + 0.769 ´ 47.94) 109 (588.154 98.154)/4
= 762 704 + 492 875 143 032 + 17 157 = 1129 704 kJ
Heat of reactions:
CO2(g) + 4 H2(g) = CH4(g) + 2 H2 (g) (1)
DHºr1 = 2 ( 241.82) + ( 74.52) [( 392.51) + 0]
= 164.65 kJ/mol CO2 reacted (exothermic)
Actual CO2 consumed as per reaction (1) = 1.68 kmol
Heat evolved = 164 650 ´ 1.68 = 276 612 kJ
CO2(g) + H2(g) = CO(g) + H2O(g) (2)
DH ºr2 = 241.82 110.53 + 393.51
= 41.16 kJ/mol CO2 (endothermic)
Actual CO2 consumed as per reaction (2) = 0.12 kmol
Heat absorbed = 41 160 ´ 0.12 = 4939 kJ
Total enthalpy of product gas mixture
= 1129 704 + 276 612 4939 = 1401 377 kJ
Let T3 be the final temperature of product gas mixture.
T3
H1 = ò (ni × c pi ) × dT
298.15
= (57.1 ´ 21.3655 + 41.1 ´ 28.6105 + 1.68 ´ 19.2494

+ 0.12 ´ 29.0277) (T3 298.15) + (64.2841 ´ 57.1
+ 41.1 ´ 1.0194 + 1.68 ´ 52.1135 + 0.12 ´ ( 2.8165)) ´ 103
Energy Balances 139
(T23 298.152)/2 + ( 41.0506 ´ 57.1 0.1476 ´ 41.1

+ 11.973 ´ 1.68 + 11.973 ´ 1.68 + 11.6437 ´ 0.12)
´ 106 (T32 298.152)/3
+ (9.7999 ´ 57.1 + 0.769 ´ 41.1 11.3173 ´ 1.68
4.7063 ´ 0.12) ´ 109 (T3 298.15)/4
H2 = 2431.68 (T3 298.15) + 3799.7 ´ 103 (T32 2982.15)/2
2328.54 ´ 106 (T33 2983.15)/3 + 571.6 ´ 109 (T 43 2984.15)/4
= 2431.68 T3 + 1899.87 ´ 109 T34 776.23 ´ 106 T 39
142.9 ´ 109 T34 724 641 168 716 + 20 542 1127
= 1401 377
Using Mathcad
T3 = 669.61 K or 396.46°C Ans.
EXERCISE 5.37
Basis: 100 kmol dry gas mixture, entering the shift converter.
Refer Exercise 5.32 (b).
T1 = 618.15 K
DH ºrT1 = 41 160 7134 + 12 993 5197 + 723
= 39 775 kJ/kmol CO
T2 = 783.15 K
DH ºrT2 = 41 160 9039 + 20 857 10 570 + 1863
= 38 049 kJ/kmol CO
Average heat of reaction, DHºrT = [ 39 775 + ( 38 049)]/2
= 38 912 kJ/kmol CO
Gas (Hº Hº + DHºf ), kJ/kmol Average Cºmp between
618 K 783 K 618 K and 783 K,
CO 95 804 90 644 31.273
H2 17 723 22 585 29.467
CO2 370 400 362 262 49.321
N2 18 029 23 126 30.891
Ar 39.946 (constant)
H2O 218 133 211 933 37.576
Partial oxidation of NG:
Sni × Cºmpi = ( 0.37 ´ 31.272 + 0.6 ´ 29.467 + 0.2 ´ 49.321
+ 0.01 ´ 39.948) 100
= 3063.7 kJ/(100 kmol dry gas × K)
Partial oxidation of FO:

Sni × Cºmpt = ( 0.46 ´ 31.273 + 0.48 ´ 29.467 + 0.05 ´ 49.321
+ 0.01 ´ 39.948) 100
= 3139.5 kJ/(100 kmol dry gas × K)
Reforming of NG:
Sni × Cºmpt = (0.15 ´ 31.273 + 0.56 ´ 29.467 + 0.07 ´ 49.321
+ 0.217 ´ 30.891 + 0.003 ´ 39.948) 100
= 3116.8 kJ/(100 kmol dry gas × K)
Average Sni × Cºmpt = (3063.7 + 3139.5 + 3146.8)/3
= 3116.7 kJ/(100 kmol dry gas × K)
For steam, accompanying the gas mixture,
ni × Cºmpt = 37.576 ´ 100 ´ x
= 3757.6 x kJ/(100 kmol × K)
Rise in temperature in shift converter,
38912 a 12.485 a
DT = = K
3116.7 + 3757.6 x 1 + 1.206 x
12.5 a
» K Ans.
1 + 1.2 x
EXERCISE 5.38
Basis: Flowrate of offgases from uranium oxide dissolver
= 38.3 Nm3/h
Flow rate = 919.2 Nm3/day º 41.01 kmol/day
NO2 entering the reactor = 41.01 ´ 0.025
= 1.025 kmol/day
Reaction: 8 NH3(g) + 6 NO2(g) = 7 N2(g) + 12 H2O(g)
DHºf : kJ/mol 45.94 33.18 0 241.82
o
DH r = 241.82 ´ 12 (45.94 ´ 8 + 6 ´ 33.18)
= 2733.4 kJ/6 mol NO2
º 455 567 kJ/kmol NO2 (exothermic)
Total heat generated = 455 567 ´ 1.025
= 466 956 kJ/d º 5.405 kW
Theoretical NH3 required = 4 ´ 1.025/3 = 1.367 kmol/d
Actual NH3 fed = 2 Nm3/h º 0.089 kmol/h
º 2.141 kmol/d
Excess NH3 = [(2.141 1.367)/1.367]/100
= 56.6% Ans. (a)
Energy Balances 141
Reactants:
. Constants of Cºmp equation
Component n i, kmol/d . . . .
n i× a i n i× bi ´ 103 n i× ci ´ 106 n i× di ´ 109
N2 11.278 337.73 57.98 148.68 56.03
O2 2.051 53.38 24.11 4.80 1.15
NO2 1.025 24.17 54.93 32.28 6.70
H2O 26.656 866.11 2.12 352.14 121.22
NH3 2.141 54.92 71.68 0.75 6.6
Total 41.099 1336.31 94.86 464.49 178.3
Enthalpy of reactants at 393.15 K (120ºC) over 298.15 K (25ºC):
f1 = 1336.31 (393.15 298.15) + 94.86 ´ 103 (393.152 298.152)/2
+ 464.49 ´ 106 (393.153 298.153)/3 178.3 ´ 109 (393.154 298.154)/4
= 126 949 + 3114 + 5301 712
= 134 652 kJ/d º 1.558 kW
Total enthalpy of product gas mixture
= f1 + DHºr
= 134 652 + 466 956
= 601 608 kJ/d º 6.963 kW
Products:
Component n i, kmol/d . . . .
N2 12.474 369.12 64.13 164.44 61.97
O2 2.051 53.38 24.11 4.80 1.15
H2O 28.706 932.72 2.28 379.23 130.54
NH3 0.774 19.85 25.91 0.27 2.39
Total 44.005 1375.07 11.83 539.14 196.05
Enthalpy of products at T K over 298.15 K,
f2 = 1375.07 (T 298.15) 11.83 ´ 103 (T2 298.152)/2
+ 539.14 ´ 108 (T3 298.153)/3 196.05 ´ 103 (T4 298.154)/4
= 1375.07 5.92 ´ 103 T2 + 179.71 ´ 106 T3 49.01 ´ 109 T4
409 771 + 525 4756 + 387
= 601 608 kJ/d º 6.963 kW
By trial and error or by Mathcad, T = 703.78 K or 430.63ºC Ans. (b)
EXERCISE 5.39
Basis: 38.3 Nm3/h offgases
Flow rate = 41.01 kmol/d (Ref. Exercise 5.38)
NO2 entering the reactor = 41.01 ´ 0.035
= 1.435 kmol/d
Theoretical NH3 required = 1.435 ´ 4/3 = 1.913 kmol/d

Excess NH3 = [(2.141 1.913)/1.913]100 = 11.92%
Total heat generated = 1.435 ´ 455 567 = 653 739 kJ/d º 7.566 kW
Reactants:
. Constants of Cºmp
Components n i kmol/d . . . .
N2 10.868 321.59 55.87 143.27 53.99
O2 2.051 53.38 24.11 4.80 1.15
NO2 1.435 33.84 76.91 45.19 9.38
H2O 26.656 866.11 2.12 352.14 121.22
NH3 2.141 54.92 71.68 0.75 6.6
Total 43.151 1329.84 118.95 446.17 173.58
Enthalpy of reactants at 393.15 K (120ºC) over 298.15 K (25ºC),
f1 = 1329.84 (393.15 298.15) + 118.95 ´ 103 (393.152 298.152)/2
+ 446.17 ´ 106 (393.153 298.153)/3 173.58 ´ 109 (393.154 298.154)/4
= 126 335 + 3904 + 5092 693
= 134 638 kJ/d º 1.558 kW
This enthalpy does not include enthalpy of nitrogen (x kmol/d) at 303.15 K (30ºC).
Total enthalpy of product gas mixture (excluding that of N2 stream),
f¢1 = 134 638 + 653 739
= 788 377 kJ/d º 9.125 kW
NH3 consumed= 1.913 kmol/d
N2 produced = 1.913 ´ 7/8 = 1.674 kmol/d
Total N2 in product stream = 10.868 + 1.674 = 12.542 kmol/d
H2O produced = 1.913 ´ 12/8 = 2.87 kmol/d
Total H2O in product stream = 26.656 + 2.87 = 29.526 kmol/d
Products (excluding extra nitrogen supply):

Components ni kmol/d . . . .
N2 12.544 371.13 64.48 165.34 62.31
O2 2.051 53.38 24.11 4.80 1.15
H2O 29.526 959.36 2.35 390.06 134.27
NH3 0.228 5.85 7.63 0.08 0.7
Total 44.347 1389.72 30.39 550.68 198.43
Enthalpy of product gas stream (excluding extra N2 supply) at 753.15 K over 298 K,
f¢2 = 1389.72 (753.15 298.15)
30.39 ´ 103 (753.152 298.152)/2
Energy Balances 143
+ 550.68 ´ 106 (753.153 298.153)/3

198.43 ´ 109 (753.154 298.154)/4
= 632 323 7266 + 73 515 15 558
= 683 014 kJ/d º 7.905 kW
Enthalpy carried by extra nitrogen in feed stream
f¢1 f¢2 = 788 377 683 014
= 105 363 kJ/d º 1.219 kW
Enthalpy of extra nitrogen at 753.15 K over 303.15 K
= 29.5909 (753.15 303.15) 5.141 ´ 103 (753.152 303.152)/2
+ 13.1829 ´ 106 (753.153 303.153)/3
4.968 ´ 109 (753.154 303.154)/4
= 133 16 1222 + 1754 389
= 13 459 kJ/kmol N2
Flow of nitrogen required to control the temperature
= 105 363/13 459
= 7.828 kmol/d
º 7.31 Nm3/h Ans.
EXERCISE 5.40
Basis: 1 kmol toluene
O2 requirement for benzaldehyde production = 1 kmol
Excess O2 = 100%
Actual O2 supply = 2 kmol
N2 supply = 2 ´ 79/21 = 7.524 kmol
Air supply = 2 + 7.524 = 9.524 kmol
DHor = 36.7 241.82 (50.17) = 328.69 kJ/mol
Side reaction is the standard combustion reaction.
DHoc = 3772.0 kJ/mol (NHV)
Toluene burnt to CO2 and H2O = 0.005 kmol
Total toluene converted = 0.13 kmol
Total oxygen consumed = 0.125 + 0.005 ´ 9
= 0.17 kmol
Toluene reacted to benzaldehyde = 0.13 0.005 = 0.125 kmol
Total heat produced at 298.15 K (25ºC)
= 0.125 ´ 328 690 + 0.005 ´ 377 200
= 42 972 kJ
Inlet gas mixture is at 448.15 K (175ºC):
Constants of Cºmp equation

Components kmol mole % ni×ai ni×bi ´ 103 ni×ci ´ 106 ni×di ´ 109
ni
C7H8 1.0 9.5 35.19 563.18 349.80 82.59
O2 2.0 19.0 52.05 23.51 4.69 1.12
N2 7.524 71.5 222.64 38.68 99.19 37.38
Total 10.524 100.0 239.500 548.01 255.30 44.09
Enthalpy of ingoing gas mixture at 448.15 K over 298.15 K,
H1 = 239.5 (448.15 298.15) + 548.01 ´ 103 (448.152 298.152)/2
255.3 ´ 106 (448.153 298.153)/3 + 44.09 ´ 109 (448.154 298.154)/4
= 35 925 + 30 673 5404 + 357
= 61 551 kJ
Outlet gas mixture at 468.15 K (195ºC):
Components kmol mole % n i× a i ni× bi ´ 103 ni× ci ´ 106 ni× di ´ 109
ni
C7H8 0.87 8.36 30.62 489.97 304.32 71.85
O2 1.83 17.59 47.63 21.51 4.29 1.03
N2 7.524 72.32 222.64 38.68 99.19 37.38
C7H8O 0.125 1.20 16.25
CO2 0.035 0.34 0.75 2.25 1.44 0.34
H2O 0.020 0.19 0.65 0.26 0.09
Total 10.404 100.00 257.30 475.05 210.60 33.69
Enthalpy of outcoming gas mixture at 468.15 K over 298.15 K,
H2 = 257.30 (468.15 298.15) + 475.05 ´ 103 (468.152 298.152)/2
210.6 ´ 106 (468.153 298.153)/3 + 33.69 ´ 109 (468.154 298.154)/4
= 43 741 + 30 943 5342 + 338 = 69 680 kJ
Heat liberated = 61 551 + 42 972 69 680
= 34 843 kJ Ans.
EXERCISE 5.41
Basis: 1 kmol S2(g)
Stoichiometric CH4 requirement = 0.5 kmol
Actual supply of natural gas = 2 kmol
Actual CH4 supply = 2 ´ 0.6 = 1.2 kmol
Excess CH4 = 1.2 0.5 = 0.7 kmol
% Excess = 0.7 ´ 100/05 = 140 Ans. (a)
Conversion = 80%
S2 reacted = 0.8 kmol
Energy Balances 145
CS2 produced = 0.8/2 = 0.4 kmol

CS2 produced 76 ´ 0.4
Ratio = = = 30.4 kg/kmol Ans.(b)
S2 fed 1
Unreacted S2 = 1.0 0.8 = 0.2 kmol
Unreacted CH4 = 1.2 0.4 = 0.8 kmol
H2S produced = 0.8 kmol
N2 entering with natural gas = 0.4 ´ 2.0 = 0.8 kmol
Reactants:
Gas kmol, ni mole % (Hº Hºo + DH fº )i, ni× (Hº H oº + DHfº)i,
kJ/kmol at 720 K kJ
(427ºC)
CH4 1.20 40.0 – 38 305 45 966
S2 1.00 33.3 22 951 22 951
N2 0.80 26.7 20 537 16 430
Total 3.00 100.0 — – 6 585
Products:
Gas kmol, ni mole % (Hº Hºo + DHºf ), ni× (Hº Hºo + DHºf ), kJ
at 977 K (704 ºC)
CH4 0.8 26.67 20 257 16 206
S2 0.2 6.67 + 33 118 + 6 624
CS2 0.4 13.33 + 32 118 + 12 843
H2S 0.8 26.66 45 137 36 110
N2 0.8 26.67 + 29 322 23 458
Total 3.0 100.00 9 391
Heat change in the reactor = 9391 ( 6585)
= 2806 kJ/kmol S2 Ans. (c and d)
Antoine constants for CS2
A = 6.0677, B = + 1169.1 and C = 31.55 at T = 298.15 K
1168.62
Log p = 4.066 83
(298.15 - 31.616)
p = 0.481 bar
or p = 48.1 kPa Ans. (e)
EXERCISE 5.42
Basis: 3 kmol H2S supply, including the bypass
Out of 3 kmol, 1 kmol H2S enters the furnace and 2 kmol bypass the furnace.
3
H2S(g) + O2(g) = SO2(g) + H2O(g) (1)
2
SO2(g) + 2 H2S(g) = 3 S(l) + 2 H2O(g) (2)
Theoretical oxygen requirement = 1.5 kmol

Oxygen supply = 40% excess
N2, entering with air = 79 ´ 2.1/21 = 7.9 kmol
N2, entering with H2S = 10 ´ 3/90 = 0.333 kmol
Composition of gases, leaving the converter:
Gas kmol mole %
O2 2.1 1.5 = 0.6 6.11
N2 0.333 + 7.9 = 8.233 83.73
H2O 1.0 10.16
Total 9.833 100.00
Ans. (a)
Heat balance across furnace boiler:
DHºr = 241.82 296.83 ( 20.63)
= 518.02 kJ/mol H2S
Since the reactants are at 298.15 K (25 ºC), DHRectants = 0
Product stream from furnace boiler:
Component ni kmol mole %
n i× a i ni× bi ´ 103 ni× ci ´ 106 ni× di ´ 109
O2 0.6 5.54 15.615 7.053 1.406 0.337
H2O 1.0 9.23 32.492 0.08 13.211 4.547
SO2 1.0 9.23 24.771 62.948 44.258 11.122
N2 8.233 76.00 243.622 42.326 108.535 40.902
Total 10.833 100.00 316.500 27.755 76.082 34.664
Enthalpy of product stream at 593.15 K over 298.15 K,
DHProducts = 316.5 (593.15 298.15) + 27.775 103 (593.152 298.152)/2
+ 76.082 ´ 106 (593.153 298.153)/3
34.664 ´ 109 (593.154 298.154)/4
= 93 368 + 3648 + 4617 1003
= 100 630 kJ
Heat transfer at Q1 = 100 630 518 020
= 417 390 kJ/kmol H2S Ans.(b)
New basis: 9000 kg/h liquid sulphur production
Production rate = 9000/32 = 281.25 kmol/h
From both the reactions when 3 kmol H2S are consumed. 3 kmol liquid sulphur
are produced. Of these 3 kmol H2S, one kmol enters the furnace boiler.
H2S entering the furnace = 281.25/3 = 93.75 kmol/h
Energy Balances 147
Heat transfer at Q1 = 417 390 ´ 93.75 kmol/h

= 39 130 313 kJ/h (heat liberation)
º 10 869.5 kW Ans. (c)
EXERCISE 5.43
Basis: 100 kmol fresh ethylene feed (96% pure)
Heat capacity constants for combined (mixed) feed:
Constants of Cºmp
Component ni kmol
ni × ai ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109
C2H4 0.5483 2.262 84.998 44.711 9.308
H2O 0.3564 11.58 0.028 4.708 1.621
N2 0.0953 2.82 0.49 1.256 0.473
Total 1.0000 16.662 84.536 38.747 7.214
Ref. Temperature T0 = 298.15 K, T1 = 573.15 K
Enthalpy of feed gas
= 2716.45 [16.662 (573.15 298.15) + 84.536 ´ 103 (573.152 298.152)/2
38.747 ´ 106 (573.153 298.153)/3 + 7.214 ´ 109 (573.154 298.154)/4]
= 2716.45 [4582.05 + 10 127.73 2089.45 + 180.37]
Hº = 2716.45 ´ 12 800.7 = 34 772 462 kJ
Real gas enthalpy,
H = 34 772 462 + 2716.45 ´ 962 = 37 385 687 kJ
DHrº = 234.95 ( 241.82 + 52.50)
= 45.63 kJ/mol enthanol (exothermic)
Total heat produced = 45 630 (1489.41 1414.94)
= 3398 066 kJ
Ideal gas conditions:
Enthalpy of products= 34 772 462 + 3 398 066
= 38 170 528 kJ
Heat capacity constants for reactor exit gas mixture:
Constants of C mp
º equation
Component ni kmol
C2 H 4 0.5356 2.210 83.029 – 43.676 9.092
H2O 0.3382 10.989 0.027 4.468 – 1.538
N2 0.0980 2.9 – 0.504 1.292 – 0.487
C2H5OH 0.0282 0.294 5.908 – 2.326 0.111
Total 1.0000 16.393 88.46 – 40.242 7.178
Enthalpy of product gas mixture

= 2641.98 [16.393 (T 298.15) + 88.46 ´ 103 (T2 298.152)/2
40.242 ´ 106 (T3 298.153)/3 + 7.178 ´ 109 (T 4 298.154]
= 38 170 528
Solving by Mathcad, T = 605.02 K or 331.87°C
Real enthalpy of product stream = 37 385 687 + 3398 066
= 40 783 753 kJ
Ideal gas enthalpy of product stream = 40 783 753 914 ´ 2641.98
= 38 368 983 kJ
Solving by Mathcad, T = 606.42 K or 333.27 °C Ans.
There is hardly any effect of residual enthalpy on reaction exit gas mixture
temperature.
EXERCISE 5.44
Standard heat of reaction at 25 °C (298.15 K),
DH°r = 479.8 92.31 (484.2) 0 (Appendix AIV.2)
= 87.91 kJ/mol reactant
Average temperature = (40 + 100)/2 = 70°C
Mean Heat Capacity at 100°C (373.15 K)
Component State Cpmi, kJ/(kg × K)
Acetic acid Liquid 1.686
Hydrogen chloride Gas 0.7977
MCA Liquid 1.88
Chloride Gas 0.45
Cpmi values are calculated using, equations given in Tables 5.1 and 5.3.
DHr at 100°C (373.15 K)
= 87.99 ´ 1000 + (1.88 + 0.7977 1.686 0.485) (373.15 298.15)
= 87 842 kJ/kmol reacant
º 87.842 kJ/mol reactant Ans.(a)
.
Let nt = Molar flow rate of gas-vapour mixture, leaving the reactor, kmol/h
1000
Basis: 100 kg/h MCA production rate molar production rate = = 10.582
94.5
kmol/h
Molar feed rate of chlorine = 1.2 ´ 10.582
= 12.6984 kmol/h
Chlorine gas, leaving the reactor = 12.6984 10.582
= 2.1164 kmol/h
Energy Balances 149
Molar flow rate of HCl = 10.582 kmol/h

nt = nCl2 + nHCl + nAA + nMCA
and pt = pCl + pHCl + PAA + PMCA
2
= pCl2 + pHCl + pvAA × xAA + pvMCA × xMCA
At 100°C (373.15 K),
1642.540
log pvAA = 4.682 06
373.15 - 39.764
pvAA = 0.569 14 bar
º 426.9 Torr
1733.960
log pvMCA = 4.690 87
373.15 - 92.154
pvMCA = 0.0331 bar
º 24.8 Torr
pt = 1.1 atm = 836 Torr
= pCl + pHCl + 0.5 ´ 426.9 + 0.5 ´ 24.8
2
pCl + pHCl = 610.15
2
pCl2 + pHCl nCl2 + nHCl
=
pt nt
610.5 10.582 + 2.1164

=
836 nt
nt = 17.3888 kmol/h
426.9 ´ 0.5 ´ 17.3888

nAA = = 4.4398 kmol/h
836
24.8 ´ 0.5 ´ 17.3888
nMCA = = 0.2579 kmol/h
836
This gas-vapour mixture, is cooled to 40°C (313 K) with the help of cooling
water in overhead condenser. Trial and error method is adopted to find the
condensation rates.
Trial - I: Assume total condensation of acetic acid and MCA.
x¢AA = Mole fraction of AA in the condensed liquid
4.4398
= = 0.9451
(4.4398 + 0.2579)
x¢MCA = 1 0.9451 = 0.0549
Assume a pressure drop of 50 Torr in the heat exchanger. Gases leave the overhead
condenser at
p¢t = 836 50 = 786 Torr and 40°C
At T = 40 + 273.15 = 313.15 K,
p¢vAA = 0.0472 bar
º 35.4 Torr
p¢vMCA = 0.0007 bar
º 0.52 Torr
786 = p¢HCL + p¢Cl + 0.9451 ´ 35.4 + 0.0549 ´ 0.52
2
p¢CL + p¢HCl = 752.51 Torr
2
752.51 10.582 + 2.1164

= nt¢
786
t = 13.2635 kmol/h
n¢
13.2635 ´ 0.9451 ´ 35.4

AA =
n¢ = 0.5646 kmol/h
786
0.0549 ´ 0.52 ´ 13.2635
MCA =
n¢
786
= 0.482 ´ 103 kmol/h
Trial II: For this trial, composition of the condensed liquid is calculated as follows.
4.4398 - 0.5646
x¢¢AA = (4.4398 - 0.5646) + (0.2579 - 0.482 ´ 10-3 )
= 0.9387
x¢¢MCA = 0.0613
p¢¢Cl + p¢¢HCl = 786 0.9387 ´ 35.4 0.0613 ´ 0.52
2
= 752.74 Torr
(10.582 + 2.1164) ´ 786
t =
n¢¢
752.74
= 13.2595 kmol/h
13.2595 ´ 0.9387 ´ 35.4
AA =
n¢¢ = 0.5606 kmol/h
786
13.2595 ´ 0.0613 ´ 0.52
MCA =
n¢¢ = 0.538 ´ 103 kmol/h
786
4.4398 - 0.5646
x¢¢¢
AA = (4.4398 - 0.5646) + (0.2579 - 0.538 ´ 10-3 )
Energy Balances 151
= 0.9377
MCA = 0.0623
x¢¢¢
Both these values are close enough to x¢¢AA and x¢¢MCA and hence new trial is not
justified.
Acetic acid condensed = (4.4398 0.5646) 60
= 232.51 kg/h
MCA condensed = (0.2579 0.538 ´ 103) 94.5
= 24.32 kg/h
Heat duty of overhead condenser:
fc = sensible heat transfer of gas-vapour mixture + Latent heat transfer for
condensation of AA and MCA vapours + Subcooling of condensed
liquid

fc = m Cl2 × CpCl2 + m HCl × CpHCl + m AA × CpAA + m MCA × CpMAA DTv
+ m AA ¢ × lMCA + m AA
¢ × lAA + m MCA ¢¢ ClMCA DTL
¢¢ × ClAA + m MCA
m Cl2 = 2.1164 ´ 71 = 150.26 kg/h
m HCl = 10.528 ´ 36.5 = 386.24 kg/h
æ 4.4398 + 0.5646 ö
m AA = çè 2 ÷ø 60
= 150.13 kg/h
(0.2579 + 0.538 ´ 10-3 ) 94.5

m MCA =
2
= 12.21 kg/h
AA = 232.75 kg/h
m¢
MCA = 24.32 kg/h
m¢
0 + 232.75
AA =
m¢¢ = 116.38 kg/h
2
0 + 24.32
MCA =
m¢¢ = 12.16 kg/h
2
Specific Heats of Liquids and Gases at 70°C (143.15 K)
Component Cpi, kJ/(kg × °C) CLi, kJ/(kg × °C)
Chlorine 0.4864
Hydrogen chloride 0.7977
Acetic acid 1.2254 1.7
MCA 1.0467 1.9
AT 70°C (143.15 K), following latent heats of vaporization are calculated using
Watson equation.
lAA = 25 668 kJ/kmol = 427.8 kJ/kg
lMCA = 33 633 kJ/kmol = 355.9 kJ/kg
fc = (150.26 ´ 0.4864 + 386.24 ´ 0.7977 + 150.13 ´ 1.2254 + 12.21 ´
1.0467) (100 40) + (232.51 ´ 427.8 + 24.32 ´ 355.9) + 116.38 ´ 1.7
+ 12.16 ´ 1.9) (100 40)
= 34676.3 + 108 123.3 + 13 248.6
= 156 048.2 kJ/h º 43.347 kW Ans.(b)
Energy balance around reactor:
Heat to be removed in jacket = Heat produced in reaction Heat removed in
overhead condenser.
= 87 842 ´ 10.582 156 579
= 772 965 kJ/h º 214.713 kW Ans.(c)
EXERCISE 5.45
The rate of chemical reaction is
dM
R = = M {e ( 0.080 73 T -40.1841) } /183 672
dG
The equation can be rewritten as
DM = Dq × M {e ( 0.080 73 T-40.1841) } /183 672
where DM = M0 M
= initial mass of reactant final mass of reactant
M 0 = 250 kg
T1 = 535 K
Energy balance:
M1Cp (T1 T0) = DHr (M0 M1)
where Cp = average heat capacity of total mass
= 1.675 kJ/(kg × k)
T1 = temperature of mass after Dq s
For Dq = 1 s
DM = 250 {e ( 0.080 73 ´ 535 - 40.1841) } /183 672
= 0.027 52 kg
M1 = M0 D M
= 250 0.027 52
= 249.972 48 kg
Energy Balances 153
Energy balance:
249.972 48 ´ 1.675 (T1 535) = 607 (0.027 52)
T1 535 = 0.04
T1 = 535.04 K
Similar iterations can be performed for 24 seconds which are tabulated below.
Time Mass of reactants, Rate of recion, Reaction temperature,
s kg kg/s K
0 250 0.027 52 535.04
1 249.972 48 0.027 60 535.08
2 249.944 88 0.027 69 535.12
3 249.917 19 0.027 77 535.16
4 249.889 42 0.027 86 535.204
5 249.861 56 0.027 96 535.245
6 249.833 60 0.028 05 535.286
7 249.805 55 0.028 14 535.327
8 249.777 41 0.028 23 535.368
9 249.749 18 0.028 32 535.409
10 249.720 86 0.028 41 535.450
11 249.692 45 0.028 50 535.491
12 249.663 95 0.028 59 535.533
13 249.635 36 0.028 68 535.575
14 249.606 68 0.028 78 535.617
15 249.577 90 0.028 87 535.659
16 249.549 03 0.028 97 535.701
17 249.520 06 0.029 06 535.743
18 249.491 00 0.029 16 535.785
19 249.461 84 0.029 25 535.828
20 249.432 59 0.029 35 535.871
21 249.403 24 0.029 45 535.914
22 249.373 79 0.029 55 535.957
23 249.344 24 0.029 65 536.000
24 249.314 59
At q = 24 s, M = 249.319 59 kg Ans.
EXERCISE 5.46
Heat of crystallisation is just opposite the heat to solution.
Heat of crystallisation = 17.58 kJ/mol (exothermic)
º 17 580/280.7
º 62.63 kJ/kg NiSO4 × 7 H2O
where molar mass of NiSO4 × 7 H2O = 280.7 Ans.
EXERCISE 5.47
Heat of crystallisation = 11.95 kJ/mol (exothermic)
CuSO4(s) + 5 H2O(l) ¾ ¾¾® CuSO4 × 5 H2O(s)
771.36 5 ( 285.83) ? DH°f
D H°r = 11.95 = (DH°f of CuSO4 × 5 H2O) ( 771.36 5 ´ 285.83)
DH°f of CuSO4 × 5 H2O = 11.95 2200.51
= 2212.46 kJ/mol Ans.
EXERCISE 5.48
Basis: 1 mol KCIO3
Molar mass of KClO3 = 122.5
Water, present in KClO3 = 5.56 mol
º 5.56 ´ 18 º 100.08 kg
Mass % KClO3 = 122.5 ´ 100/(122.5 + 100.08)
= 55.04
For preparation of 1000 kg solution,
KClO3 dissolved = 0.55 ´ 1000 = 550 kg
DH = 37 260 kJ/kmol KClO3 (endothermic)
Heat absorbed = 37 260 ´ 550/122.5 = 167 290 kJ Ans.
EXERCISE 5.49
(a) Basis: 200 kg NaClO3 dissolved to produce 40% solution
From Fig. 5.35, integral heat of solution for 40% solution
= + 157 kJ/kg NaClO3 (endothermic)
For dissolution of 200 kg NaClO3,
heat absorbed = 157 ´ 200 = 31 400 kJ Ans.
(b) Basis: 500 kg of 30% NaClO3 solution
NaClO3 dissolved = 500 ´ 0.3 = 150 kg
From Fig. 5.35, integral heat solution for 30% solution,
= 176.3 kJ/kg NaClO3 (endothermic)
For 150 kg NaClO3 dissolution, heat absorbed = 150 ´ 176.3
= 26 445 kJ Ans.
(c) Integral heat of solution of 40% soln. = + 157 kJ/kg NaClO3
Integral heat of solution of 20% soln. = + 190 kJ/kg NaClO3
Energy Balances 155
Heat of dilution = 190 (157)

= 33 kJ/kg NaClO3 (endothermic)
Heat added for dilution = 33 kJ/kg NaClO3 Ans.
EXERCISE 5.50
Molar mass of KOH = 56.1056
Molar mass of H2O = 18.0153
mol of Molar mass mass mole Enthalpy HE, Excess HE¢, Excess
H2O/mol of 1 mol fraction of fraction of enthalpy, enthalpy,
of KOH KOH and KOH in of KOH formation kJ/mol kJ/kmol
number of solution in at 298.15 K, KOH solution
mol H2O wi solution kJ/mol KOH
0 –424.764
3 110.1515 0.5093 0.2500 –469.462 –44.698 –11174.50
3.5 119.1592 0.4708 0.2222 –471.302 –46.538 –10341.78
4 128.1668 0.4378 0.2000 –472.955 –48.191 –9638.20
4.5 137.1745 0.4090 0.1818 –474.503 –49.739 –9043.45
5 146.1821 0.3838 0.1667 –475.712 –50.948 –8491.33
6 164.1974 0.3417 0.1429 –477.093 –52.329 –7475.57
8 200.2280 0.2802 0.1111 –478.775 –54.011 –6001.22
10 236.2586 0.2375 0.0909 –479.725 –54.961 –4996.45
12 272.2892 0.2061 0.0769 –480.306 –55.542 –4272.46
15 326.3351 0.1719 0.0625 –480.825 –56.061 –3503.81
20 416.4116 0.1347 0.0476 –481.189 –56.425 –2686.90
25 506.4881 0.1108 0.0385 –481.302 –56.538 –2174.54
30 596.5646 0.0940 0.0323 –481.369 –56.605 –1825.97
40 776.7176 0.0722 0.0244 –481.461 –56.697 –1382.85
50 956.8706 0.0586 0.0196 –481.520 –56.756 –1112.86
75 1407.2531 0.0399 0.0132 –481.595 –56.831 –747.78
100 1857.6356 0.0302 0.0099 –481.637 –56.873 –563.10
150 2758.4006 0.0203 0.0066 –481.700 –56.936 –377.06
200 3659.1656 0.0153 0.0050 –481.742 –56.978 –283.47
A plot of HE vs mole fraction of KOH is prepared in Excel and equation is fitted.

HE = 386.583x13 + 311.412x12 4.513x1 56.9851
where HE = Excess enthalpy, kJ/mol KOH at 298.15 K
R 2 = 0.9994
Another plot of H E¢ vs x1 x2 is prepared in Excel and equation is fitted.
HE¢ = Excess enthalpy, kJ/kmol solution at 298.15 K
HE¢ = 12 280x12 x22 62 695x1 x2 + 80.196
where HE¢ = Excess enthalpy, kJ/kmol solution at 298.15 K
R 2 = 0.9998
Another plot of HE¢¢vs x1x2 is prepared in Excel and equation is fitted.

HE¢¢ = 2687.7 x12 x22 43.552 x1x2 + 0.6235
where HE¢¢ = Excess enthalpy, kJ/kg solution at 298.15 K
R 2 = 0.9999
x1 = mole fraction of KOH in aqueous solution
Range of x1 = 0 to 0.25, wi = 0 to 0.51
Heat of dilution chart:
Mass fraction of HE¢¢, Excess
KOH, wi enthalpy,
kJ/kg solution
0.5093 101.45
0.4708 86.79
0.4378 75.20
0.4090 65.93
0.3838 58.09
0.3417 45.53
0.2802 29.97
0.2375 21.15
0.2061 15.69
0.1719 10.74
0.1347 6.45
0.1108 4.29
0.0940 3.06
0.0722 1.78
0.0586 1.16
0.0399 0.53
0.0302 0.30
0.0203 0.14
0.0153 0.08
Usong above data, following diagram is prepared.

Heat of dilution chart for KOH-H2O system
0
Heat of dilution, kJ/kg solution
0 0.1 0.2 0.3 0.4 0.5 0.6

–20
–40
–60
–80
–100
–200
mass fraction of KOH
Energy Balances 157
EXERCISE 5.51
(a) Locate two points on Fig. 5.16. One point corresponds to 60% NaOH at
373 K (100°C). Another point corresponds to pure water (i.e. 0% NaOH)
at 308 K (35°C). Draw a line joining the two points. The line intersects
vertical axis of 10% NaOH at 335 K (62°C).
(b) H1 = Enthalpy of 10% NaOH soln. at 335 K (62°C)
= 231.3 kJ/kg solution (from Fig. 5.16)
H2 = Enthalpy of 10% NaOH soln. at 298.15 K (25°C)
= 100 kJ/kg solution (from Fig. 5.16)
Enthalpy to be removed = 231.3 100 = 131.3 kJ/kg solution
Ans. b (i)
Specific heats of 10% NaOH solution at 335 K (62°C) and 298.15 K (25°C) are
3.84 and 3.78 kJ/(kg solution × K) as read from Fig. 5.4.
Average specific heat = (3.84 + 3.78)/2
= 3.81 kJ/(kg soln × K)
Heat removed = 3.81 (335 298)
= 141 kJ/kg solution Ans. b (ii)
EXERCISE 5.52
Basis: 100 kg 32% N solution
Urea dissolved = 50 kg
N from urea = 50 ´ 0.4665
= 23.325 kg
Required N from NH2NO3 = 32 23.325
= 8.675 kg
80.0434 ´ 8.675
NH4NO3 dissolved =
2 ´ 14,0067
= 24.787 kg º 0.3097 kmol º 309.7 mol
H2O in solution = 100 50 24.787
= 25.213 kg
Associated urea = 1.1758 ´ 0.3097
= 0.3641 kmol
º 21.869 kg

o
m = 0.3097 ´ 1000/25.213
= 12.2833 molality of NH4NO3 × 1.1758 NH2CONH2
50
Additional urea dissolved = 0.3641
60.0553
= 0.8326 0.3641
= 0.4685 kmol º 468.5 mol

Water = 25.213 kg = 1.3995 kmol
For additional urea dissolution,
Waber 1.3995
= = 2.99, say 3
Urea 0.4685
DH°f of urea crystals = 333.51 kJ/mol urea
DH°f of NH2CONH2, 3 H2O = 320.98 kJ/mol urea
Heat of solution, H Ei = 320.98 (333.51)
= + 12.346 kJ/mol urea
For NH4NO3× 1.1758 NH2CONH3,
HE2 = 40.3044 2.5962 m o
+ 0.1582 (mo 2
) 3.4782 (m
o 3
)
E 2
H 2 = 40.3044 2.5962 ´ 12.2833 + 0.1582 ´ (12.2833) 3.4782
´ (12.2833)3 ´ 103
= 25.838 kJ/mol NH4NO3× 1.1758 NH2CONH2
Total heat effect,
HE = 12.346 ´ 468.5 + 25.838 ´ 309.7
= 5784.1 + 8002.0
= 13 786.1 kJ at 298.15 K (endothermic) Ans.
EXERCISE 5.53
Basis: 100 kg 20% N solution
NH4NO3 dissolved = 30 kg º 0.3748 kmol
28.0134 ´ 30
N from NH4NO3 =
80.0434
= 10.5 kg
Required N from urea = 20 10.5
= 9.5 kg
9.5
Urea dissolved = = 20.364 kg
0.4665
º 0.3391 kmol
H2O in solution = 100 30 20.364
= 49.636 kg
º 2.755 kmol
Urea/NH4NO3 = 0.3391/0.3748
= 0.9048
Energy Balances 159
Since ratio of 1.1758 is required, NH4NO3 is dissolved additionally.

0.3391
Associated NH4NO3 = = 0.2884 kmol º 288.4 mol
1.1758
0.2884 ´ 1000
m
o
= = 5.81
49.636
Additional NH4NO3 dissolved = 0.3748 0.2884
= 0.0864 kmol º 86.4 mol
Water 2.755
NH 4 NO3 = 0.0864 = 31.887, say 30
DH°f of NH4NO3 crystals = 365.56 kJ/mol NH4NO3
DH°f of NH4NO3 × 30 H2O = 342.105 kJ/mol NH4NO3
Heat of solution,
HE1 = 342.105 (365.56)
= + 23.455 kJ/mol NH4NO3
For dissolution of NH4NO3× 1.1758 NH2CONH2,
HE2 = 40.3044 2.5962 (5.81) + 0.1582 ´ (5.81)2 3.4782
´ 103 (5.81)3
= 29.8784 kJ/mol NH4NO3× 1.1758 NH2CONH2
Total heat effect,
HE = 23.455 ´ 288.4 + 29.878 ´ 86.4
= 6764.4 + 2581.5
= 9345.9 kJ (endothermic) Ans.
EXERCISE 5.54
When mole fraction of ester is 0.95 in solution,
enthalpy of mixing = 326.6 kJ/kg solution
Molar mass of ester (CH3COOC2H5) = 88
Mass of CH3COOC2H5 per kmol mixture, m2 = 88 ´ 0.95
Integral heat to solution of ester = 326.6/(88 ´ 0.95)
= 3.907 kJ/kg ester
In a similar manner, following table is prepared.
Mole Mass of mole Mass of Mass Internal heat
fraction of C2H5OH fraction CH3COOC2H5 fraction of solution
C2H5OH per kmol of per kmol of kJ/kmol kJ/kg
mixture CH3COOC2H5 mixture ester soln. ester
(m1) kg (m2) kg (H) (H/m2)
0.05 2.3 0.95 83.6 0.973 326.6 3.907
(Contd.)
(Contd.)
0.10 4.6 0.90 79.2 0.945 596.1 7.527
0.20 9.2 0.80 70.4 0.884 1032.3 14.663
0.30 13.8 0.70 61.6 0.817 1319.8 21.425
0.40 18.4 0.60 52.8 0.742 1467.0 27.784
0.50 23.0 0.50 44.0 0.657 1486.1 33.775
0.60 27.6 0.40 35.2 0.561 1385.8 39.369
0.70 32.2 0.30 26.4 0.451 1176.3 44.557
0.80 36.8 0.20 17.6 0.324 859.1 48.813
0.90 41.4 0.10 8.8 0.175 531.3 60.375
0.95 43.7 0.05 4.4 0.091 245.8 55.864
Integral heat of mixing (in kJ/kg ester) and mass fraction of ester are plotted
below. Ans.
70.0
60.0
INTERGRAL HEAT OF MIXING kJ/kg ESTER
50.0
40.0
30.0
20.0
10.0
0.0
0.091 0.175 0.324 0.451 0.561 0.657 0.742 0.817 0.884 0.945 0.973
MASS FRACTION OF ESTER
EXERCISE 5.55
Basis: 1 kmol mixture
Enthalpy of 0.18 kmol ethanol at 318.15 K over 273.15 K:
318.15
H1 = 0.18 ò Cl1 dT
273.15
= 0.18 [ 325.137 (318.15 273.15) + 4137.87 ´ 103
(318.152 273.152)/2 14 030.7 ´ 103 (318.153 273.153)/3
+ 17 035.4 ´ 103 (318.154 273.154)/4]
= 0.18 [ 14 631 + 55 051 55 295 + 19 925]
= 909 kJ
Energy Balances 161
Enthalpy of 0.82 kmol n-hexane at 318 K over 273 K:

318.15
H2 = ò Cl2 dT
273.15
= 0.82 [31.421 (318.15 273.15) + 976.058 ´ 103 (318.152
273.152)/2 2353.68 ´ 103 (318.159 273.159)/3
+ 3092.73 ´ 109 (318.154 273.154)/4]
= 0.82 [1414 + 12 986 9276 + 3617]
= 7167.6 kJ
Enthalpy of mixture at 318 K
= 909 + 7167.6 561.4
EXERCISE 5.56
Basis: 100 kg mixed acid
Refer Exercise 3.14.
For producing 100 kg mixed acid having 39% HNO3, 42% H2SO4 and 19%
H2O,
68.3% HNO3 requirement = 57.1 kg
97.9% H2SO4 requirement = 42.9 kg
Component (Ref. Fig. 5.21) (Ref. Fig. 5.20) Enthalpy Enthalpy
(Acid) Enthalpy at specific heat at 303 K at 313 K
273 K (0 °C) kJ/(kg × K) (0 °C) (0 °C)
kJ/kg kJ/kg kJ/kg
68. 3 % HNO3 191.8 2.6 113.8
97.9% H2SO4 10.5 1.42 + 32.1
Mixed acid 226.9 2.05 144.9
Heat of mixing = 144.9 ´ 100 (113.8 ´ 57.1 + 32.1 ´ 42.9)
= 14 490 ( 6498 + 1377)
= 9377 kJ (exothermic) Ans.
EXERCISE 5.57
Let x = amount of 98% H2SO4 to be added, kg and
y = amount of 69% HNO3 to be added, kg
Total acid after mixing = 100 + x + y
H2SO4 balance:
44.4 + 0.98 x = 0.4 (100 + x + y) (1)
HNO3 Balance:
11.3 + 0.69 y = 0.25 (100 + x + y) (2)
Solving the equations, x = 22.84 kg 98% H2SO4
y = 44.11 kg 69% HNO3 Ans. (a)
Amount, (Ref. Fig. 5.21) mi × hi

Acid kg Enthalpy at kJ
mi 273 K (0 °C), hi
kJ/kg
spent acid 100 215.8 21 580
69% HNO3 44.11 191.8 8 460
98% H2SO4 22.84 10.5 600
fortified mixed acid 166.95 284.7 47 531
Heat of mixing = 47 531 ( 21 580 8460 600)
= 16 891 kJ/100 kg or 168.91 kJ/kg spent acid Ans.(b)
EXERCISE 5.58
Basis: 100 L solution containing 4.5% NH3
Use Fig. 5.22.
Locate a point representing liquid ammonia (w = 1.0) at 240 K (33°C).
Locate another point representing water (w = 0) at 298 K (25°C).
Join both the points. Line crosses 4.5% NH3 at 305 K (32°C) having an enthalpy
value of 93.16 kJ/kg solution.
Enthalpy of 4.5% NH3 at 298.15 K(25°C) = 67.17 kJ/kg solution
Change in enthalpy = 93.16 67.17 = 25.99 kJ/kg solution (exothermic)
Total solution = 100 ´ 0.98 = 98 kg
Heat evolved = 25.99 ´ 98 = 2547.0 kJ Ans.(i)
Ammonia dissolved = 98 ´ 0.045 = 4.41 kg
º 0.259 kmol
Use data, contained in Table 5.59.
For use of the Data of Table 5.59, heat of formation of liquid NH3 is required at
240 K ( 33°C). From Fig. 5.22,
Enthalpy of anhydrous NH3 at 298.15 K (25°C) = 464.9 kJ/kg NH3
Enthalpy of anhydrous NH3 at 240 K ( 33°C) = 211.1 kJ/kg NH3
Heat evolved by cooling anhydrous NH3 = 464.9 211.1
= 253.8 kJ/kg
º 4322.5 kJ/kmol NH3
D H°f at 298.15 K (25°C) of vapour NH3 = 46.11 kJ/mol NH3
Use Eq. (5.25). l v = 23 346 kJ/kmol at T = 239.7 K
n = 0.38, Tc = 405.6 K (Ref. Table 5.5)
lv é 405.5 298.15 ù
0.33
LM
107.5 OP 0.33
23.325
= ê
ë 405.5 239.8 û
ú =
N
165.8 Q
l v = 23.35 ´ 0.848 = 19 775 kJ/kmol at 298.15 K
D H°f of liquid NH3 at = 46 110 4322.5 19 775
= 70 207.5 kJ/kmol
Energy Balances 163
D H°f of 4.51% NH3 solution (Ref. Table 5.60) = 80 073 kJ/kmol

Heat change = 80 073 (70 236.5) = 9836.5 kJ/kmol NH3
Heat evolved = 9836.5 ´ 0.259
= 2547.7 kJ Ans. (ii)
EXERCISE 5.59
Basis: 1000 kg 15% solution
NH3 content of the solution = 1000 ´ 0.15 = 150 kg
º 8.8075 kmol
From Table 5.59,
D H°f at 298.15 K (25°C) of 32% NH3 solution = 77.707 kJ/mol NH3
15.9% NH3 solution = 79.319 kJ/mol NH3
4.5% NH3 solution = 80.073 kJ/mol NH3
When 32% NH3 solution is diluted to 15.9% NH3 soln.,
heat evolved = 79.319 ( 77.707) = 1.612 kJ/mol NH3
When 4.5% NH3 soln. is concentrated to 15.9% NH3 soln.,
heat absorbed = 79.319 ( 80.073) = + 0.754 kJ/mol NH3
Now on Fig. 5.22, locate points representing 32% NH3 (mass) at 298.15 K
(25°C) and 4.5% (mass) NH3 at 298.15 K (25°C). Join both the points.
Measure distances from intersection point on 15.9% NH3.
Distances to both the points are measured to be 24.4 and 17.6 linear units,
respectively.
24.4
Requirement of 4.5% soln. = ´ 1000 = 580.6 kg
(24.4 + 17.6)
Ammonia content of 4.5% soln. = 580.6 ´ 0.045 = 26.13 kg
º 1.534 kmol
Heat absorbed = 1.534 ´ 0.754 ´ 1000 = 1156.8 kJ
Requirement of 32% soln. = 1000 580.6
= 419.4 kg
NH3 content of 32% soln. = 419.4 ´ 0.32 = 134.2 kg
º 7.88 kmol
Heat evolved = 7.88 ´ 1.612 ´ 1000
= 12 702.6 kJ
Net heat change = 12 702.6 1156.8
= 11 545.8 kJ (evolved) Ans.
EXERCISE 5.60
Basis: 100 kmol/h gas mixture entering the absorber
Gas mixture enters the absorber at 318.15 K (45°C) and leaves from the top at
303.15 K (30°C).
Total pressure at absorber top = 6.85 kPa g
= 108.175 kPa a
Vapour pressure of water at 303 K (30°C), pw = 4.2415 kPa [Table 6.13]

Moisture content of gas mixture, leaving the absorber
= 4.2415/(108.175 4.2415)
Total water leaving the absorber in the gas mixture
= 0.0408 (1 0.2445) 100
= 3.082 kmol/h º 55.5 kg/h
HCl absorbed = 24.45 kmol/h
º 891.5 kg/h
Aqueous acid produced = 891.5/0.3
= 2971.5 kg/h
Water content of the acid = 2971.5 891.5
= 2080.0 kg/h
Total water fed to absorber = 2080.0 + 55.5
= 2135.5 kg/h
From Table 5.79, standard heats of formation of 30% aqueous HCl and 5%
aqueous HCl solutions are 155.1 and 165.0 kJ/mol HCl (by interpolations),
respectively.
Heat evolved due to absorption at 298.15 K = standard heat of formation of 30%
acid standard heat of formation of HCl gas
= 155.1 ( 92.31)
= 62.79 kJ/mol HCl (exothermic)
Total heat evolved f1 = 62 790 ´ 24.45
= 1535 216 kJ/h
º 426.449 kW
Feed gas temperature = 318.15 K (45°C)
.
Component ni heat capacity equation constants
kmol/h .
ni × ai
.
ni × bi ´ 103
.
ni × ci ´ 106
.
ni × di ´ 109
CH4 53.80 1035.62 2803.71 644.15 608.87
CH3Cl 18.30 247.83 1922.50 867.44 143.86
CH2Cl2 2.65 44.81 372.20 249.17 63.04
CHCl3 0.65 19.67 98.20 77.14 21.55
CCl4 0.15 7.52 22.15 19.79 5.90
HCl 24.45 741.05 186.04 324.23 105.96
Total 100.00 2096.50 5032.72 245.16 480.48
Outgoing gas-mixture from absorber: Temp. = 30 K (30°C)
Energy Balances 165
.
Component ni heat capacity equation constants
kmol/h . . . .
CH4 53.80 1035.62 2803.71 644.15 608.87
CH3Cl 18.30 247.83 1922.50 867.44 143.86
CH2Cl3 2.65 44.81 372.20 249.17 63.04
CHCl3 0.65 19.67 98.20 77.14 21.55
CCl4 0.15 7.52 22.15 19.79 5.90
H2O 3.082 104.93 29.74 101.70 63.02
Total 78.632 1460.38 5189.02 467.76 437.54
Reference temperature, T0 = 298.15 K (25°C)
Enthalpy of feed gas f2 = 2096.50 (318.15 298.15)
+ 5032.72 ´ 103 (318.152 298.152)/2
245.16 ´ 106 (318.153 298.153)/3
480.48 ´ 109 (318.154 298.154)/4
= 41 930 + 31 017 466 281
= 72 200 kJ/h
º 20.056 kW
Enthalpy of absorber off-gas, f3 = 1460.38 (303.15 298.15)
+ 5189.02 ´ 103 (303.152 298.152)/2
467.76 ´ 106 (303.153 298.153)/3
437.54 ´ 109 (303.154 298.154)/4
= 7302 + 7800 211 59
= 14 832 kJ/h
º 4.12 kW
Enthalpy of feed water f4 = 2135.5 ´ 4.1868 (303.15 298.15)
= 44 705 kJ/h
º 12.418 kW
Enthalpy of outgoing acid (30%) H5 = 0 kJ/h at 298.15 K
Total heat of to be removed = f1 + f2 f3 + f4
= 426.449 + 20.055 4.12 + 12.418
= 454.802 kW Ans. (a)
If 5% acid is produced,
Total aqueons acid produced = 891.5/0.05
= 17 830 kg/h
Water content of acid = 17 830 891.5
= 16 938.5 kg/h
Total water fed = 16 938.5 + 55.5 = 16 994 kg/h
Enthalpy of feed water f4 = 16 994 ´ 4.1868 (303.15 298.15)
= 355 752 kJ/h
º 98.82 kW
Heat evolved due to absorption at 298.15 K = 165.0 ( 92.31)
= 72.69 kJ/mol HCl
f¢1 = 72 690 ´ 24.45 = 1777 271 kJ/h
º 493.686 kW
Enthalpy of outgoing acid (5% cocn.) = f¢1 + f2 f3 + f¢4
= 493.686 + 20.055 4.12 + 98.82
= 608.441 kW
Temperature rise for outgoing acid = 608.441 ´ 3600/(17 830 ´ 4.19)
= 29.31 K
Temperature of outgoing acid = 29.31 + 298.15 = 327.46 K (54.3°C)
Ans. (b)
EXERCISE 5.61
HE = H Hid [Eq. (5.74)]
Hid = x1 H1 + x2 H2
Reference temperature, t0/T0 = 0°C/273.15 K
Enthalpy of cyclohexane (1) at 50°C over 0°C,
H1 = 155.78 (323.15 273.15)
= 7789 kJ/kmol
Enthalpy of cyclohexanone (2) at 50°C over 0°C,
H2 = 176.84 (323.15 273.15)
= 8842.0 kJ/kmol
HE can be calculated for x1 = 0.1 and x2 = 0.9 as
HE = 0.1 ´ 0.9 [3836.7 959.3 (0.9 0.1) + 815.2 (0.9 0.1)2 485.6
(0.9 0.1)3]
= 300.81 kJ/kmol mixure (endothermic)
In a similar manner, HE can be calculated for x1 = 0.1 to 1 in steps of 0.1.
x1 HE Hid H
(endothermic)
0 0 8842.0 8842.0
0.1 300.81 8736.8 9037.6
0.2 551.95 8631.5 9183.5
0.3 746.00 8526.2 9272.2
0.4 881.66 8420.9 9302.6
0.5 959.18 8315.6 9274.8
0.6 975.61 8210.2 9185.8
0.7 920.21 8104.9 9025.1
0.8 769.70 7999.6 8769.3
0.9 483.70 7894.3 8378.0
1.0 0 7789.0 7789.0
All enthalpy values are in kJ/kmol.
Energy Balances 167
dH
H1 = H + x2 (1)
dx1
dH
Similarly, H 2 = H x1 (2)
dx1
H = Hid + HE
= 7789 x1 + 8842.0 x2 + x1x2 [3836.7 959.3 (x2 x1) + 815.2 (x2 x1)2
485.6 (x2 x1)3]
Substituting x2 = 1 x1 and simplifying,
H = 3884.8 x15 + 6451.2 x14 4137.8 x13 1635.6 x12 + 2153.9 x1 + 8842.1
dH
= 19424 x14 + 25 804.8 x13 12 413.4 x12 3271.2 x1 + 2153.9
dx1
dH
Substituting x2 = 1 x1, H and in Eq. (1),
dx1
H1 = 15 539.2 x15 38 777.6 x14 + 34 080.4 x13 10 777.8 x12 3271.2 x1
+ 10 996.0 (3)
or
H 2 = 15 539.2x15 19 353.6 x14 + 8275.6 x13 + 1635.6 x12 + 8842.1 (4)
Using Eq. (3) and Eq. (4), following table is prepared
x1 H H1 H2
0 8842.0 8 842.0
0.1 9037.6 10 591.5 8 865.0
0.2 9183.5 10 126.2 8 947.7
0.3 9272.2 9 688.5 9 093.7
0.4 9302.6 9 310.6 9 297.1
0.5 9274.8 8 988.0 9 561.5
0.6 9185.8 8 697.4 9 918.6
0.7 9025.1 8 415.8 10 447.0
0.8 8769.3 8 139.0 11 290.6
0.9 8378.0 7 900.3 12 677.7
1.0 7789.0 7 789.0
Following is the plot of H vs x1, H1 and H 2 are evaluated at x1 = 0.4 and x1 = 0.7.
10 500
H2 at x1 = 0.7
10 000
9500
H2 at x1 = 0.4 H1 at x1 = 0.4
9000
H1 at x1 = 0.7
kJ/kg solution
8500
Enthalpy (H) 8000
7500
0 0.2 0.4 0.6 0.8 1
x1
Enthalpy of cyclohexane (x1)-Cyclohexanone (x2) Solutions at 50°C (325.15 K)
EXERCISE 5.62
t0/T0 = 0°C/273.15 K
Enthalpy of benzene (1) at 298.15 K over 273.15 K,
H1 = 129.8 (298.15 273.15)
= 3245 kJ/kmol
Entalpy of cyclohoxane (2) at 298.15 K over 273.15 K,
H2 = 150.83 (298.15 273.15)
= 3770.75 kJ/kmol
H = 490.664 x1 + 645.318 x1 3309.315 x12 + 2628.911 x1 + 3770.75
4 3
H1 = 1471.992 x14 3253.292 x13 + 5245.269 x12 6618.63 x1 + 6399.661

H 2 = 1471.992 x14 1290.636 x13 + 3309.315 x12 + 3770.75
x1 HE H H1 H2
(endothermic)
0 3770.75 3770.75
0.1 282.97 4001.14 5787.15 3802.70
0.2 502.94 4168.54 5262.08 3895.15
0.3 662.01 4275.03 4810.23 4045.66
0.4 761.11 4321.56 4420.92 4255.32
0.5 800.01 4307.88 4087.00 4528.75
0.6 777.24 4232.54 3804.84 4874.10
0.7 690.24 4092.96 3574.35 5303.05
0.8 535.19 3885.34 3398.97 5830.83
0.9 307.67 3604.74 3285.69 6476.20
1.0 3245.0 3245.0
Energy Balances 169
Following is the plot of H vs x1, H1 and H 2 are evaluated at x1 = 0.4 and x1 =

0.7.
5400
H2 at x1 = 0.7
5000
4600
H2 at x1 = 0.4 H1 at x1 = 0.4
4200
kJ/kg solution
3800
Enthalpy (H)
H1 at x1 = 0.7
3400
3000
0 0.2 0.4 0.6 0.8 1
x1
Enthalpy of Benzene(1)-Cyclohexane(2) Solutions at 25°C (298.15 K)
EXERCISE 5.63
t0/T0 = 0°C/273.15 K
Enthalpy of 1,2-dichloroethane(1) at 40°C (313.15 K) over 0°C (273.15 K)
H1 = 123.9 (313.15 273.15) = 4956 kJ/kmol
Enthalpy of dimethyl carbonate(2) at 40°C (313.15 K) over 0°C (273.15 K)
H2 = 173.33 (313.15 273.15) = 6933.2 kJ/kmol
H = 1040 x14 + 2161.41 x13 598.17 x12 2500.41 x1 + 6933.2
4 3 2
H1 = 3120 x1 8482.82 x1 + 7082.4 x1 1196.34 x1 + 4432.79
H 2 = 3120 x14 4322.82 x13 + 598.17 x12 + 6933.2
x1 HE H H1 H2
(exothermic)
0 0 6933.2 – 6933.2
0.1 –56.25 6679.24 4375.81 6935.17
0.2 –112.95 6424.82 4413.95 6927.54
0.3 –160.87 6179.18 4507.54 6895.59
0.4 –193.30 5949.04 4624.41 6832.12
0.5 –205.99 5738.69 4739.87 6737.39
0.6 –197.21 5549.69 4836.71 6619.16
0.7 –167.71 5381.47 4905.23 6492.69
0.8 –120.76 5230.70 4943.20 6380.70
0.9 –62.11 5091.64 4955.88 6313.41
1.0 0 4956.03 4956.03 –

Following is the plot of H vs x1 × H1 and H 2 are evaluated at x1 = 0.3 and x1 =

0.6.
7000
H2 at x1 = 0.3
H2 at x1 = 0.6 6500
6000
kJ/kg solution
Enthalpy (H)
5500
5000 H1 at x1 = 0.3
H1 at x1 = 0.6
4500
0 0.2 0.4 0.6 0.8 1
x1
Enthalpy of 1,2-Dichlorothane(1) - Dimethyl Carbonate(2) solution at 40°C
(313.15 K)
EXERCISE 5.64
Basis: 100 Nm3/h vent stream
100
Molar flow rate = = 4.4615 kmol/h
22.414
Bromine in the vent stream = 4.4615 ´ 0.0125
= 0.0558 kmol/h
NaOH required = 2 ´ 0.0558 = 0.1116 kmol/h
º 4.464 kg/h
Excess NaOH used is 20%
Actual NaOH used = 4.464 ´ 1.2
= 5.357 kg/h
Excess NaOH = 5.537 4.464 = 0.893 kg/h º 0.0223 kmol/h
5.357
Aqueous solution rate = = 107.14 kg/h
0.05
Water in solution = 107.14 5.357
= 101.783 kg/h
º 5.650 kmol/h
Water produced = 0.0558 kmol/h
2 NaOH(sol) + Br2(g) = NaOBr(sol) + NaBr(sol) + H2O(l)
DH°f 470.11 30.91 334.3 361.665 285.83
DH°r = 334.3 361.665 285.83 + 30.91]
DH°r = 72.485 kJ/mol Br2
Energy Balances 171
Heat generated = 72.485 ´ 1000 ´ 0.0558

= 4044.66 kJ/h
º 1.1235 kW Ans.(a)
Component kmol/h mole % kg/h mass %
NaOBr 0.0558 0.96 6.634 5.72
NaBr 0.0558 0.96 5.741 4.95
NaOH 0.0223 0.38 0.893 0.77
H2O 5.7058 97.70 102.792 88.56
Total 5.8397 100.00 116.060 100.00
Solid concentration of solution = 100 88.56

= 11.44% by mass Ans.(b)
EXERCISE 5.65
Basis: Flow rate of moist flue gas = 265 000 Nm3/h
Refer solution of Exercise 4.46.
Molar flow rate of ingoing gas mixture
= 7584.43 kmol/h at 106.6 kPa and 175°C (448.15 K)
Moisture, entering with gas mixture
= 422.22 kmol/h
Dry flue gas flow rate = 7584.43 422.22 = 7162.21 kmol/h
Molar flow rates of incoming and outgoing flue gas (dry) remain constant as
SO2 reacted equals CO2 generation.
Moisture in outgoing gas mixture = 937.53 kmol/h
Water evaporated in absorber = 937.53 422.22 = 515.31 kmol/h
º 9275.6 kg/h
Composition of solution purged from system
Component kg/h mass % kmol/h mole %
Na2SO3 544.67 5.13 4.3213 0.79
Na2CO3 305.48 2.87 2.8822 0.52
H2O 9 776.73 92.00 542.6904 98.69
Total 10 626.88 100.00 549.8939 100.00
Molar mass of solution being purged

10 626.88
= = 19.325 kg/kmol
549.8939
Fresh aqueous 30 % NaOH is made-up and its flow rate is 2545.7 kg/h. It enters
at 32°C (305.15 K). 1 kg solution contains 0.3 kg NaOH or 0.002 83 kmol NaOH
and 0.7 kg H2O or 0.038 86 kmol H2O. In this solution,
H2O 0.038 86
= = 13.73 kmol/kmol
NaOH 0.002 83
In the circulating solution,
H2O 98.69
Na 2SO3 = 0.79 = 124.92 say 125
H2O 98.69
Na 2 CO3 = = 189.79 say 190
0.52
In all three cases, water to chemical ratio is quite high and hence standard heat of
formation of solution having 1 molality concentration (repressented by 'ai' in
Annexure V.1) values can be taken for calculations.
Reaction:
Na2CO3(sol) + SO2(g) = Na2SO3(sol) + CO2(g)
DH°f 1157.38 296.83 1115.87 393.51
DH°r = 1115.87 393.51 [1157.38 296.83]
= 55.17 kJ/mol SO2 reacted
SO2 reacted = 276.66 kg/h
º 4.3185 kmol/h
Heat generated, f1 = 55.17 ´ 1000 ´ 4.3185
= 238 252 kJ/h
º 66.181 kW
Enthalpy of water at 32°C (305.15 K), same as that of make-up solution
= 134.0 kJ/kg
Enthalpy of water vapour at 50°C (323.15 K)
= 2592.2 kJ/kg
Heat picked up by water = 2592.2 134.0
= 2458.2 kJ/kg
Heat absorbed by water, f2 = 9275.6 ´ 2458.2
= 22 801 280 kJ/h
º 6333.689 kW
Mean heat capacity of flue gas,
C°mp = 30.7 kJ/(kmol dry gas × K)
Heat given up by flue gas
f3 = 7162.21 ´ 30.7 (448.15 323.15)
= 27 484 981 kJ/h
º 7634.717 kW
Energy Balances 173
Enthalpy of make-up solution = 0 kJ/h

Heats of formation of make-up solution and that of diluted solution are nearly
same and hence heat of dilution is neglibigle.
Final solution can be assumed to leave at 50°C (323.15 K).
Enthalpy of purge solution at 50°C (323.15 K) over 32°C (305.15 K),
f4 = 10 626.88 ´ 4 (323.15 305.15)
= 765 135 kJ/h
º 212.538 kW
Net heat exchange in the heat exchanger,
f = f1 + f3 f2 f4
= 66.181 + 7634.717 6333.689 212.538
= 1154.671 kW (exothermic)
Heat, amounting to 1154.671 kW is required to be removed in the heat exchanges.
Rise in cooling water temperature is 8°C (8 K).
1154.671 ´ 3600
Required cooling water flow =
4 ´8
= 129 900 kg/h
º 129.9 m3/h Ans.
EXERCISE 5.66
Refer solution of Exercise 5.44. Final vent gases have following composition
Component kmol/h mole % kg/h mass %
Cl2 2.1164 15.96 150.065 26.34
HCl 10.5820 79.79 385.829 67.71
Acetic acid (AA) 0.5646 4.25 33.905 5.95
Total 13.2630 100.00 569.799 100.00
Reactions:
2 NaOH(sol) + Cl2(g) = NaOCl(sol) + H2O(l) + NaCl(sol) (1)
NaOH(sol) + HCl(g) = NaCl(sol) + H2O(l) (2)
NaOH(sol) + CH3COOH(g) = CH2COONa(sol) + H2O(l) (3)
Aqueous solution of 10% NaOH is used for scrubbing. Consider standard enthalpies
of formation of NaOH, NaOCl, NaCl and CH3COONa in 'ai' state for calculation
of heats of reaction.
From Appendix V.1 values are taken.
DH°r1 = (347.3) + (407.27) + (285.83) 2[470.11]
= 100.18 kJ/mol Cl2
DH°r2 = 407.27 285.83 [470.11 92.31]

= 130.68 kJ/mol HCl
DH°r3 = 726.13 285.83 [470.11 432.6]
= 109.25 kJ/mol AA
In the absorber, absorption of three components is assumed 100%.
Total heat effect,
f = 100.18 ´ 1000 ´ 2.1164 130.68 ´ 1000 ´ 10.582 109.25 ´ 1000
´ 0.5646
= 1656 559 kJ/h (exothermic)
º 460.155 kW
Total NaOH consumed for all three reactions
= 2 ´ 2.1164 + 10.582 + 0.5646
= 15.3794 kmol/h
º 615.176 kg/h
For completion of reactions, 10% excess is used.
NaOH used = 615.176 ´ 1.1
= 676.69 kg/h
NaOH leftover in final solution = 676.69 615.176
= 61.5 kg/h
676.69
Solution introduced at top =
0.1
= 6766.9 kg/h
Water in the solution = 6766.9 676.69
= 6090.2 kg/h
NaOCl produced = 2.1164 kmol/h
º 157.55 kg/h
Water produced by reactions (2) and (3)
= 10.582 + 0.5646 + 2.1164
= 13.263 kmol/h
º 238.937 kg/h
NaCl produced = 10.582 + 2.1164 kmol/h = 12.6984 kmol/h
º 724.13 kg/h
CH3COONa produced = 0.5646 kmol/h
= 46.32 kg/h
Energy Balances 175

NaOCl 157.55 2.16
NaCl 742.13 10.20
CH3COONa 46.32 0.64
H2O 6329.14 87.00
Total 7275.14 100.00
Solids in final solution = 100 87.0

= 13.0 %
Heat capacity of solution = 3.5 kJ/(kg × K)
Rise in temperature of solution
1656 559
=
7275.14 ´ 3.5
= 65.06 K or °C
Aqueous 10% solution is introduced at 32°C (305.15 K).
Temperature of outgoing solution = 32.5 + 65.06
= 97.56°C say 97.6°C or 370.75 K Ans.
EXERCISE 5.67
Basis: 100 kg 19.1% H2SO4
SO3 in the acid = 15.6 kg º 0.195 kmol (ref. Table 5.64)
H2O in the acid = 100 15.6 = 84.4 kg
º 4.689 kmol
Strong acid: oleum having 29 mass % free SO3
From Table 5.64, it can be inferred that 100 kg oleum will contain 87 kg SO3 and
13 kg water.
Resultant acid has 53.8% H2SO4 strength. Thus again from Table 5.64, this
resultant 100 kg acid will contain 44 kg SO3 and 56 kg H2O.
Let x = Amount of oleum, required to be added, kg
SO3 balance:
15.6 + 0.87 x = (100 + x) 0.44
x = 66.05 kg
SO3 from oleum = 66.05 ´ 0.87 = 57.46 kg º 0.718 kmol
SO3 in resultant acid = 15.6 + 57.46
= 73.06 kg
º 0.913 kmol
H2O from oleum = 66.05 57.46 = 8.59 kg
º 0.477 kmol
H2O in resultant acid = 166.05 73.06 = 92.99 kg
º 5.166 kmol
Energy balance:
Enthalpy of original weak solution + Enthalpy of oleum + Heat of dissolution
= Enthalpy final solution
0.195 ( 157.005) 1000 + 4.689 ( 0.084) 1000 + 0.718 ( 10.886) 1000 +
0.477 ( 81.643) 1000 + DHm = 0.913 ( 125.981) 1000
+ 5.166 ( 3.559) 1000
Solving the equation, DHm = 55 636 kJ/100 kg weak acid
= 556.36 kJ/kg week acid Ans.
EXERCISE 5.68
From Fig. 5.5,
heat capacity of 53.8% acid at 291 K (18°C) = 2.404 kJ/(kg × K)
heat capacity of 53.8% acid at 373 K (100°C) = 2.550 kJ/(kg × K)
Average heat capacity of 53.8% acid = 2.477 kJ/(kg × K)
Rise in temperature = 55 636/(166.05 ´ 2.477)
= 135.3 K
From Fig. 5.18, boiling point of 53.8% acid is 405 K (132°C). Therefore aqueons
acid will boil.
EXERCISE 5.69
Basis: 100 kg oleum containing 41.2% free SO3
SO3 conent = 89.2 kg (Ref. Table 5.64)
º 1.115 kmol
Water content of oleum = 100 89.2 = 10.8 kg º 0.6 kmol
Heat balance:
(1.115 kmol SO3 is 0.6 kmol H2O) + ¥ kmol H2O + DHm
= (1.115 kmol SO3 in ¥ kmol H2O)
DHm + 1.115 ( 10 886) + 0.6 ( 81 643) = 1.115 ( 181 079)
or DHm = 140 779 kJ/100 kg oleum diluted Ans.
EXERCISE 5.70
Let M be the kmol of the binary mixture in the flask after time q having the mole
fraction x of the components A. The fraction dM kmol boil off during the time
interval dq. Consequently let the composition of the binary drp by dx.
Q q = lv (M0 M)
or Q dq = lv dM (1)
Component A, lost from the liquid mixture during time dq
= M x (M d M) (x dx) (2)
Energy Balances 177
Component A, gained by the vapour mixture, produced during time interval

dq = dM × y
é ax ù
= dM ê ú (3)
ë1 + (a - 1) x û
Equating Eq. (2) and Eq. (3),
é ax ù
M x (M dM) (x dx) = dM ê ú (4)
ë1 + (a - 1) x û
Neglecting second order term dM × dx,
é ax ù
x dM + M dx= dM ê ú (5)
ë1 + (a - 1) x û
Dividing Eq. (5) by dM and substituting value of dM from Eq. (1),
é M lv ù é d x ù é ax ù
x ê ú ê ú = ê ú (6)
ë Q û ë dq û ë1 + (a - 1) x û
Eq. (1) can be rewritten as M = M0 (Q q/lv) (7)
Substituting this value of M in Eq. (6),
æ Q ×q ö l d x ax
x - ç M0 - ÷ × = (8)
è l v ø Q dq 1 + (a - 1) x
M 0 lv é Qq ù d x ax
ê1 - ú = x
Q ë M l
0 v û dq 1 + (a - 1) x
(a - 1)(1 - x) x
= 1 + (a - 1) x (9)
Let K = Q/(M0lv) a constant

1 dx (a - 1)(1 - x) x
[1 Kq] = (10)
K dq 1 + (a - 1) x
[1 + (a - 1) x] d x dq
= (11)
(a - 1)(1 - x) x K (1 - Kq )
[(1 - x) + x + (a - 1) x]d x dq
= (12)
(a - 1)(1 - x) x K (1 - Kq)
dx dx dx dq
+ + = (13)
K (a - 1) x K (a - 1)(1 - x) K (1 - x) (1 - Kq )
1 édx a dx ù dq
ê + ú = (14)
K (a - 1) ë x (1 - x) û (1 - Kq )
Integrating Eq. (14),

1 é x dx x dx ù q dq
K (a - 1) ê ò x + a ò (1 - x ) ú = ò (1 - K q ) (15)
ë x0 x û 0
1 é x (1 - x) ù ln(1 - Kq )
êln a ln ú = (16)
K (a - 1) ë x0 (1 - x0 ) û K
1 x (1 - x0 )a
ln = ln (1 K q) (17)
(a - 1) x0 (1 - x)a
x (1 - x0 )a
or (1 Kq)(a 1) = for Kq < 1 Q.E.A.
x0 (1 - x)a
EXERCISE 5.71
Basis: 5 kg n-heptane/n-octane mixture, containing 50 mole % each
Mass of 1 kmol mixture = 0.5 ´ 100 + 0.5 ´ 114
= 107 kg
5
5 kg mixture = = 0.0467 kmol
107
Q 0.5 ´ 3600
Constant K = = = 1.1506 h1
M 0 lv 0.0467 ´ 33 500
x0 = 0.5 mole fraction of n-heptane
(a) for x = 0.3
x (1 - x0 )a 0.3(1 - 0.5) 2.16
= = 0.290 08
x0 (1 - x)a 0.5(1 - 0.3) 2.16
Therefore (1 Kq)(a 1) = 0.290 08 [Ref. Eq. (17) of Exc. 5.70]
(1 Kq) = 0.290 08(1/1.16) = 0.3441
Kq = 1 0.3441 = 0.6559
q = 0.6559/1.1506 = 0.57 h
º 34.2 min Ans.(a-i)
Qq = lv (M0 M) [Ref. Eq. (1)]
0.5 ´ 3600 ´ 0.57 = 33 500 (0.0467 M)
or M = 0.016 07 kmol
1 kmol final mixture will contain (0.3 ´ 100 + 0.7 ´ 114)
= 109.8 kg material.
0.016 07 kmol mixture = 0.016 07 ´ 109.8 = 1.764 kg Ans.(a-ii)
Energy Balances 179
(b) : q = 15 min = 0.25 h

(1 Kq) = 1 1.1506 ´ 0.25 = 0.712 35
(1 Kq)(a 1) = (0.712 35)1.16 = 0.674 72
x(1 - 0.5)2.16 x (0.5)2.16
2.16 = ´
0.5(1 - x) (1 - x) 2.16 0.5
x
= 0.447 57 ´
(1 - x) 2.16
= 0.672 72
or x = 1.5077 (1 x)2.16
By trial and error, x = 0.4366 or 43.66 mole % n-heptane Ans. (b-i)
Overall material balance
0.5 ´ 3600 ´ 0.25 = 33 500 (0.0467 M)
or M = 0.0333 kmol
Molar mass of final mixture = 0.4366 ´ 100 + 114 ´ 0.5635
= 107.89
Left over quantity in the flask = 107.89 ´ 0.0333
= 3.59 kg Ans. (b-ii)
EXERCISE 5.72
Basis: Ammonia feed to burner = 3266 Nm3/h
= 145.71 kmol/h
This basis is choosen to be same as that assumed in Exercise 4.48.
Total feed = Ammonia + Air (dry)
= 145.71 + 1311.41 = 1457.12 kmol/h
Ammonia content of the feed = 145.71 ´ 100/1457.12
= 10% (check !)
Yield of NO = Combustion efficiency as derived in Exercise 4.48
= 95%
Since both the conditions of the example are satisfied, the calculations of Exercise
4.48 can be utilised for the balance calculations.
Heat of reactions:
There are two reactions taking place in burner.
Reaction (1):
4 NH3 + 5 O2 = 4 NO + 6 H2O
4 ( 46.11) 5 (0) 4 (90.25) 6 ( 241.82) DH¢f , kJ/mol
DH°r1 = 6(241.82) + 4(+90.25) [4(46.11)]
= 905.48 kJ/4 mol NH3
º 226.37 kJ/mol NH3
Ammonia reacted as per reaction (1) = 138.45 kmol/h

Heat generated as per reaction (1) f1 = 226.37 ´ 1000 ´ 138.45
= 31 340 927 kJ/h at 298.15 K
º 8705.813 kW
Reaction (2):
4 NH3 + 3 O2 = 2 N2 + 6 H2O
4 ( 46.11) 3 (0) 2 (0) 6( 241.82) DH°f, kJ/mol
DH°r2 = 6 ( 241.82) 4 ( 46.11)
= 1266.48 kJ/4 mol NH3
Ammonia reacted as per reaction (2) = 145.71 138.45
= 7.26 kmol/h
Heat generated as per reaction (2) f2 = 316.62 ´ 1000 ´ 7.26
= 2 298 661 kJ/h
= 638.517 kW
Moisture, entering with air = 1311.41 ´ 0.016 ´ 29/18
= 33.805 kmol/h
.
Component ni Heat capacity equation constants
. . . .
kmol/h ai × n i bi× n i ´ 103 ci× n i ´ 106 di× n i ´ 109
NH3 145.71 3 737.5 4 878.5 51.3 449.3
O2 275.40 5 658.1 22 058.1 17 195.1 4 674.1
N2 1 036.01 30 656.5 5326.1 13 657.6 5 146.9
H2O 33.805 1 098.4 2.7 446.6 153.7
Total 1 490.925 41 150.5 21 613.2 3 039.6 9 218.0
C°mp = 37 413.0 + 16 734.7 ´ 103 T 3090.9 ´ 106 T2 + 9667.3 ´ 109 T 3

air
C°mp = 3737.5 + 4878.5 ´ 103 T + 51.3 ´ 106 T2 449.3 ´ 109 T 3
am
Air is preheated to 260°C (533.15 K) and introduced to the reactor.
Enthalpy of air at 533.15 K over 298.15 K,
553.15
f3 = ò C°mp dT
298.15 air
= 11 416 807.1 kJ/h

= 3171.335 kW
Energy Balances 181
Product stream from reactor

.
. . . .
kmol/h n i × ai n i × bi ´ 103 n i × ci ´ 106 n i × di ´ 109
NO 138.450 4 082.4 284.2 1 569.7 667.3
O2 96.895 1 990.7 7 760.8 6 049.8 1 644.5
N2 1039.645 30 764.0 5 344.8 13 705.5 5 165.0
H2O 252.375 8 200.2 20.1 3 334.1 1 147.7
Total 1 527.365 45 037.3 2 151.9 12 559.5 5 335.5
Product stream temperature is to be limited to 910°C (1183.15 K).

Enthalpy of reactor exit gas stream at 1183.15 K over 298.15 K.
1183.15
f4 = ò 45 037.3 + 2151.9 ´ 103 T + 12 559.5 ´ 106 T2 5335.5
298.15
´ 109 T3) dT
= 45 488 086.1 kJ/h
º 12 635.579 kW
Let enthalpy of superheated ammonia be f5 at T K.
f3 + f5 + f1 + f2 = f4
f5 = 45 488 086.1 11 416 807.1 31 340 927 2298 661
= 431 691 kJ/h
T
= ò Comp dT
298.15 am
Solving by mathcad,
T = 378.45 K or t = 105.3°C Ans.
6
Stoichiometry and
Unit Operations
EXERCISE 6.1
Basis: Feed rate = 4000 kg/h
Ethanol content = 4000 ´ 0.3 = 1200 kg/h
Water content = 4000 1200 = 2800 kg/h
1200 2800
Molar feed rate, F = +
46 18
= 26.087 + 155.556
= 181.643 kmol/h
Ethanol with NBP = 78.25 °C (351.4 K) is a more volatile component.
26.087
Ethanol content in feed, zF =
181.643
= 0.1436 at bubble point
Mole fraction of ethanol in distillate,
(92 / 46)
xD = (92 / 46) + (8 /18)
= 0.8182
Bottom product is nearly pure water.
xB = 0
Ethanol balance:
F × z F = D × xD + xB × W
181.643 ´ 0.1436 = 0.8182 D + 0 ´ W
D = 31.88 kmol/h
W= F D
= 181.643 31.88
= 149.763 kmol/h
Stoichiometry and Unit Operations 183
Using data, contained in Table 6.21 enthalpy-concentration diagram for ethanol-

water binary is prepared as under.
100 373
P = 1.01 325 bar a
Temperature, °C 95 368
Temperature, K
90 363
85 358
80 353
75 348
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mole Fraction of Ethanol
t-x-y Diagram For Ethanol & Water
49100
P = 1.01 325 bar a
49000
48900
Enthalpy of Vapour, kJ/mol Mixture

48800
48700
48600
10200 48500
9800 48400
Enthalpy of Liquid, kJ/kmol Mixture
9400 48300
9000 48200
8600 48100
8200 48000
7800
7400
7000
6600
0.0 01 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mole Fraction of Ethanol
Enthalpy-Concentration Diagram For Ethanol & Water
Reflux ratio = 2 kmol/kmol

Overhead vapour flow = (2 + 1)D
= 3 ´ 31.88
= 95.64 kmol/h
From the enthalpy-concentration diagram, following values are read.
For feed, ZF = 0.1436 HL = 6915 kJ/kmol mixture
For distillate, xD = 0.8182, HV = 48 900 kJ/kmol mixture

H L = 9000 kJ/kmol mixture
For bottom, xB = 0, HL = 7550 kJ/kmol water
Heat duty of overhead condenser,
fC = 95.64 (48 900 9000)
= 3816 036 kJ/h º 1060.01 kW
Enthalpy of feed, fF = 181.643 ´ 69 15
= 1256 061 kJ/h
º 348.906 kW
Ethalpy of bottom product,
fB = 149.763 ´ 7550
= 1130 711 kJ/h
º 314.086 kW
Enthalpy of distillate product,
fD = 31.88 ´ 9000
= 286 920 k/h
º 79.7 kW
Heat duty of reboiler, fRB = fC + fB + fD fF
= 286 920 + 1130 711 + 3816 036 1256 061
= 3977 606 kJ/h
º 1104.891 kW Ans.
EXERCISE 6.2
Basis: 10 000 kg/h feed
Let D and B be the amount of distillate and bottom products, respectively.
D + B = 10 000 (1)
Balance of DEA:
0.5 ´ 10 000 = 0.99 D + 0.05 B
19.8 D + B = 100 000 (2)
Solving the equations, B = 5212.8 kg/h
D = 4787.2 kg/h Ans. (a)
Enthalpy balance:
Enthalpy of distillate product, f1 = 4787.2 ´ 372.2
= 1781 795 kJ/h
º 494.94 kW
Reflux ratio = 0.8 kmol/kmol product
Total vapours, condensed in the overhead condenser
= 4787.2 (1 + 0.8) = 8617 kg/h
Heat (latent heat only) duty of the condenser,

f2 = 8617 (1572.6 372.2)
= 10 343 847 kJ/h
º 2873.29 kW Ans. (b)
Enthalpy of feed, f3 = 10 000 ´ 418.7 = 4187 000 kJ/h
= 1163.06 kW
Enthalpy of bottoms, f4 = 5212.8 ´ 558.1
= 2909 263.7 kJ/h º 809.13 kW
Heat load of reboiler, f5 = Enthalpy of distillate + Enthalpy of bottoms + Heat
removed in condenser Enthalpy of feed
= 494.94 + 808.13 + 2873.29 1163.06
= 3013.3 kW Ans. (c)
EXERCISE 6.3
Basis: Fresh feed rate of 10 000 kg/h of 50:50 mixture of toluene and
methylcyclohexane (MCH) by mass.
Let T1 and T2 be the extractive distillation column and solvent recovery column,
respectively.
Toluene feed to T1 = 5000 kg/h
It is desired to recover 95% toluene as an overhead product of 90% purity from
T2.
Material balance over T2:
Toluene in overhead product = 5000 ´ 0.95 = 4750 kg/h
Overhead product rate = 4750/0.99
= 4798 kg/h
MCH in bottom product = 4798 4750 = 48 kg/h
Bottom product of T2 tower is the recycled solvent.
Recycled solvent = 3.3 ´ 10 000 = 33 000 kg/h
Presence of toluene in the bottom product = 0.9%
Phenol in the recycled solvent = 33 000 ´ 0.991
= 32 703 kg/h
Toluene in the recycled solvent = 33 000 32 703
= 297 kg/h
Composition of F2:

Toluene 4750 + 297 = 5 047 13.35
MCH 48 0.13
Phenol 32 703 86.52
Total 37 798 100.00
Material balance over T1:

Toluene unrecovered = 5000 4750 = 250 kg/h
This unrecovered toluene finds its ways into the overhead product from T1.
MCH in the overhead product = 5000 48 = 4952 kg/h
Since phenol content of overhead product is 0.2%,
Overhead product rate = (250 + 4952)/0.998
= 5212.42 kg/h
Phenol in the overhead product = 5212.42 (250 + 4952)
= 10.42 kg/h
Make-up phenol rate will be same as loss of phenol in the overhead product.
Ans.
EXERCISE 6.4
Basis: Fresh feed, F = 100 kg
Let recycle stream be V3 kg.
Total feed to C 1 = F + V3
= 100 + V3 kg
Both streams are azeotropes and contain 96% (by mass) ethanol. Overhead vapour
from C1 is a ternary azeotrope.
Component Molar mass mole % kg mass %
C2H5OH 46 22.8 1048.8 18.48
C6H6 78 53.0 4204.2 74.12
H2O 18 23.3 419.4 7.40
Total 100.0 5672.4 100.00
Bottom product W1 from C 1 is pure ethanol. Hence all water appear in the
ternary azeotrope.
Ethanol entering C 1 = 0.04 (100 + V3) kg
0.04(100 + V3 )
Overhead vapour = = 54.054 + 0.540 54 V3
0.074
Material balance across C 2:
Entire benzene of D1 comes out in V2.
Benzene balance:
0.751 V2 = 0.11 D1
D1 = 6.827 V2
Ethanol balance:
Ethanol in W2 = 0.53 D1 0.125 V2
= 0.53 (6.827 V2) 0.125 V2

= 3.4933 V2 kg
Water balance:
Water in W2 = 0.35 D1 0.124 V2
= 0.35 (6.827 V2) 0.124 V2
= 2.2655 V2 kg
Quantity of W2 = 3.4933 V2 + 2.2655 V2
= 5.7588 V2 kg
Material balance across C 3:
Water, entering in fresh feed (F), must be purged out as W3 stream.
W2 = V3 + 4
5.7588 V2 V3 = 4 (1)
Water in V3 = 2.2655 V2 4
But V3 contains 4% water.
0.04 V3 = 2.2655 V2 4
or 56.6375 V2 V3 = 100 (2)
V 2 = 1.887 kg and V3 = 6.8669 kg
Component V3 W3 W2
kg mass % kg mass % kg mass %
C2H5OH 6.5922 96.00 0 0 6.5922 60.66
H2O 0.2747 4.00 4.000 100.00 4.2747 39.34
Total 6.8669 100.00 4.0000 100.00 10.8669 100.00
Component V2 D1 V1
kg mass % kg mass % kg mass %
C2H5OH 0.2359 12.50 6.8281 53.54 10.6751 18.48
C6H6 1.4171 75.10 1.4171 11.11 42.8160 74.12
H2O 0.2340 12.40 4.5087 35.35 4.2747 7.40
Total 1.8870 100.00 12.7539 100.00 57.7658 100.00
Reflux R = V1 + V2 D1
= 57.7658 + 1.887 12.7539
= 46.8989 kg/100 kg fresh feed
Composition of Reflux
Component kg mass %
C2H5OH 4.0829 8.71
C6H6 42.8160 91.29
H2O 0 0
Total 46.8989 100.00
EXERCISE 6.5
(a) From Fig. 6.26,
Stream, leaving reaction section= R + P kmol
Light component balance:
R xR = (R+ P) xE P xP
( R + P) xE - Pxp
or xR =
R
Since the above equation does not involve the term Fp, it is evident that
the recycle composition is independent of Fp, i.e. feed to the distillation
column. Ans. (i)
Light component balance across the distillation column:
D × xD + P × xP = FP xE
and D = FP P
FP × xE - P × xP
xD =
FP - P
From the above relationship, it can be inferred that as FP decreases, xD
increases for a given xE and xP. Maximum value of xD can be unity.
For xD = 1,
Fpm P = Fpm × xE P × xP
or F pm = P (1 xP)/(1 xE) Ans. (ii)
(b) Fig. 6.27,
Light component balance across the distillation column:
FP = B + P
xE × FP = B × xB + P × xP
FP xE - P × xP
xE =
Fp - P
From the above relationship, it can be seen that as FP decreases, xB
decreases for a given xE and xP. Minimum value of xB can be zero.
For xB = 0,
Fpm xE = P × xP
F pm = P × xP /xE Ans.
EXERCISE 6.6
Molar mass of ACN = 41.0519
Molar mass of H2O = 18.0153
Feed contains 50% ACN by mass. 1 kg feed solution contains 0.5 kg or 0.0122
kmol ACN and 0.5 kg or 0.0278 kmol H2O.
0.0122
Mole fraction of ACN in feed =
(0.0122 + 0.0278)
= 0.305
Mole fraction of H2O in feed = 1 0.305
= 0.695
Basis: 100 kmol fresh feed
Mixed feed to CI = 100 + R kmol
Recycle stream contains 0.6 mole fraction ACN.
ACN in mixed feed = 100 ´ 0.305 + 0.6 R
= 30.5 + 0.6 R kmol
Bottom product from CI is pure water. Bottom product from CII is 99.0 mole %
ACN. ACN of fresh feed must be purged out as the bottom product of CII.
30.5
Quantity of bottom product from CII = = 30.81 kmol
0.99
Water in bottom product = 30.81 30.5
= 0.31 kmol
ACN, contained in mixed feed is distilled as an azeotrope, containing 69.0 mole
% ACN.
30.5 + 0.6 R
Quantity of D1 =
0.69
= 44.203 + 0.8696 R
Water in D1 = 44.203 + 0.8696 R 30.5 0.6 R
= 13.703 + 0.2696 R kmol
D1 is fed to CII.
Water in D2 = 13.703 + 0.2696 R 0.31
= 13.393 + 0.2696 R kmol
D2 is the azeotrope containing 40% water.
(13.393 + 0.2696 R )
Quantity of R =
0.4
= 33.4825 + 0.674 R
R = 102.7 kmol/100 kmol fresh feed Ans.
EXERCISE 6.7
Basis: 100 m3/h of feed
Specific volume of feed gas mixture at 100 kPa and 318.15 K
= 26.455 m3/kmol (Ref. Table 7.8)
Feed gas rate = 100/26.455 = 3.78 kmol/h
HCl in the feed gas = 3.78 ´ 0.35 = 1.323 kmol/h
Nitrogen in the feed = 3.78 1.323 = 2.457 kmol/h
HCl absorbed = 1.323 ´ 0.96 = 1.27 kmol/h
HCl unabsorbed = 1.323 1.27 = 0.053 kmol/h
0.053 ´ 100
HCl content of outgoing dry gas mixture =
(2.457 + 0.053)
= 2.11% Ans. (b)
Vapour pressure of H2O at 308 K (35 °C) = 5.6216 kPa (Table 6.13)
5.6216 kmol
Water content of gas mixture = = 0.0596
100 - 5.6216 kmol dry gas
Total outgoing gas mixture = (2.457 + 0.053)(1 + 0.0596)
= 2.66 kmol/h
Specific volume of outgoing gas mixture at 98 kPa and 308.15 K
= 26.144 m3/kmol (Ref. Table 7.8)
Volumetric flow rate = 2.66 ´ 26.144 = 69.543 m3/h
Ans. (a)
D H°f of 3.9% HCl solution = 165.36 kJ/mol HCl
(Ref. Table 5.79)
D H°f of gaseous HCl at 298.15 K = 92.31 kJ/mol HCl
Heat of solution at 298.15 K = 165.36 ( 92.31)
= 73.05 kJ/mol HCl
Heat generated, f2 = 73.05 ´ 1000 ´ 1.27
= 92 774 kJ/h at 298.15 K
º 25.770 kW
Heat balance:
C°mp equation constants
Component Inlet kmol 3
N2 2.457 72.705 12.631 32.39 12.206
HCl 1.323 40.099 10.067 17.544 5.733
Total 3.780 112.804 22.698 49.934 17.939
HCl absorbed = 1.27 kmol/h = 46.355 kg/h

46.355
Final solution flow = = 1188.59 kg/h
0.039
Assume water input at 25°C (298.15 K).
Component Outlet kmol C mp

º equation constants
ni
ni × ai ni × bi ´ 103 ni× ci ´ 106 ni × di ´ 109
N2 2.457 72.705 12.631 32.39 12.206
H2O 0.15 4.874 0.012 1.982 0.682
HCl 0.053 1.606 0.403 0.703 0.230
Total 2.660 79.185 13.022 35.075 13.118
Enthalpy of incoming gas mixture, f1 = 112.804 (318.15 298.15)
22.698 ´ 103 (318.152 298.152)/2 + 49.934 ´ 106 (318.153 2983)/3
17.939 ´ 109 (318.154 298.154)/4
= 2256.1 139.8 + 94.8 10.5 = 2200.6 kJ/h º 0.611 kW
Enthalpy of outgoing gas mixture, f3 = 79.185 (303.15 298.15)
13.022 ´ 103 (303.152 298.152)/2 + 35.075 (303.153 298.153)/3
13.118 ´ 109 (303.154 298.154)/4
= 396 19.6 + 15.9 1.8 = 390.5 kJ/h º 0.108 kW
Heat content of final solution, f4
= 2200.6 + 92 774 390.5
= 94584.1 kJ/h º 26.273 kW
94 584.1
Rise in temperature of final solution =
1188.59 ´ 4.19
= 19 K over 298.15 K
Final temperature = 298.15 + 19
= 317.15 K or 44°C Ans. (c)
EXERCISE 6.8
Basis: 1425 m3/h of gas at 303 K and 101.325 kPa
Specific volume V = 24.876 m3/kmol (Table 7.8)
Flow rate of gas = 1425/24.876
= 57.28 kmol/h
SO2 content of ingoing gas = 57.28 ´ 0.148 = 8.48 kmol/h
Inerts in the feed gas = 57.28 8.48
= 48.8 kmol/h
SO2 content of outgoing gas mixture = 1%

Flow rate of outgoing gas mixture = 48.8/0.99
= 49.29 kmol/h
SO2 in outgoing gas mixture = 49.29 48.8 = 0.49 kmol/h
SO2 absorbed = 8.50 0.49 = 8.01 kg mol/h
º 512.64 kg/h
Water flow rate = 16.5 L/s = 59 400 kg/h
Flow rate of final solution = 59 400 + 512.64 = 59 912.64 kg/h
SO2 content of final solution = 512.64 ´ 100/59 912.64
= 0.86% Ans.
EXERCISE 6.9
Basis: 100 kg fresh feed
Refer Fig. E6.3
Point F on the ternary diagram represents 76% C9, 18% AcOH and 6% Ac2O by
mass. This point lies above the top binodal curve. Since distillation boundary
passes between the two binodal curves, one fractionating column will be sufficient
to separate total C9 from the feed mixture and the top product from column1
will be a ternary azeotrope. Point N represents pure C9. Join NS which will
intersect base line (0% C9) at S. Point R2 represents an azeotrope of C9 and
AcOH (63.4% by mass).
Quantity of mixture (represented by) S FN
=
Quantity of N FS
Since FN + FS = 100 kg (i.e. fresh feed)
Quantity of S = [FN/(FN + FS)]
= 4.9 units ´ 100/20.4 units = 24 kg
Quantity of N = 100 24 = 76 kg of C9
Simple mass balance will also give the same result.
Feed A lies on line SR2 and also on the binodal curve.
Quantity of mixture (represented by) S AR2 5.6 units

= =
Quantity of mixture (represented by) A SR2 7 units
Quantity of mixture (represented by) A = 7 ´ 24/5.6 = 30 kg
Composition of A is read from the ternary diagram as AcOH: 0.728,
Ac2O: 0.2 and C9: 0.072 (mass fractions).
Quantity of R2 = Quantity of A Quantity of S
= 30 24
= 6 kg
Ternary Diagram for HOAc Ac20 C9:Naphtha
Naphtha (C9)
Naptha
0.9
F
0.7 B
IN M
OD
AL
DIST CU
2O
ILLA RV R1 M
E
Ac
TION as
BOU s%
s%
0.5 NDA C9
RY
as
M
1.0
D

0.3 R2
E
6.0
LIN
0.
E
3
LIN
TIF
TIF
0.3 0.5
1.0
0.5
0.7 0.1
6.0 BINODAL CURVE A

6.0
Ac20 S HOAc
Mass % HOAc ¾ ¾¾®
Fig. E6.3 Solutionof Exercise 6.8
AD is a tieline, drawn in proportion to other sideby tielines, which intersects top

binodal curve at R1
Quantity of mixture (represented by) D AD1 9.7 units

= =
Quantity of mixture (represented by) A R1 D 2.7 units
Quantity of D = 9.7 ´ 30/2.7 = 107.8 kg
Quantity of R1 = 107.8 30 = 77.8 kg
Compositions of R1 and D are calculated from the diagram as follows.
Stream Composition, mass fraction
AcOH Ac2O C9
R1 0.372 0.072 0.559
D 0.47 0.108 0.422
Join ND. Point M lies on ND.
Quantity of N DM 76 units
= =
Quantity of D NM 107.8 units
DM DM 76 76
= = =
ND DM + TN 76 + 107.8 1838
.
ND = 12.4 units
DM = 12.4 ´ 76/183.8 = 5.13 units
Composition of M is read from the diagram as:
AcOH: 27.6%, Ac2O: 6.3% and C9: 66.1% (mass %)
All the resuls are summarised for N = 1000 kg/h in Table 6.24 in the text.
Ans.
EXERCISE 6.10
Basis: 6500 m3/h of feed gas in terms of H2
Actual flow of feed gas = 6500/0.78
= 8333.3 m3/h
This flow is rated at 101.3 kPa and 300.15 K (27 ºC). However, the actual
conditions are 1.6 MPa g and 473.15 K(200 ºC).
Assuring ideal gas law,
actual flow = (101.3 ´ 8333.3 ´ 473.15)/(300.15 ´ 1701.3)
= 782.3 m3/h Ans. (a)
Rest calculations will be based on 101.3 kPa and 300.15 K (27 ºC).
CO2 in inlet gas mixture = 8333.3 ´ 0.165 = 1375 m3/h
(H2 + inerts) = 8333.3 1375 = 6958.3 m3/h
Outgoint gas mixture = 6958.3/0.995

= 6993.3 m3/h
CO2 in outgoing gas mixture = 6993.3 6958.3 = 35 m3/h
CO2 absorbed = 1375 35 = 1340 m3/h
Specific vol. at 101.3 kPa and 298.15 K (25 ºC), V = 24.465 m3/kmol
CO2 absorbed = 1340/24.465 = 54.77 kmol/h Ans. (b)
Initial concn. of CO2 in lean TEA solution = 2420 mL/L
Flow of lean TEA aqueous solution = 900 L/min
CO2 in inlet solution = 2.42 ´ 900/1000 = 2.18 m3/min
CO2 in rich solution = 2.18 + (1340/60) = 24.51 m3/min
CO2 concn. in outgoing solution = 24.51 ´ 1000/0.9
= 27 237 mL/L Ans. (c)
EXERCISE 6.11
Basis: 3000 m3/h of gas mixture at 101.3 kPa and 300.15 K (27 ºC)
Actual flow rate at 4 bar g and 523.15 K (250 ºC)
= 101.325 ´ 3000 ´ 523.15/(300.15 ´ 501.325)
= 1056.8 m3/h Ans. (a)
Rest other calculations are based on 101.325 kPa and 298.15 K (25 ºC).
CO2 in inlet gas = 3000 ´ 0.18 = 540 m3/h
CO2 free gas mixture = 3000 540 = 2460 m3/h
Flow of outgoing gas mixture = 2460/0.998
= 2464.9 m3/h
CO2 in outgoing gas mixture = 2464.9 2460
= 4.9 m3/h
CO2 absorbed = 540 4.9 = 535.1 m3/h
º 535.1/24.465 º 21.87 kmol/h Ans. (b)
Change in CO2 content of DAPOL solution
= 5800 2200 = 3600 mL/L
Flow rate of aqueous DAPOL solution
. ´ 106
5351
=
60 ´ 3600
= 2477.3 L/min
º 41.3 L/s Ans. (c)
EXERCISE 6.12
Basis: 0.625 L/s (37.5 L/min = 2250 L/h) MEA solution flow rate
Gas inlet flow = 1000 m3/h of dry gas mixture
Gas enters the absorber at 101.3 kPa a and 333.15 K (60 ºC).
Vapour pressure of water at 333.15 K, pw = 19.92 kPa (Ref. Table 6.13)
Moisture content of incoming gas mixture
19.92
= = 0.2447 kmol/kmol dry gas
101.325 - 19.92
Flow of dry incoming gas mixture = 38.3 kmol/h
Moisture, entering the absorber = 38.3 ´ 0.2447 = 9.372 kmol/h
Vapour pressure of water at 318.15 K (45 ºC) = 9.582 kPa (Ref. Table 6.13)
Moisture content of outgoing gas mixture = 9.582/(90 9.582)
Flow of dry outgoing gas mixture = 34.75 kmol/h
Water vapours, leaving the absorber = 34.75 ´ 0.119
= 4.135 kmol/h
Water vapours condensed = 9.372 4.135
= 5.237 kmol/h
º 94.27 kg/h
Inlet gas mixture:
Component ni Cºmp equation constants
kmol
ni × ai ni × bi ´ 103 ni × ci ´ 106 ni × bi ´ 109
N2 8.50 251.52 43.70 112.05 42.23
H2 25.51 729.85 26.00 3.77 19.62
CO 0.19 5.52 0.54 2.21 0.89
CO2 3.98 85.03 255.85 163.38 39.00
CH4 0.12 2.31 4.25 1.44 1.36
H2O 9.37 304.45 0.75 123.78 42.61
Total 47.67 1378.68 244.61 72.33 28.47
Enthalpy of inlet gas at 333.15 K over 298.15 K,
f1 = 1378.68 (333.15 298.15) + 244.61 ´ 103 (333.152 298.152)/2
+ 72.33 ´ 106 (333.153 298.153)/3
28.47 ´ 109 (333.154 298.154)/4
= 48 254 + 2702 + 252 31
= 51 177 kJ/h º 14.216 kW
Outlet gas mixture:
Component kmol Cmp
ni
ni × ai ni × bi ´ 103 ni × ci ´ 106 ni × bi ´ 109
N2 8.50 251.52 43.70 112.05 42.23

(contd.)
(contd.)
H2 25.51 729.85 26.00 3.77 19.62
CO 0.19 5.52 0.54 2.21 0.89
CO2 1.61 34.40 103.50 66.09 15.78
CH4 0.12 2.31 6.25 1.44 1.36
H2O 4.14 139.07 0.34 56.54 19.46
Total 40.07 1162.67 91.85 102.38 28.54
Enthalpy of outlet gas at 318.15 K over 298.15 K,
f2 = 1162.67 (318.15 298.15) + 91.85 ´ 103 (318.152 298.152)/2
+ 102.38 ´ 106 (318.153 298.153)/3
28.47 ´ 109 (318.154 298.154)/4
= 23 253 + 566 + 197 17
= 23 996 kJ/h
º 6.667 kW
Assume that water is condensed at an average temperature of
(333 + 318)/2 = 325.5 K
lv of water at 325.5 K = 2376 kJ/kg (Table AIV.1)
Heat removed due to condensation
f3 = 94.27 ´ 2376 = 223 986 kJ/h
º 62.218 kW
Enthalpy of feed solution = 2250 ´ 4.19 (318.15 298.15)
= 188 550 kJ/h
º 52.375 kW
Flow of outgoing solution = 2250 + 2.35 ´ 44 + 94.27
= 2447.67 kg/h
Heat of absorption = 2.35 ´ 44.0098 ´ 1675
= 173 234 kJ/h
= 48.12 kW (exothermic)
Enthalpy of feed gas + Enthalpy of feed solution + Heat of absorption + Heat of
condensation = Enthalpy of outgoing gas + Enthalpy of outgoing solution
Let T = temperature of outgoing solution, K
3600 (14.216 + 52.375 + 48.12 + 62.218)
= 6.667 ´ 3600 + 2447.67 ´ 4.19 (T 298.15)
10 255.7 (T 298.15) = 3600 ´ 170.262
T 298.15 = 59.77
T = 357.9 K or 84.75°C Ans.
EXERCISE 6.13
Basis: 25 000 m3/h feed gas
Molar
Mole feed rate = 25 000/22.414
= 1115.4 kmol/h
Gas Molar mass kmol/h kg/h
H2 2 921.3 1 842.6
HCl 36.5 12.3 449.0
N2 28 129.4 3 623.2
CCl4 154 52.4 8 069.6
Total 1115.4 13 984.4
13 984.4
Average molar mass of gas mixture =
1115.4
= 12.54
HCl absorbed = 12.3 ´ 0.999 = 12.29 kmol/h
Reaction: HCl (g) + NaOH(ai) = NaCl(ai) + H2O(l)
DHºf 92.31 470.11 407.27 285.83
DHºR = 407.27 285.83 ( 92.31 470.11)
= 130.68 kJ/mol HCl
NaOH required = 12.29 kmol/h
º 491.6 kg/h
Pressure of gas at oulet = 3.38 bar g
= 4.393 25 bar a
Gas mixture will leave saturated at 311.15 K (38ºC) at the top.
Total pressure = 338 kPa a
Vapour pressure of H2O at 311.15 K (38ºC), pw = 6.624 kPa (Table 6.13)
Water content of outgoing gas mixture = 6.624/(439.325 6.624)
Molar flow rate of outgoing dry gas mixture = 1115.4 12.29
= 1103.11 kmol/h
Water vapours, accompanying gas mixture = 1103.11 ´ 0.0153
= 16.878 kmol/h
º 303.8 kg/h
Composition of solution, leaving the absorber:
NaCl 12.29 ´ 58.5 = 719.0 17.65
NaOH 3930 ´ 0.15 491.6 = 97.9 2.40
H2O 12.29 ´ 18 + 3930 ´ 0.85 303.8 = 3257.9 79.95
Total 4074.8 100.00
Ans. (a)
Total heat generated = 12.29 ´ 1000 ´ 130.68

= 1606 057 kJ/h
= 446.127 kW Ans. (b)
Use Fig. 5.16 for heat of solution calculations:
Locate a point, representing 50% NaOH solution at 303 K (38ºC).
Locate another point, representing 0% NaOH at 327 K (30ºC). Join the points.
The line interesects 15% axis at 327 K (54ºC).
Enthalpy of 15% solution at 327 K (54ºC) = 187.5 kJ/kg soln.
Enthalpy of 15% solution at 311 K (38ºC) = 118.8 kcal/kg soln.
Total heat to be removed = (187.5 118.8)3930
= 269 991 kJ/h º 75 kW Ans. (c)
EXERCISE 6.14
Basis: Ammonia flow to burner = 3266 Nm3/h
Following data are tabulated from Excercise 4.48
Components Dry inlet gas Dry outlet gas
kmol/h mole % kmol/h mole %
NO 138.45 10.86 2.80 0.20
O2 96.9 7.60 71.47 5.10
N2 1039.65 81.54 1326.73 94.70
Total 1275.00 100.00 1401.00 100.00
Pressure of inlet gas mixture = 0.15 MPa g
= 251.325 kPa a
Vapour pressure of H2O at 40ºC = 7.375 kPa (Ref. Table 6.13)
Water content = 7.375/(251.325 7.375) = 0.0302 kmol/kmol dry gas
Water, accompanying ingoing gas = 0.0302 ´ 1275
= 38.505 kmol/h
º 693.1 kg/h
Pressure of outgoing gas mixture = 10 kPa g
= 111.325 kPa a
Vapour pressure of H2O at 323 K (50ºC) = 12.335 kPa
12.335
Water content = = 0.1246 kmol/kmol dry gas
(111325
. - 12.335)
Water, accompanying outgoing gas = 0.1246 ´ 1401
= 174.56 kmol/h
º 3142.2 kg/h
Total water in reactor outlet gas mixture = 252.375 kmol/h (Ref.Exercise 5.72)
Water, entering with secondary air = 363.39 ´ 29 ´ 0.016
= 168.6 kg/h
º 9.37 kmol/h
Water condensed in the cooler = 252.375 + 9.37 38.505
= 223.24 kmol/h
= 4018.32 kg/h at 313 K (40ºC)
Acid produced = 135.65 kmol/h
(same as NO consumed)
= 8546 kg/h at 100% concn. of HNO3
Final strength of acid = 58% (by mass)
Final acid quantity = 8546/0.58 = 14 734.5 kg/h
Water content of acid = 14 734.5 8546 = 6188.5 kg/h
Water consumed in the reaction = 135.65/2
= 67.825 kmol/h
º 1220.9 kg/h
Water balance across absorber:
Let a be the amount of demineralised water added,
4018.32 + a + 693.1 = 6188.5 + 3142.2 + 1220.9
a = 5840.18 kg/h
Reaction:
2 NO(g) + 1.5 O(g) + H2O(l) = 2 HNO3(l)
DHºf 2 ´ 90.309 0 286.021 2 ( 174.213)
DHºr = 2 (174.213) (2 ´ 90.309 286.021)
= 243.023 kJ/2 mol NO
Heat of reaction at 298.15 K (25 ºC) = 243.023 ´ 135.65 ´ 1000/2
= 16 483 035 kJ/h (exothermic)
º 4578.62 kW
Air introduced at 311 K (40 ºC) = 363.39 kmol/h (secondary)
O2 feed = 76.31 kmol/h
N2 feed = 287.08 kmol/h
Base temperature T0 = 298.15 K (25 ºC)
Enthalpy of water vapour at 313 K (40 ºC) over 298.15 K (25 ºC)
= 2574.4 104.77 = 2469.63 kJ/kg
Enthalpy of water vapour at 323 K (50ºC) over 298.15 K (25ºC)
= 2592.2 104.77 = 2487.43 kJ/kg
For finding the cooling load, enthalpy balance across the absorber has to be
made.
Absorber inlet gas enthalpy:
Temperature of inlet gas = 313.15 K (40ºC)
C mp
Component ni
kmol ni × ai ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109
NO 138.45 4 082.4 – 284.2 1 569.7 – 667.3
O2 96.90 2 521.9 1139.1 – 227.0 – 54.5
N2 1039.65 30 764.2 – 5344.8 13 705.6 – 5165.0
Total 1275.00 37 368.5 – 4489.9 15 048.3 – 5886.8
Enthalpy of inlet gas, f1 = 37 368.5 (313.15 289.15)

4489.9 ´ 103 (313.152 298.152)/2
+ 15 048.3 ´ 106 (313.153 298.153)/3
5886.8 ´ 109 (313.154 298.154)/4
= 558 511 kJ/h
º 155.142 kW
Enthalpy of moist air at 313.15 K over 298.15 K
313.15
o
= ò Cmpair dT (use data from Exercise 5.72
298.15
= 186 690 kJ/h (by Mathcad)

º 51.858 kW
Absorber outlet gas enthalpy:
Temperature of outlet gas = 323.15 K (50°C)
C mp
Component ni ni × ai ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109

kmol
NO 2.80 82.6 – 5.7 31.7 – 13.5
O2 71.47 1 860.1 840.1 – 167.4 – 40.2
N2 1326.73 39 259.1 – 6820.7 17 490.2 – 6591.2
Total 1400.00 41 201.8 – 5986.3 17 354.5 – 6644.9
Enthalpy of outgoing gas mixture, f2 = 41 201.8 (323.15 298.15)
5586.3 ´ 103 (323.152 298.152)/2
+ 17 354.5 ´ 106 (323.153 298.153)/3

6644.9 ´ 109 (323.154 298.154)/4
= 1020 458 kJ/h º 283.461 kW
Heat of dilution : Ref. Table 6.25
DHºf of 58% HNO3 liquid = 197.00 kJ/mol HNO3 (by interpolation)
DHºf of 100% HNO3 liquid = 174.1 kJ/mol HNO3
Enthalpy change = 197.00 ( 174.1)
= 22.9 kJ/mol HNO3
Heat evolved at 298.15 K, f3 = 135.65 ´ 22 900
= 3106 385 kJ/h º 862.885 kW
Heat capacity of 58% HNO3 = 2.64 kJ/(kg × K) from Fig. 5.20
Enthalpy of liquid 58% HNO3 over 298.15 K (25 °C) = 2.64 (313.15 298.15)
= 39.6 kJ/kg at 313.15 K
Total enthalpy of 58% acid = 14 734.4 ´ 39.6
= 583 482 kJ/h º 162.078 kW
Heat evolved at 313.15 K (40°C) (net) = 862.885 162.078
= 700.807 kW
Enthalpy of condensate from cooler
= 4018.32 ´ 4.1868 (313.15 298.15)
= 252 359 kJ/h º 70.1 kW
Enthalpy of condensate + Enthalpy of make-up water
+ Enthalpy of inlet gas + Enthalpy of secondary air
+ Heat of reaction at 298.15 K (25°C)
+ Heat of dilution at 313 K (40°C)
= Enthalpy of tail gas + Heat removed by cooling water (DH)
+ Enthalpy of 58% acid
70.1 + 0 + 155.142 + 51.858 + (2469.63 ´ 693.1)/3600 + 4578.62
+ 700.807 = 283.461 + (2487.43 ´ 3142.2)/3600 + DH
D H = 3809.029 kW
æ 3809.029 ´ 3600 ö
Cooling water circulation rate = ç
è 8 ´ 4.1868 ´ 1000 ÷ø
= 409.6 m3/h Ans.
EXERCISE 6.15
Basis: 1000 kg/h oil-free solid meal
Solvent feed = 0.665 ´ 1000 = 665 kg/h
Oil content of solvent = 665 ´ 0.015 = 9.975 kg/h
Benzene in the solvent = 665 9.975 = 655.025 kg/h
Underflow, rate U = 0.507 ´ 1000 = 507 kg/h

Oil content of underflow = 507 ´ 0.1183 = 60 kg/h
Benzene content of underflow = 507 60 = 447 kg/h
Total solution, entering with meal charge:
Oil flow = 0.4 ´ 1000 = 400 kg/h
Benzene = 0.025 ´ 1000 = 25 kg/h
Total solution, C = 400 + 25 = 425 kg/h
Overall material balance: C + S = U + O
Overflow, O = C + S U = 425 + 665 507
= 583 kg/h
Balance of oil:
C xo + S yo = O yo + U xu
FG 0.4 IJ + 665 ´ 0.015 = 583 y
425
H 0.4 + 0.025 K o + 507 ´ 0.1183
Solving the equation, yo = 0.6 or 60% Ans.
EXERCISE 6.16
Basis: 7500 kg 29.6% Na2SO4 solution
Na2SO4 in the solution = 7500 ´ 0.296 = 2220 kg
Water in the solution = 7500 2220 = 5280 kg
Water lost by evaporation = 5280 ´ 0.05 = 264 kg
Water in the crystals and mother liquor = 5280 264
= 5016 kg
Let x be the amount of crystals produced.
Quantity of mother liquor = 5016 + 2220 x
= 7236 x kg
Balance of Na2SO4:
Na2SO4 in mother liquor = 0.183 (7236 x)
= 1324.19 0.183 x kg
x kg crystals will contain = (142 x/322) = 0.441 x kg Na2SO4
where molar mass of Na2SO4 = 142 and
Molar mass of Na2SO4 × 10 H2O crystals = 322
0.441 x + 1324.19 0.183 x = 2220
x = 3472.1 kg crystals
Mother liquor quantity = 7236 3472.1 = 3763.9 kg Ans.
EXERCISE 6.17
Basis: 100 kg initial solution
FeSO4 in solution = 28 kg
Associated water in crystals (FeSO4 × 7 H2O) = (126 ´ 28)/152
= 23.21 kg
FeSO4 × 7 H2O dissolved in water = 28 + 23.21
= 51.21 kg
Copper as dissolved = 51.21/0.96 = 53.34 kg
Free water in solution = 100 53.34 = 46.66 kg
Free water and impurities remain constant during crystallization and the total
quantity of the two figures should be taken for calculation purpose.
By cooling, solubility of FeSO4 is reduced to 20.51 kg per 100 kg water.
Associated water = (20.51 ´ 126)/152 = 17.0 kg
Free water = 100 17 = 83 kg
FeSO4 × 7H2O quantity = 20.51 + 17 = 37.51 kg
Crystals of FeSO4 × 7H2O per 1000 kg free water
= 37.51 ´ 100/83 = 45.19 kg
In the original solution, crystals of FeSO4 × 7H2O per
100 kg free water = (23.21 + 28) 100/(46.66 5)
= 122.92 kg
Yield per 100 kg free water = 122.92 45.19
= 77.73 kg
For 500 kg yield, original solution requirement
= (109.75 + 100) 500/77.73 = 1349.2 kg
Copperas to be charged = 1349.2 ´ 0.5334 = 719.7 kg Ans.
EXERCISE 6.18
Basis: 1000 kg/h of feed (fresh) containing 20% NaNO3
Since the mother liquor of constant composition is recycled, whatever NaNO3
enters the system, the same must go out.
NaNO3 in fresh feed = 0.2 ´ 1000 = 200 kg/h
Crystals of NaNO3 contain 4% water.
Crystals quantity = 200/0.96 = 208.33 kg/h Ans. (a)
Chemically bonded water = 208.33 200 = 8.33 kg/h
Let the quantity of recycled mother liquor = W kg/h
Solution fed to crystalliser = W + 208.33 kg/h
Feed to the crystallizer contains 58% NaNO3.
NaNO3 in the solution = 0.58 (W + 208.33)
= 0.58 W + 120.83 kg/h

Water in the solution = 0.42 (W + 208.33) 8.33
= 0.42 W + 79.17 kg/h
NaNO3 in the mother liquor = 0.5 (0.42 W + 79.17)
= 0.21W + 39.59 kg/h
NaNO3 balance over crystalliser:
0.58 W + 120.83 = 200 + 0.21 W + 39.59
W = 320.97 kg/h Ans. (b)
NaNO3 in mother liquor = (0.21 ´ 320.97) + 39.59
= 106.99 kg/h
Water in mother liquor = 320.97 106.99 = 231.98 kg/h
Mixed feed:
NaNO3 content = 106.99 + 200 = 306.99 kg/h
Water content = 800 + 213.98 = 1013.98 kg/h
Mixed feed = 306.99 +1013.98
= 1320.97 kg/h Ans.(c)
NaNO3 content of mixed feed = 306.99 ´ 100/(306.99 + 1013.98)
= 23.2% Ans. (d)
EXERCISE 6.19
Basis: 675 kg/h liquid paraffin
Sensible heat lost by paraffin, f1 = 675 ´ 2.93 (332 320)
= 23 733 kJ/h º 6.59 kW
Mechanical energy = 17 kW
Total heat gained by water = 1.92 ´ 3600 ´ 4.1868 ´ 5.8
= 167 847 kJ/h
º 46.62 kW
Heat taken up by water owing to crystallisation
= 46.62 17 6.59 = 23.03 kW
Crystals produced = 23.03 ´ 3600/168.7 = 491.5 kg/h
Crystallisation = 491.5 ´ 100/675 = 72.8% Ans.
EXERCISE 6.20
Basis: 100 kg feed
Water in the feed = 17.5 kg
Water in mother liquor = 17.5/2 = 8.75 kg
Urea in mother liquor = 8.75 ´ 205/100 = 17.94 kg
Quantity of mother liquor = (8.75 + 17.94)/(1 0.016)
= 27.12 kg
Biuret in mother liquor = 27.12 26.69 = 0.43 kg

Biuret in crystals = 0.5 0.43 = 0.07 kg
Urea crystallised = 82 17.94 = 64.06 kg
Yield of urea crystals = (64.06 ´ 100)/82 = 78.12%
0.07 ´ 100
Biuret content of urea crystals =
(64.06 + 0.07)
= 0.11% Ans.
EXERCISE 6.21
NaCl content of the mixture = 400 kg
NH4Cl content = 1000 400 = 600 kg
Since NaCl is less soluble than NH4Cl (at 323 K), all NH4Cl will dissolve and a
definite quantity of NaCl will remain undissolved.
Quantity of NaCl which will dissolve with 600 kg NH4Cl
= 14.26 ´ 600/22.50 = 380.3 kg
NaCl undissolved = 400 380.3 = 19.7 kg Ans. (a-i)
Quantity of saturated solution = 380.3 + 600 + (600 ´ 100/22.50)
= 3647 kg Ans. (a-ii)
Water content of saturated solution = 3647 380.3 600
= 2666.7 kg
NaCl which can be present in saturated solution at 283 K (10 °C)
= 18.25 ´ 2666.7/100 = 486.7 kg
Additional NaCl which can be dissolved = 486.7 380.3
= 106.4 kg
NH4Cl remaining undissolved from the added mixture
= 106.4 ´ 60/40 = 159.6 kg
NH4Cl in saturated solution at 283 K = 12.49 ´ 2666.7/100
= 333.1 kg
NH4Cl crystallized out = 600 333.1 = 266.9
Total NH4Cl separated = 266.9 + 159.6 = 426.5 kg
Ans. (b i)
Additional salt treated = 106.4 + 159.6
= 266 kg Ans. (b ii)
NH4Cl which can be present in saturated solution at 373 K (100 °C)
= 33.98 ´ 2666.7/100 = 906.1 kg
Additional NH4Cl which can be dissolved= 40 ´ (906.1 600)/60
= 204.1 kg
NaCl remaining undissolved = 40 ´ 306.1/60
= 204.1 kg
NaCl in saturated solution at 373 K = 10.77 ´ 2666.7/100
= 287.2 kg
NaCl crystallized out = 380.3 287.2 = 93.1 kg
Total NaCl separated = 204.1 + 93.1 = 297.2 kg
Additional salt which can be treated = 204.1 + 306.1
= 510.2 kg Ans. (c)
EXERCISE 6.22
(a) Basis: 100 kg aqueous 20 % urea solution
Refer given below figure.
Solubility isotherms
100% Isoconcs of nitrogen
H2O Phase boundaries
–5°C
A
–10°C
ICE (H2O)
NH
4N
20%N
O
–20°C
3
C
2O
25%N
–26.5°C
0°
–20
H
–1
C
°C
0°C
0°
30%N
C
–2
C
0°
35%N °C
1020°C
C
40%N CO(Nh2)2 30°
NH4NO3
100% 100%
CO(Nh2)2 B
CO(Nh2)2 NH4NO3
Fig. E6-4(a) Ternery Solubility Diagram of Ammonium Nitrate-Urea-Water System
Point A represents 20% urea while point B represents 100 % NH4NO3. Join AB.
It intersects 25% N (isocon) at C.
AC
Requirement of NH4NO3 = ´ 100
BC
2.031 units
= ´ 100
1.285 units
= 158.05 kg
Salt-out temperature is read as 17.9°C (291.05 K). Ans.

Algebraic method:
Let ma kg a NH4NO3 is required.
Nitrogen balance:
0.4596 ´ 0.2 ´ 100 + 0.35 ma = (100 + ma) 0.25
ma = 158.08 kg
(b) Basis: 100 kg aqueous 40% NH4NO3 solution
H2O Phase boundaries
–5°C
–10°C
ICE (H2O)
NH
E
4N
20%N
O3
–20°C
C
2O
25%N –26.5°C
0°
–20
H
–1
C
°C
0°C
0°
30%N
F C
–2
0°
35%N °C
10 0°C
2 °C
40%N CO(Nh2)2 30
NH4NO3
100% 100%
D
CO(Nh2)2 NH4NO3
CO(Nh2)2
Fig. E6-4(b) Ternery Solubility Diagram of Ammonium Nitrate-Urea-Water System
Point D represents 100% urea and point E represents 40% NH4NO3. Join DE. It
intersects 30% N isocon at F.
EF
Requirement of urea = ´ 100
DF
1.578 units
= 1.574 units ´ 100
= 100.25 kg
Salt-out temperature is read as 24.4°C (297.55 K) Ans.
Algebraic method:
Let mb kg urea is required.
Nitrogen balance:
0.35 ´ 0.4 ´ 100 + 0.4596 mb = (100 + mb) 0.3
mb = 100.25 kg
(c) Let mc kg aqueous ammonium nitrate solution of 50% strength is required

to be mixed with 100 kg of 70% urea solution.
H 2O Phase boundaries
–5°C
–10°C
ICE (H2O)
NH
4N
20%N
O3
–20°C
H
C
2O
25%N –26.5°C
0°
–20
H
–1
C
°C
0°C
0°
30%N
C
I
–2
0°
G
35%N °C
1020°C
C
40%N CO(Nh2)2 30°
NH4NO3
100% 100%
CO(Nh2)2 NH4NO3
CO(Nh2)2
Fig. E6-4(c) Ternery Solubility Diagram of Ammonium Nitrate-Urea-Water System
Point G represents 70% urea while point H represents 50% NH4NO3. Join GH. It
intersects 25% N isocon at I.
HI
NH4NO3 required = ´ 100
GI
1.104 units
= 1.155 units ´ 100
mc = 95.58 kg
Salt-out temperature is read as 8.3°C (264.85 k) Ans.
Algebraic method:
Nitrogen balance:
100 ´ 0.7 ´ 0.4596 + mc ´ 0.5 ´ 0.35= (100 + mc) 0.25
mc = 95.6 kg
EXERCISE 6.23
In example 5.48, solution contains 42.02 kg NH4NO3, 37.63 kg urea and 20.35
kg H2O.
Point representing this concentration on Fig. 6.32 reads salt out temperature to
be -7.9°C (265.25 K) Ans(a)
When the above solution is cooled to 20°C, it will cool on the phase boundary
line between NH4NO3 and urea. At 20°C, solution concentration is read as 37%
NH4NO3, 30% urea and 33% H2O (by mass).
Basis: 100 kg original solution.
It contains 20.35 kg water. Final solution contains 33% water.
20.35
Final solution = = 61.67 kg
0.33
NH4NO3 in final solution = 61.67 ´ 0.37 = 22.82 kg
Urea in final solution = 61.67 ´ 0.3 = 18.50 kg
Water in final solution = 61.67 22.82 18.5 = 20.35 kg
NH4NO3 crystallized out = 42.02 22.82
= 19.2 kg
Urea crystallized out = 37.63 18.50
= 19.13 kg
Total crystallized mass = 19.2 + 19.13 = 38.33 kg
NH4NO3 in the mass = (19.2 ´ 100)/38.33
= 50.09%
Urea in the mass = 100 50.09 = 49.91 % Ans.
EXERCISE 6.24
Moisture content = 5 ppm (v/v)
= 5 moles/106 moles
(a) Total pressure = 101.325 kPa
If p = vapour pressure of water/ice at DP
p 5
= 6
101.325 ´ 1000 10
or p = 0.5066 Pa
From Table 6.12 DP = 65.5°C (207.65 K)
(b) Total pressure = 0.8 MPa = 0.8 ´ 106 Pa
p 5
6
= 6 Or p = 4 Pa
0.8 ´ 10 10
From Table 6.12, DP = 48.05°C (225.1 K) Ans
EXERCISE 6.25
Basis: Purge gas rate = 8000 Nm3/h
= 356.9198 kmol/h (dry)
Vapour pressure of ice at 40°C,
p w = 12.841 Pa (Ref. Table 6.12)
Total pressure = 45 bar a
= 45 ´ 105 Pa
12.841
Moisture in purge gas =
(45 ´ 105 - 12.841)
kmol
= 2.8536 ´ 106
kmol dry gas
Moisture, condensed in cold box in 300 days
= 356.9198 ´ 24 ´ 300 ´ 2.8536 ´ 106
= 7.3332 kmol
º 132.1 kg Ans.
EXERCISE 6.26
Vapour pressure of water of 308.15 K (35°C) = 5.6216 kPa (ps)
% RH = 80
Partial pressure of water, p = 0.8 ´ 5.6216
= 4.4973 kPa
Vapour pressure of water at 304.15 K (31°C)= 4.4911 kPa (Table 6.13)
Hence DP of air is 304.15 K (31 °C). Ans. (b)
4.4973 18
Absolute humidity H = ´
(100 4.4973) 29
= 0.0292 kg/kg dry air Ans. (a)
5.6216 18
Saturation humidity Hs = ´
(100 5.6216) 29
= 0.036 97 kg/kg dry air
Saturation = (0.0292 ´ 100)/0.036 97 = 79.0% Ans. (c)
Humid heat, CH = 1.006 + (1.84 ´ 0.0292)
= 1.06 kJ/(kg × K) Ans. (d)
Latent heat of evaporation (lv) at 304.15 K (31 °C) = 2428.3 kJ/kg
Enthalpy, i = 1.06 (304.15 273.15) + (2428.3 ´ 0.0292)
= 103.8 kJ/kg dry air Ans. (e)
EXERCISE 6.27
Basis: 1 kg dry air
From Fig. 6.15:
At 367 K DB and 300.5 K WB, H1 = 20.7 g/kg dry air
and DP1 = 298.5 K (25.5°C)
At 303 K DB and 50% RH, H2 = 13.2 g/kg dry air
and DP2 = 291.2 K (18.2°C)
Moisture to be removed = 20.7 13.2
= 7.5 g/kg dry air
At DP1, lv1 = 2441.35 kJ/kg and at DP2, lv2 = 2458.54 kJ/kg
Average lv = (2441.35 + 2458.54)/2 = 2450 kJ/kg
Since the air will be fully saturated after the spray chamber, from Fig. 6.15,
i1 = 87.5 kJ/kg dry air
i2 = 51.5 kJ/kg dry air
Cooling load on the spray chamber = (87.5 51.5)
+ 0.0075 (307.15 291.2) ´ 4.1868
= 36.5 kJ/kg dry air
Humid volume of air at 307 K DB and 300.5 K WB.
VH = 0.899 m3/kg dry air
1
Mass flow rate of air = 60 000/0.899
= 66 740.8 kg dry air/h
Cooling load of the spray chamber = 66 740.8 ´ 36.5
= 2436 039 kJ/h
º 676.67 kW º 192.53 TR Ans. (a)
Humid heat of saturated air, CHs = 1.006 + (1.84 ´ 0.0132)
= 1.03 kJ/(kg dry air × K)
Heating load on the heater = 66 740.8 ´ 1.03 (303 291.2)
= 811 168 kJ/h
º 225.32 kW
Latent of evaporation of water at 400 kPa a, lv = 2133 kJ/kg (Table AIV.2)
Steam consumption = 811 168/2133 = 380.3 kg/h Ans. (b)
(c) Desired NCL = 10 g moisture/kg dry air
At this humidity level let vapour pressure of water be pv.
pv
´ 0.622 = 0.01
(101.325 - pv )
pv = 1.604 kPa
From Table 6.13, DP = 14.02°C (287.17 K)
i¢2 at 14.02°C = 39 kJ/kg dry air
Cooling load for NCL = 87.5 39 + (0.0207 0.01)
(307.15 287.17) ´ 4.186 8
= 48.5 + 0.9
Total cooling load = 66 704.8 ´ 49.4
= 329 522 kJ/h
º 915.34 kW
º 260.45 TR
At H = 0.01 kg/kg dry air and RH = 50%, DB requirement can be read as 25.2°C
(298.35 K) from Fig. 6.15.
C¢Hs = 1.006 + 1.84 ´ 0.01
= 1.0244 kJ/(kg dry air × K)
Heating load = 66 704.8 ´ 1.0244 (298.35 287.17)
= 763 956 kJ/h
º 212.20 kW
Steam consumption for NCL = 763 956/2133
= 358.2 kg/h Ans.(c)
Note: Calculations show that for achieving NCL conditions, refrigeration
requirement is 35.3% higher.
EXERCISE 6.28
Vapour pressure of water at 313.15 K (40 °C) = 7.375 kPa
7.375 18.015
Absolute humidity, H = ´
(117.3 7.375) 44.01
= 0.0275 kg/kg dry CO2 Ans.
EXERCISE 6.29
Vapour pressure of water 291.15 K (18°C) = 2.0624 kPa
2.0624 18.015
Absolute humidity in chlorine gas = ´
(101.325 2.0624) 70.906
= 0.005 279 kg/kg dry Cl2
On wet chlorine basis,

2.0624 18.015
humidity = ´ = 0.005 171 kg/kg wet Cl2
101.325 70.906
º 5171 ppm by mass Ans.
EXERCISE 6.30
Basis: 4 kmol HCl gas
Based on Table 5.53, following data are tabulated.
Component kmol Molar mass kg
HCl 0.8 36.5 29.2
O2 0.55 32 17.6
Cl2 1.6 71 113.6
N2 5.079 28 142.21
H2O (1.6) 18 (28.8)
Total 8.029 (9.629) 302.61 (331.41)
Average molar mass of dry gas= 302.61/8.029
= 37.69
At the outlet of Trombone cooler, part of HCl will have been absorbed in condensed
water.
Average molar mass of dry gas without HCl
302.61 29.2
= = 37.821
8.029 0.8
Average of both molar mass = (37.69 + 37.821)/2
= 37.756
Vapour pressure of water at 323 K (50°C) = 12.335 kPa (Table 6.13)
Water vapours in the outgoing gas mixture
12.335 18.015
= ´ = 0.066 08 kg/kg dry air
(101.325 12.335) 37.756
Water content of gas mixture, exit of cooler
= 302.61 ´ 0.066 08 = 20.0 kg
Water content of ingoing gas mixture = 28.8 kg
Water condensed in the cooler = 28.8 20.0 = 8.8 kg
Aqueous acid = 8.8/0.67 = 13.134 kg/4 kmol HCl fed
º 3.284 kg/kmol HCl fed
HCl in aqueous acid = 13.134 8.8
= 4.334 kg
Note: HCl to the tune of 4.334 kg is reduced from the exit gas quantity of
302.61 kg. Therefore one more trial is attempted.
Water content of exit gas mixture = (302.61 4.334) ´ 0.066 08
= 19.71 kg º 1.09 kmol
Water condensed = 28.8 19.71 = 9.09 kg
Aqueous acid = 9.09/0.67 = 13.567 kg/4 kmol HCl feed
º 3.39 kg/kmol HCl feed
close to previous value
HCl absorbed = 9.09 ´ 0.333/0.667 = 4.538 kg
º 0.124 kmol

Components ni kmol
HCl 0.68 20.610 5.174 9.017 2.947
O2 0.55 14.314 6.465 1.288 0.309
Cl2 1.60 45.674 38.207 34.181 10.356
H2O 1.09 35.416 0.087 14.400 4.96
N2 5.079 150.292 26.111 66.956 25.232
Total 8.999 266.306 13.474 54.904 22.474
Enthalpy of gas mixture at 323.15 above 298.15 K

= 266.306 (323.15 298.15) + 13.474 ´ 103 (323.152 298.152)/2
+ 54.904 ´ 106 (323.153 298.153)/3 22.474 ´ 109 (323.154 298.154)/4
= 6657.7 + 104.6 + 132.4 16.8
= 6877.9 kJ
Enthalpy to be removed to condense water = 9.09 ´ 2382.9 = 21.660.6 kJ
From Table 5.79,
DH°f of 33% aqueous acid = 152.9 kJ/mol HCl
DH°f of gaseous HCl = 92.31 kJ/mol HCl
Net heat change = 152.9 ( 92.31)
= 60.59 kJ/mol HCl
HCl dissolved in water = 0.8 0.68 = 0.12 kmol
Heat of dilution = 60 590 ´ 0.12
= 7270.8 kJ (exothermic) at 298.15 K (25 °C)
Sensible heat of HCl solution = (9.09 + 4.538) ´ 2.6 (50 25)
= 886 kJ over 298.15 K (25 °C)
Enthalpy of inlet gas at 599.5 K

= 91.520.2 kJ (Ref. Example 5.39)
Enthalpy to be removed in Trombone cooler
= 91 520 + 21 660.6 + 7270.8 6877.9 886
= 112.688 kJ/4 kmol HCl fed
º 28 172 kJ/kmol HCl Ans.
EXERCISE 6.31
Refer solution of exercise 4.23.
Basis: Urea feed rate = 350 kg/h
Total CO2 liberated = 5.833 kmol/h
CO2 leave at 7 bar and 80°C (353.15 K).
Antoine equation for SO3:
892.175
log p = 4.205 15 T - 103.564
At T1 = 353.15 K,
892.175
log p1 = 4.205 15
(353.15 - 103.564)
or p1 = 4.27 bar
4.27
SO3, carried with CO2 = 7 - 4.27
= 1.5641 kmol/kmol CO2

SO3 quantity = 5.833 ´ 1.5641
= 9.1234 kmol/h at reactor outlet
In the condenser,mixture is cooled to 30°C (303.15 K).
p2 of SO3 = 346.1 Torr = 0.4614 bar
0.4614
SO2, leftover in CO2 = (6.7 - 0.4614)
= 0.074 kmol/kmol CO2

SO3 quantity in CO2 at the outlet of condenser,
= 5.833 ´ 0.074
= 0.4316 kmol/h
SO3 condensed (refluxed) = 9.1234 0.4316
= 8.6918 kmol/h
º 695.344 kg/h
Latent heat removal, f3 = 695.344 ´ 42.55
= 29 587 kJ/h
º 8.219 kW
Gas mixture ingoing to condenser
.
kmol/h ni × ai ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109
CO2 5.8330 124.62 374.97 –239.45 57.16
SO3 9.1234 201.06 1109.62 –838.14 222.33
Total 14.9 564 325.68 1484.59 –1077.59 279.49
Enthalpy of ingoing gas mixture at 353.15 K over 298.15 K,
353.15
f1 = ò (325.68 + 1484.59 ´ 103 T 1077.59 ´ 106 T2 + 279.49
298.15
´ 109 T 3) dT
= 38 737 kJ/h
º 10.760 kW
Gas mixture outcoming from condenser
.
CO2 5.8330 124.62 374.97 –239.45 57.16
SO3 0.4316 9.51 52.49 –39.65 10.52
Total 6.2646 134.13 427.46 –279.10 67.68
Enthalpy of outgoing gas mixture from condenser at 303.15 K over 298.15 K,

303.15
f2 = ò (134.13 + 427.46 ´ 10 3 T 279.10 ´ 10 6 T 2 + 67.68
298.15
´ 109 T 3) dT
= 1196.4 kJ/h º 0.332 kW
Heat load of condenser,
fc = 38 737 + 29 587 1196.4
= 67 127.6 kJ/h
º 18.647 kW Ans.
EXERCISE 6.32
Basis: 1103.1 kmol/h HCl free gas, entering the compressor (Ref. Excercise 6.13)
Antoine constants:
A = 4.02291 B = 1221.781 and C = 45.739 (Ref. Table 5.4)
Use Antoine equation 5.24.
Vapour pressure of CCl4 at 313.15 K (40 °C), pv is given by
1221.781
log p = 4.022 91
(313.15 45.739)
or pv = 0.2844 bar º 28.44 kPa
Total p = 1130 kPa a
CCl4free gas = 1103.1 52.4 = 1050.7 kmol/h
CCl4 content of gas mixture exit affercooler
æ 28.44 ö
= ç ´ 1050.7
è 1130 28.44 ÷ø
= 27.127 kmol/h
CCl4 condensed = 52.4 27.127 = 25.273 kmol/h
º 3887.6 kg/h Ans.
EXERCISE 6.33
Basis: 780 kmol of benzene-nitrogen mixture, entering the absorber
Vapour pressure of benzene at 313.15 K (40°C) = 24.39 kPa
This vapour pressure is calculated using Antoine constants (Ref. Table 5.4);
A = 4.01814 B = 1203.835 and C = 53.226 and using Eq. (5.24).
Benzene content of incoming gas mixture = (24.39 ´ 780)/104
= 182.9 kmol
N2 entering with benzene = 780 182.9 = 597.1 kmol
Vapour pressure of benzene at 283.15 K (10°C) = 6.06 kPa (Calculated)
Benzene content of outgoing gas mixture = 6.06/(101.325 6.06)
Benzene unadsorbed = 0.0636 ´ 597.1 = 37.976 kmol
Benzene removal in adsorber = 182.9 37.976 = 144.924 kmol
º 11 320.3 kg
For removal of 1000 kg/h of benzene, the mass flow rate of bone
dry nitrogen = 597.1 ´ 28 ´ 1000/11 320.3
= 1476.9 kg/h Ans.(a)
Change in benzene content of BD activated carbon
= 0.35 0.05 = 0.3 kg/kg
Required mass flow rate of BD activated carbon

= 1000 ´ 1.0/0.3 = 3333 kg/h
Ans.(b)
For removing 1000 kg/h benzene at 333.15 K (60°C), the initial mixture of
benzene-nitrogen needs to be compressed. This means the gas will be compressed
to saturation pressure at 333 K.
Vapour pressure of benezene at 333.15 K (60°C) = 52.187 kPa (calculated)
Let total pressure after compression be p kPa. After compression and cooling to
333 K (60°C), benzene concentration should be 38.03 kmol/597.2 kmol dry N2.
52.187 37.976
= or p = 872.7 kPa a Ans. (c)
p - 52.187 597.1
EXERCISE 6.34
Basis: 1 kg bone dry soybean flakes
C6H14 removed = 0.61 0.025 = 0.585 kg/kg BD flakes
º 0.0068 kmol/kg BD flakes
New basis: 760 kmol gas mixture, entering the vessel.
For calculating vapour pressures of n-Hexane at various temperatures, Antoine
constants from Table 5.5 are used.
A = 4.00 266, B = 1171.530, C = 48.784
Use Eq. (5.24).
Temperature K (°C) Vapour pressure, bar (kPa)

283.15 (10) 0.1009 (10.09)
293.15 (20) 0.1616 (16.16)
343.15 (70) 1.0539 (105.39)
n-Hexane in the inlet mixture = (10.09 ´ 760)/101.325 = 75.68 kmol
N2 in the mixture = 760 75.68
= 684.32 kmol
Partial pressure of n-hexane in outgoing mixture
= 105.39 ´ 0.65 = 68.504 kPa
Quantum of n-hexane in the outgoing stream
68.504
= ´ 684.32 = 1428.31 kmol
(101.325 68.504)
n-Hexane evaporated in N2 stream = 1428.31 75.68
= 1352.63 kmol
º 116 326 kg
Wet gases, leaving desolventiser

= (1428.31 + 684.32) 0.0068/1352.63
= 0.0106 kmol/kg BD flakes Ans. (a)
Specific volume at 101.325 kPa and 343.15K (70°C),
V = RT/p = (8.314 ´ 343.15)/101.325 = 28.156 m3/kmol
Total wet gases, leaving the desolventiser
= 25 000 ´ 0.0106 = 265 kmol/h
Volumetric flow rate of gases = 265 ´ 28.156
= 7461.34 m3/h Ans. (b)
Let the pressure after compression be p kPa.
16.16 10.09
=
p 101.325
p = 162.3 kPa a Ans. (c)
EXERCISE 6.35
Basis: 100 kg/h wet pigment
Water in the pigment = 50 kg/h
Water in the dried pigment = 50 ´ 0.03/0.97
= 1.55 kg/h
Water evaporated = 50 1.55 = 48.45 kg/h
Air required for evaporation of water = 48.45 ´ 100/2.08
= 2329.3 m3/h Ans. (c)
Vapour pressure of H2O at 294 K (21°C) = 2.485 kPa (Ref. Table 6.13)
Moisture content of incoming air = 2.485/(114 2.485)
= 0.022 28 kmol/kmol dry air
º 0.0218 kmol/kmol wet air
Specific volume of air at 114 kPa and 373.15 K(100°C),
V = RT/p = (8.314 ´ 373.15)/114 = 27.213 m3/kmol
Molar flow rate of air = 2329.3/27.213
= 85.6 kmol moist air/h
Moisture, entering with air = 85.6 ´ 0.0218
= 1.866 kmol/h
BD air = 85.63 1.866 = 83.764 kmol/h
BD air requirement = 83.764/48.45
= 1.7289 kmol/kg moisture removed
Ans. (a)
H2O evaporated = 48.45/18 = 2.692 kmol/h
Total air, leaving the drier = 85.63 + 2.692 = 88.322 kmol/h (wet)
Moisture in outgoing air = 1.867 + 2.692 = 4.559 kmol/h
If p = partial pressure of H2O in outgoing air,

p/108 = 4.559/88.322
or p = 5.575 kPa
From Table 6.13, dew point = 308 K (34.85°C) Ans. (b)
EXERCISE 6.36
Miscella contains 40% edible oil (having 872 molar mass) and 60% n-hexane.
(60 / 86)
Mole fraction of n-hexane = (60 / 86) + (40 / 872)
= 0.9383
Absolute pressure in vessel = 760 197.5
= 562.5 Torr
º 0.7401 atm
º 0.75 bar
At t/T = 60°C/333.15 K, using Antoine constants vapour pressure of n-hexane =
0.7636 bar.
Partial pressure of n-hexane over
miscella = 0.9383 ´ 0.7636 (Raoult's law)
= 0.7165 bar
n-Hexane content of vapour from vessel
0.7165
= (0.75 - 0.7165)
= 21.388 kmol/kmol inerts

3
Basis: Ejector pulling out 25 m /h at 310 Torr and 40°C (313.15 K)
Specific volume of ideal gas at 310 Torr (0.4133 bar) and
313.15 760
313.15 K = 22.414 ´
273.15 310
= 62.9974 m3/kmol
25
Gas mixture being ejected from the cooler (with cooling water) =
62.9974
= 0.3968 kmol/h
Vapour pressure of n-hexane at 313.15 K
= 0.3726 bar
n-Hexane content of gas mixture
0.3762
= (0.4133) = 0.9015 kmol/kmol mixture
n-Hexane loss = 0.9015 ´ 0.3968

= 0.3577 kmol/h
º 30.7635 kg/h
30.7635 ´ 24
Specific n-Hexane loss =
200
= 3.692 kg/t soya flakes
º 5.723 L/t soya flakes Ans.(a)
After incorporation of the chiller, temperature of gas mixture, leaving the chiller
is 10°C (263.15 K).
Vapour pressure of n-hexane at 263.15 K = 0.0293 bar
0.0293
n-Hexane loss = ´ 0.3968
0.4133
= 0.0281 kmol/h
º 2.419 kg/h
º 58.061 kg/d
º 0.2903 kg/t soya flakes
º 0.45 L/t soya flakes Ans.(b)
Enthalpy balance:
(a) System with only cooler:
Gas mixture leaving cooler
.
O2 0.0082 0.2134 0.0964 –0.0192 –0.0046
N2 0.0309 0.9144 –0.1589 0.4074 –0.1535
n-C6H14 0.3577 –1.5793 208.1540 –111.5517 23.2216
Total 0.3968 –0.4515 208.0915 –111.1635 23.0625
t0/T0 = 25°C/298.15 K
Enthalpy of gas mixture, leaving cooler, at 313.15 K,
313.15
f2 = ò (0.4515 + 208.0915 ´ 103T 111.1635 ´ 106 T 2 + 23.0625
298.15
´ 109T 3) dT
= 6.8 + 954.05 155.81 + 9.9
= 801.34 kJ/h º 0.223 kW
n-Hexane in gas mixture entering condenser = (21.388 ´ 0.0391)
= 0.8363 kmol/h
Gas mixture entering condenser
.
O2 0.0082 0.2134 0.0964 0.0192 0.0056
N2 0.0309 0.9144 0.1589 0.4074 0.1535
n-C6H14 0.8363 3.6924 487.0695 259.7882 52.6225
Total 0.8754 2.5646 487.0070 259.4000 52.4634
Eenthalpy of gas-mixture entering condenser at 333.15 K
333.15
f1 = ò (2.5646 + 487.007 ´ 10 3 T 259.4 ´ 10 6 T 2 + 52.4634
298.15
´ 109 T 3) dT
= 89.8 + 5380.3 905.5 + 57.9
= 4442.9 kJ/h
º 1.234 kW
n-Hexane condensed = 0.8363 0.3577
= 0.4786 kmol/h
40 + 60
Average temperature of condensation = = 50°C or 323.15 K
2
Latent heat of n-hexane at 323.15 K,
0.38
é 507.6 - 323.15 ù
lv2 = 28.85 ê ú
ë 507.6 - 341.9 û
= 30.05 kJ/mol
Heat given up during condensation
f3 = 0.4786 ´ 30.050
= 14 381.9 kJ/h º 3.995 kW
Heat duty of cooler = f1 + f3 f2
= 4442.3 + 14 381.9 801.3
= 18 022.9 kJ/h
º 5.006 kW
(b) System with cooler and chiller:
Gas mixture, leaving chiller
.
O2 0.0082 0.2134 0.0964 0.0192 0.0056
N2 0.0309 0.9144 0.1589 0.4074 0.1535
n-C6H14 0.0281 0.1241 16.3520 8.7632 1.8242
Total 0.0692 1.0039 16.2895 8.3750 1.6651
Enthalpy of gas mixture at 263.15 K over 298.15 K

263.15
f4 = ò (1.0039 + 16.2895 ´ 103 T 8.3750 ´ 10 6 T2 + 1.665 ´
298.15
109 T 3) dT
= 35.1 160.0 + 23.1 1.3
= 173.3 kJ/h º 0.048 kW
40 - ( -10)
Average temperature of condensation =
2
= 25°C or 298.15 K
0.38
é 507.6 - 298.15 ù
lv = 28.85 ê ú
3
ë 507.6 - 341.9 û
= 31.537 kJ/mol at 298.15 K
n-Hexane condensed in chiller = 0.3577 0.0281
= 0.3296 kmol/h
Heat given-up during condensation,
f5 = 0.3296 ´ 31 537
= 10 394.6 kJ/h
Heat load of chiller = f2 + f5 f4
= 801.3 + 10 394.6 (173.3)
= 11 369.2 kJ/h
º 3.158 kW
º 0.899 TR Ans.
EXERCISE 6.37
Basis: 5 m/s paper speed
Production rate = 5 ´ 3600 ´ 3.8 ´ 0.081 ´ 24/1000
= 133 t/d on BD basis Ans.(a)
Water content of paper, leaving the drier
= 0.05 ´ 133 ´ 1000/24 = 277 kg/h Ans.(bi)
Filler Content = 0.2 ´ 0.95 ´ 133 ´ 1000/24 = 1052.92 kg/h
Ans.(bii)
Fiber in paper = 0.8 ´ 0.95 ´ 133 ´ 1000/24
= 4211.7 kg/h Ans.(biii)
Water in the paper, leaving the presses
= (1052.92 + 4211.72) 0.6/0.4
= 7897 kg/h
Evaporation in the drier = 7897 277 = 7620 kg/h Ans.(c)
EXERCISE 6.38
Basis: 1000 kg/h dried product
0.3
X1 = = 0.4286 kg moisture/kg dry solid
1 - 0.3
0.02
X2 = º 0.0204 kg moisture/kg dry solid
1 - 0.02
.
mc = mass flow rate of dry carbon pellets
= 1000 (1 0.02)
= 980 kg/h
.
Let msi = mass flow rate of ingoing superheated steam, kg/h
.
mso = mass flow rate of outcoming superheated steam, kg/h
Energy balance:
. . . .
mc × is1 + msi × Hsi = mc × is2 + mso × Hso + fL
where is1 = enthalpy of dry solid
= Cs(Ti T0) + XiCl(Ti T0)
= 1.3146 (303.15 273.15) + 0.4286 ´ 4.1868
´ (303.15 273.15)
= 93.272 kJ/kg dry solid
is2 = Cs (T t0) + X2Cl(T T0)
= 1.3146 (383.15 273.15) + 0.0204 ´ 4.1868
´ (383.15 273.15)
= 154 kJ/kg dry solid
From Appendix IV.2,
Hsi = 3074.5 kJ/kg at 300°C (573.15 K)
Hso = 2776.3 kJ/kg at 150°C (423.15 K)
These values are at atmospheric pressure.
. .
980 ´ 93.272 + msi ´ 3074.5 = 980 ´ 154 + mso ´ 2776.3 + fL
Heat loss fL is 5% of total heat input
. .
0.95 (980 ´ 93.272 + msi ´ 3074.5) = 980 ´ 154 + mso ´ 2776.3 (1)
Material balance:
. . .
mo(X1 X2) = msi mso
. .
msi mso = 980 (0.4286 0.0204)
= 400 kg/h (2)
.
msi = 8130.15 kg/h
.
mso = 8530.15 kg/h Ans.
EXERCISE 6.39
Basis: Solution feed rate = 970 kg/h
.
Let ma = mass flow rate of air through the drier on dry basis, kg/s
H1 = Humidity of ingoing air
= 0.036 kg moisture/kg dry air (Fig. 6.15)
0.75
X1 = = 3 kg moisture/kg dry solid at inlet
(1 - 0.75)
0.03
X2 = = 0.030 93 kg moisture/kg dry solid at outlet
(1 - 0.03)
.
ms = mass flow rate of dry solid
= 970 ´ 0.25 = 242.5 kg/h º 0.067 36 kg/s
Moisture balance:
. .
ms(X1 X2) = ma (H2 H1)
.
ma(H2 0.036) = 0.067 36 (3 0.030 93) (1)
Enthalpy of solid at inlet above 0°C (273 K),
is1 = Cs (ti 0) + X1 CL (ti 0)
= 1.4 (60 0) + 3 ´ 4.1868 (60 0)
Enthalpy of solid at outlet above 0°C (273 K)
is2 = Cs(t0 0) + X2CL(t0 0)
= 1.4 (70 0) + 0.030 93 (70 0)
Enthalpy of at inlet of dryer above 0°C (273.15 K),
ia1 = 1.006 (TDP 273.15) + H1.iws1 + CH (TDB1 TDP)
2
TDB1 = 280 + 273.15
= 553.15 K
TDP = 35 + 273.15 = 308.15 K
CH1 = 1.006 + 1.84 H1 = 1.006 + 1.84 ´ 0.036
= 1.072 24 kJ/(kg dry air × K)
iws1 = Enthalpy of saturated water vapour at 35°C (308.15 K)
= 2565.4 KJ/kg (Appendix IV.1)
ia1 = 1.006 (308.15 273.15) + 0.036 ´ 2565.4 + 1.072 24
(553.15 308.15)
Enthalpy of air, leaving the dryer,
ia2 = 1.006 (TDP 273.15) + H2.iws2 + CH (TDB2 TDP)
2
TDB2 = 80 + 273.15 = 353.15 K
Enthalpy balance of dryer:

. . . .
msis1 + ma × ia1 = ms × ias2 + ma × ia2 + fL
. .
0.067 36 ´ 837.6 + ma × 390.26 = 0.06736 ´ 100.65 + ma × ia2 + fL
. .
56.421 + 390.26 ma = 6.7798 + ma × ia2 + fL
fL = Heat loss
.
= 0.1 (56.421 + 390.26 ma)
44 = ma (ia2 351.23) (2)
ia2 = 1.006 (TDP 273.15) + H2 × iws2 + (1.006 + 1.84 H2) (353.15 TDP)
(3)
Assume TDP = 54 + 273.15 = 327.15 K
iws2 = 2599.2 kJ/kg (Appendix IV.1)
pv2 = 15.002 kPa
15.002 18
H2 = (101.325 - 15.002) ´ 29
= 0.107 87 kg/kg dry air Ans(b)

ia2 = 1.006 (327.15 273.15) + 0.107 87 ´ 2599.2 + (1.006 + 1.84
´ 0.107 87) (353.15 327.15)
.
From Eq. (1), ma (0.107 87 0.036) = 0.2
.
ma = 2.7828 kg/s º 10 018 kg/h of dry air Ans.(a)
From Eq. (2), ia2 351.23 = 44/2.7828
ia2 = 367.04 kJ/kg dry air
This value is close enough to ia2, calculated earlier.
Hence tDP = 54°C or TDP = 327.15 K
Heat duty of air heater,
.
f = ma(ia1 iaa)
Enthalpy of air at the heater inlet,
iaa = 1.006 (308.15 273.15) + 0.036 ´ 2565.4
f = 2.7828 (390.26 - 127.56)
= 731.042 kW
731.357
Fuel oil consumption = 41 300 ´ 0.7
= 0.025 29 kg/s
º 91.03 kg/h Ans.(c)
EXERCISE 6.40
Basis: Feed flow rate of 50% solution = 50 000 kg/h
Caustic soda content of feed = 50 000 ´ 0.5
= 25000 kg/h
Concentrated solution leaves the evaporator with 75% concentration.
25 000
Flow of 75% solution = = 33 333.33 kg/h
0.75
Evaporation rate = 50 000 33 333.33
= 16 666.67 kg/h
Energy balance:
Ws× ls = Wc× Hc + Wv × Hv WF × HF
Boiling point of pure water at 100 Torr a pressure = 51.1°C (324.25 K)
Boiling point of 75% solution = 51.1 + 81
= 132.1°C or 405.25 K
Enthalpy of feed (50% solution),
HF = 320 kJ/kg solution (Fig. 5.16)
Enthalpy of final concentrated 75% solution,
H C = 1050 kJ/kg solution (Fig.5.16)
Enthalpy of superheated vapour at 100 Torr (13.33 kPa) abs pressure and 132.1°C
(405.25 K)
= 2748.5 kJ/kg (Appendix AIV.3)
Latent heat of steam at 6 bar a,
l s = 2085 kJ/kg (Appendix A IV.2)
Ws ´ 2085 = 33 333.33 ´ 1050 + 16 666.67 ´ 2748.5
50 000 ´ 320
Ws = 31 083.94 kg/h º 8.63 kg/s
Water evaporated
Economy of evaporator =
Steam consumed
16 666.67
= 31 083 = 0.5362 kg/kg
Note: High boiling point elevation results in lower economy.
EXERCISE 6.41
Basis: Weak liquor flow = 50 L/s
Mass flow rate = 1.08 ´ 24 ´ 50 ´ 3600
= 4665 600 kg/d
Solids in the weak liquor = 4665 600 ´ 0.15 = 699 840 kg/d
Flow of concentrated liquor = 699 840/0.55
= 1272 436.4 kg/d

Evaporation = 4665 600 1272 436.4
= 3393 163.6 kg/d
º 141 381.8 kg/h Ans. (a)
Steam economy = 141 381.8/28 500
= 4.961 kg evaporation/kg steam Ans. (b)
EXERCISE 6.42
Basis: Weak liquor flow rate = 530 L/min (= 8.85 L/S)
Mass flow rate = 530 ´ 1.05 ´ 60 = 33 390 kg/h
Solids in the weak liquor = 33 390 ´ 0.1 = 3339 kg/h
Mass flow rate of concentrated liquor, leaving the final (4th)
Stage = 3339/0.5
= 6678 kg/h
Evaporation = 33 390 6678
= 26 712 kg/h (total in four effects) Ans. (a)
Effect No. temperature, saturation latent heat of

K (°C) pressure, kPa a evaporation, kJ/kg
1st 376 (103) 112.5 2249.1 (lv1)
2nd 367 (94.0) 81.5 2272.8 (lv2)
3rd 353.5 (80.5) 48.0 2308.0 (lv3)
4th 324.6 (51.6) 13.3 2379.2 (lv4)
Steam pressure in the shell of 1st stage = 103 kPa g
Saturation temperature = 394 K (121°C)
Latent heat of evaporation of steam (lv5) = 2199.7 kJ/kg (Appendix IV.2)
Heat balance across each effect:
1st effect:
Wa × lv5 = WF cpF (Tl TF) + (WF Wl) lv1
2199.7 Wa = 33 390 (376 313) ´ 4.1868 + (33390 W1) 2249.1
Wa = 38 143.69 1.0225 W1 (1)
2nd effect:
(WF W1) lv1 = W1 cp2 (T2 T1) + (W1 W2) lv2
(33 390 W1) 2249.1 = W1 (367 376) ´ 4.1868 + (W1 W2) 2272.8
75 097 449 2249.1 W1 = 37.68 W1 + 2272.8 W1 2272.8 W2
W1 = 16 747.05 + 0.5068 W2 (2)
3rd effect:
(W1 W2) lv2 = W2 cp3 (T3 T2) + (W2 W3) lv3
(W1 W2) 2272.8 = W2 (353.5 367) ´ 4.1868 + (W2 W3) 2308.0
W1 1.991 W2 = 1.0155 W3 (3)
4th effect:
(W2 W3) lv3 = W3 cp4 (T4 T3) + (W3 W4) lv4
(W2 W3) 2308 = W3 (324.6 353.5) ´ 4.1868 + (W3 6678) 2379.2
W2 1.978 W3 = 6884.01 (4)
Rewriting Eq. (4),
1.978 W3 = W2 + 6884.01
or W3 = 0.5056 W2 + 3480.3 (5)
Substitute the value of W3 in Eq. (3).
W1 1.991 W2 = 0.5134 W2 3534.24
or W1 1.4776 W2 = 3554.24 (6)
W1 0.5068 W2 = 16 747.05 (2)
() (+) ()
W2 = 20 281.29
or 0.9708 W2 = 20 895.6 kg/h
W1 = 27 337 kg/h, W3 = 14 045.1 kg/h and
Ws = 10 191.6 kg/h
Steam economy = 26 712/10 191.6
= 2.621 kg evaporation/kg steam Ans.
Simultaneous equations (1) to (4) can be conveniently solving with Mathcad.
EXERCISE 6.43
Basis: Weak liquor flow rate = 530 L/min (same as Excercise - 6.33)
Effect temperature, saturation latent heat of

No. K(°C) pressure, kPa a evaporation, kJ/kg
1st 362 (89.0) 67.5 2287.4 (lv1)
2nd 347.5 (74.5) 37.6 2323.0 (lv2)
3rd 337.5 (64.5) 24.5 2347.6 (lv3)
4th 324.6 (51.6) 13.3 2379.1 (lv4)
Heat balance across each effect:
1st effect:
Ws lv = W2 cp2 (T1 T2) + (W2 W1) lv1
2199.7 Ws = W2 (362 347.5) 4.1868 + (W2 6678) 2287.4
Ws = 1.0675 W2 6944.2 (1)
2nd effect:
(W2 W1) lv1 = W3 cp3 (T2 T3) + (W3 W2) lv2
(W2 6678) 2287.4 = W3 (347.5 337.5) ´ 4.1868 + (W3 W2) 2323.0
1.9495 W2 W3 = 6459.24 (2)
3rd effect:
(W3 W2) lv2 = W4 cp4 (T3 T2) + (W4 W3) lv3
(W3 W2) 2323.0 = W4 (337.5 324.6) ´ 4.1868 + (W4 W3) 2347.6
2.0106 W3 W2 = 1.0318 W4 (3)
4th effect:
(W4 W3) lv3 = WF cpF (T4 T1) + (WF W1) lv4
(W4 W3) 2347.6 = 33 390 (324.6 313) 4.1868 + (33 390 W4) 2379.1
2.0134 W4 W3 = 34 528.8 (4)
From Eq. (2), W2 = 3313.28 + 0.513 W3 (5)
Substitute W2 in Eq. (3).
2.0106 W3 3313.28 0.513 W3 = 1.034 W4
1.4976 W3 1.034 W4 = 3313.28
W3 0.69 W4 = 2211.39 (6)
Add Eq. (4) and Eq. (6) which yield W4 = 27 762 kg/h
Eq. (6) yields, W3 = 21 367 kg/h
Eq. (5) yields, W2 = 14 275 kg/h
Eq. (1) yields, Ws = 8294 kg/h
Steam economy = 26 712/8294
= 3.221 kg evaporation/kg steam
Ans.
Use of Mathcad is recommended for solving simultaneous equations.
EXERCISE 6.44
Basis: Pulp handling rate = 175 t/d
Feed rate of pulp slurry = (175 ´ 1000)/(3600 ´ 24 ´ 0.015)
= 135.03 kg/s
Salt in the slurry = 135.03 ´ 0.0925
= 12.49 kg/s
Liquor in the feed (with dissolved salt) = 135.03 ´ 0.985
= 133.0 kg/s
Flow of washed cake = 175 ´ 1000/(3600 ´ 24 ´ 0.18)
= 11.253 kg/s
Salt in the washed cake = 11.253 ´ 0.0163
= 0.183 kg/s
Liquor in washed cake (with dissolved salt) = 11.253 ´ 0.82

= 9.227 kg/s
Wash water, entering 2nd stage = 590 L/min = 9.833 kg/s
Strong liquor, leaving 1st stage = 135.03 + 9.833 11.253
= 133.61 kg/s
Salt in strong liquor = 12.49 0.183
= 12.307 kg/s
Let amount of salt in mud, leaving 1st stage = a kg/s and amount of salt in wash
liquor, entering 1st stage = b kg/s.
Salt balance around 1st stage:
12.49 + b = 12.307 + a
a b = 0.183 (1)
Liquor balance around 1st stage:
Liquor in washed liquor will be in equilibrium with the washed cake.
Liquor
Ratio = in washed cake = 9.227/0.183
Salt
= 50.421
Liquor in washed liquor = 50.421 × b
F 133.61 I a
133.0 + 50.421 b = 133.61 +
H 12.307 K
a + 4.644 b = 0.0562 (2)
Solving the equations, a = 0.249 kg/s
b = 0.066 kg/s
(12.307 0.249)
Efficiency of 1st stage = ´ 100
12.307
= 97.98% say 98%
(0.249 0.183)
Efficiency of 2nd stage = ´ 100
0.249
= 26.51%
(12.307 0.183)
Efficiency (overall) = ´ 100
12.307
= 98.51 % Ans.
EXERCISE 6.45
Basis: 100 00 kg/h feed to the fractionator
F+S=W+Q+O
where S, W, Q and O are unknowns.

Balance of CH2Cl2:
0.0168 ´ 10 000 + S ´ 0 = W ´ 0 + Q + 0.0763 + O ´ 0.907
11.89 O + Q = 2201.83 (2)
Balance of CH3OH:
0.0202 ´ 10 000 + S ´ 0 = W ´ 0 + Q ´ 0.1606 + O ´ 0.093
0.58 O + Q = 1257.78 (3)
Solving Eq. (2) and Eq. (3)
O = 83.47 kg/h and Q = 1209.37 kg/h Ans. (a)
Reflux ratio = 0.5
Molar Upper layer (Q) Lower layer (O)

Components
mass kg/h kmol/h mole % kg/h kmol/h
CH2Cl2 85 92.28 1.086 1.86 75.71 0.891
CH3OH 32 194.22 6.069 10.39 7.76 0.243
H2O 18 922.87 51.271 87.75
Total 1209.37 58.426 100.00 83.47 1.134
Total products, drawn from the fractionator
= 58.426 + 1.134 = 59.56 kmol/h
Reflux stream = 0.5 ´ 59.56 = 29.78 kmol/h
Reflux stream will have the same composition at as that of Q.
Composition of overhead vapours from fractionator:
Component kmol/h mole % kg/h
CH2Cl2 1.086 + 29.78 ´ 0.186 + 0.891 = 2.531 2.83 215.14
CH3OH 6.069 + 29.78 ´ 0.1039 + 0.243 = 9.400 10.53 300.94
H2O 51.271 + 29.78 ´ 0.8775 = 77.403 86.64 1393.25
Total 89.34 100.00 1909.38
Partial pressure of CH2Cl2 = 101.325 ´ 0.0283 = 2.867 kPa
Partial pressure of CH3CH = 101.324 ´ 0.1053 = 10.669 kPa
Partial pressure of H2O = 101.325 ´ 0.8664 = 87.788 kPa
Latent heat of evaporation:

Compo- Antoine constants Calculated Latent heat of
nents (Ref. Table 5.4) Saturation evaporation (lv)
Temperature
A B C K (°C) kJ/kmol kJ/kg
CH2Cl2 4.536 91 1327.016 20.474 238.75 (34.4°C) 31.72 373.5
CH3OH 5.204 09 1581.341 33.500 289.55 (16.4°C) 38.62 1205.3
H2O 4.6543 1435.264 64.848 369.52 (96.37°C)
H2O From Appendix (A IV.2) 369.5 K 2267.3
Heat removed in overhead condenser =

378.5 ´ 215.14 + 1205.3 ´ 300.99 + 1393.25 ´ 2267.3
= 80 355 + 362 783 + 3158 916 = 3602 054 kJ/h
º 1000.571 kW
Heat content of bottom product = W (373 318) ´ 4.1868
= 259.58 W kJ/h º 0.072 W kW
Heat supplied to feed = 0 kJ/h on the basis of ref. temp.
Heat to be supplied by steam = Heat removed in the condenser + Heat of
products + Heat in bottom product Heat of feed
= 1000.571 + 0.072 W kW
Enthalpy of saturated steam at 451.3 kPa = 2743 kJ/kg (Table AIV.2)
Heat supplied by steam = 2743 158.5 = 2584.5 kJ/kg
Total heat supplied = 2584.5 S kJ/h
From Eq. (1), W = F + S Q O
= 10 000 + S 1209.37 83.47
= 8707.16 + S kg/h
Heat supply rate = Heat loss rate = 1.02 (enthalpy to be supplied)
2584.5 S = [1000.571 + 0.072 (8707.16 + S)] 1.02 ´ 3600
2584.5 S = 5976 131 + 264.38 S
2320.12 S = 5976 131
S = 2575.8 kg/h Ans.(b)
W = 8707.16 + 2575.8
= 11 282.9 kg/h Ans.(c)
7
Combustion
EXERCISE 7.1
GCV = 24 070 kJ/kg on dry ash-free basis
Moisture in coal = 100 24.6 49.8 20.3 = 5.3%
GCV on as-received basis = 24 070 ´ (1 0.203 0.053)
= 24 070 ´ 0.744
= 17 908 kJ/kg
º 7699 Btu/lb
% C = 5.88 + 0.005 12 [7699 (40.5) (0.7)]
± 0.0053 [80 100 (24.6/49.8)]1.55 [Ref. Eq. (7.3)]
Since 100 (24.6)/49.8 < 80
% C = 5.88 + 39.27 + 1.06 = 46.21 Ans.
EXERCISE 7.2
Basis: 100 kg air dried coal
GCV = 27 235 kJ/kg on dry ash-free basis
O2 content of coal = 18.6 kg
= 0.581 kmol
Equivalent H2 = 2 ´ 0.581
= 1.162 kmol
Net H = 3.5 (1.162 ´ 2) = 1.176 kg or 1.176% Ans. (a)
Moisture in coal = 4 kg
Combined water = 1.162 ´ 18 4 = 20.916 4
= 16.916 kg or 16.916% Ans. (b)
GCV on as-received basis = 27 235 ´ (1 0.142 0.04)
= 22 278 kJ/kg º 9578 Btu/lb
Dülongs formula:
GCV = 33 950 ´ 0.615 (1 0.04) + 144 200 ´ 0.011 76 + 9400 ´ 0.004
= 20 044 + 1696 + 37.6
= 21 777.6 kJ/kg on as-received basis Ans. (c)
Calderwood equation:
Since 100(26.7/55.1) < 80
% C = 5.88 + 0.005 12(9578 40.5 ´ 0.4)
+ 0.0053 [80 (100 ´ 26.7/55.1)]1.55
= 5.88 + 48.96 + 1.11 = 55.96% Ans. (d)

Mass of ash-free, moisture-free coal = 26.7 + 55.1
= 81.8 kg
VM = 26.7 ´ 100/81.8 = 32.64%
FC = 55.1 ´ 100/81.8 = 67.36% Ans. (e)
Oxygen requirement:
Element Mass, Molar kmol O2 requirement

kg Mass kmol
Carbon 59.04 12 4.92 4.92
Hydrogen 3.36 2 1.68 0.84
Sulpher 0.38 32 0.012 0.012
Oxygen 17.86 32 0.558 () 0.558
Total 84.0 (dry) 7.170 5.214
Theoretical O2 requirement = 5.214 kmol

Specific air requirement = 5.214/(0.21 ´ 100)
= 0.248 kmol/kg dry coal
Theoretical air requirement = 5.214 ´ 29/(0.21 ´ 100)
= 7.2 kg/kg dry coal Ans. (f)
Excess air = 60%
Total O2 supply = 5.214 ´ 1.6 = 8.342 kmol
N2 from air = 8.342 ´ 79/21 = 31.383 kmol
Total N2 in flue gases = 31.383 + (1.8 ´ 0.96)/28 = 31.445 kmol
Total moisture in flue gas = (4.0/0.96)/18 + 1.68 = 1.911 kmol
Analysis of flue gases:
Gas kmol Actual wet analysis Orsat analysis

CO2 4.92 11.88 12.48
SO2 0.012 0.03
O2 3.128 7.55 7.92
N2 31.445 75.92 79.60
H2O 1.911 4.62
Total 41.416 (wet) 100.00 100.00
39.505 (dry)
Ans.(g)
EXERCISE 7.3
Basis: 100 kg fuel oil
(Carbon + Hydrogen) content of fuel oil = 100 1.37
= 98.63 kg
Carbon in the fuel oil = 9.33 ´ 98.63/10.33
= 89.08 kg
Combustion 237
Hydrogen in fuel oil = 98.63 89.08

= 9.55 kg
º 4.775 kmol
H2O produced by combustion = 4.775 kmol º 85.95 kg
NCV = GCV 2442.8 (H2O production) [Ref. Eq. (7.1)]
= 41 785 2442.8 ´ 85.95/100
= 39 685.4 kJ/kg Ans.
EXERCISE 7.4
(a) Gaseous n-propanol:
Formula: C3H8O
Water formed = 4 mol/mol n-propanol
= 72.06 kg/kmol n-propanol
NCV = 2068.65 2442.8 ´ 72.06/1000
= 1892.72 kJ/mol Ans.
(b) Liquid acetone:
Formula : C3H6O
Water formed = 3 mol/mol acetone
= 54.045 kg/kmol acetone
NCV = GCV 2442.8(H2O produced)
= 1790.02 2442.8 ´ 54.045/1000
= 1658.00 kJ/mol Ans.
EXERCISE 7.5
NCV of CH4 = 802.62 kJ/mol at 298.15 K (Ref. Appendix V.2)
(a) Specific energy consumption
= 22.0193 ´ 802.62 ´ 103/106
= 17.673 GJ/t NH3 Ans.
(b) Specific energy consumption
= 25.9715 ´ 802.62 ´ 103/106
= 20.845 GJ/t NH3 Ans.
EXERCISE 7.6
Specific energy consumption
= 31.2091 ´ 802.62 ´ 103/106
= 25.049 GJ/t CH3OH Ans.
EXERCISE 7.7
NCV of motor spirit = 44 050 kJ/kg at 298.15 K (ref. Example 5.29)
NCV of ethanol liquid = 1235.49 kJ/mol
Molar mass of ethanol = 46.0684 kg/kmol
1234.97 ´ 1000
NCV of ethanol liquid =
46.0684
= 26 807.3 kJ/kg at 298.15 K
NCV of the blend = 44 050 ´ 0.9 + 26 807.3 ´ 0.1
= 42 325.7 kJ/kg at 298.15 K Ans.
CO2 generated by motor spirit alone
0.8486 ´ 44.0098
=
12
= 3.112 kg/kg
CO2 generated by blend = 0.8486 ´ 44.0098 ´ 0.9 + 2 ´ 44.0098 ´ 0.1

12 46.0684
= 2.9919 kg/kg
Comparison on NCV basis:
3.112 ´ 106
CO2 generated by motor spirit =
44 050
= 70.65 kg/GJ
2.9919 ´ 106
CO2 generated by blend =
42 325.7
= 70.68 kg/GJ
In both cases, CO2 generated are practically same on heat release basis.
EXERCISE 7.8
Basis: 1 mol associated gas
Component mol Molar ni × Mi Calorific values ni × GCVi ni × NCVi

ni mass g kJ/mol kJ
Mi GCVi NCVi
CH4 0.744 16.0425 11.936 890.65 802.62 662.64 597.15
C2 H 6 0.084 30.0690 2.526 1560.69 1428.64 131.10 120.01
C3 H 8 0.074 44.0956 3.263 2219.17 2043.11 164.22 151.19
i-C4H10 0.017 58.1222 0.988 2868.20 2648.12 48.76 45.02
n-C4H10 0.020 58.1222 1.162 2877.40 2657.32 57.55 53.15
i-C5H12 0.005 72.1488 0.361 3528.83 3264.73 17.64 16.32
n-C5H12 0.004 72.1488 0.289 3535.77 3271.67 14.14 13.09
N2 0.043 28.0135 1.205 — — — —
CO2 0.009 44.0095 0.396 — — — —
Total 1.000 — 22.126 1096.05 995.93
GCV = 1096.05 ´ 1000/22.126 = 49 536.7 kJ/kg

NCV = 995.93 ´ 1000/22.126 = 45 011.8 kJ/kg
Combustion 239
At 101.325 kPa and 298.15 K (25 °C), specific volume = 24.465 m3/kmol
GCV = 1096.05 ´ 1000/24.465 = 44 800.7 kJ/m3
NCV = 995.93 ´ 1000/24.465 = 40 708.4 kJ/m3 Ans.
EXERCISE 7.9
Basis: 100 mol refinery gas
Refer tabular calculations given below:
Component mole ni ni × Mi, kg ni × GCVi, kJ ni × NCVi, kJ

H2 74.0 148 21 151.4 17 894.7
CH4 13.5 216 12 023.8 10 835.4
C2H6 7.4 222 11 549.1 10 571.9
C3H8 3.6 158.4 7 989.0 7 355.2
n-C4H10 1.2 69.6 3 452.9 3 188.8
n-C5H12 0.3 21.6 1 060.7 981.5
Total 100.0 835.6 57 226.9 50 827.5
3
GCV = 572.269 ´ 1000/24.465 = 23 391 kJ/m
NCV = 508.275 ´ 1000/24.465 = 20 776 kJ/m3
Average molar mass = 835.6/100 = 8.356
GCV = 572 269/8.356 = 68 486 kJ/kg
NCV = 508 275/8.356 = 60 828 kJ/kg Ans.
EXERCISE 7.10
Basis: 100 mol purge gas:
Component mol, Molar ni × Mi, g ni × GCVi ni × NCVi
ni mass, Mi kJ kJ
H2 69.0 2 138 19 722.3 16 685.6
N2 23.0 28 644
Ar 2.7 40 108
CH4 5.3 16 84.8 4 720.4 4 253.9
Total 100.0 974.8 24 442.7 20 939.5
GCV = 244.42 kJ/mol

NCV = 209.4 kJ/mol
Average molar mass = 9.748
GCV = 244.427 ´ 1000/9.748 = 25 075 kJ/kg
NCV = 209.518 ´ 1000/9.748 = 21 493 kJ/kg Ans. (a)
Theoretical O2 requirement = (69/2) + (5.3 ´ 2)
= 45.1 mol
N2, entering with O2 = 79 ´ 45.1/21 = 169.66 mol
Theoretical air requirement = 45.1 + 169.66 = 214.76 mol (dry)
Specific dry air requirement = 214.76 ´ 29/974.8

= 6.39 kg/kg purge gas Ans.(b)
Actual O2 supply = 1.2 ´45.1 = 54.12 mol
Actual N2 entry = 54.12 ´ 79/21 = 203.59 mol
Composition of dry flue gases:
Component mol mole % (dry)

CO2 5.3 2.18
Ar 2.7 1.11
N2 203.59 + 23.0 = 226.59 93.01
O2 54.12 45.1= 9.02 3.70
Total 243.61 100.00
Ans.(c)
EXERCISE 7.11
Basis: 100 mol SNG
Component ni Molar mass ni × Mi g ni × GCVi , ni × NCVi ,
mol Mi kJ kJ
CH4 96.59 16 1545.44 86 027.9 77 525.1
H2 1.29 2 2.58 368.7 311.9
CO 0.22 28 6.16 62.3 62.3
CO2 2.00 44 88.00
Total 100.00 1642.18 86 458.9 77 899.3
GCV = 864.589 ´ 1000/16.4218 = 52 649 kJ/kg
NCV = 778.993 ´ 1000/16.4218 = 47 437 kJ/kg
or GCV = 864.589/22.414 = 38 574 kJ/Nm3
NCV = 778.993/22.414 = 34 755 kJ/Nm3 Ans.
EXERCISE 7.12
Basis: 100 kmol tail gas (wet). Data in the following table are extracted from
Table 4.20 and Table 4.21.
Component ni (GCV)i ni × GCVi (NCV)i ni × (NCV)i
kmol kJ/kmol kJ kJ/kmol kJ
CO2 1.17 — — — —
CO 0.13 282 980 36 787.4 282 980 36 787.4
H2 0.26 285 830 74 315.8 241 820 62 873.2
CH4 0.08 890 650 71 252.0 802 620 64 209.6
(CH3)2O 0.13 2107 400 273 962.0 1931 380 251 079.4
O2 11.28 — — — —
N2 76.67 — — — —
H2O 10.28 — — — —
Total 100.00 456 317.2 414 949.6
Combustion 241
GCV = 456 317.2(22.414 ´ 100) = 203.6 kJ/Nm3

NCV = 414 949.6(22.414 ´ 100) = 185.1 kJ/Nm3 Ans.
EXERCISE 7.13
Basis: 100 kmol dry flue gases
O2, accounted for = 10.6 + 8.7
= 19.3 kmol
O2 supplied from air = 21 ´ 80.7/79 = 21.452 kmol
O2 unaccounted = 21.452 19.3 = 2.152 kmol
Hydrogen burnt = 2.152 ´ 2 = 4.304 kmol
Water formed = 4.304 kmol
Carbon burnt = 10.6 katom
º 127.2 kg
Total air supplied = 80.7 + 21.452 = 102.152 kmol
New Basis: 100 kg coal
Carbon content of coal = 65 kg
Carbon in the refuse = [12.7 ´ 0.086/(1 0.086)] = 1.195 kg
Carbon burnt = 65 1.195 = 63.805 kg
Dry air supply = 102.152 ´ 63.805/127.2
= 51.241 kmol
Dry air 51.241 ´ 29
Ratio = = 14.86 kg/kg Ans. (a)
Coal 100
(100 + 4.304)63.805
Flue gas quantity =
127.2
= 52.32 kmol (wet)
For 100 kmol dry flue gas basis:
Component kmol, ni Molar mass, Mi ni × Mi, kg
CO2 10.6 44 466.4
O2 8.7 32 278.4
N2 80.7 28 2259.6
H2O 4.304 18 77.5
Total 104.304 3081.9
Average molar mass = 3081.9/104.304 = 29.547 (wet)
flue gas 52.32 ´ 29.547
Ratio = = 15.46 kg/kg fuel (wet basis) Ans.(b)
coal 100
Hydrogen burnt = 4.304 ´ 2 ´ 63.805/127.2
= 4.32 kg/100 kg coal
Hydrogen content of coal = 4.32% Ans. (c)
EXERCISE 7.14
Basis: 100 kmol of dry flue gases
N2 in flue gas = 100 10.6 6.0 = 83.4 kmol
O2 accounted = 10.6 + 6.0 = 16.6 kmol
O2 supplied through air = 21 ´ 83.4/79 = 22.17 kmol
Theoretical oxygen requirement = 22.17 6.0
= 16.17 kmol
Excess air = 6.0 ´ 100/16.17 = 37.1% Ans. (a)
Carbon content of fuel = 10.6 katom = 127.2 kg
Oxygen, consumed for burning of hydrogen = 22.17 16.6
= 5.57 kmol
Hydrogen burnt = 5.57 ´ 2 = 11.14 kmol
º 22.28 kg
Ratio C:H = 127.22/22.28 = 5.71 kg/kg Ans. (b)
EXERCISE 7.15
Basis: 100 kmol fuel gas mixture
Combustion reactions:
CH4 + 2 O2 = CO2 + 2 H2O
C2H4 + 3 O2 = 2 CO2 + 2 H2O
C6H6 + 7.5 O2 = 6 CO2 + 3 H2O
Component kmol Theoretical O2 Total carbon,
requirement, kmol kmol
CO2 3.4 3.4
C2H4 3.7 + 11.10 7.4
C6H6 1.5 + 11.25 9.0
O2 0.3 0.30
CO 17.4 + 8.70 17.4
H2 36.8 + 18.40
CH4 24.9 + 49.80 24.9
N2 12.0
Total 100.00 + 98.95 62.1
Total CO2, produced by complete combustion = 62.1 kmol

Total dry flue gas quantity = 62.1/0.10
= 621 kmol
(N2 + O2) in fuel gas = 621 62.1 = 558.9 kmol
Combustion 243
N2 from fuel = 12 kmol

(N2 + O2) from air = 558.9 12
= 546.9 kmol
N2 corresponding to theoretical O2 = 79 ´ 98.95/21
= 372.24 kmol
Since the mixture (N2 + O2) of the flue gases (i.e. 546.9 kmol) does not
contain (total) theoretical oxygen,
excess air = 546.9 372.24 = 174.66 kmol
O2 in flue gases = 174.66 ´ 0.21 = 36.68 kmol
N2 in flue gases = 174.66 36.68 = 137.98 kmol
Total N2 in flue gas = 12 + 372.2 + 137.98
= 522.18 kmol
Excess air = 36.68 ´ 100/98.95
= 37.07% Ans. (a)
Composition of dry flue gas:
Component kmol Orsat analysis, mole %

CO2 62.1 10.00
O2 36.68 5.91
N2 522.18 84.09
Total 620.96 100.00
Ans.(b)
EXERCISE 7.16
Basis: 100 kmol dry flue gas mixture
Component kmol kmol of C kmol of O2
CO2 12.4 12.4 12.4
CO 3.1 3.1 1.55
O2 5.4 5.40
N2 79.1
Total 100.00 15.5 19.35
O2 supplied through air = 21 ´ 79.1/79 = 21.03 kmol

Unaccounted O2 = 21.03 19.35 = 1.68 kmol
This O2 is used for hydrogen burning.
Unburnt C = 15.5 ´ 0.15/0.85 = 2.735 kmol
O2, required for complete combustion = 15.5 + 2.735 + 1.68
= 19.915 kmol
Excess O2 = 21.03 19.915 = 1.115 kmol
Excess air = 1.115 ´ 100/19.915 = 5.6% Ans.
EXERCISE 7.17
Comparison of the fuels is to be made on NCV basis.
(A): Basis 100 kmol bottled LPG
Gas kmol Molar mass Mass, ni × Mi LCVi, ni × LCVi

ni Mi kg kJ/kmol kJ
C2 H 6 1.2 30 36.0 1428 640 1 714 368
C3 H 2 25.2 44 1108.8 2043 110 51 486 372
i-C4H10 23.9 58 1386.2 2648 120 63 290 068
n-C4H10 49.7 58 2882.6 2657 320 132 068 800
Total 100.0 — 5413.6 248 559 610
LCV = 248 559 610/5413.6 = 45 914 kJ/kg
Cost of bottled LPG on LCV basis = 30 ´ 106/45 914
= Rs. 653.4 per GJ
(B) Basis: 1 kmol associated gas
Volume of 1 kmol gas is 22.414 Nm3.
Gas ni, kmol LCVi, kJ/kmol ni × LCVi, kJ
CH4 0.866 802 620 695 069
C2 H 8 0.086 1428 640 122 863
C3 H 8 0.039 2043 110 79 681
n-C4H10 0.007 2657 320 18 601
i-C4H10 0.002 2648 120 5 296
Total 1.000 921 510
LCV = 921 510/22.414 = 41 113 kJ/Nm3

Cost of associated gas on LCV basis = 15 ´ 106/41 113
= Rs. 364.85 per GJ
Thus associated gas is cheaper than bottled LPG. Ans.
EXERCISE 7.18
Basis: 100 kmol blast furnace (fuel) gas
Gas kmol, ni Molar mass Mass O2 requirement,
Mi ni × Mi kg kmol
H2 3.2 2 6.4 1.6
CO 26.2 28 733.6 13.1
CO2 13.0 44 572.0 Nil
N2 57.6 28 1612.8 Nil
Total 100.0 2924.8 14.7
Average molar mass of fuel gas = 2924.8/100
= 29.25
Theoretical N2 entry = 14.7 ´ 0.79/0.21
= 55.3 kmol from air
Combustion 245
Total dry air entry = 14.7 + 55.3 = 70 kmol

Absolute humidity of air at 298.15 K (25 °C) DB and 291 K (18°C) WB
= 10.2 g/kg dry air (Ref. Fig. 6.15)
º 0.0164 kmol/kmol dry air
Moisture, entering with air = 0.0164 ´ 70
= 1.148 kmol
Total wet air = 14.7 ´ 32 + 55.3 ´ 28 + 1.148 ´ 18
= 2039.5 kg
Theoretical air requirement = 2039.3/2924.8
= 0.7 kg/kg fuel Ans. (a)
Excess air = 20%
Actual dry air supply = 70 ´ 1.2 = 84 kmol
Moisture entry = 84 ´ 0.0164 = 1.378 kmol
O2 in the flue gas = (84 70)0.21
= 2.94 kmol
N2 from air = 84 ´ 0.79 = 66.36 kmol
Composition of flue gas:
Gas kmol Actual analysis Orsat analysis
(wet) mole % mole %
CO2 26.2 + 13.0 = 39.2 22.97 23.60
O2 2.94 1.72 1.77
N2 66.36 + 57.6 = 123.96 72.63 74.63
H2O 3.2 + 1.378 = 4.578 2.68 —
Total 170 678 (wet) 100.00 100.00
166 100 (dry)
Total heat released by the combustion of 100 kmol blast
furnace gas = 3.2 (241 820) + 26.2 (282 980)
= 773 824 + 7414 076
= 8187 900 kJ at 298.15 K
Take reference temperature = 298.15 K (25°C)
Enthalpy of fuel gas:
Component ni, kmol C°

mp constants
ai × ni ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109

H2 3.2 91.554 32.621 – 0.472 2.461
CO 26.2 760.526 – 73.792 305.065 – 123.305
CO2 12.0 256.386 771.409 – 492.607 117.599
N2 57.6 1704.436 – 296.122 759.335 – 286.157
Total 100.0 2812.902 434.116 571.321 – 289.402
Enthalpy of fuel gas at 333.15 K over 298.15 K,
H1 = 2812.902 (333.15 298.15) + 434.116 ´ 103 (333.152 298.152)/2
+ 571.321 ´ 106 (333.153 298.153)/3
289.402 ´ 109 (333.154 298.154)/4
= 98 452 + 4794 + 200 319

= 103 127 kJ
Enthalpy of flue gases (total) = 8187 900 + 103 127 = 8291 027 kJ
Flue gas:
Heat capacity CO2 O2 N2 H2O Total

constants
ni, kmol 39.2 2.94 123.96 4.578 170.678
(ni × ai)1 837.528 76.516 708.998 148.749 1771.791
(ni × ai)2 1457.221 54.193 745.592 115.175 2372.181
(ni × bi)1 ´ 103 2519.937 34.560 – 123.178 0.364 2431.683
(ni × bi)2 ´ 103 910.894 63.849 76.598 97.428 1148.769
(ni × ci)1 ´ 106 – 1609.184 – 6.887 315.862 60.479 – 1239.730
(ni × ci)2 ´ 106 – 289.249 – 24.416 – 9.709 – 24.447 – 347.821
(ni × di)1 ´ 109 384.156 – 1.653 – 119.033 – 20.818 242.652
(ni × di)2 ´ 109 32.195 3.398 0.055 2.209 37.857
Suffixes 1 and 2 refer to the constants for temperature ranges 298.15 to 1500
K and 1500 to 4000 K, respectively.
Enthalpy of flue gas at 1500 K over 298.15 K
= 1771.791 (1500 298.15) + 2431.683 ´ 103 (15002 298.152)/2
1239.83 ´ 106 (15003 298.153)/3
+ 242.652 ´ 109 (15004 298.154)/4
= 2129 693 + 2627 672 1383 760 + 306 628
= 3680 233 kJ
Enthalpy of flue gas above 1500 K at T K
= 2372.181 (T 1500) + 1148.769 ´ 103 (T2 15002)/2
347.821 ´ 106 (T3 15003)/3
+ 37.857 ´ 109 (T4 15004)/4
= 8291 027 3680 233
= 4610 794 kJ
By trial and error or by Mathcad, T = 2782.71 K or 2509.56°C Ans.

Combustion 247
EXERCISE 7.19
Basis: 100 kg coal
Carbon content of coal = 46.21 kg (refer Exercise 7.1)
º 3.85 katom or kmol
Sulphur content of coal = 0.7 kg
º 0.022 katom or kmol
Considering SO2 as CO2 in the flue gases,
CO2 content of flue gases = 3.85 + 0.022
= 3.872 kmol
Total dry flue gases mixture = 3.872/0.088
= 44 kmol
O2 content of flue gases = 44 ´ 0.092
= 4.05 kmol
N2 content of flue gases = 44 3.872 4.05
= 36.078 kmol
O2 from air = (21 ´ 36.078)/79
= 9.59 kmol
O2 accounted = 3.872 + 4.05 = 7.922 kmol
O2 unaccounted = 9.59 7.922
= 1.668 kmol
This O2 is used to burn the net hydrogen of the coal.
Net H2 in flue = 1.668 ´ 2 = 3.336 kmol
Water vapours in flue gases:
Moisture of coal = 5.3 kg
Moisture, sprinkled over coal = 5 kg
Total moisture due to coal firing = 10.2 kg
º 0.567 kmol
Absolute humidity of air at 307 K (34°C) DB and 297 K(24°C) WB
Moisture, entering through air = 0.0239 (9.590 + 36.078)
= 1.092 kmol
Water produced by burning net H2 = 3.276 kmol
Total moisture in flue gases = 0.567 + 1.092 + 3.336
= 4.995 kmol
Composition of flue gases:
Gas kmol mole % (wet basis) Orsat analysis

CO2 3.85 7.85 8.80
SO2 0.022 0.04
O2 4.05 8.27 9.20
N2 36.078 73.65 82.00

H2O 4.995 10.19
Total 48.995 (wet) 100.00 100.00
44.000 (dry)
Partial pressure of water vapours in flue gases, p

= 0.1019 ´ 100 = 10.19 kPa
From Table 6.13, dew point = 46.2°C (319.35 K)
Temperature of water, entering the economiser is 311.15 K(38°C) which is lower
than the dew point. This is undesirable. Corrosion is envisaged.
Refuse contains 5.9% combustibles. It is assumed that this is carbon. Rest 94.1%
is ash.
Carbon in the refuse = 20.3 ´ 0.059/0.941
= 1.273 kg
º 0.106 kmol
O2 required for burning carbon of refuse = 0.106 kmol
Theoretical oxygen requirement = 3.872 + 1.668 + 0.106
= 5.648 kmol
Excess O2 = 9.59 5.648 = 3.942 kmol
Excess air = (3.942 ´ 100)/5.648
= 69.8% say 70%
New basis: 2500 kg/h firing rate
Dry air supplied = (9.59 + 36.078) 2500/100
= 1141.7 kmol/h
Moist air supplied = (9.59 + 36.078 + 1.092) 2500/100
= 1168.88 kmol/h
Volumetric flow rate = 1168.88 ´ 8.314 ´ 307.15/100
= 29 849 m3/h
Molar flow rate of flue gases = 48.995 ´ 2500/100
= 1224.88 kmol/h
Volumetric flow rate = 1224.88 ´ 8.314 ´ 463.15/100
= 47 165 m3/h
Heat Balance:
Heat supplied by burning fuel, f1 = 2500 ´ 17 908
= 44 770 000 kJ/h
º 12 436.11 kW
Heat gain:
Economiser: Heat gained by water, f4 = 12 150 (368 311)4.1868
= 2899 568 kJ/h
º 805.436 kW
Boiler pressure: At 0.9 MPa g, i.e. 10.013 bar a
Ts = 453 K (180°C), H = 2776.3 kJ/kg
Enthalpy of water at 368 K = 397.99 kJ/kg
Combustion 249
Heat supplied in the boiler, f5 = (2776.3 397.99) ´ 12 150

= 28 896 467 kJ/h
º 8026.8 kW
Superheater:
Enthalpy of steam at 0.9 MPa g and 473 K (180°C) = 2826.6 kJ/kg
Specific enthalpy gain in the superheater = 2826.6 2776.3
= 50.3 kJ/kg
Total heat gained in superheater, f6 = 50.3 ´ 12 150
= 611 145 kJ/h º 169.763 kW
Total moisture, evaporated in the boiler = 0.567 + 3.336
= 3.903 kmol/100 kg coal
º 0.7031 kg/kg coal
Total moisture evaporated = 0.7031 ´ 2500
= 1757.75 kg/h
lv at DP [46.2°C)] = 2392.8 kJ/kg
Heat lost in evaporation, f8 = 1757.75 ´ 2392.8
= 4205 944 kJ/h º 1168.318 kW
Ash content of the refuse = 2500 ´ 0.203 = 507.5 kg/h
Combustibles (as C) = 507.5 ´ 0.059/0.941 = 31.82 kg/h
Heat lost in refuse, f11 = 32 762 ´ 31.82
= 1042 487 kJ/h
º 289.58 kW
Heat loss in flue gas:
Basis: 100 kg coal

Component ni × kmol ai × ni ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109
CO2 3.872 82.727 248.908 – 158.948 37.945
O2 4.050 117.932 4.031 – 49.647 162.503
N2 36.078 1067.581 – 185.477 475.613 – 179.236
H2O 4.995 162.333 0.398 66.027 – 22.728
Total 48.995 1430.573 67.860 333.745 – 1.516
Heat loss in the flue gas for 2500 kg/h firing rate
2500
f7 = [1430.333 (463.15 298.15) + 67.860 ´ 103 (463.152 298.152)/2
100
+ 333.745 ´ 106 (463.153 298.153)/3
1.516 ´ 109 (463.154 298.154)/4]
= 25 ´ 248 355
= 6208 875 kJ/h

º 1724.688 kW
enthalpy, kW %
Heat input, burning of fuel 12 436.11 100.0
Heat output:
1. Useful heat gain:
Economiser 805.44 6.48
Boiler 8 026.80 64.54
Superheater 169.76 1.37
2. Heat loss in flue gases 1 724.688 13.87
3. Heat loss due to evapn. 1 168.318 9.39
4. Heat loss in refuse 289.58 2.33
5. Unaccounted heat loss 251.524 2.02
Total 12 436.11 100.00
(805.44 + 8026.8 + 169.76)

Boiler efficiency = ´ 100 = 72.4% Ans.
12 436.11
= 6.48 + 64.54 + 1.37 = 72.39% on GCV basis
Specific steam production
12 150
= = 4.86 kg/kg coal at actual conditions Ans.
2500
EXERCISE 7.20
Basis: 100 kg fuel oil
Component Mass, kg kmol O2 requirement, kmol
Carbon 84.0 7.000 7.000
Hydrogen 12.7 6.350 3.175
Sulphur 0.4 0.013 0.013
Oxygen 1.2 0.038 () 0.038
Nitrogen 1.7 0.061
Total 100.0 13.462 10.15
Total dry air = 10.15 + 38.183 = 48.333 kmol
Specific theoretical dry air requirement = 48.333 ´ 29/100
= 14.02 kg/kg fuel Ans. (a)
Moisture entering with air = 0.0155 kg/kg dry air (Ref. Fig. 6.15)
Incoming moisture = 48.333 ´ 0.025 = 1.208 kmol
Combustion 251
Composition of flue gases with theoretical air:

Gas kmol mole % (dry basis)
CO2 7.00 15.50 (Orsat)
SO2 0.013 —
H2O 6.35 + 1.208 = 7.558 —
O2 Nil —
N2 38.183 + 0.061 = 38.244 84.50
Total 52.815 (wet) 100.00
45.257 (dry)
Theoretical CO2 in flue gases = 15.50% Ans.(c)
Total dry gas gases = 45.257 kmol/100 kg fuel oil
º 0.4526 kmol/kg fuel oil
º 10.14 Nm3/kg fuel oil Ans. (b-i)
Total wet flue gases = 52.815 kmol/100 kg fuel oil
º 0.528 16 kmol/kg fuel oil
º 11.84 Nm3/kg fuel oil Ans. (b-ii)
Let x = actual O2 supply, kmol
N2, entering with O2 = 79x/21 = 3.762x kmol
Total dry air = x + 3.762x = 4.762x kmol
Excess O2 = x 10.15 kmol
Total flue gas mixture = 7.013 + x 10.15 + 3.762x + 0.061
= 4.762x 3.076 kmol (dry)
CO2 content in flue gas = [7.013/(4.762x 3.076)] = 0.065
x = 23.268 kmol
Excess air = (23.268 10.15) 100/10.15 = 129.24%
Ans. (d-i)
Total dry flue gases = (4.762 ´ 23.268) 3.076
= 107.726 kmol/100 kg fuel oil
º 1.077 26 kmol/kg fuel oil
Moisture, entering with air = 0.025 ´ 4.762 ´ 23.268
= 2.77 kmol
Total moisture in flue gases = 6.35 + 2.77
= 9.12 kmol
Total wet flue gases = 107.726 + 9.12 = 116.846 kmol/100 kg fuel oil
º 1.1685 kmol/kg fuel oil
Volume of flue gases at 100.7 kPa and 643.15 K (370 °C)
= 1.1685 ´ 8.314 ´ 643.15/100.7
= 62.047 m3/kg fuel oil Ans. (d-ii)
Mole fraction of moisture in flue gases
= 9.12/(107.726 + 9.12) = 0.078 05
Partial pressure of water vapours,
p = 100.7 ´ 0.078 05 = 7.86 kPa
Dew point = 314.35 K (41.2°C) (Ref. Table 6.13)
Ans. (e)

Component ni × kmol
ai × ni ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109
CO2 7.013 149.836 450.824 287.888 68.727
O2 13.118 381.982 13.550 160.808 526.348
N2 87.595 2592.015 450.326 1154.756 435.172
H2O 9.120 296.328 0.726 120.482 41.472
Total 116.846 3420.161 14.774 826.542 118.431
Heat lost in flue gases = 3420.161 (643.15 298.15)

+ 14.774 ´ 103 (643.152 298.152)/2
+ 826.542 ´ 106 (643.153 298.153)/3
+ 118.431 ´ 109 (643.154 298.154)/4
= 1179 956 + 2398 + 65 954 + 4528
= 1253 136 kJ
Specific enthalpy loss = 1253 136/100 = 12 531.4 kJ/kg fuel oil Ans.( f )
EXERCISE 7.21
Basis: 100 kg furnace oil
Oxygen requirement:
Element Mass, kg kmol O2 requirement, kmol

Carbon 85.65 7.138 7.138
Sulphur 3.00 0.094 0.094
Hydrogen 11.35 5.675 2.838
Total 100.00 12.907 10.070
Total (Orsat) CO2 in flue gases = 7.138 + 0.094 = 7.232 kmol

Total dry flue gas mixture = 7.232/0.115 º 62.887 kmol
Let x = kmol of oxygen supplied
Total flue gas mixture = 7.232 + (x 10.07) + 3.762x
= 4.762x 2.838 kmol
= 62.887 kmol
or x = 13.802 kmol
Excess air = (13.802 10.07) 100/10.07 = 37.06%
N2 in flue gases = 3.762 ´ 13.802 = 51.923 kmol
Humidity of air at 308 K DB and 302.5 K WB = 0.0242 kg/kg dry air
(ref. Fig. 6.15)
Moisture, entering with air = 0.0242 ´ 29 ´ 65.725/18.015
= 2.563 kmol
Total moisture in flue gases = 5.675 + 2.563 = 8.238 kmol
Combustion 253
Gas kmol, ni Molar mass, ni × Mi, mole % Orsat

Mi kg (wet basis) analysis, %
CO2 7.138 44 314.07 10.04 11.50
SO2 0.094 64 6.02 0.13
H2O 8.238 18 148.29 11.58
O2 3.732 32 119.42 5.25 5.93
N2 51.923 28 1453.84 73.00 82.57
Total 71.125 (wet) 2041.64 100.00 100.00
62.887 (dry)
Partial pressure of water vapours, p = (100 0.12) ´ 0.1158

= 11.57 kPa
Dew point = 321.85 K (48.7 °C) (Ref. Table 6.13)
Heat balance: Refer Table 7.13 for nomenclature in the text.
Steam pressure = 14 bar g = 15.013 bar a
Ts = 471.4 K (198.4°C), H = 2790 kJ/kg, h = 844.7 kJ/kg
Production of steam = 76.2 ´ 1000/6.25 = 12 192 kg/h
Continuous blow down = 1000 kg/h
hsw = 482.5 kJ/kg and hfw = 343.31 kJ/kg
Total boiler feed water input = 12 192 + 1000 = 13 192 kg/h
f4 = 13 192 (482.5 343.31) = 1836 195 kJ/h º 510.05 kW
Useful heat in economiser, f 4 = 12 192(482.5 343.31)
= 1697 005 kJ/h = 471.39 kW
Heat lost in blowdown water, f²12 = 1000(482.5 343.31)
= 139 190 kJ/h º 38.66 kW
f5 = (2790.0 482.5) 12 192 = 28 133 040 kJ/h º 7814.73 kW
Heat lost in blow-down, f¢12 = (844.7 482.5) 1000
= 362 200 kJ/h º 100.61 kW
Total heat loss in blow-down, f12 = 38.66 + 100.61 = 139.27 kW
Enthalpy of steam of 15 bar, a and 553.15 K (280°C)
= 2993.7 kJ/kg
f6 = (2993.7 2790) 12 192
= 2483 510 kJ/h
º 869.86 kW
Absolute humidity of flue gases = 148.29/(2041.68 148.29)
= 0.0783 kg/kg dry gas
CH = 1.006 + 1.84 ´ 0.0783 = 1.15 kJ/(kg × K)
Fuel firing rate = 6630/6.25
= 1060.8 kg/h
f7 = 2041.68 ´ 1060.8 ´ 1.15(550.15 298.15)/100

= 6276 529 kJ/h º 1743.48 kW (approximate calculations)
ni × kmol
Component
ai ni ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109
CO2 7.232 154.515 464.903 – 296.878 70.873
O2 3.732 108.672 3.714 – 45.749 149.743
N2 51.923 1536.448 – 266.936 684.496 – 257.953
H2O 8.238 267.670 0.656 108.830 – 37.461
Total 71.125 2067.305 202.337 405.699 – 74.798
1060.8
Heat lost in flue gas, f7 = [2067.305 (550.15 298.15)]
100
+ 202.337 ´ 103 (550.152 298.152)/2
+ 450.699 ´ 106 (550.153 298.153)/3
74.798 ´ 109 (550.154 294.154)/4]
= 10.608 (520 960.9 + 21 619.3 + 3488.4 16)
= 10.608 ´ 546 067
= 5792 679 kJ/h
º 1609.08 kW
Moisture, produced by burning H2 of fuel oil
= 5.675 ´ 18 ´ 1060.8/100 = 1084.18 kg/h
lv at 321.85 K (48.7°C) = 2388.4 kJ/kg
Heat loss due to evaporation of moisture = f8
= 1084.18 ´ 2388.4 = 2589 456 kJ/h º 719.29 kW
Dry air supply = 65.725 ´ 29 ´ 1060.8/100
= 20 219.11 kg/h
CH = 1.006 + 1.84 ´ 0.0242 = 1.0505 kJ/(kg dry air × K)
f3 = 20 219.11 ´ 1.0505 (308.15 298.15) = 212 402 kJ/h º 59.00 kW
f2 = 1060.8 ´ 1.675 (350.15 298.15) = 92 396 kJ/h = 25.67 kW
f1 = 1060.8 ´ 43 040 = 45 656 832 kJ/h º 12 682.45 kW
Thermal efficiency of the boiler
= (471.39 + 7814.73 + 689.86) 100/12 682.45
= 70.77% (Ref. Table 7.52)
Specific volume of air at 100.0 kPa and 308 K = 25.623 m3/kmol
(Ref. Table 7.8)
Molar flow rate of air = (65.725 + 2.563) 1060.8/100
= 724.4 kmol/h
Combustion 255
Volumetric flow rate of air = 724.4 ´ 25.623

= 18 561.3 m3/h
Molar flow rate of flue gases = 71.125 ´ 1060.8/100
= 754.494 kmol/h
Volumetric flowrate of flue gases = 754.494 ´ 8.314 ´ 550.15/99.82
= 34 572 m3/h Ans.
All the above results are tubulated in Table 7.52 in the text.
EXERCISE 7.22
Basis: 1 kmol methanol
CH3OH(l) + 3/2 O2(g) = CO2(g) + 2 H2O(g)
Theoretical O2 requirement = 1.5 kmol
N2 entering with air = 79 ´ 1.5/21 = 5.643 kmol
Stoichimetric air requirement = 1.5 + 5.643
= 7.143 kmol
º 207.15 kg
Ratio, stoichiometric air/fuel = 207.15/32
= 6.47 kg dry air/kg methanol Ans. (a)
NCV of liquid fuel = 638.24 kJ/mol at 298.15 K (25°C)
(Ref. Table AV.2)
Excess air = 40%
Excess O2 = 2.1 1.5 = 0.6 kmol
Actual N2 supply = 79 ´ 2.1/21 = 7.9 kmol
Component kmol Orsat analysis

dry wet mole %
CO2 1.0 1.0 10.53
N2 7.9 7.9 83.16
O2 0.6 0.6 6.31
H2O 2.0
Total 9.5 11.5 100.00
Since liquid methanol and air are available at 298.15 K (25°C), their enthalpies are
0 kJ/kmol at reference temperature.
Heat capacity CO2 N2 O2 H2O Total
constants
ni × kmol 1.0 7.9 0.6 2.0 11.5
(ni × ai)1* 21.366 233.768 15.615 64.984 335.733
(ni × ai)2* 37.174 245.834 11.060 50.317 344.385
(ni × bi)1 ´ 103 64.284 40.614 7.053 0.159 30.882

(ni × b)2 ´ 103 23.237 25.256 13.030 42.564 104.087
(ni × ci)1 ´ 106 41.051 104.145 1.405 26.421 88.109
(ni × ci)2 ´ 106 7.379 3.201 4.983 10.680 26.243
(ni × di)1 ´ 109 9.8 39.247 0.337 9.095 38.879
(ni × di)2 ´ 109 0.821 0.018 0.693 0.965 2.497
*
Suffixes 1 and 2 refer to the constants for temperature ranges 298.15 1500 K
and 1500 4000 K, respectively.
Enthalpy of flue gas at 1500 K above 298.15 K
= 335.733 (1500 298.15)
+ 30.882 ´ 103 (15002 298.152)/2
+ 88.109 ´ 106 (15003 298.153)/3
38.879 ´ 109 (15004 298.154)/4
= 403 551 + 33 371 + 98 345 49 130
= 486 137 kJ
Let T be AFT.
Enthalpy of flue gas above 1500 K
= 344.385 (T 1500)
+ 104.087 ´ 103 (T2 15002)/2
26.243 ´ 106 (T 3 15003)/3
+ 2.497 ´ 109 (T 4 15004)/4
= 638 240 (NCV of 1 kmol CH3OH) 486 137 = 152 103
By trial and error, T = 1833.27 K or 1560.12°C) Ans.
EXERCISE 7.23
Basis: Firing rate = 3000 Nm3/h
GCV = 38 574 kJ/Nm3
Total heat input = 3000 ´ 38 574 = 1.157 22 ´ 108 kJ/h
º 32 145 kW
Total enthalpy of steam at 65 bar a and 673 K = 3170.8 kJ/kg (Table AV.3)
Enthalpy of water at 373 K (100 °C) = 419.06 kJ/kg (Table AV.1)
Enthalpy, supplied for steam raising = 3170.8 419.06
= 2751.74 kJ/kg
Combustion 257
Steam generation = 1.157 22 ´ 108 ´ 0.83/2751.74

= 34 905 kg/h or 34.905 t/h Ans.
New basis: 100 kmol SNG
Air requirement
Component kmol katom C kmol H2 kmol O2
CH4 96.59 96.59 193.18 —
H2 1.29 — 1.29 —
CO 0.22 0.22 — 0.11
CO2 1.90 2.00 — 1.90
Total 100.00 98.71 194.47 2.01
194.47 0.22
Theoretical O2 requirement = 98.71 + 2.01 +
2 2
=194.045 kmol
Actual O2 supply = 194.045 ´ 1.1
=213.345 kmol
Excess O2 = 213.345 194.045 = 19.4 kmol
N2, entering through air = 79 ´ 213.345/21
=802.584 kmol
Moisture entering with air = 0.018 ´ (213.345 + 802.584)
=18.287 kmol
Total moist air =213.345 + 802.584 + 18.287
=1034.186 kmol
Specific combustion air requirement
= 1034.186/100
= 10.342 kmol/kmol SNG Ans.(b)
Total moisture in flue gas = 194.47 + 18.287 = 212.757 kmol
Composition of flue gas mixture
Component kmol Wet gas analysis Orsat

mole % gas analysis
mole %
CO2 98.710 8.71 10.72
O2 19.400 1.71 2.11
N2 802.584 70.81 87.17
H2O 212.757 18.77
Total 1133.451 (wet) 100.00 100.00
920.694 (dry)
Take reference temperature, T0 = 298.15 K (25°C)

equation constants
ni 0.0871 0.7081 0.0171 0.1877 1.0000
(ni × ai)1* 1.861 20.953 0.445 6.099 29.358
(ni × ai)2* 3.238 22.035 0.315 4.722 30.310
(ni × bi)1 ´ 103 5.599 3.640 0.201 0.015 2.175
(ni × bi)2 ´ 103 2.024 2.264 0.371 3.995 8.654
(ni × ci)1 ´ 106 3.576 9.335 0.040 2.480 8.199
(ni × ci)2 ´ 106 0.643 0.287 0.142 1.002 2.074
(ni × di)1 ´ 109 0.854 3.518 0.010 0.854 3.528
(ni × di)2 ´ 109 0.072 0.002 0.020 0.091 0.185
*
Suffixes 1 and 2 refer to the constants for temperature ranges 298.15 to 1500
K and 1500 to 4000 K, respectively.
Total heat liberated by combustion of SNG (based on NCV)
77 899.3 ´ 1000
= = 778 993 kJ/kmol SNG
100
Enthalpy of flue gas at 1500 K above 298.15 K,
H1 = 1133.451 [29.358 (1500 298.15)
+ 2.175 ´ 103 (15002 298.152)/2
+ 8.199 ´ 106 (15003 298.153)/3
3.528 ´ 109 (15004 298.154)/4]
= 42 327.4 ´ 1133.451 = 47 976 034 kJ
Let T be the flame temperature.
Enthalpy of flue gas above 1500 K (upto T)
= 778 993 ´ 100 47 976 034
= 29 923 266 kJ/100 kmol SNG
Hence
1133.451 [30.310 (T 1500) + 8.654 ´ 103 (T2 15002)/2
2.074 ´ 106 (T3 15003)/3 + 0.185 ´ 109 (T4 15004)/4]
= 29 926 186
Solving by Matcad
T = 2155.25 K or 1882.1°C Ans.(c)
Combustion 259
EXERCISE 7.24
Basis: 100 kmol SNG
Let x kmol flue gas be recycled having GCV = 0 kJ/kmol
Total mixed gas = 100 + x kmol
GCV balance (100 + x) 288 200 = 864 589 ´ 100
or x = 200.0 kmol
Let a be kmol of O2 in recycle flue gas and b be kmol of H2O in recycle flue gas.
(CO2 + N2) in flue gas recycle = 200 a b kmol
Theoretical O2 demand = 194.045 a kmol
Actual O2 supply = 1.1 (194.045 a) = 213.345 1.1 a kmol
Excess O2 = 213.345 1.1 a (194.045 a)
= 19.4 0.1 a kmol
79
N2 entering with O2 = (213.345 1.1 a)
21
= 802.584 4.138 a
Total dry air = 213.345 1.1 a + 802.584 4.138 a
= 1015.929 5.238 a kmol
Moisture, entering with air = 0.018 (1015.929 5.238 a)
= 18.287 0.0943 a kmol
Total moisture in flue gas = 194.47 + 18.287 0.0943 a + b
= 212.757 0.0943 a + b kmol
Flue Gas Composition:
Component kmol
CO2 98.71
N2 802.584 4.138 a
H2O 212.757 0.0943 a + b
O2 19.400 0.1 a
CO2 + N2 200 a b from recycled flue gas
Total 1333.451 5.3323 a
19.4 0.1 a a
O2 balance: =
1333.451 5.3323 a 200
5.3323 a2 1353.451 a + 3880 = 0
Solving for a, a = 2.9 kmol (only positive root)
º 1.45% in flue gas
H2O balance:
212.757 0.0943 a + b b
=
1333.451 5.3323 a 200
Substituting value of a,
212.484 + b b
=
1317.987 200
or b = 38.01 kmol or 19.005% in flue gas

(CO2 + N2) in recycle flue gas = 200 2.9 38.01
= 159.09 kmol
It will be safe to assume CO2/N2 ratio, same as that of combustion gases.
Check:
Theoretical O2 demand = 194.045 2.9
= 191.145 kmol
Excess O2 = 210.260 191.145 = 19.115 kmol
79
N2 entering alongwith O2 = ´ 210.260
21
= 790.978 kmol
Moisture in air = 1001.238 ´ 0.018 = 18.022 kmol
Total moisture in flue gas = 194.47 + 18.022 + 38.01
= 250.502 kmol
Component kmol Wet analysis Dry analysis
mole % mole %
CO2 98.71 + 17.66 = 116.37 8.83 10.90
O2 19.115 1.45 1.79
N2 790.978 + 141.43 = 932.408 70.72 87.31
H2O 250.502 19.00
Total 1318.395 (wet) 100.00 100.00
1067.893 (dry)
200 kmol
Recycle ratio = = 0.1517 Ans. (a)
1318.398 kmol
Heat Capacity Data:
constants
ni, kmol 0.0883 0.7072 0.0145 0.1900 1.0000
(ni × ai)1* 1.887 20.927 0.377 6.173 29.364
(ni × ai)2* 3.282 22.007 0.267 4.780 30.336
(ni × bi)1 ´ 103 5.676 3.636 0.170 0.015 2.225
(ni × bi)2 ´ 103 2.052 2.261 0.315 4.044 8.672
(ni × ci)1 ´ 106 3.625 9.323 0.034 2.510 8.174
(ni × ci)2 ´ 106 0.652 0.287 0.120 1.015 2.074
(ni × di)1 ´ 109 0.865 3.513 0.008 0.864 3.520
(ni × di)2 ´ 109 0.073 0.002 0.017 0.092 0.184
*
Suffixes 1 and 2 refer to the constants for temperature ranges 298.15 1500 K
and 1500 4000 K, respectively.
Combustion 261
Enthalpy of recycle flue gas at 448.15 K above 298.15 K, H¢

= 200 [29.364 (448.15 298.15) + 2.225 ´ 103 (448.152 298.152)/2
+ 8.174 ´ 106 (448.153 298.153)/3 3.52 ´ 109 (448.154 298.154)/4]
= 200 [4400.2 + 124.4 + 172.8 28.5]
= 200 ´ 4668.9 = 933 780 kJ
Enthalpy of total flue gas
= Heat of combustion + H¢
= 77 899 300 + 933 780
= 78 833 080 kJ/1318.395 kmol flue gas
º 59 794.7 kJ/kmol flue gas
Enthalpy of total flue gas upto 1500 K above 298.15 K
H1 = 29.364 (1500 298.15) + 2.225 ´ 103 (15002 298.152)/2
+ 8.174 ´ 106 (15003 298.153)/3 3.52 ´ 109 (15004 298.154)/4
= 35 291.1 + 2404.2 + 9123.5 4448.0
= 42 370.8 kJ/kmol flue gas
Enthalpy of flue gas above 1500 K= 59 794.7 42 370.8
= 17 423.9 kJ/kmol
Hence 30.336 (T 1500) + 8.672 ´ 103 (T2 15002)/2
2.074 ´ 106 (T3 15003)/3 + 0.184 ´ 109 (T 4 15004)/4 = 17 423.9
Solving for T by Mathcad,
T = 1935.3 K or 1662.15°C Ans. (c)
Combustion air requirement
æ 1001.238 +18.022 ö 1019.26
=ç ÷ =
è 100 ø 100
= 10.1926 kmol/kmol fuel Ans. (b)
EXERCISE 7.25
Basis: 100 kmol dry blue gas
N2 content = 2.4% which comes from air.
O2 entering with N2 = 21 ´ 2.4/79 = 0.638 kmol
Total O2, available in blue gas, is calculated in the table given below:
Gas kmol kmol C kmol O2 kmol H2

H2 48.5 48.5
CO 44.2 44.2 22.1
CO2 2.3 2.3 2.3
N2 2.4
O2 1.0 1.0
CH4 1.6 1.6 3.2
Total 100.0 48.1 25.4 51.7
O2 appeared in blue gas after decomposition of steam

= 25.4 0.638 = 24.762 kmol
Total steam decomposed = 24.762 ´ 2 = 49.524 kmol
H2, available from decomposition = 49.524 kmol
Net hydrogen from fuel = 51.7 49.524
= 2.176 kmol
º 4.352 kg
Carbon content of gas = 48.1 kmol º 577.2 kg
New basis: 100 kg coal
Total combustibles = FC + VM = 26.9 + 52.9 = 79.8 kg
Refuse = 17.5/(1.0 0.19) = 21.605 kg
Carbon content of refuse = 21.605 17.5 = 4.105 kg
Thus coal used for production of 100 kmol
blue gas = (577.2 + 4.352) ´ 100/(79.8 4.105)
= 768.283 kg
Carbon used up = 577.2 ´ 75.695/(577.2 + 4.352)
= 75.129 kg
Total carbon in fuel = 75.129 + 4.105 = 79.234 kg or mass % Ans.(c)
Net hydrogen = 79.8 79.234 = 0.566 kg or 0.57 mass %
Ans.(c)
steam decomposed (49.524 ´ 18.015)
Ratio, =
coal charged 768.283
= 1.16 kg/kg Ans. (b)
Dry blue gas produced = 100 ´ 100/768.283
= 13.02 kmol/100 kg coal Ans. (a)
EXERCISE 7.26
Basis: 100 kmol dry blue gas
H2 49.0 — — 49.0
CH4 0.8 0.8 — 1.6
CO 41.0 41.0 20.5 —
CO2 4.7 4.7 4.7 —
N2 4.5 — — —
Total 100.0 46.5 25.2 50.6
As N2 comes from air,
O2 supply from air = 4.5 ´ 21/79 = 1.196 kmol
Unaccounted O2 = 25.2 1.196 = 24.004 kmol
Unaccounted O2 is available from decomposition of steam.
Steam decomposed = 24.004 ´ 2 = 48.008 kmol
steam decomposed 48.008
Ratio, = = 0.48 kmol/kmol
coal charged 100
Combustion 263
H2 produced by decomposition of steam = 48.008 kmol

Net H2 from coal = 50.6 48.008 = 2.592 kmol
New basis: 100 kmol dry carburetted water gas

H2 37.0 37.0
CH4 14.0 14.0 28.0
CO 30.5 30.5 15.25
CO2 5.6 5.6 5.6
C3H6 7.0 21.0 21.0
O2 0.4 0.4
N2 5.5
Total 100.0 71.1 21.25 86.0
O2 from air = 21 ´ 5.5/79 = 1.462 kmol
It is assumed that fuel oil, used for carburettion, does not contain N2.
O2 provided from decomposition of steam = 21.25 1.462
= 19.788 kmol
Steam decomposed = 19.788 ´ 2
= 39.576 kmol
H2, produced by decomposition = 39.576 kmol
Net H2 from oil = 86.0 39.576 = 46.424 kmol
steam decomposed 39.576
Ratio, = = 0.396 kmol/kmol
dry carburetted gas 100
Let x be kmol of dry blue gas and y be kg of fuel oil sprayed for making 100 kmol
dry carburetted water gas. 80% C of fuel oil appears in final gas.
Carbon, available for carburettion = 0.87 ´ 0.8/12
= 0.058 kmol/kg fuel oil
Similarly, hydrogen available for carburettion
= 0.13 ´ 0.9/2
= 0.0585 kmol/kg fuel oil
Balance of carbon:
0.465 x + 0.058 y = 71.1
Balance of net hydrogen:
0.025 92 x + 0.0585 y = 46.424
Solving the simultaneous equations,
x = 57.03 kmol blue gas (dry)
y = 768.51 kg fuel oil sprayed
Total steam, decomposed for producing 100 kg dry carburetted gas
= 39.576 kmol
Steam, decomposed for producing 57.03 kmol dry blue gas
= 57.03 ´ 0.480 08 = 27.374 kmol
Steam, decomposed during carburettion = 39.576 27.374
= 12.202 kmol
º 219.64 kg
additional steam decomposed
Ratio, = 219.64/100
dry carburetted gas
= 2.196 kg/kmol Ans. (c)
dry carburetted water gas 100
Ratio, =
dry blue water gas 57.03
= 1.754 kmol/kmol Ans. (b)
fuel oil used for carburetion 768.5
Ratio, =
dry blue gas 57.03
= 13.48 kg/kmol Ans. (a)
EXERCISE 7.27
Basis: 100 kmol producer gas
H2 10.5 — — 10.5
CH4 2.1 2.1 — 4.2
C2H 4 0.4 0.8 — 0.8
CO 22.0 22.0 11.0 —
CO2 7.7 7.7 7.7 —
N2 57.3 — — —
Total 100.0 32.6 18.7 15.5
Mass, kg 391.2 598.4 31
New basis: 100 kg coal
Carbon content of refuse = [18.5/(1 0.062)]0.062
= 1.223 kg
Carbon utilised = 62 1.223 = 60.777 kg
Thus coal, used for 100 kmol dry producer gas
= 391.2/0.607 77 = 643.64 kg
N2 from coal = 643.64 ´ 0.06 = 38.62 kg º 1.38 kmol
O2 from coal = 643.64 ´ 0.093 = 59.86 kg º 1.87 kmol
N2 from air = 57.3 1.38 = 55.92 kmol
O2 from air = 21 ´ 55.92/79 = 14.86 kmol
O2 accounted for = 14.86 + 1.87 = 16.73 kmol
O2 from decomposition for steam = 18.7 16.73 = 1.97 kmol
Steam decomposed = 1.97 ´ 2 = 3.94 kmol
H2 produced due to decomposition of steam = 3.94 kmol
Vapour pressure of water 298.15 K (25°C), pw = 3.166 kPa (Table 6.13)
Humidity of producer gas = 3.166/(106.7 3.166)
Water vapours with producer gas = 0.306 ´ 100
Combustion 265
= 3.06 kmol
H2 from fuel = 15.5 3.94 = 11.56 kmol º 23.12 kg
Check from fuel analysis:
H2 from fuel = 643.64 ´ 0.036 = 23.17 kg
Moist producer gas:
Gas kmol, ni Molar mass, Mi mass, kg (ni × Mi)
H2 10.5 2 21.0
CH4 2.1 16 33.6
C2H4 0.4 28 11.2
CO 22.0 28 616.0
CO2 7.7 44 338.8
N2 57.3 28 1604.4
H2O 3.06 18 55.08
Total 103.06 2680.08
moist producer gas 2680.08
Ratio =
coal 643.64
= 4.16 kg/kg Ans. (a)
Dry air = 14.86 ´ 32 + 55.92 ´ 28 = 2041.28 kg
Absolute humidity of air at 311 K (38°C) DB and 299 K (26°C) WB,
Moisture from air = 16.4 ´ 2041.28/1000
= 33.477 kg º 1.86 kmol
moist air (2041.28 + 33.477)
Ratio, = = 3.223 kg/kg
coal 643.64
Ans. (b)
Steam supplied = 3.94 + 3.06 1.86 = 5.14 kmol
º 92.52 kg
Ratio, steam/coal = 92.52/643.64 = 0.144 kg/kg Ans. (c)
Energy balance:
Basis: 100 kmol dry producer gas
Base temperature: 298.15 K (25°C)
Enthalpy of steam at 4 bar a and 623 K (350°C) = 3170 kJ/kg
(Ref. Table AV.3)
Enthalpy of steam over 298.15 K (25°C) = 3170 104.8 = 3065.2 kJ/kg
Total enthalpy of supplied steam = 92.52 ´ 3065.2
= 283 592 kJ
Humid heat of air, CH = 1.006 + 1.84 ´ 0.0164
= 1.036 kJ/(kg dry air × K)
Total enthalpy of air = 2041.28 ´ 1.036 (311 298)
= 27 492 kJ
Calorific value of coal on as-received basis = 27 800 (1 0.185)
= 22 657 kJ/kg (dry)
Enthalpy of coal = 22 657 ´ 643.64

= 14 582 951 kJ
Component kmol × ni
H2 10.5 206.407 103.978 3036.805 – 7786.180
CH4 2.1 40.424 109.438 25.143 – 23.770
C2 H 4 0.4 1.650 62.009 – 32.618 6.790
CO 22.0 638.609 – 61.963 256.161 – 103.539
CO2 7.7 164.514 494.988 – 316.090 75.459
N2 57.3 1695.559 – 294.579 755.380 – 284.666
H2O 3.06 99.426 0.244 40.425 – 13.915
Total 103.06 2846.589 414.115 3765.206 – 8129.821
Enthalpy of producer gas at 1200.15 K over 298.15 K
= 2846.589 (1200.15 298.15) + 414.115 ´ 103 (1200.152 298.152)/2
+ 3765.206 ´ 106 (1200.153 298.153)/3
8129.821 ´ 109 (1200.154 298.154)/4
= 2567 623 + 279 775 + 2135 545 4198 471
= 784 472 kJ
Sensible heat of producer gas over 298.15 K (25 °C) = 784 472 kJ
Latent heat of water vapours at 298.15 K (25 °C) = 2442.8 kJ/kg
Heat, lost in evaporating formed water of coal = 11.56 ´ 18 ´ 2442.8
= 508 298 kJ
Calorific value of producer gas:
Gas kmol, ni GCVi, kJ/mol ni × GCVi, kJ
H2 10.5 285.83 3001 215
CH4 2.1 890.65 1870 365
C2H4 0.4 1411.2 564 480
CO 22.0 282.98 6225 560
Total 35.0 11 661 620
Enthalpy balance is given in Table 7.54 in the text. Ans.
EXERCISE 7.28
Basis: 100 kg waste liquor to be incinerated
Let x kmol of natural gas be required as the stabilizing fuel. Water liquor incineration:
Component kg kmol O2 requirement, kmol
Carbon 7.5 0.625 0.625
Hydrogen 0.5 0.250 0.125
Sulphur 5.7 0.178 0.178
Oxygen 12.5 0.391 () 0.391
Water 58.8 3.267 .Nil
Total 85.0 4.711 0.537
Combustion 267
New basis: 100 kmol natural gas (Ref. Table 7.7 in the text)
Components kmol O2 requirement CO2 production H2O production
kmol kmol kmol
CH4 89.4 178.8 89.4 178.8
C2H8 5.0 17.5 10.0 15.0
C3H8 1.9 9.5 5.7 7.6
C4H10 (total) 1.0 6.5 4.0 5.0
CO2 0.7 0.7
Total 98.0 212.3 109.8 206.4
Total theoretical O2 requirement for 100 kg waste liquor
incineration = 0.537 + (212.3 x/100)
= 0.537 + 2.123 x kmol
Total heat liberated at 298.15 K (25 °C) = 3520 ´ 100 + (855 320 x/100)
= 352 000 + 8553.20 x kJ
Actual O2 supply = 1.15 (0.537 + 2.123 x)
= 0.6176 + 2.4415 x kmol
Excess O2, appearing in flue gas = 0.0806 + 0.3185 x kmol
N2 supplied through air = 3.762 (0.6176 + 2.4415 x)
= 2.3234 + 9.1849 x kmol
Flue gas:
Component kmol
CO2 0.625 + 1.098 x = 0.625 + 1.098 x
H2O 3.267 + 0.25 + 2.064 x = 3.517 + 2.064 x
SO2 0.178
N2 0.02 x + 2.3234 + 9.1849 x = 2.3234 + 9.2049 x
O2 0.0806 + 0.3185 x
Total 6.7240 + 12.6854 x
Absolute enthalpies: (Ref. Table 5.22 from text)
Component (H° H°o + DH°f ), kJ/kmol at Absolute enthalpy

different, kJ
1200 K 475 K 298.15 K 1200 K 475 K 1200 K 298.15
CO2 339 593 376 906 384 158 37 313 44 565
H2O 194 796 223 245 229 252 28 449 34 456
SO2 303 331 340 659 347 992 37 328 44 661
N2 + 36 699 + 13 745 + 8 613 22 954 28 086
O2 + 38 399 + 13 900 + 8 597 24 499 29 802
Enthalpy of flue gas at 1200 K above 298.15 K
= (0.625 + 1.098 x) 44 565 + (3.517 + 2.064 x) 34 456
+ 0.178 ´ 44 661 + (2.3234 + 9.2049 x) 28 086
+ (0.0806 + 0.3185 x) 29 802

= 224 642 + 388 071 x kJ
However, this enthalpy rise is solely due to heat liberation due to natural gas
combustion:
224 642 + 388 071 x = 352 000 + 8553.2 x
or x = 0.3356 kmol NG/100 kg waste liquor
º 7.522 Nm3 NG/100 kg waste liquor
Flue gas analysis: Substituting the value of x, following table is obtained.
Component kmol Wet gas Dry gas Orsat
analysis, % analysis, % analysis, %
CO2 0.9935 9.05 14.67 17.30
H2O 4.2097 38.34
SO2 0.1780 1.62 2.63
N2 5.4126 49.29 79.93 79.93
O2 0.1875 1.70 2.77 2.77
Total 10.9813 (wet) 100.00 100.00 100.00
6.7716 (dry)
Furnace pressure p = 103.5 kPa
Partial pressure of water, pH O = 103.5 ´ 0.3834
2
= 39.682 kPa
From Steam Tables (Table 6.13),
Water dew point = 348.85 (75.7°C) Ans. (bi)
A = ln (pH O) = ln (39.682) = 3.6809
2
Partial pressure of SO2, pSO = 103.5 ´ 0.0162
2
= 1.6767 kPa
B = ln (pSO ) = ln (1.6767) = 0.5168
2
Substituting the values of A and B, sulphurous acid (H2SO3) dew point can be
calculated.
(1000/TDP) = 3.5752 0.1845 ´ 3.6809 9.333 ´ 104 ´ 0.5168
9.13 ´ 104 ´ 0.5168 ´ 3.6809
= 3.5752 0.6791 0.0005 0.0017 = 2.8939
Sulphurous acid dew point
TDP(SO ) = 1000/2.8939
2
= 345.55 K or 72.4°C Ans. (b-ii)
For liquid fuel (i.e. waste liquor), C/H mole ratio = 0.625/0.25
Excess air = 15%
From Fig. 7.3, sulphuric and dew point TDP(SO3) = 426 K
= 153°C Ans. (b-iii)
Enthalpy available for steam generation
= Enthalpy of flue gas at 1200 K above 475 K
= 0.9935 ´ 37 313 + 4.2057 ´ 28 449 + 0.178 ´ 37 328
+ 5.4126 ´ 22 954 + 0.1875 ´ 24 499 = 292 311 kJ
Combustion 269
Enthalpy of saturated steam at 15 bar g (16.01 bar a) = 2791.8 kJ/kg

Enthalpy of water at 350 K (77°C) = 322.33 kJ/kg
Enthalpy supplied for steam generation = 2791.8 323.33
= 2469.47 kJ/kg steam
Enthalpy to be supplied for 5000 kg/h steam
generation = 2469.47 ´ 5000
= 12 347 350 kJ/h
º 3429.82 kW
Boiler efficiency = 85%
12 347 350 ´ 100
Waste liquor firing rate = = 4969.5 kg/h
292 311 ´ 0.85
Ans. (a-i)
Stabilizing fuel (NG) firing rate = 0.3356 ´ 49.695
= 16.6775 kmol/h
º 373.81 Nm3/h Ans. (a-ii)
EXERCISE 7.29
Combustion reaction:
F m I m
H
Cn Hm + n +
4 K
O2 = n CO2 +
2
H2O
Basis: 1 mol fuel

m
Theoretic oxygen required = n + mol
4
m
Let actual oxygen supply = n + + y mol
4
F m I
Total N2 = 3.762 n +
H 4 K
+ y from air and CO2 = n mol
y
==
4.762 y + [n + (m /4)]3.762 + n
Where excess O2 = y mol
Solving the equation for y,
= LMF n + m I3.762 + nOP
y=
(1 - 4.762 = ) NH 4 K Q
By definition,
100 y
% excess air =
[n + ( m / 4)]
100 = LM
19.048 + 3.762r OP
=
(1 - 4.762 =) N
4+r Q
where r = m/n
4
For methane, r = = 4 and = = 5/100 = 0.05
1
100 ´ 0.05 LM
19.048 + 3.762 ´ 4 OP
% excess air =
[1 - ( 4.762 ´ 0.05)] N
4+4 Q
5(19.048 + 15.048)
= = 27.97% Ans.
(1 - 0.2381)8
EXERCISE 7.30
Basis: 1 mol fuel
Inerts content of fuel = a mol
Combustibles = (1 a) mol
Combustion reaction:
F m I m
(1 a)Cn Hm + (1 a) n +
H 4 K
O2 = (1 a)n CO2 + (1 a)
2
H2O
F m I
Theoretical O2 required = (1 a) n +
H 4 K
+ y mol
In flue gases,
O2 = y mol i.e. excess oxygen
Fm I
Total N2 = 3.762(1 a) n +
H4
+ y mol
K
CO2 = (1 a)n mol, Inerts = a mol
Mole fraction of oxygen in flue gases,
y
==
4.762 y + (1 - a ) n + ( m / 4) 3.762 + (1 - a )n + a
= m F I
y=
(1 - 4.762 =)
[3.762 (1 a) n +
4 H
+ n(1 a) + a]
K
By definition,
100 y
% excess air =
(1 - a)[n + ( m / 4)]
=
100= LM
19.048 + 3.762 r
+
4a OP
(1 - 4.762=) N (4 + r ) n(1 - a)( 4 + r ) Q
=
100= LM19.048 + 3.762r + c OP
(1 - 4.762=) N (4 + r ) Q f
where cf = correction factor

Combustion 271
4a
=
n(1 a)( 4 + r )
-
Now when a = 0.05
cf = 4 ´ 0.05/(1 ´ 0.95 ´ 8) = 0.0263
5 LM
19.048 + 15.048 OP
% excess air =
(1 - 0.2381) N 8
+ 0.0263
Q
= 5 ´ 34.307/(0.7619 ´ 8)
= 28.14 Ans.
EXERCISE 7.31
Basis: 1 mol fuel
Combustion reactions can be written as under:
F m I m
1 1 H 4 K
x1 Cn Hm + x1 n1 + 1 O2 = x1 n1 CO2 + x1 1 H2O
2
F m2 I m
x2 Cn Hm + x2 n2 +
2 2 H 4 K
O2 = x2 n2 CO2 + x2 1 H2O
2
F mi I mi
H
x1 Cni Hmi + xi ni +
4 K
O2 = xi ni CO2 + xi
2
H2O
i mj FG IJ
Theoretical O2 required = å xj n j +
1 4 Hmol
K
i mj FG IJ
Actual O2 supply = å xj n j +
1 4 H K
+ y mol
Mole fraction of O2 in flue gases,
= y
==
( 4.762 y + 3.762) é i æ mj ö ù i
êå x j ç n j + ÷ + xj ú + å xjnj
ëê 1 è 4 ø ûú 1
= é i æ mj ö i ù
y= ê3.762å x j ç n j + ÷ + å xi n j ú
(1 - 4.762=) ëê 1 è 4 ø 1 ûú
By definition,
100 y
% excess air =
i æ mj ö
å xj çnj + ÷
1 è 4 ø
Substituting the value of y and solving the equation,
é i ù
ê å xjnj ú
100= 1
% excess air = ê3.762 + i i ú
(1 - 4.762=) ê
ånj xj + å xjmj ú
ëê 1 1 ûú
=
100= LM
19.048 + 3.762 rm OP
(1 - 4.762=) 4 + rm N Q
i i
åx m j j å x j n j rj
1
where, rm = 1 = i
and rj = mj / nj
i
å xjnj å xjnj
1 1
EXERCISE 7.32
Basis: 1 mol fuel
Combustion reactions can be written as follows:
m F I
x1(1 a1) Cn Hm + x1 (1 a1) n1 + 1 O2
1 1 4 H K
m1
= x1 (1 a1)n1 CO2 + x1 (1 a1) H2O
2
m F I
x2(1 a2) Cn Hm + x2 (1 a2) n2 + 2 O2
2 2 4 H K
m2
= x2 (1 a2)n2 CO2 + x2(1 a2) H2O
2
m F I
xi (1 ai)Cni Hmj + xi (1 ai) n4 + i O2
4 H K
m
= xi (1 ai) ni CO2 + xi (1 a2) i H2O
2
i
Theoretical O2 required = å x j (1 aj) [nj + (mj /4)] mol
1
i
Let actual O2 supply = å x j (1 aj) [nj + (mj /4)] + y mol
1
Mole fraction of O2 in flue gases,
y
==
é ì i üù
ê4.762 y + 3.762 íå x j (1 - a j )[n j + (m j /4)]ýú
ê î1 þú
ê i 1 ú
ê +å (1 - a j )n j x j + å x j a j ú
ë 1 i û
Solving for y,
= é ìi ü
y= ê3.762 íå x j (1 - a j )[n j + (m /4)]ý
(1 - 4.762=) ë î1 þ
i i ù
+ å x j nj (1 aj) + å x j a j ú
1 1 û
Combustion 273
By definition,
% excess air = 100 y

i
å x j (1 - a j )[n j + (m j /4)]
1
Substituting the value of y and solving the equation,

é i i ù
ê å x j n j (1 - a j )å x j × a j ú
= 1 1
% excess air = ê3.762 + i ú
(1 - 4.762= ) ê
å x j (1 - a j )[n j + (m j /4)] ú
êë 1 úû
é i ù
ê å xjaj ú
= 1 1
= ê3.762 + + i ú
(1 - 4.762= ) ê 1 + rm ú
x
å j (1 - a j )[ n j + ( m j /4)]
êë 1 úû
=
= LM
3.762 rm + 19.048
+ c fm OP
(1 - 4.762=) 4 + rmN Q
i i
å x j m j (1 - a j ) å x j n j rj (1 - a j )
1 1
where rm = i
= i
å x j n j + (1 - a j ) å x j n j (1 - a j )
1 1
and cfm = åi 4 x a i
å [n j x j ][(1 - a j )(4 + rj )]
j j
1 1
EXERCISE 7.33
Fuels Firing in Reformer Furnace
Fuel Firing rate ai ri
kmol/h mole fraction xi
Natural gas 375 0.590 0.028 2.75
Tail gas 158 0.249 0.820 5.55
Naphtha 102.3 0.161 0.005 1.75
[(1 - 0.28) 0.59 ´ 2.75 + (1 - 0.82) 0.249 ´ 5.55 + (1 - 0.005) 0.161 ´ 1.75]
rm =
[(1 - 0.28) 0.59 + (1 - 0.82) 0.249 + (1 - 005) 0.161]
(1.1682 + 0.2488 + 0.2803) 1.6973
= = = 2.695
(0.4248 + 0.0448 + 0.1602) 0.6298
[4 ´ 0.59 ´ 0.028 + 4 ´ 0.249 ´ 0.82 + 4 ´ 0.161 ´ 0.005]
Cfm =
[0.59 (1 - 0.028)(4 + 2.75) + 0.249 (1 - 0.82) (4 + 5.55)
+ 0.161 (1 - 0.005) (4 + 1.75)]
(0.0661 + 0.8167 + 0.0032) 0.886

= =
(3.871 + 0.428 + 0.9211) 5.2201
= 0.1697
100 ´ 0.035 é (19.048 + 3.762 ´ 2.695) ù
Excess air = ê + 0.1697 ú
(1 - 4.762 ´ 0.035) ë (4 + 2.695) û
3.5 é 29.1866 ù
= ê + 0.1697 ú
0.8333 ë 6.695 û
= 19.02 % Ans.
8
Stoichiometry and
Industrial Problems
EXERCISE 8.1
Basis: 100 L/min 3 N potassium solution, entering the tower
Concentration of K in solution = 39 ´ 3
= 117 g/L
Ingoing solution:
K in K2CO3 form = 0.7 ´ 117 = 81.9 g/L
K2CO3 in solution = 138 ´ 81.9/78 = 144.9 g/L
K in KHCO3 form = 0.3 ´ 117 = 35.1 g/L
KHCO3 in solution = 100 ´ 35.1/39 = 90 g/L
Outcoming solution :
K in K2CO3 form = 0.32 ´ 117 = 37.44 g/L
K2CO3 in solution = 138 ´ 37.44/78 = 66.24 g/L
K in KHCO3 form = 0.68 ´ 117 ´ 100/39 = 204 g/L
Ans. (a)
Liquor rate = 1.65 L/s = 5940 L/h
K2CO3 in entering solution = 144.9 ´ 5940/1000 = 860.7 kg/h
KHCO3 in entering solution = 90 ´ 5940/1000 = 534.6 kg/h
K2CO3 in outgoing solution = 66.25 ´ 5940/1000
= 393.5 kg/h
KHCO3 in outgoing solution = 204 ´ 5940/1000
= 1211.8 kg/h
Chemical reaction, accompanying absorption is as follows:
K2CO3 + CO2 + H2O = 2 KHCO3
Molar mass 138 44 18 2 ´ 100
K2CO3 converted to KHCO3 = 860.7 393.5 = 467.2 kg/h

CO2 absorbed = 467.2 ´ 44/138 = 149 kg/h Ans. (b)
H2O reacted = 467.2 ´ 18/138 = 60.9 kg/h
Total KHCO3 produced = 467.2 + 149.0 + 60.9

= 677.1 kg/h
Total KHCO3 in outgoing solution = 534.6 + 677.1
= 1211.7 kg/h
This calculated total KHCO3 tallies with the figure of 1211.8 kg/h, calculated
earlier.
New basis: 100 kmol of incoming gas mixture
CO2 content = 18 kmol
Outgoing gas mixture contains 6.9% CO2.
Quantity of outgoing gas mixture = 82/(1 0.069)
= 88.08 kmol
CO2 absorbed = 100 88.08 = 11.92 kmol
CO2 recovery = 11.92 ´ 100/18 = 66.2% Ans. (c)
CO2 absorption rate for 1.65 L/s flowrate = 149/44
= 3.386 kmol/h
Incoming gas rate = 100 ´ 3.386/11.92
= 28.4 kmol/h Ans. (d)
EXERCISE 8.2
Basis: 100 kmol dry flue gas, leaving boiler furnace. Let x kmol dry air mixes
with flue gas.
Balance of dry flue gas across RAH:
100 ´ 0.14 = (100 + x) 0.125
x = 12 kmol
Thus 0.12 kmol dry air mixes with one kmol dry flue gas. Ans. (a)
Dew point of flue gas = 319.3 K (46.3°C)
Vapour pressure of water at 319.3 K, pw = 10.242 kPa
Total pressure of flue gas, leaving boiler furnace,
p = 100 kPa
10.242
Moisture, present in flue gas from boiler, =
(100 - 10.242)
= 0.114 kmol/kmol dry flue gas
Total wet flue gas = 100 + 11.4 = 111.4 kmol
Humidity of air at 313 K DB and 295 K WB
= 0.0134 kg/kg dry air
= 0.0216 kmol/kmol dry air
Dry air mixing with flue gas = 12 kmol
Wet air mixing with flue gas = 12 (1 + 0.0216)
= 12.259 kmol
Stoichiometry and Industrial Problems 277
Wet Flue Gas Before RAH

Component kmol
ai bi ´ 103 ci ´ 106 di ´ 109
CO2 14.0 299.12 899.98 574.71 137.20
O2 3.0 78.08 35.27 7.03 1.69
N2 83.0 2456.04 426.70 1094.18 412.34
H2O 11.4 370.41 0.91 150.60 51.84
Total 111.4 3203.65 509.46 663.04 328.67
Combustion Air
Component kmol
ai bi ´ 103 ci ´ 106 di ´ 109
O2 0.21 5.47 2.47 0.49 0.12
N2 0.78 23.08 4.01 10.28 3.87
Ar 0.01 0.21
H2O 0.0216 0.70 0.29 0.10
Total 1.0216 29.46 1.54 10.08 4.09
Reference temperature, T0 = 298.15 K (25°C)
Enthalpy of flue gas, entering RAH;
z
523.15
H1 = (3203.65 + 509.46 ´ 103 T + 663.04 ´ 106 T 2 328.67 ´ 109 T 3) dT
298.15
= 788 175 kJ/100 kmol dry flue gas from boiler
Enthalpy of flue gas, leaving RAH (excluding air being mixed),
z
433.15
H2 = (3203.65 + 509.46 ´ 103 T + 663.04 ´ 106 T 2 328.67 ´ 109 T 3) dT
298.15

12 kmol dry air (with accompanying moisture) mixes with flue gas at 313.15 K
and heat upto 433.15 K. Enthalpy of air at 313.15 K,
z
313.15
H3 = (29.46 1.54 ´ 103 T + 10.08 ´ 106 T 2 4.09 ´ 109 T 3) dT
298.15
= 447.21 kJ/kmol dry air

Enthalpy of air at 433.15 K,
z
433.15
H4 = (29.46 1.54 ´ 103 T + 10.08 ´ 106 T 2 4.09 ´ 109 T 3) dT
298.15

Heat transferred in RAH to combustion air

H5 = H1 H2 12 (H4 H3)
= 788 175 467 501 12 (4057.17 447.21)
º 2773.5 kJ/kmol dry flue gas, entering RAH Ans. (b)
100
Combustion air required =
1.045
= 95.694 kmol wet air
º 93.67 kmol dry air
Let T be the temperature of combustion air after RAH.
z
T
(93.67) (29.46 1.54 ´ 103 T + 10.08 ´ 106 T2 4.09 ´ 109 T3) dT = 277 354
298.15
Solving by Mathcad, T = 396.95 K or 123.8°C Ans. (c)

12 ´ 100
Increase in capacity of air blower =
93.67
= 12.81% Ans. (d)
Instead of RAH, a tubular heater is used,
heat transfer duty, H¢5 = 788 175 467 501
= 320 674 kJ/100 kmol dry flue gas
T¢
3
(93.67) ò (29.46 1.54 ´ 10 T ¢ + 10.08 ´ 106 T¢2 4.09 ´ 109 T¢3) dT = 320 674
298.15
Solving by Mathcad, T ¢ = 412.25 K or 139.1°C Ans.
EXERCISE 8.3
Basis: 4000 kg/h production rate of 1,3-butadiene
Molar feed rate of n-butane = 1.818 ´ 3600/58 = 6545.5/58
= 112.85 kmol/h
Butene-1 formed = 112.85 kmol/h
H2 produced due to reaction (1) = 112.85 kmol/h
Butadiene formed = 4000/54 = 74.07 kmol/h
Butene-1 consumed to produce butadiene = 74.07 kmol/h
H2 produced due to reaction (2) = 74.07 kmol/h
Butene-1 consumed to produced ethylene = 112.85 74.07
= 38.78 kmol/h
Butene-1 recycled = 6.642 kg/s = 23 911 kg/h = 426.96 kmol/h
Ethylene produced = 38.78 ´ 2 = 77.56 kmol/h
Yield of butadiene = 74.07 ´ 100/112.85 = 65.64%

Total H2 produced = 112.85 + 74.07 = 186.92 kmol/h
Offgas analysis:
.
Component n i, kmol/h mole %
H2 186.92 70.67
C2H4 77.56 29.33
Total 264.48 100.00
Composition of hot gases, leaving reactor:
.
Component n i, kmol/h mole %
Butene-1 426.96 55.77
1, 3-Butadiene 74.07 9.68
Hydrogen 186.92 24.42
Ethylene 77.56 10.13
Total 765.51 100.00
Ans. (a)
Enthalpy of reactants:
.
Component kmol/h Temp., (H° H°o+ DH°f )i n i × (H° H°o + DH°f )i
.
ni K (°C) kJ/kmol kW
n-Butane 112.85 920 (647) 24 494 767.82
Butene-1 426.95 920 (647) 131 000 15 536.24
Total 539.80 16 304.06
Enthalpy of products:
.
Component kmol/h Temp., (H° H°o+ DH°f )i n i × (H° H°o + DH°f )i
.
ni K (°C) kJ/kmol kW
Butene-1 426.96 810 (537) 110 850 13 146.50
1, 3-Butadiene 74.07 810 (537) 204 386 4 205.24
Hydrogen 186.92 810 (537) 23 386 1 214.25
Ethylene 77.56 810 (537) 105 220 2 266.91
Total 765.50 20 832.90
Heat of reactions, DHr = 20 832.9 16 304.06
= 4528.84 kW (endothermic) Ans. (b)
At T = 273.15 K:
Antoine constants from Table .5.4,
A = 3.997 98, B = 941.662 and C = 32.753
p = 1.2047 bar or 120.5 kPa
F 425 27315
. I
0.38
lv = 22 470
H 425 268.7 K
= 22 223 kJ/kmol
(H° H°o + DH°f ) at 273.15 K of 1,3-butadiene = 139 270 kJ/kmol
Total heat to be removed for condensation of 1,3-butadiene
= (204 386 139 270) + 22 223
= 87 339 kJ/kmol
Total heat removed = 87 339 ´ 74.07/3600
= 1797 kW Ans. (d)
EXERCISE 8.4
It can be noticed that the concentration of a component in the effluents changes
with respect to time. This is because when the acid is introduced, the bed is full
of water which is replaced by acid during the course of time. Till the water is
replaced by acid, no appreciable chlorides can be found in the effluents. After
sometime (about 10 minutes in this case), chlorides start appearing in the effluents
and its concentration reach to a peak value at the end of the acid introduction
step. At the start of slow rinse, the bed is full with acidic water, and hence the
concentration of chlorides taper out as the slow rinse proceeds.
It can be further noticed that FMA is observed in the effluents after a longer
period. This is because acid is completely consumed by cations in the beginning.
Such an example can be solved by a geometric technique. A graph is plotted
(refer Fig. E8.1) of the concentration of chloride and FMA vs. time.
Area under the chloride curve from the start of acid introduction step to the end
of slow rinse step = 191.67 square units. It is desired to segregate 85% of these
chlorides.
Chlorides to be segregated = 191.67 ´ 0.85
= 162.92 square units.
Careful evaluation of the chloride curve indicates that area, corresponding to
163.60 square units, is represented by a period of 50 minutes; ranging from 20
minutes from the start of acid introduction step. Ans. (a)
Area under the chloride curve 20 minutes to 52 minutes (i.e. 32 minutes) from
the start of acid introduction step = 107.421 square units
Area under the chloride curve from the start of slow rinse period to the end of
segregation period = 163.60 107.421 = 56.179 square units
Volume of concentrated effluent = (32 ´ 63/60) + (18 ´ 54/60)
= 33.6 + 16.2
= 49.8 m3 Ans. (b ii)
Volume of dilute effluents = (20 ´ 63/60) + (27 ´ 54/60)
= 21 + 24.3
= 45.3 m3 Ans. (b ii)
Acid Entry Slow Rinse
60000
54000
48000
42000
Concentration in mg/L
36000
30000
24000
e Curve
18000
Chlorid
e
urv
12000
AC
FM
6000
0
10 20 30 40 50 60 70 80 90 100
Time in minutes
Concentration of chlorides:
Scales of the graph: x-axis: 2 units = 10 min
y-axis: 2 unit = 6000 mg/L (i.e. ppm)
Thus 4 square unit = 10 ´ 6000 = 60 000 (min × ppm)
Chloride (Cl):
Concentrated stream:
Acid introduction step:
Area = 60 000 ´ 107.421/4 = 1611 315 (min × ppm)
Chlorides, eluted in 32 min = 1611 315/32
= 50 354 ppm or g/m3
Chlorides, eluted in acid introduction step, i.e. in
33.6 m3 = 50 354 ´ 33.6
= 1691 881 g
Slow rinse step:

Area of chloride elution = 60 000 ´ 56.179/4 = 842 685 (min × ppm)
Chlorides, eluted in 18 min = 842 685/18
= 46 816 ppm or g/m3
Chlorides, eluted in slow rinse step, i.e. in
16.2 m3 = 46 816 ´ 16.2 = 758 417 g
Total chlorides in concentrated stream
= 1691 881 + 758 417
= 2450 298 g
º 2450.3 kg
Average concentration of chlorides in concentrated stream
= 2450 298/49.8
= 49 203 g/m3 or ppm Ans. (ci)
Weak stream:
Area under the chloride curve upto first 20 min from start of acid introduction
= 7.647 sq. units
Area = 60 000 ´ 7.647/4 = 114 705 (min × ppm)
114 705
Chlorides, eluted in 20 min =
20
= 5732 ppm or g/m3
Chlorides, eluted in acid introduction step, i.e. in
21 m3 = 5732 ´ 21 = 120 377 g
Slow rinse step:
Area under the chloride curve after 72 min = 19.919 sq. units
Chlorides, eluted in (52 + 45 70 =) 27 min
= 19.919 ´ 60 000/4 = 298 785 (min × ppm)
Chlorides, eluted = 298 785/27 = 11 066 ppm or g/m3
Chlorides eluted in 24.3 m3 = 11 066 ´ 24.3
= 268 907 g
Total chlorides in weak effluent stream = 120 377 + 268 907
= 389 284 g
º 389.3 kg
Average concentration of chlorides in weak
effluent stream = 389 284/45.3
= 8593 g/m3 or ppm
Free Mineral Acidity (FMA):
Concentrated stream:
Area under FMA curve during acid introduction step = 36.232 sq. units
Area = 36.232 ´ 60 000/4 = 543 480 (min × ppm)

FMA, eluted in 32 min = 543 480/32
= 16 984 ppm or g/m3
FMA, eluted in 33.6 m3 = 16 984 ´ 33.6
= 570 654 g
Slow rinse step:
Area under FMA curve, during slow rinse = 49.885 sq. units
Area = 49.885 ´ 60 000/4 = 748 275 (min × ppm)
FMA, eluted in 18 min = 748 275/18
= 41 571 ppm or g/m3
FMA, eluted in 16.2 m3 = 41 571 ´ 16.2
= 673 448 g
Total FMA in concentrated stream = 570 654 + 673 448
= 1244 102 g
º 1244.1 kg
Average concentration of FMA in concentrated stream
= 1244 102/49.8
= 24 982 g/m3 or ppm Ans. (c ii)
Weak stream
There is no weak stream during acid introduction step.
Slow rinse step:
Area under FMA curve during slow rinse
= 15.631 sq. units
Area = 15.631 ´ 60 000/4 = 234 465 (min × ppm)
FMA, eluted in 27 min = 234 465/27 = 8684 ppm or g/m3
FMA, eluted in 24.3 m3 = 8684 ´ 24.3 = 211 019 g º 211.0 kg
Average concentration of FMA in weak effluent stream
= 211 019/45.3 = 4658 g/m3 or ppm
Chlorides curves give total acid introduced
Total HCl (100%) consumed during regeneration
= (2450 298 + 389 284) 36.5/(36.5 ´ 1000)
= 2919.48 kg as 100% HCl
º 9.268 t as 31.5% HCl Ans.(d)
Total FMA = (673 448 + 211 019)/1000 = 884.47 kg
Excess acid = 884.47 ´ 100/(2919.48 884.47) = 43.5%
Ans. (e)
EXERCISE 8.5
Concentrations of all hydrocarbons, except ethane, are above the higher limit. By
pressure purging, it is required to bring down the concentrations below the lower
limits. It may further be noted that butane (total) concentration is 73.6% by
volume (highest amongst all hydrocarbons) and its lower limit is 1.9% by volume
(lowest). Hence, if butane concentration is brought down below 1.9%, bullet
will be safe for hotwork.
p1 = 0.25 bar g = 1.263 25 bar a
p2 = 2.5 bar g = 3.513 25 bar a
c0 = 73.6% by vol.
1.263 25
c1 = ´ 73.6 = 26.46% after first cycle of purging
3.513 25
Similarly, after repeated purgings
c2 = 0.359 57 ´ 26.46 = 9.518%
c3 = 0.359 57 ´ 9.518 = 3.422%
c4 = 0.359 57 ´ 3.422 = 1.230% which is less than 1.9%.
Thus 4 cycles of pressure purging are required. Ans. (a)
Similar calculations can be made for other hydrocarbons.
Gas Concentration after 4 cycles

Ethane 0.02
Propane 0.42
Butane 1.23
Total 1.67
Nitrogen in bullet after 4 cycles = 100 1.67
= 98.33% Ans.(b)
Nitrogen requirement at 0.25 bar g and 308.15 K
= (p2 p1)/p1
(3.513 25 1.263 25)
=
1.263 25
= 1.781 m3/(m3 vessel volume × cycle)
Total nitrogen requirement = 1.781 ´ 4 ´ 22
= 156.728 m3 at 0.25 bar g and 308.15 K
27315
. 1.263 25
º 156.728 ´ ´
308.15 1.013 25
º 173.2 Nm3 Ans.(c)
EXERCISE 8.6
Solution Refer data of Exercise 8.5.
Assume that bullet is at atmospheric pressure after nitrogen purgings.
Specific volume of gas at 1.013 25 bar a and 308.15 K
0.083 14 ´ 308.15
V m1 = = 25.284 57 m3/kmol
1.013 25
22
Total gas inside the bullet =
25.284 57
= 0.8701 kmol
At the end of purging with nitrogen and at atmospheric pressure (i.e. at
101.325 kPa),
hydrocarbons = 0.8701 ´ 0.0167 = 0.0145 kmol
N2 in bullet = 0.8701 0.0145 = 0.8556 kmol
Air pressurization is done upto 4 bar g or 5.013 25 bar a.
0.083 14 ´ 308.15
V m2 = = 5.1104 m3/kmol
5.013 25
Total gas in bullet after pressurization
22
= = 4.305 kmol
5.1104
Air introduced = 4.305 0.8701 = 3.4349 kmol
O2 introduced = 3.4349 ´ 0.21 = 0.7213 kmol
O2 in bullet after first pressurization cycle
0.7213
= = 0.1675 or 16.75% (v/v)
4.305
After depressurization to atmospheric pressure, again quantity of gas in bullet
will be 0.8701 kmol.
Oxygen in bullet = 0.8701 ´ 0.1675
= 0.1457 kmol
After second cycle of pressurization,
total oxygen in bullet = 0.1457 + 0.7213
= 0.867 kmol
0.867
O2 concentration in bullet =
4.305
= 0.2014 or 20.14% (v/v)
Thus oxygen concentration will be well above 18% after 2 cycles of pressurization.
Ans. (a)
Compressed air requirement = 3.4349 ´ 2
= 6.8698 kmol
Volumetric air requirement = 6.8698 ´ 22.414
= 154 Nm3 Ans. (b)
EXERCISE 8.7
Basis: 10 500 kg/h feed to bent tube evaporator
Solids in feed = 10 500 ´ 0.3155 = 3312.75 kg/h
Water in feed = 10 500 3312.75 = 7187.25 kg/h
Bent tube evaporator :
Amount of 60% liquor = 3312.75/0.6 = 5521.25 kg/h
Evaporators load = 10 500 5521.25 4978.75 kg/h
Vapours are produced at 383 K.
Saturation pressure at 383 K for water = 143.3 kPa a
From steam tables, h = 461.32 kJ/kg, H = 2691.3 kJ/kg
and lv = 2230.0 kJ/kg (Table AIV.2)
Take base temperature T0 = 298.15 K (25°C)
Heat given to vapours = 2691.3 104.8 = 2586.5 kJ/kg
Total heat in vapours = 2586.5 ´ 4978.75/3600 = 3577.09 kW
Enthalpy to be supplied to feed = 5521.25 ´ 225.7/3600
= 346.15 kW
Total heat load of the evaporator = 3577.09 + 346.15
= 3923.24 kW
At p = 190 kPa g, Ts = 405.4 K (132.4°C) lv = 2166.6 kJ/kg
Steam consumption in the evaporator = 3923.24 ´ 3600/2166.6
= 6518.8 kg/h
Wiped film evaporator:
Amount of 90% liquor = 3312.75/0.9 = 3680.83 kg/h
Water evaporated = 5521.25 3680.83 = 1840.42 kg/h
Enthalpy of liquid leaving the evaporator
= 3680.83 ´ 202.2/3600 = 206.74 kW
Enthalpy of liquid, entering the evaporator
= 346.15 kW
Temperature of water vapours = 410 K (137°C)
At T = 410 K, ps = 3.32 bar a and H = 2729.2 kJ/kg
Enthalpy of vapours = 1840.42 (2729.2 104.8)/3600
= 1341.67 kW
Total heat load of evaporator = 1341.67 + 206.74 346.15
= 1202.26 kW
For steam at p = 12 bar g, Ts = 464.6 K and lv = 1970.7 kJ/kg
Steam consumption = 1202.26 ´ 3600/1970.7 = 2196.2 kg/h
Auger Agitated Calciner:

Enthalpy of liquid, entering the calciner
= 206.74 kW
Enthalpy of dry solid mixture = 3312.75 ´ 581.5/3600
= 535.1 kW
Water evaporated in calciner = 3680.83 3312.75
= 368.08 kg/h
Temperature of vapours = 473 K(200°C)
ps = 15.55 bar a of water
However, the vapours are produced at 101.325 kPa a and 473 K (200°C).
Total enthalpy of water vapours = 2875.4 kJ/kg
Enthalpy of water vapours = [(2875.4 104.8) 368.08]/3600
= 283.28 kW
Heat transfer in calciner = 535.1 + 283.28 206.74
= 611.64 kW
Results are summarised in Table 8.52 in the text.
EXERCISE 8.8
Basis: 1000 kg cell liquor
NaOH content of liquor = 1000 ´ 0.109 = 109 kg
NaCl content of liquor = 1000 ´ 0.1526 = 152.6 kg
Water in the liquor = 1000 109 152.6 = 738.4 kg
Reaction: 2 NaOH + SO2 = Na2SO3 + H2O
Molar mass 2 ´ 40 64 126 18
Since reaction goes to completion,
Na2SO3 produced = 126 ´ 109/80 = 171.67 kg
Water produced = 18 ´ 109/80 = 24.53 kg
Evaporation loss = 71 kg
Final quantity of water = 738.4 + 24.53 71
= 691.93 kg
Concentration of NaCl in sulphited liquor
= 152.6 ´ 100/691.93
= 22 g/100 g water or 22 kg/100 kg water
From Fig. 8.14, at 373.15 K (100°C), the solubility of Na2SO3 in the presence of
22 kg NaCl/100 kg water = 7.75 kg/100 kg water
Dissolved Na2SO3 in solution = 7.75 ´ 691.93/100
= 53.63 kg
Na2SO3 crystallized = 171.7 53.63 = 118.07 kg
Yield of Na2SO3 = 118.07 ´ 100/171.7 = 68.8% Ans. (a)
In the second case, water is partially evaporated till the invariant composition is
reached at 373.15 K (100°C).
Solubility of NaCl at this point = 38 kg/100 kg water
Solubility of Na2SO3 at this point = 3.0 kg/100 kg water
To attain solubility of 38 kg NaCl/100 kg water, final water quantity after evapn.
= 152.6 ´ 100/38
= 401.6 kg
Water to be evaporated = 691.93 401.6 = 290.33 kg
Na2SO3 in final solution = 3 ´ 4.016 = 12.05 kg
Na2SO3 crystallised = 171.7 12.05 = 159.65 kg Ans.(b-i)
Overall Yield = 159.65 ´ 100/171.7 = 93.0%
Ans.(b-ii)
In the third case, common salt is added to the extent that the invariant composition
at 373.15 K (100°C) is attained.
Final quantity of NaCl in solution = 38 ´ 691.93/100
= 262.93 kg
Salt added = 262.93 152.6
= 110.33 kg Ans.(c-i)
Na2SO3 in solution = 3 ´ 691.93/100 = 20.76 kg
Yield of Na2SO3 = 171.7 20.76 = 150.94 kg
Overall Yield = 150.94 ´ 100/171.7 = 87.9%
Ans. (c ii)
Instead of concentrating the sulphited liquor, if cooling of solution is carried out
to 273.15 K (0°C), yield of Na2SO3 can be improved. From Fig. 8.14 at invariant
point,
NaCl concn. = 33.6 kg/100 kg H2O at 273.15 K
For NaCl concn. of 22.0 g/100 g H2O at 273.15 K(0°C),
solubility of Na2SO3 = 5.0 kg/100 kg H2O
These crystals are heptahydrate.
Na2SO3 in solution = 5 ´ 691.93/100 = 34.6 kg
Yield of crystals = 171.7 34.6 = 137.1 kg
Water, associated with crystals = 18 ´ 7 ´ 137.1/126
= 137.1 kg
Thus water, retained in the solution = 691.93 137.1
= 554.83 kg
This change in water quantity will change the solubility of NaCl and Na2SO3.
Due to this reason, a trial and error method is required.
After a number of trial and error iterations,
solubility of NaCl = 152.6 ´ 100/554.82
= 27.5 kg/100 kg H2O
This gives an indication that the final solubility if NaCl in the solution will be
higher than that of 27.5 kg/100 kg H2O.
Assume final solubility = 28 g NaCl/100 g H2O
Final quantity of water = 152.6 ´ 100/28
= 545 kg
From Fig. 8.14, solubility of Na2SO3 at 273.15 K (0°C) in presence of 28 kg
NaCl/100 kg H2O = 4.25 kg/100 kg H2O.
Na2SO3 in solution = 4.25 ´ 545/100 = 23.16 kg
Na2SO3 crystallised = 171.7 23.16 = 148.54 kg Ans.(d-i)
Water, associated with crystals = 148.54 ´ 18 ´ 7/126
= 148.54 kg
Final water quantity = 691.93 148.54 = 543.39 kg
This quantity closely tallies with 545 kg water.
Overall Yield = 148.54 ´ 100/171.7 = 86.5% Ans. (d-ii)
EXERCISE 8.9
Basis: 5000 kg/h MgCl2 as product rate
Amount of final product = 5000/0.9 = 5555.6 kg/h
MgO present in final product = 5555.6 ´ 0.05 = 277.8 kg/h
H2O in final product = 5555.6 5000 277.8 = 277.8 kg/h
1 mole MgO = 1 mole MgCl2
277.8 kg/h MgO corresponds to 95.3 ´ 277.8/40.3 = 656.9 kg/h MgCl2.
HCl produced = 2 ´ 36.5 ´ 656.9/95.3 = 503.2 kg/h
H2O consumed = 18 ´ 656.9/95.3 = 124.1 kg/h
Total MgCl2 in the feed = 5000 + 656.9 = 5656.9 kg/h
Feed contains 48% solids (by mass).
Feed rate = 5656.9/0.48 = 11 785.2 kg/h
Evaporation in the dryer = Total feed (Amount of MgCl2 + Mass of water in
product Mass of water reacted)
= 11 785.2 (5656.9 + 277.8 124.1)
= 5974.6 kg/h Ans. (a)
Calculation of total heat load requires following considerations.
(i) Latent heat of water vapours.
(ii) Heat of crystallisation of MgCl2 from the solution.
(iii) Heat of reaction between MgCl2 and H2O.
(iv) Sensible heat of water vapour from the feed temperature to outlet gas
temperature.
(v) Sensible heat of solids from feed temperature to the outlet gas temperature.
(vi) Heat loss from the system
lv of water at 101.325 kPa a = 2256.9 kJ/kg

Heat supplied for evaporation, f1 = 5974.6 ´ 2256.9/3600
= 3745.6 kW
In addition, sensible heat will be supplied to the water vapour to raise its temperature
from 393 K to the outlet gas temperature, i.e. 573 K.
Average heat capacity of water vapour between 393 K and 573 K
= 1.985 kJ/(kg × K).
Sensible heat, f2 = 5974.6 ´ 1.985 (573 393)/3600
f2 = 592.98 kW
Reaction: MgCl2(s) + H2O(l) = MgO(s) + 2 HCl(g)
DH°f 601.7 285.83 601.7 2 ´ 92.31
DH°r = 601.7 2 ´ 92.31 [ 641.32 285.83]
= +140.83 kJ/mol MgCl2 at 298.15 K (25°C) (endothermic)
º + 70.415 kJ/mol HCl at 298.15 K (25°C) (endothermic)
º + 1931.25 kJ/kg HCl at 298.15 K (25°C) (endothermic)
Change in DH°r with respect to the temperature is neglected.
Heat absorbed during reaction, f3 = 1931.25 ´ 503.2/3600
= 269.95 kW
Heat of crystallisation = (heat of solution)
= [801.15 (641.32)] = 159.83 kJ/mol MgCl2
= 1678.7 kJ/kg MgCl2 at 25°C (298.15 K)
(endothermic)
Heat absorbed during crystallisation,
f4 = 5656.9 ´ 1678.7/3600 = 2637.84 kW
Heat to be supplied to HCl, f5 = 503.2 ´ 0.816 (573 393)/3600
= 20.53 kW
Heat, supplied to MgCl2, f6 = 5000 ´ 0.873 (573 393)/3600
= 218.25 kW
Heat, supplied to MgO, f7 = 277.8 ´ 1.277 (573 393)/3600
= 17.74 kW
Heat supplied to water present in final solid mixture,
f8 = 277.8 ´ 4.1868 (573 393)/3600
= 58.15 kW
8
Total heat load, f = å fi
1
= 3745.6 + 592.98 + 269.95 + 2637.84
+ 20.53 + 218.25 + 17.74 + 58.15
= 7561.04 kW Ans.(b)
.
Enthalpy of dry flue gases, f9 = n ´ 1.006 (798 573)/3600
.
= 0.0629 n kW
.
where n = dry flue gas flow, kg/h
For enthalpy of water vapours, use total enthalpy of water vapour at 101.325
kPa and 798 K (525°C) and 573 K (300°C).
Enthalpy of water at 798 K = 3541.7 kJ/kg over 273.15 K
Enthalpy of water at 573 K = 3074.5 kJ/kg over 273.15 K
Enthalpy of water vapours accompanying flue gas,
.
f10 = n ´ 0.03 (3541.7 3074.5)/3600
= 0.0039 n kW
Total heat given up by flue gas = f9 + f10
.
= (0.0629 + 0.0039)n
.
= 0.0668 n kW
= 7561.04 kW
.
n = 113 189 kg/h of dry flue gas
º 3903.07 kmol/h
Water vapours = 113 189 ´ 0.03/18
= 188.65 kmol/h
Total wet flue gas = 3903.07 + 188.65
= 4091.72 kmol/h
Specific volume of gas at 101.325 kPa a and 798 K
= (8.314 14 ´ 798.15)/101.325
= 65.492 m3/h
Incoming flue gas rate = 4091.72 ´ 65.492
= 267 975 m3/h Ans.(c-i)
Outgoing gas mixture = 4091.72 + (503.2/36.5) + (5726.4/18)
(124.1/18)
= 4091.72 + 13.79 + 318.13 6.89
= 4416.75 kmol/h
Specific volume of gas at 101.325 kPa a and 573 K
= 8.314 14 ´ 573.15/101.325
= 47.029 m3/kmol
Volumetric flow rate of outgoing gas mixture
= 4416.75 ´ 47.029 = 207 715 m3/h
Ans.(c-ii)
Notes: (a) The reaction, mentioned in the above example, takes place in two
steps.
MgCl2 + 2 H2O = Mg(OH)2 + 2 HCl
Mg(OH)2 = MgO + H2O
However, overall reaction is sufficient for mass and heat balances.

(b) The system will be under slight positive pressure. However, in solving the
problem, the pressure difference is neglected.
(c) The product discharge temperature is assumed to be equal to the outlet flue
gas temperature. This is a safe assumption.
EXERCISE 8.10
Basis: 186 minutes of operation
Hydrogen liberated = Hydrogen from electrolysis of water
Hydrogen equivalent to SO4, migrated from
catholyte + Hydrogen from electrolysis of H2SO4
= Hydrogen from electrolysis of water
Hydrogen equivalent to SO4, produced by
decomposition of FeSO4 Hydrogen equivalent
to SO4 + Hydrogen from electrolysis of H2SO4
= Hydrogen from water + Hydrogen equivalent to SO4,
produced by decomposition of FeSO4.
O2 liberated = 3.331 Nm3 = 0.1486 kmol º 4.756 kg
Equivalent hydrogen = 2 ´ 4.756/16 = 0.5945 kg
Fe deposited = 5.313 kg
Equivalent hydrogen = 2 ´ 5.313/56 = 0.1897 kg
Hydrogen liberated = 0.5945 0.1897 = 0.4048 kg
º 0.2024 kmol º 4.54 Nm3 Ans. (b)
Let a = amount of final catholyte,
b = amount of final anolyte and
c = total amount of water evaporated; all in kg
Fe balance at the cathode:
Fe in final catholyte = Fe in initial catholyte Fe deposited
(0.018 ´ 56/152)a = (15.6 ´ 56/152) 5.313
a = 65.6 kg Ans. (a i)
SO4 balance at the cathode:
SO4 in final catholyte = SO4 in the initial catholyte SO4 migrated to anode
compartment
H2SO4 in initial anotyte = 0.03 ´ 59 = 1.77 kg
SO4 migrated = (0.177 b 1.77) 96/98 kg
SO4 in initial catholyte = (3.9 ´ 96/98) + (15.6 ´ 96/152)
= 3.8204 + 9.8526 = 13.6730 kg
SO4 in final catholyte = 65.6 [(0.018 ´ 96/152) + (0.0155 ´ 96/98)]
= 1.7418 kg
1.7392 = 13.6730 [(0.177 b 1.77) 96/98]
b = 78.81 kg Ans.(a-ii)
Overall material balance yields evaporation.

Evaporation = 100 + 59 65.6 78.81 5.313 4.756 0.405
= 4.116 kg Ans.(c)
4
Current = 4000 ´ 186 ´ 60 = 4464 ´ 10 coulombs
= 4464 ´ 104/96 580 = 462.208 Faradays
Equivalent mass of Fe = 56/2 = 28
Theoretical Fe liberation = 462.208 ´ 28
= 12 942 g
º 12.942 kg
actual Fe liberation
Current efficiency = ´ 100
theoretical Fe liberation
= 5.313 ´ 100/12.942
= 41.05% Ans. (d)
EXERCISE 8.11
Basis: 100 kmol NG (natural gas) input
Let a, b, c and d be kmol of H2, CO, CO2 and H2O, respectively in the reactor
outlet gases.
Let e be kmol of CH4 and f be kmol of O2 supply (98% by vol.)
Inerts (Ar + N2) in supply NG = 1.95 + 0.4 = 2.35 kmol
Inerts (Ar) in O2 supply = 0.02f kmol
Inerts in outgoing gas mixture = 2.35 + 0.02f kmol
Total moles of outgoing gas mixture,
n = a + b + c + d + e + 2.35 + 0.02f kmol
CH4 balance :
e
= 0.0035 (1)
n
H2 balance:
a + d + 2e = 93.25 ´ 2 + 3.32 ´ 3 + 0.88 ´ 4 + 0.2 ´ 5
= 186.5 + 9.96 + 3.52 + 1.00
= 200.98 (2)
Carbon balance:
b + c + e = 93.25 + 3.32 ´ 2 + 0.88 ´ 3 + 0.2 ´ 4
= 93.25 + 6.64 + 2.64 + 0.8
= 103.33 (3)
O2 balance:
0.5 b + c + 0.5 d = 0.98 f
b + 2 c + d = 1.96 f (4)
Limiting reaction is steam-methane reaction. Its approach to equilibrium is 30 K.
Since this reaction is endothermic, the composition of outgoing gas mixture will
be determined by chemical equilibrium at 1395 30 = 1365 K.
Now as per Daltons law,

pi = p × yi and yi = ni /n
æ (e / n) p × ( d / n ) p ö edn 2
Therefore, Kp1 = ç 3÷
= 3 2 = 2.5207 ´ 105
è (b / n) p × [(a / n) p] ø a bp
System pressure, p = 2.0 MPa a = 19.7385 atm a
edn 2
Kp1 = = 2.5207 ´ 105
a b (19.7385) 2
3
edn 2
or 3
= 9.8209 ´ 103 (5)
a b
Shift reaction is exothermic and hence it reaches almost to completion at such a
high temperature. Thus chemical equilibrium of shift reaction at 1395 K is taken
for calculations.
( a / n) × (c / n) × p 2
Kp2 = = 0.4465
(b / n) × ( d / n) × p 2
ac
or = 0.4465 (6)
bd
Six simultaneous equations will yield six unknowns. Equations (5) and (6) are
complicated. Therefore trial and error method is suggested.
Iteration-1: Let n = 300 kmol. The increase in number of moles is evident as
reforming reaction is a primary reaction.
e = 0.0035 ´ 300 = 1.05 kmol
a + d 200.98 2 ´ 1.05 = 198.88 kmol
b + c = 103.33 1.05 = 102.28 kmol
Substitute values of n and e in Eq. (5),
1.05 ´ d (300) 2
= 9.8209 ´ 103
a 3b
1.05 ´ (300 ) 2 ´ 10 3 d d
or b= ´ 3 = 9.6223 ´ 106 3
9.8209 a a
Within this iteration, assume a value of d, obtain values of a, b and c. Calculate
the ratio (ac/bd) which should be 0.4465 [Ref. Eq. (6)].
Let d1 = 30 kmol; a = 168.88 kmol
b = 59.93 kmol, c = 42.35 kmol
ac/ad = 168.88 ´ 42.35/(30 ´ 59.93) = 3.978 # 0.4465
Assume d 2 = 35 kmol; a = 163.38 kmol
b = 77.22 kmol, c = 25.06 kmol
ac/ad = 1.5149 # 0.4465
d, kmol a, kmol b, kmol c, kmol ac /ad

(assumed)
30 168.88 59.93 42.35 3.978 > 0.4465
35 163.88 77.22 25.06 1.5149 > 0.4465
37 161.88 83.94 18.34 0.9559 > 0.4465
39 159.88 91.83 10.45 0.4665 > 0.4465
39.5 159.88 93.88 8.40 0.361 < 0.4465
39.1 159.78 92.23 10.05 0.4453 < 0.4465
1.96 f = 92.23 + 2 ´ 10.05 + 39.1 = 151.43

f = 77.26 kmol
n = 159.78 + 92.23 + 10.05 + 39.1 + 1.05 + 2.35 + 77.26 ´ 0.02
= 306.105 kmol
Iteration-2:
Let n = 306 kmol
e = 0.0035 ´ 306 = 1.07 kmol
a + d = 200.98 1.07 ´ 2 = 198.84
b + c = 103.33 1.07 = 102.26
1.07 ´ d ´ (306) 2
3
= 9.8209 ´ 102
a b
or b = 10.2018 ´ 106 d/a3
Iteration:
d, kmol a, kmol b, kmol c, kmol ac / ad

(assumed)
39.1 159.74 97.862 4.398 0.1841 < 0.4465
38 160.84 93.17 9.09 0.4130 < 0.4465
37.8 161.04 92.335 9.925 0.4579 > 0.4465
37.85 160.99 92.544 9.716 0.44655 ; 0.4465
1.96 f = 92.544 + 2 ´ 9.716 + 37.85
= 149.826
or f = 76.442 kmol
n = 160.99 + 92.544 + 9.716 + 37.85 + 1.05 + 2.35 + 76.442 ´ 0.02
= 306.049 kmol
; 306 kmol (nearly same as assumed)
O2 supply = 0.7644 kmol/kmol natural gas Ans. (a)
Mathcad can be of particular use for solving such simultaneous equations.
Values of iterative calculations are used in following tables.
Analysis of exit gas mixture:
Component dry gas wet gas

kmol mole % kmol mole %
H2 160.990 60.03 160.990 52.60
CO 92.544 34.50 92.544 30.24
CO2 9.716 3.62 9.716 3.17
H2O — — 37.850 12.37
CH4 1.070 0.40 1.070 0.35
N2 1.950 0.73 1.950 0.64
Ar 1.929 0.72 1.929 0.63
Total 268.199 100.00 306.049 100.00
Steam/dry exit gas = 37.850/268.199
= 0.1411 kmol/kmol Ans.(b)
Enthalpy of reactants: Ref. Table 5.22
Component kmol Temperature Enthalpy, kJ/kmol ni × (H° H°o DH°f )i

ni K (H° H°o + DH°f )i kJ
CH4 93.25 422 52 247 4 871 996
C2H6 3.32 422 49 736 165 123
C3 H8 0.88 422 56 164 49 424
n-C4H10 0.20 422 64 005 12 801
N2 1.95 422 12 187 + 23 765
O2 74.91 400 12 277 + 919 673
Ar 1.929 400
Total 176.439 4 155 906
Enthalpy of products: Ref. Table 5.22
Temperature of product stream = 1395 K
Component kmol Temperature Enthalpy, kJ/kmol ni × (H° H°o DH°f )i
ni K (H° H°o + DH°f )i kJ
H2 160.99 1395 + 41 315 + 6 651 282
CO 92.544 1395 – 70 120 – 6 489 197
CO2 9.716 1395 – 328 410 – 3 190 833
H2O 37.85 1395 – 186 030 – 7 041 238
CH4 1.07 1395 + 12 386 + 13 253
N2 1.95 1395 + 43 372 + 84 576
Ar 1.929 1395 — —
Total 306.049 9 972 157
Enthalpy, supplied to argon = 20.7723 (1395 400) ´ 1.929
= 39 869 kJ
Enthalpy change during reactions, DH

= 9972 157 (4155 906) + (39 869)
= 5856 120 kJ (exothermic) per 100 kmol
º 5856 kJ/kmol feed gas Ans. (c)
Relatively small exothermic enthalpy change can be attributed to heat loss from
the system by radiation. As such the reaction proceeds autothermally.
Note: For iterative calculations, a spreadsheet (such as Excel) or a mathematical
software (such as Mathcad) can be very useful. Refer Example 9.14).
EXERCISE 8.12
Let x kg be the fuel oil required for decomposition.
Reactions: H2SO4 = H2O + SO3 (A)
SO3 = SO2 + 1/2 O2 (B)
2 NH4HSO4 + 1/2 O2 = N2 + 5 H2O + 2 SO2 (C)
C + O2 = CO2 (D)
H2 + 1/2 O2 = H2O (E)
Carbon of organics, present in spent acid = 5.1 ´ 5/6.1
= 4.18 kg
Hydrogen of organics, present in spent acid = 5 4.18
= 0.82 kg
Carbon content of fuel oil = 6.2 x/(7.2 ´ 12) = 0.0718 x kmol
Hydrogen content of fuel oil = 1 ´ x/(7.2 ´ 2) = 0.0694 x kmol
Component kg Molar mass kmol O2 requirement, kmol
H2SO4 20 98 0.2041 0.1021
NH4HSO4 45 115 0.3913 + 0.0978
Cm Hn C 4.18 12 0.3483 + 0.3483
H 0.82 2 0.4100 + 0.2050
H2O 30.0 18 1.6667
Total 100.00 3.0204 0.5490
Total SO2, formed by decomposition = 0.2041 + 0.3913

= 0.5954 kmol
H2O formed by decomposition = 1.6667 + 0.41 + 2.5 ´ 0.3913 + 0.2041
= 3.2591 kmol
CO2 formed = 0.3483 kmol
N2 formed = 0.5 ´ 0.3913 = 0.1957 kmol
Fuel oil combustion yields CO2 = 0.0718 x kmol
H2O = 0.0694 x kmol
O2 required in exit gas mixture = 1.2 ´ 0.5954
= 0.7145 kmol
Total dry gas mixture = SO2 content + CO2 content

+ O2 content + N2 content
O2 required for combustion of fuel = 0.0718 x + (0.0694/2) x
= 0.1065 x kmol
Total oxygen supply = 0.1065 x + 0.5490 + 0.7145
= 1.2635 + 0.1065 x kmol
Corresponding N2 supply from air = (79/21) (1.2635 + 0.1065 x)
= 4.7532 + 0.4006 x kmol
Total N2 in exit gas mixture = 0.1957 + 4.7532 + 0.4006 x
= 4.9489 + 0.4006 x kmol
Total dry gas mixture = 0.5954 + 0.3483 + 0.0718 x + 0.7145
+ 0.4006 x + 4.9489
= 6.6071 + 0.4724 x kmol
0.5954
= 0.06
(6.6072 + 0.4724 x )
Solving the equation, x = 7.0219 kg fuel oil/100 kg spent acid
Total dry air supply = 1.2635 + 0.1065 x + 4.7532 + 0.4006 x
= 6.0167 + 0.5071 x
= 6.0167 + 0.5071 ´ 7.0219
= 9.5775 kmol
Humidity of air = 12.8 g/kg dry air @
DB = 308 K, and WB = 296 K
= 0.0206 kmol/kmol dry air
(Ref. Fig. 6.15)
Moisture of air = 0.0206 ´ 9.5775 = 0.1975 kmol
Total water in exit gas mixture = 3.2591 + 0.0694 x + 0.1975
= 3.9439 kmol
Total exit gas mixture = 0.5954 + 0.3483 + 0.0718 ´ 7.0219
+ 0.7145 + 0.4006 ´ 7.0219
+ 4.9489 + 3.9439
= 13.8682 kmol (wet)
New basis: 860 t/d spent acid
Hourly feed rate = 860 000/24 = 35 833.3 kg/h
Multiplying factor, based on original feed rate of 100 kg = 358.333
LHV of fuel oil = 43 000 kJ/kg
Heat liberated by combustion = 43 000 ´ 7.0219 ´ 358.333/3600
= 30 054.35 kW
Organics in spent acid = 5 ´ 358.333
= 1791.67 kg/h
LHV of organics = 41 870 kJ/kg

Heat liberated by combustion = 1791.67 ´ 41 870/3600
= 20 838.12 kW
Total air requirements = (9.5775 + 0.1975)
= 9.775 kmol/100 kg spent acid
Combustion air requirements = 9.775 ´ 358.333
= 3502.7 kmol/h (moist)
Enthalpy of dry air = 1.006 ´ 9.5775 ´ 358.333 ´
29 (723.15 298.15)/3600
= 11 820.11 kW
Enthalpy of water vapour at 101.325 kPa and 723.15 K = 3382.4 kJ/kg
Enthalpy of water vapour at 298.15 K = 2547.3 kJ/kg
Enthalpy of water vapours at 723.15 K accompanying air
= 0.1975 ´ 358.333 (3382.4 2547.3) ´ 18/3600
= 295.50 kW
Total enthalpy of wet air = 11 820.11 + 295.50
= 12 115.61 kW
Total heat supplied = enthalpy of air + combustion heat of fuel
and organics
= 12 115.61 + 30 054.25 + 20 838.12
= 63 007.98 kW
Heat utilisation = 98%
Heat utilised = 63 007.98 ´ 0.98 = 61 747.82 kW
Heat of solution of NH4HSO4 = 1019.85 (1026.96)
= + 7.11 kJ/kmol NH4HSO4 (endothermic)
º 61.768 kJ/kg NH4HSO4
Total NH4HSO4 dried = 45 ´ 358.333 = 16 125 kg/h
Heat supplied during crystallization
= 61.768 ´ 16 125/3600
f1 = 276.27 kW (exothermic)
Acid concentration of spent acid (without NH4HSO4)
= [20/(20 + 30)] ´ 100 = 40%
This is to be dehydrated to 100%.
SO3 in dilute acid = (40 ´ 80)/(98 ´ 80) = 0.408 kmol
H2O in dilute acid = (0.408 ´ 18 + 60)/18 = 3.741 kmol
H 1 = 2.093 kJ/mol H2O (Ref. Table 5.64)
H 2 = 135.65 kJ/mol SO3 (Ref. Table 5.64)
At 100% concentration, = H 1 = H 2 = 44.34 kJ/mol
Dehydration:
Dilute acid + Heat of mixing = 100% acid + water
( 2093 ´ 3.741) + ( 135 650 ´ 0.408) + DH

= ( 0.408 ´ 44 340) + ( 0.408 ´ 44 340) + 0
Heat of dilution, DH = 18 091 18 091 + 7830 + 55 345
= + 26 993 kJ/100 kg 40% acid (H2SO4)
(endothermic)
Original acid rate = (20/0.4) ´ 358.333
= 17 916.65 kg/h
Heat to be supplied for dehydration, f2
= 17 916.65 ´ 26 993/(100 ´ 3600)
= 1343.40 kW
Enthalpy of vaporization of water at 291.15 K (18°C) = 2459 kJ/kg
Water to be evaporated = 30 ´ 358.33 ´ 0.6 = 10 750 kg/h
Heat, supplied for evaporation f3
= 10 750 ´ 2459/3600
= 7342.85 kW
Reaction 1: H2SO4(l) = H2O(g) + SO2(g) + 1/2 O2(g)
DH°r1 = 241.82 296.83 ( 813.99)
= + 275.34 kJ/mol H2SO4 º 2807.3 kJ/kg H2SO4 (endothermic)
Reaction 2: 4 NH4HSO4(s) + O2(g) = 2 N2(g) + 10 H2O(g) + 4 SO2(g)
DH°r2 = [10 ( 241.82) + 4 ( 296.83)] [4 ( 1026.96)]
= + 502.32 kJ/4 kmol NH4HSO4
º + 125.58 kJ/mol NH4HSO4 (endothermic)
º + 1091.0 kJ/kg NH4HSO4
Total heat of reaction = [(17 916.65 10 750) 2807.3
+ 16 125 ´ 10 91]/3600
f4 = 10 475.36 kW (endothermic)
Since calculations of heats of reactions involve water in the vapour phase, f3
need not be considered for product waters.
4
Total heat to be supplied = å fi
i
= 1343.40 + 7342.85 + 104 75.36 276.27

= 18 885.34 kW
Sensible heat of product gaseous stream over 298.15 K,
f6 = 61 747.82 18 885.34 = 43 362.48 kW
Assume mean specific heat of product gas stream to be 1.255 kJ/(kg × K).
Flue gas flow rate = 13.8682 ´ 358.333 = 4969.43 kmol/h (wet)
Average molar mass of product gas stream
= 0.5954 ´ 64 + 0.8525 ´ 44 + 0.7145 ´ 32
+ 7.7619 ´ 28 + 3.9439 ´ 18
= 386.8 kg/13.8682 kmol

º 27.89 kg/kmol
Let the final temperature of product gas stream be T K.
4969.43 ´ 27.89 ´ 1.255 (T 298.15)/3600 = 43 362.48
T 298.15 = 897.47
T = 1195.62 K (922.47°C)
This temperature is lower than the desired decomposition temperature of about
1275 K (1002°C).
2nd iteration:
Final desired temperature = 1275 K
Additional heat to be supplied = 4969.43 ´ 27.89 (1275.15 1195.62) 1.255/3600
= 3842.62 kW
Additional fuel, required to be fired
= 3842.62 ´ 3600/(43 000 ´ 358.333)
= 0.8978 kg/100 kg spent acid
New x = 7.0219 + 0.8978 = 7.9197 kg/100 kg spent acid
Total dry air supply = 6.0167 + 0.5071 ´ 7.9197
SO2 in exit gas mixture = 0.5954 ´ 100/(6.6071 + 0.4724 ´ 7.9197)
= 5.75%
Mositure, entering with air = 10.033 ´ 0.0206
Moist air = 10.033 + 0.2067 = 10.2397 kmol/100 kg spent acid
Total moisture in exit gas mixture
= 3.2591 + 0.0694 ´ 7.9197 + 0.2067
Flow rate of exit gas mixture = 6.6071 + 0.4724 ´ 7.9197 + 4.0154
This means, exit gas mixture flow rate will increase by 14.3638/13.8682 = 1.0357
times or 3.57% increase. This increase in exit gas mixture will require additional
fuel to raise the exit gas temperature to 1275 K. For a rise of (1275.15 1195.62)
= 79.53 K, addition fuel required is 0.8978 kg/100 kg spent acid.
Due to increase in exit gas flow rate, additional fuel required
(14.3638 - 13.8682)1000 ´ 0.8978
=
13.8682 ´ 79.53
= 0.4034 kg/100 kg spent acid
New x = (7.9197 + 0.4034) = 8.3231 kg/100 kg spent acid
3rd iteration:
Assume x = 8.6 kg/100 kg spent acid
SO3 in exit gas mixture = 0.5954 ´ 100/(6.6071 + 8.6 ´ 0.4724)
= 5.57%
Total dry air supply = 6.0167 + 0.5071 ´ 8.6
= 6.0167 + 4.3611 = 10.3778 kmol
Moisture with air = 10.3778 ´ 0.0205
Total moisture in exist gas mixture
= 3.2591 + 0.0694 ´ 8.6 + 0.2138
CO2 in exit gas mixture = 0.3483 + 0.0718 ´ 8.6
N2 in exit gas mixture = 4.9489 + 0.4006 ´ 8.6
Component kmol Heat capacity C°mp equation constants

ni ai × ni ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109
SO2 0.5954 17.748 37.479 26.351 6.622
CO2 0.9658 20.635 62.086 39.647 9.465
O2 0.7145 18.595 8.399 1.674 0.402
N2 8.3941 248.389 43.154 110.659 41.702
H2O 4.0697 132.233 0.324 53.764 18.507
Total 14.7395 434.600 65.134 96.751 44.524
Additional heat liberated = (8.6 7.0219) 43 000 ´ 358.333/3600
= 6754.41 kW
Total heat of exit gas mixture = 43 362.48 + 6754.41 = 50 116.89 kW
º 180 420 804 kJ/h
Additional heat available from air is neglected.
Enthalpy of exit gas at T K over 298.15 K
= 358.333 [434.6 (T 298.15) + 65.134 ´ 103 (T2 298.152)/2
+ 96.751 ´ 106 (T 3 298.153)/3 44.524 ´ 109 (T 4 298.154/4]
= 180 420 804
= 155 732 T 46 408 136 + 11.67 T2 1036 343
+ 0.0116 T3 317 563 3.99 ´ 106 T4 + 31466
= 49 239.12 ´ 3600 = 177 260 832
3.99 ´ 106 T 4 + 0.0116 T3 + 11.67 T2 + 155 732 T = 224 991 408
By trial and error or by Mathcad, T = 1261.69 K or 988.54°C
This temperature is lower than 1275 K.
4th iteration:
Let x = 8.6 + 0.3 = 8.9 kg/100 kg spent acid
Dry air = 6.0167 + 0.5071 ´ 8.9 = 10.53 kmol
Moisture with air = 10.53 ´ 0.0206 = 0.2169 kmol
Total moisture in exit gas mixture
= 3.2591 + 0.0694 ´ 8.9 + 0.2169
= 4.0937 kmol
CO2 in exit gas mixture = 0.3483 + 0.0718 ´ 8.9
= 0.9873 kmol
N2 in exit gas mixture = 4.9469 + 0.4006 ´ 8.9
= 8.5122 kmol
Component kmol Dry Heat capacity C°mp equation constants
gas
ni ai × ni ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109
mole %
SO2 0.5954 5.51 14.748 37.479 26.351 6.622
CO2 0.9873 9.13 21.094 63.468 40.529 9.675
O2 0.7145 6.61 18.595 8.399 1.674 0.402
N2 8.5122 78.75 251.884 43.761 112.215 42.289
H2O 4.0937 133.013 0.326 54.081 18.616
Total 14.9031 100.00 439.334 65.911 97.742 45.01
Additional heat generted = 0.3 ´ 43 000 ´ 358.333/3600
= 1284.03 kW
Total heat of exit gas mixture = 50 116.89 + 1284.03
= 51 400.92 kW
º 185 043 312 kW
Enthalpy of exit gas at T K over 298.15 K Ans. (i)
3
= 358.333 [439.334 (T 298.15) + 65.911 10 (T 298.15)/2
+ 97.742 ´ 106 (T 298.153)/3 45.01 ´ 109 (T 298.154)/4]
= 185 043 312 kJ
By trial and error, T = 1274.28 K or 1001.13°C Ans.(i)
This temperature is very close to 1275 K and hence acceptable.
Total fuel oil fired = 8.9 ´ 358.333
= 3189.2 kg/h
º 76.54 t/d Ans.(iii)
Enthalpy of exit gas at 623.15 K over 298.15 K
= 358.333 [439.334 (623.15 298.15) + 65.911 ´ 103 (623.15 298.152)/2
+ 97.742 ´ 106 (623.153 298.153)/3
+ 45.01 ´ 109 (623.154 298.154)/4]

= 358.333 ´ 158 063 = 56 639 189 kJ/h
= 15 733.11 kW
Heat liberated due to additional fuel firing
= (8.9 7.0219) 43 000 ´ 358.333/3600
= 8038.43 kW
Total moist air = (6.0167 + 0.5071 ´ 8.9) 1.0206
= 10.7469 kmol
Additional heat due to air= (10.7469 9.775) 12 115.61/9.775
= 1204.62 kW
Partial pressure of water vapours in exit gas stream,
pH O = 4.0937 ´ 106.7/14.9031
2
= 29.309 kPa º 219.84 Torr
A = ln (pH2O) = 3.3779
Water dew point = 341.6 K (68.6°C) (Ref. Table 6.13) Ans. (ii)
pSO = 0.5954 ´ 106.7/14.9031 = 4.263 kPa º 31.97 Torr
2
B = ln (pSO2) = 1.45
Sulphurous acid dew point (Ref. Exercise 7.28):
1000/TDP = 3.5752 0.1845 ´ 3.3779
9.333 ´ 104 ´ 1.45
9.13 ´ 104 (3.3779 ´ 1.45)
TDP(SO2) = 339.45 K (66.3°C)
Therefore air must be introduced at about 345 K (72°C). a 5 K margine.
Enthalpy of air 345 K (72°C)
= 10.53 (1.006 + 1.84 ´ 0.0128) 358.33 (345 298.15)/3600
= 50.72 kW
Enthalpy of air at 723 K (450°C) = 10.7469 ´ 12 115.61/9.775
= 13 320.23 kW
Enthalpy supplied in air preheater = 13 320.23 50.72
= 13 269.51 kW
º 12 404.73 kJ/kmol
Total air required in furnace for decomposition
= (10.7469) 358.333
= 3850.97 kmol/h (moist)
Heat, given up by exit gas stream in air preheater
= 51 400.92 15 733.11
= 35 667.81 kW
Total air preheated = 35 667.81 ´ 3600 ´ 0.98/12 404.73
= 10 144.19 kmol/h
Portion of air, sent to furnace = 3850.97 ´ 100/10 144.19

= 38.0 %
Air, used for steam generation = 10 144.19 3850.97
= 6293.22 kmol/h
This air is utilised for saturated steam generation at 11 bar a.
At p = 11 bar a, Ts = 457.1 K (184.1°C), h = 781.12 kJ/kg
l v = 1998.5 kJ/kg and H = 2779.7 kJ/kg from Steam Tables (AIV.2)
Since steam temperature is 457.1 K, it may not be economical to cool the air
below 510 K (237 °C).
Enthalpy of air at 510.15 K over 298.15 K
= 6293.22 ´ 29 (1.006 + 1.84 ´ 0.0128) (510.15 298.15)/3600
= 11 065.54 kW
Steam generation = 11 065.54 ´ 3600 ´ 0.98/(2779.7 104.8)
= 14 594.7 kg/h say 14.59 t/h Ans. (iv)
EXERCISE 8.13
Basis: 1 kmol benzene formation in reactor (net)
Profit a (conversion)0.5
Profit a (yield)3
Therefore porfit function a (conversion)0.5 (yield)3
Profit function is to be maximised. Since the values of conversion and
corresponding yield are available in Table 8.56, a graph (Fig. E8.2) of conversion
vs. profit [i.e. (conversion)0.5 (yield)3] is plotted. Another (second) graph is plotted
for conversion vs. yield.
Conversion, % 50 66 70 75 85
Relative Profit Function 0.686 0.776 0.780 0.790 0.742
From the first graph, for a maximum profit, conversion = 76%
Corresponding yield = 96.55% from the second curve
Toluene charged to the reactor (by definition)
= 1/(conversion ´ yield)
= 1/(0.76 ´ 0.9685) = 1.3586 kmol
Let x, y and z be the kmol of benzene, methane and diphenyl in the gross feed to
the reactor, respectively.
Total oil in the gross feed = 1.3586 + x + z kmol
H2 in the gross feed = 5(1.3585 + x + z) kmol
Toluene reacted = 1.3586 ´ 0.76
= 1.0325 kmol (total)
Total benzene produced = 1.0325 kmol
H2 utilised in conversion to benzene = total benzene formed
= 1.0325 kmol
0.82 100

0.80 99
Max. Profit
Relative Profit Function
0.78 98
0.76 97
Yield, %
96.55
on
e r si
0.74 96
nv
Yie
Co
/S
ld
tV
V/S
ofi
0.72
Co
Pr
95
nve
rsio
n
0.70 94
0.68 93
50 60 70 76 80 90 100
Conversion
Hydrogen formed in side reaction = (1.0325 1)/2

= 0.016 25 kmol
Toluene reacted = 1.0325 kmol (total)
Methane formed = 1 + 0.0325 = 1.0325 kmol
Amounts of the components in the exit of reaction:
Hydrogen = 6.793 + 5 x + 5 z 1.0325 + 0.016 25
= 5.776 75 + 5x + 5z kmol = 6.0933
Methane = 1.0325 + y kmol = 6.0877
Benzene = 1 + x kmol
Toluene = 1.3586 1 0.0325 = 0.3261 kmol
Diphenyl = z + 0.016 25 = 0.021 67 kmol
The effluent gas mixture goes to the phase separator. Let x1 kmol benzene escape
in the vapour phase while x2 kmol benzene are recycled to the reactor. This does
not include the liquid product, used for quenching reactor exit stream. This small
quantity is fixed on the basis of temperature control and is independent of liquid
product, processed further for recovery of benzene.
Benzene in vapour phase
= 0.005
Benzene in liquid phase
x1/(1 + x2) = x2
Benzene column separates 95% benzene.
0.05(1 + x2) = x2
x2 = 0.052 63 kmol
x1 = 0.005 (1.052 63) = 0.005 263 kmol
Similarly, toluene column separates only 75% diphenyl
(z + 0.016 25) 0.25 = z
z = 0.005 42 kmol
H2 in exit stream = 5.776 75 + 5 ´ 0.057 89 + 0.005 42 ´ 5
= 5.776 75 + 0.289 45 + 0.0271
= 6.0933 kmol
CH4 in exit stream = 1.0325 + y kmol
Both these components leave in total in vapour phase from the seperator as the
concentration ratios in vapour phase to liquid phase is ¥ (infinite).
Benzene in vapour phase, x1 = 0.005 263 kmol
Toluene in vapour phase = 0.001 ´ (0.3261 toluene in vapour phase)
= 0.000 3258 kmol
Diphenyl in vapour phase = 0 kmol
Compositions of vapour stream from the separator, recycle gas stream and purge
gas stream are same.
H 2 in vapour phase
= 0.5
Total gas in vapour phase
6.0933
= 0.5
(6.0933 + 1.0325 + y + 0.005 263 + 0.000 3258)
y = 5.0552 kmol
Total vapour phase mixture = 6.0933/0.5 = 12.1866 kmol
Methane in vapour phase = 1.0325 + 5.0552
= 6.0877 kmol
Let A kmol are purged out and M kmol is the quantity of fresh feed.
Methane balance:
Methane in recycle stream + methane in make-up gas
= Methane in gross fed
[(12.1866 A) 6.0877/12.1866] + 0.05 M = 5.0552
0.4995 A 0.05 M = 1.0325
(1)
Hydrogen balance:
Hydrogen in recycle stream + Hydrogen in make-up gas
= Hydrogen in gross feed
(12.1866 A)0.5 + 0.95 M = 6.793 + 5 ´ 0.057 89 + 5 ´ 0.005 42
= 7.109 55
0.5 A + 0.95 M = 1.016 25
(2)
Solving the simultaneous equations,
M = 2.2775 kmol and A = 2.2948 kmol
Composition of steam from phase separator:
Component vapour phase liquid phase

kmol kg mole % kmol kg mass %
H2 6.093 3 12.186 6 50.00 0
CH4 6.087 7 79.062 4 49.95 0
C6H6 0.005 363 0.410 5 0.043 1.052 63 82.105 14 71.14
C7H8 0.000 3258 0.029 97 0.007 0.325 7742 29.971 23 25.97
C12H10 0 0 0 0.021 67 3.337 18 2.89
Total 12.186 589 91.689 47 100.00 1.400 0742 115.41355 100.00
Benzene column:
Benzene recovered = 78 kg (final net product)
Bottom product = 115.413 55 78 = 37.413 55 kg
Toluene column:
Diphenyl in bottom product = 0.021 67 ´ 0.75
= 0.016 25 kmol
º 2.502 89 kg
Toluene in fresh feed = 1.3586 0.325 7742
= 1.032 858 kmol
º 85.02 kg
All these calculations can be prorated for 1000 kg/h benzene product from benzene
column. These data are summarised in Table 8.55. Also these data are summarised
in Fig. 3.6. Ans.
EXERCISE 8.14
Basis: Product gas stream from Reactor-II = 100 kmol/h
HCN in the product gas stream = 5.9 kmol/h
Reaction (ii):
CH4 consumed = 5.9 kmol/h
NO consumed = 5.9 kmol/h
H2O produced = 5.9 kmol/h
5.9
H2 produced = = 2.95 kmol/h
2
Let a, b and c kmol/h of CH4, consumed as per reaction (iii), (iv) and (v),
respectively.
H2 produced = 4b + 3c as per reactions (iv) and (v)
CO2 produced = a + b as per reactions (iii) and (iv)
CO produced = c = 1.2 kmol/h
Let d be the consumption (in kmol/h) of NH3 as per reaction (vi)
H2O produced = 1.5 d
Total H2 produced = 2.95 + 4b + 3c = 7.5 kmol/h
Substituting value of c, b = 0.2375 kmol/h
CO2 in product gas stream = 2.0 kmol/h = a + b
a = 2 0.2375 = 1.7625 kmol/h
O2 consumed as per reaction (iii) = 1.7625 ´ 2
= 3.525 kmol/h
3
O2 consumed as per reaction (vi) = d kmol/h
4
N2 produced by reaction (vi) = 0.5 d kmol/h
N2 comes from air, introduced in Reactor I and that produced by reaction (vi).
N2 from air = 56.7 0.5 d
100
Total dry air = (56.7 0.5d)= 71.7722 0.6329 d
79
H2O, entering with air = 0.024 (71.7722 0.6329)d
= 1.7225 0.0152 d kmol/h
NO production by reaction (i) = NO consumed by reaction (ii)
= 5.9 kmol/h
H2O produced by reaction (i) = 1.5 ´ 5.9
= 8.85 kmol/h
Total H2O accounted = 5.9 + 2a + 1.5d + 8.85 + 1.7225 0.0152d
= 16.4725 + 2a + 1.4848 d
= 25.1
Substituting value of a, d = 3.4365 kmol/h
Total dry air, entering Reactor I = 71.7722 3.4365 ´ 0.6325
= 69.5972 kmol/h
H2O, entering Reactor I with air = 1.7225 0.0152 ´ 3.4365
= 1.6699 kmol/h
21
O2, entering Reactor I in air = (56.7 0.5d)
79
21
= (56.7 0.5 ´ 3.4365)
79
= 14.6154 kmol/h
N2, entering Reactor I = 56.7 0.5 ´ 3.4365
= 54.9818 kmol/h
NH3, reacted as per reaction (vi) = d = 3.4365 kmol/h
Total NH3, consumed in both reactors = 5.9 + 3.4365 + 1.6 = 10.9365 kmol/h
Mixed feed entering Reactors I
. .
Component ni mole% Heat capacity (n i × Cop1) Equation constant
. . . .
NH3 10.9365 13.30 280.52 366.16 3.85 33.72
O2 14.6154 17.78 380.38 171.81 34.24 8.22
N2 54.9818 66.89 1626.96 282.66 724.82 273.15
H2O 1.6699 2.03 54.26 0.13 22.06 7.59
Total 82.2036 100.00 2342.12 255.44 716.49 322.68
Exit Gas Stream From Reactor I

. .
Component ni mole % Heat capacity (n i × Cop2) equation constant
. . . .
NH3 5.0365 6.02 129.19 168.63 1.77 15.53
O2 7.2404 8.65 188.44 85.11 16.96 4.07
N2 54.9818 65.71 1626.96 282.66 724.82 273.15
NO 5.9000 7.05 173.97 12.11 66.89 28.44

H2O 10.5199 12.57 341.81 0.84 138.98 47.84
Total 83.6786 100.00 2460.37 40.19 915.50 369.03
Total CH4 consumed in Reactor II = a + b + c + 5.9 = 1.7625 + 0.2375 + 1.2

+ 5.9 = 9.1 kmol/h Ans. (b)
Gas Stream Entering Reactor II
. .
Component ni mole % Heat capacity (ni × C op3) equation Constant
. . . .
NH3 5.0365 5.43 129.19 168.63 1.77 15.53
O2 7.2404 7.80 188.44 85.11 16.96 4.07
N2 54.9818 59.26 1626.96 282.66 724.82 273.15
NO 5.9000 6.36 173.97 12.11 66.89 28.44
H2O 10.5199 11.34 341.81 0.84 138.98 47.84
CH4 9.1000 9.81 175.17 474.23 10.90 102.99
Total 92.7786 100.00 2635.34 434.04 926.40 472.02
Final Gas stream leaving Reactor II

. .
Component ni mole % Heat capacity (ni × C op4) equation Constant
. . . .
NH3 1.6 1.6 41.04 53.57 0.56 4.93
N2 56.7 56.7 1677.80 291.49 747.47 281.69
HCN 5.9 5.9 192.89 133.29 25.78 2.41
H2O 25.1 25.1 815.55 2.00 331.59 114.14
CO2 2.0 1.2 42.73 128.57 82.10 19.60
CO 1.2 2.0 34.83 3.38 13.97 5.65
H2 7.5 7.5 214.58 7.65 1.11 5.77
Total 100.00 100.0 3019.42 30.21 984.60 383.45
Energy Balance:
Enthalpy of Reactor I inlet stream 1 at t1/T1 = 900°C (1173.15 K) over 25°C
(298.15 K),
1173.15
f1 = o
ò (ni C p1 ) dT
298.15
= 244 0897 kJ/h º 678.027 kW
Standard heat of reaction (i):
DH or1 = 3(241.82) + 2(90.25) [2(46.11) + 0]
= 452.74 kJ/2 mol NH3 º 226.37 kJ/mol NH3
Heat produced = 226.37 ´ 1000 ´ 5.9
f2 = 1335 583 kJ/h º 371.0 kW
Enthalpy of Reactor I outlet stream over 25°C (298.15 K):
f3 = f1 + f2 = 2440 897 + 1335 583

= 3776 480 kJ/h º 1049.022 kW
T2
= ò (ni × C p2 ) dT
o
298.15
Solving by Mathcad, T2 = 1595.4 K or t2 = 1322.25°C Ans. (c)
Reactor II:
Reaction (ii)
DH or2 = 241.82 + 135.14
= (74.52 + 90.25)
º 122.41 kJ/mol NO
Reaction (iii)
DHor3 = 393.51 + 2(241.82) (74.52)
= 802.63 kmol/CH4. It is NCV of CH4(g).
Reaction (iv)
DHor4 = 393.51 [2(241.82)] (74.52)]
= +164.65 kJ/mol CH4
Reaction (v):
DHor5 = 110.53 [74.52 + 2 ´ (241.82)]
= +447.63 kJ/mol CH4
Reaction (vi):
DHor6 = 3(241.82) 2 (46.11)
= 633.24 kJ/2 mol NH3
Total heat of reaction in Reactor II.
f4 = 122.41 ´ 1000 ´ 5.9 802.63 ´ 1000 ´ 1.7625 + 164.65
´ 0.2375 ´ 1000 + 447.63 ´ 1000 ´ 1.2 316.52 ´ 1000
´ 3.4365
= 722 219 1414 635 + 39 104 + 537 156 1087 721
= 2648 315 kJ/h º 735.643 kW
Enthalpy of exit stream from Reactor II at 1100°C (1373.15 K) over 25°C
(298.15 K),
1373.15
o
f5 = ò (ni × C p4 ) dT
298.15
= 3774 010 kJ/h º 1048.336 kW
Enthalpy of gas stream, enteries Reactor II,
f6 = f5 f4
= 3774 010 2648 315
= 1125 695 kJ/h º 312.693 kW
T3
= ò ( Sni × C p3 ) dT
o
298.15
Solving by Mathcad
T3 = 671.80 K or t3 = 398.65°C
Methane is introduced at 35°C (308.15 K).

Enthalpy of methane at 35°C (308.15 K) over 25°C (298.15 K)
f7 = 175.17 (308.15 298.15) + 474.23 ´ 103 (308.152
298.152)/2 + 10.9 ´ 106 (308.153 298.153)/3 102.99
´ 109 (308.154 298.154)/4
= 1751.7 + 1437.6 + 10.0 28.7
= 3170.6 kJ/h º 0.881 kW
Enthalpy of exit stream of Reactor-I, required to be mixed to have a mixture
temperature of 671.80 K.
f8 = f6 f7 = 1125 695 3170.6
= 1122 524 kJ/h º 311.812 kW
T2¢
= ò ( Sni × C p2 ) dT
o
298.15
T ¢2 = 724.15 K or t¢2 = 451.0°C Ans. (d)
Enthalpy to be extracted from exit gas stream from Reactor I (i.e. cooling from
1595.4 K to 724.15 K),
f9 = 3776 480 1122 524
= 2653 956 kJ/h º 737.21 kW
Enthalpy of mixed feed, entering Reactor I, at 35°C (308.15 K) over 25°C
(298.15 K):
308.15
o
f10 = ò (ni × C p1 ) dT
298.15
= 247 642 kJ/h ´ 6.879 kW
Enthalpy required to raise mixed feed, entering Reactor I, to 900°C (1173.15 K)
from 35°C (308.15 K),
1173.15
o
f11 = ò (ni × C p1 ) dT
298.15
= 2416 134 kJ/h º 671.148 kW
Enthalpy amounting 671.148 kW is to be derived by exchanging heat with Reactor I
exit gas stream.
Enthalpy of exit gas stream from Reactor I,
f12 = 3776 480 2416 134
= 1360 346 kJ/h º 377.874 kW
In other words, enthalpy available from exit gas stream from Reactor I is more
than required by mixed feed (to Reaactor I). Actual temperature of Reactor I exit
gas stream will be higher than 451.0°C (724.15 K)
T3
o
ò (ni × C p2 ) dT = 1360 346
298.15
Solving by Mathacad, T3 = 809.05 K or t3 = 535.9°C
Since exit gas stream from Reactor I is specified to be 1100°C (1373.15 K),
there will be a heat loss from the system.
Heat loss = 1360 346 1122 524

= 237 822 kJ/h º 66.062 kW Ans. (f)
Note: In normal run,heat input in the heater will not be required. It will be in use
only during start-up.
Air/Ammonia feed ratio in the mixed feed
(69.5972 + 1.6699)
= = 6.519 kmol/kmol Ans. (a)
10.9315
EXERCISE 8.15
Basis: Fresh feed rate F = 100 kmol/s
H2 in F = 100 ´ 0.7 = 70 kmol/s
Inerts in F = 100 ´ 0.01 = 1 kmol/s
Let a = CO in mixed feed, kmol/s
b = CO2 in mixed feed, kmol/s
H2 in mixed feed = 1.05 (2a + 3b)
= 2.1 a + 3.15 b
Presence of CO, CO2 and H2 in MF
= a + b + 2.1a + 3.15 b
= 3.1a + 4.15 b kmol/s
Methanol in MF = 0.45 mole %
Inerts in MF = 10.0 mole %
MF = (3.1a + 4.15 a)/(1.0000 0.1 0.0045)
= 3.46175 a + 4.63 428b kmol/s
Methanol in MF = (3.46175a + 4.634 28b) 0.0045
= 0.015 57 a + 0.020 85 b kmol/s
Inerts in MF = (3.461 75 a + 4.634 28b)0.1
= 0.346 18 a + 0.463 43 b kmol/s
Let x and y be kmol/s of CO and CO2 reacted, respectively.
Composition of Converter Exit Gas Mixture
Component kmol/s
CO ax
CO2 by
H2 2.1a + 3.15b 2x 3y
CH3OH 0.015 57 a + 0.020 85b + x + y
H2O y
Inerts 0.346 18a + 0.463 43 b
Total 3.461 75a + 4.634 28 b 2x 2y
Gas mixture, leaving the converter, contains 3 mole % methanol.
(0.015 57 a + 0.020 85b + x + y )
= 0.03 (1)
(3.461 75a + 4.634 28b - 2 x - 2 y )
Let c kmol/s of methanol are condensed alongwith y kmol/s of water.
Gas mixture after methanol condensation,

T = 3.461 75 a + 4.634 28 b 2x 2y y c
= 3.461 75a + 4.634 28 b 2x 3y c kmol/s
Methanol balance:
Methanol in recycle gas stream = methanol in mixed feed
(0.015 57a + 0.020 85 b + x + y c) - (0.015 57 a + 0.020 85 b + x + y - c) P

T
= 0.015 57a + 0.020 85 b
x + y c = - (0.015 57 a + 0.020 85b + x + y - c) P (2)

T
T P + 100 = M
= 3.461 75a + 4.634 28 b
Simplifying,
2x + 3y + c = 100 P (3)
Hydrogen balance:
2x + 3y + (2.1a + 3.15 b - 2 x - 3 y ) P = 70 (4)

T
Inerts balance:
(0.346 18a + 0.463 43b) P = 1 (5)
T
Reaction equilibrium of water gas reaction at 275°C (584.15 K) in converter exit
gas mixture:
(b - y ) (2.1a + 3.15 b - 2 x - 3 y )
K=
(a - x) y
= 69 (6)
Solving six simultaneous equations by Mathcad,
Mathcad output:
a = 133.849 kmol/s
b = 140.201 kmol/s
c = 26.733 kmol/s
x = 16.253 kmol/s
y = 10.526 kmol/s
P = 9.184 kmol/s
Compositions of Gas streams
Converter inlet
(mixed feed M) Converter outlet
kmol/s mole % kmol/s mole %
CO 133.849 12.02 117.596 11.10
CO2 140.201 12.60 129.675 12.24
H2 722.716 64.93 658.632 62.16

Inerts 111.308 10.00 111.308 10.51
CH3OH 5.009 0.45 31.788 3.00
H2O Nil Nil 10.526 0.99
Total 1113.083 100.00 1059.525 100.00
Composition of Gas Streams

Gas mixture after
condensation Purge steam
kmol/s mole % kmol/s mole %
CO 117.596 11.50 1.056 11.50
CO2 129.675 12.69 1.165 12.69
H2 658.632 64.43 5.917 64.43
Inerts 111.308 10.89 1.000 10.89
CH3OH 5.055 0.49 0.045 0.49
Total 1022.266 100.00 9.184 100.00
Compositions of Gas Streams

Recycle (R) stream Fresh feed (M-R)
Component kmol/s mole % kmol/s mole %
CO 116.540 11.50 17.309 17.31
CO2 128.510 12.69 11.691 11.69
H2 652.715 64.43 70.000 70.00
Inerts 110.308 10.89 1.000 1.00
CH3OH 5.010 0.49 Nil Nil
Total 1013.083 100.00 100.000 100.00
Aqueous methanol condensed = 26.733 + 10.526
= 37.259 kmol/s
Mass flow rate of equeous methanol
= 26.733 ´ 32.0419 + 10.526 ´ 18.0153
= 856.576 + 189.629
= 1046.205 kg/s
Concentration of aqueous solution
856.576 ´ 100
=
1046.205
= 81.87 mass %
16.253 ´ 100
Conversion of CO =
133.849
= 12.14% per pass
10.526 ´ 100
Conversion of CO2 =
140.201
= 7.51% per pass
(16.253 ´ 2 + 10.526 ´ 3) 100
Conversion of H2 =
722.716
= 8.87% per pass
1013.083
Recycle ratio = = 10.131 kmol/kmol fresh feed
100
Enthalpy balance:
Reference temperature, T0 = 298.15 K
Heat Capacity Equation Constants for Converter Inlet Gas Stream Component
.
Component ni Heat capacity equation constant
. . . .
kmol/s ni × ai ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109
CO 133.849 3885.3 377.0 1558.5 629.9
CO2 140.201 2995.5 9012.7 5755.4 1374.0
H2 722.716 20 677.3 736.7 106.7 555.8
Ar 33.392 693.6
CH4 77.916 1499.8 4060.5 932.9 881.8
CH3OH 5.009 124.6 254.8 293.7 226.0
Total 1113.083 29 876.1 13 687.7 3077.0 192.1
Heat Capacity Equation Constants for Converter Exit Gas Stream

.
Component ni Heat capacity equation constant
. . . .
kmol/s ni × ai ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109
CO 117.596 3413.5 331.2 1369.3 553.4
CO2 129.675 2770.6 8336.0 5323.2 1270.8
H2 658.632 18843.8 671.4 97.2 506.5
Ar 33.392 693.6
CH4 77,916 1499.8 4060.5 932.9 881.8
CH3OH 31.788 790.5 1617.2 1863.6 1434.5
H2O 10.526 342.0 0.8 139.1 47.9
Total 1059.525 28 353.8 14 354.7 1115.5 1140.3
Standard heats of reaction:

CO(g) + 2 H2(g) = CH2OH(g)
DH or1 = 200.94 (110.53)
= 90.41 kJ/mol CO reacted
CO2(g) + 3 H2(g) = CH3OH(g) + H2O(g)
DH or2 = 200.94 + (241.82) (393.51)
= 49.25 kJ/mol CO2 reacted.

Both are exothermic reactions.
Total heat released
f2 = 90.41 ´ 1000 ´ 16.253 + 49.25 ´ 1000 ´ 10.526
= 1469 433.7 + 518 405.5
= 1987 839.2 kJ/s or kW
Enthalpy of converter exit gas stream at 275°C (548.15 K) over 298.15 K,
548.15
f3 = ò (28.353.8 + 14 354.7 ´ 103 T 1115.5 ´ 106
298.15
T2 1140.3 ´ 109 T3) dT
= 8532 126.9 kJ/s or kW
Enthalpy of converter inlet gas stream,
f1 = 8532 126.9 1987 839.2
= 6544 287.7 kJ/s or kW
T1
= ò (29876.1 + 13 687.7 ´ 103 T 3077.0 ´ 106
298.15
T 2 + 192.1 ´ 109 T 3) dT
Solving by Mathacad
T1 = 486.47 K or t1 = 213.32°C Ans.
Thus ingoing gas stream is to be heated from 66°C (339.15 K) to 213.32°C
(486.47 K).
Heat exchange in the heat exchanger (HE-1),
486.47
f4 = ò (29876.1 + 13 687.7 ´ 103 T 3077.0 ´ 106
339.15
T2 + 192.1 ´ 109 T 3) dT
= 5157 753 kJ/h
º 1432.709 kW
If temperature of reactor exit gas stream after cooling in HE-1 is T 2,
248.15
ò (28 353.8 + 14 354.7 ´ 10 3 T 1115.5 ´ 10 6
T2
T2 1140.3 ´ 109 T 3) dT = 5157 753 kJ/h

Solving by Mathcad, T 2 = 399.86 K or t2 = 126.71°C Ans.
EXERCISE 8.16
Heat duty of chiller, fch = 1500 kW
.
Let mch be the mass flow rate of chilled water.
.
fch = mch × CL × Dt
. 1500
mch = = 119.423 kg/s
4.1868 ´ (12 - 9)
» 430 m3/h
In the chiller, water is used as a refrigerant.
Latent heat of water at 6°C (279.15 K)
= 2487.4 kJ/kg
1500
Evaporation rate of water =
2487.4
.
m1 = 0.603 kg/s
.
Let m2 = Mass flow rate of SA solution, entering
absorber, kg/h
.
m3 = Mass flow rate of WA solution, leaving
absorber, kg/h
. .
m3 m2 = Water evaporation in chiller + Water vapour
formed due to flashing of water, coming
from condenser
= 0.603 ´ 3600 + x
= 2170.8 + x
Also considering overall material balance,
. .
m3 m2 = Amount of water from condenser
=y
Enthalpy of water in condenser
= 191.83 kJ/kg at 45.83°C (318.98 K)
Enthalpy of water at 6°C = 25.31 kJ/kg
Change in enthalpy will result in flashing.
y (191.83 25.31) = x ´ 2487.4
y = 14.938 x
= 2170.8 + x
x = 155.75 kg/h
. .
m3 m2 = 2170.8 + 155.75
= 2326.55 kg/h (1)
LiBr balance:
. .
m2 ´ 0.633 = m3 ´ 0.595
. .
m2 = 0.94 m3
.
Substituting value of m2 in Eq. (1),
.
0.06 m3 = 2326.55
.
m3 = 38 775.83 kg/h
.
m2 = 36 449.28 kg/h
Heat of dilution will be assumed constant at 498 kJ/kg for determining heat
duties of the generator and absorber.
Heat duty of absorber fa = Heat of dilution of LiBr solution + Heat of
condensation of water vapour + sensible heat
change in solution
= 2326.55 ´ 498 + 2326.55 ´ 2487.4
æ 38 775.83 + 36 449.28 ö
+ ç ÷ø 1.842 (48.9 40)
è 2
= 1158 621.9 + 5787 060.5 + 616 612.7
= 7562 295.1 kJ/h
º 2100.638 kW
Heat duty of generator,
fg = Sensible heat change of WA from 75°C
(348.15 K) to 88.9°C (362.05 K) + Sensible
heat change from 88.9°C (362.05 K) to
101.6°C (374.75 K) + Heat of concentration
of LiBr solution + Latent heat of vaporization
of water at 45.83°C (318.98 K)
= 38 775.83 ´ 1.842 (88.9 75)
é 38 775.83 + 36 449.28 ù
+ ê ú 1.842 (101.6
ë 2 û
88.9) + 2326.55 ´ 498 + 2326.55 ´ 2392.97
= 992 808.6 + 879 885.5 + 1158 621.9 + 5567 364.4
= 8598 680.6 kJ/h º 2388.522 kW
Saturated steam at 1.85 bar a:
l v = 2208.5 kJ/kg
Steam consumption in generator,
. 8598 680.6
ms = = 3893.4 kg/h
2208.5
º 1.0815 kg/s
Coefficient of performance:
Effective refrigeration achieved
COP =
Total heat input to generator
1500
= = 0.628 kW/kW
2388.522
Heat duty of condenser, fc = Cooling superheated water vapour +
condensation
= 2326.55 (2690.6 2584.8) + 2326.55
´ 2392.97
= 246 149 + 5567 364.4
= 58 13 513.4 kJ/h
º 1614.865 kW
Cooling water enters at 32°C (305 K) into absorber coils and leave at 40°C
(313 K) from the condenser.
Total heat duty = fa + fc
= 2100.638 + 1614.865
= 3715.503 kW
. 3715.503
Required CW flow, mcw =
8 ´ 4.1868
= 110.929 kg/s
º 399.3 m3/h
Rise in CW temperature across absorber
2100.638
= = 4.523°C or K
110.929 ´ 4.1868
Rise in CW temperature across condenser = 8 4.523 = 3.477°C or K
EXERCISE 8.17
Before attempting the actual steam balance, enthalpies of steam at different
pressure/temperature, of condensates and boiler feed water are to be tabulated.
Steam or Pressure, Temperature, Condition Enthalpy
Condensate or MPa a K (°C) kJ/kg
BFW
Steam 4.6 673 (400) Superheated 3205.3
Steam 0.95 450.8 (177.7) Saturated 2774.2
Steam 0.1013 373 (100) Saturated 2676.0
Steam 0.014 325.7 (52.6) 0.955 DF 2489.7
Steam 0.014 325.7 (52.6) 0.867 DF 2280.6
Condensate 0.014 325.7 (52.6) Saturated 220.0
Condensate 0.014 373 (100) Saturated 419.1
Condendsate 0.014 450.8 (177.7) Saturated 752.8
BFW 4.9 394 (121) Subcooled 508.0
Turbine A:
Heat transfer in turbine = 3205.3 3010.5 = 194.8 kJ/kg
1426 ´ 3600
Steam requirement in turbine = = 27 740.2 kg/h
0.95 ´ 194.8
Let x1 kg/h BFW is introduced in steam at 0.95 MPa a and 553 K (280°C).
x1 ´ 508.0 + 27 740.2 ´ 3010.5 = (27 740.2 + x1) 2774.2
x1 = 2891.3 kg/h
Total saturated steam at 0.95 MPa a = 27 740.2 + 2891.3
= 30 631.5 kg/h
Turbine B:
Heat transfer in turbine = 3205.3 2489.7 = 715.6 kJ/kg
5974 ´ 3600
Steam requirement in turbine = = 31 635.4 kg/h
0.95 ´ 715.6
Turbine C:
Total energy requirement = 2460 ´ 3600/0.95
= 9322 105.3 kJ/h or 2589.5 kW
Saturated steam requirement for absorption refrigeration = 5940 kg/h
Let x2 kg/h BFW is used for desuperheating steam @ 0.1013 MPa a and 473.15 K
(200°C).
5940 ´ 2676.0 = x2 ´ 508 + (5940 x2) 2875.3
x2 = 500.1 kg/h
Superheated extraction steam = 5940 500.1
= 5439.9 kg/h from Turbine C
Enthalpy removed in extraction part of Turbine C:
= 5439.9 (3205.3 2875.3)
= 1795 167 kJ/h º 498.7 kW
Enthalpy removal in condensing part
= 2589.5 498.7 = 2090.8 kW
º 7526 938 kJ/h
Steam requirement = 7526 938/(3205.3 2280.6)
= 8139.9 kg/h
Total steam input to Turbine C
= 5439.9 + 8139.9 = 13 579.8 kg/h
say 13 580 kg/h
Total condensate to surface condenser
= 8139.9 + 31 635.4 = 39 775.3 kg/h
Enthalpy of total condensates, entering deaerator
= 39 775.3 ´ 220 + 5940 ´ 419.1 + 30 631.5 ´ 752.8
= 34 299 413 kJ/h º 9527.6 kW
Loss of enthalpy = 5%
Let x3 kg/h be superheated steam, used in deaerator.
Total condensate, entering deaerator = 39 775.3 + 30 631.5 + 5940.0
= 75 346.8 kg/h
34 299 413 ´ 0.95 + x3 ´ 3205.3 = (76 346.8 + x3) 508.0
x3 = 2298.5 kg/h
BFW flow = 76 346.8 + 2298.5 = 78 645.3 kg/h
Total steam requirement @ 46 bar a and 673 K (400°C)

= 2298.5 + 27 740.2 + 31 635.4 + 13 579.8
= 75 253.9 kg/h
say 75 254 kg/h Ans.
EXERCISE 8.18
Basis: Power requirement = 6832 kW
Specific Steam Requirements of Turbines
Initial Final Enthalpy Actual Soevific
Steam steam available energy steam
Conditions conditions for energy conversion consumption
conversion, (97%), in turbine,
kJ/kg kJ/kg kg/kWh
64 bar a 39 bar a 91.2 88.464 40.6945
440°C 385°C
(713 K) (658 K)
3273.3 kJ/kg 3182.1 kJ/kg
39 bar a 4.4 bar a 313.2 303.804 11.8497
385°C 205°C
(658 K) (478 K)
3182.1 kJ/kg 2868.9 kJ/kg
64 bar a 12 kPa a 705.9 684.723 5.2576
440°C 50°C (323 K)
(713 K) 99% dry
3273.4 kJ/kg 2567.4 kJ/kg
39 bar a 12 kPa a 614.7 596.259 6.0376
385°C 50°C (323 K)
(658 K) 99% dry
3182.1 kJ/kg 2567.4 kJ/kg
BFW Requirements for Desuperheating
Initial steam conditions Final steam conditions BFW
Pressure Temp. Enthalpy Pressure Temp. Enthalpy requirement,
bar a °C(K) kJ/kg bar a °C (K) kJ/kg kg/kg initial
Steam
64 440 (713) 3273.3 39 385 (658) 3182.1 0.0333
39 385 (658) 3182.1 15 Satd. 2789.9 0.1669
39 385 (658) 3182.1 4.4 Satd. 2741.9 01912
4.4 205 (478) 2868.9 4.4 Satd. 2741.9 0.0552
Nomenclature will be same as that followed in Example 8.7.

Saturated 15 bar a steam requirement = 3 t/h
3
Equivalent MP steam = = 2.5709 t/h
(1 + 0.1669)
Saturated LP steam header:
Requirement = 13.5 + a t/h
Exhaust from BFW and FD turbines = c + d
Equivalent saturated LP steam
Production = (1 + 0.0552) (c + d) + 1.1912 g
1.0552 (c + d) + 1.1912 g = 13.5 + a (1)
Deaerator:
Equation remains unchanged
a 0.11 b 0.11 e = 1.815 (2)
Power turbine:
(b + c + d + g + 2,5709 - 1.0333 h) 1000 1000 e
+ = 6832
40.6945 5.2476
or 5.2576 b + 5.2576 c + 5.2576 d + 5.2576 g
+ 40.6945 e 5.4327 h = 1461.7433 (3)
FD fan turbine:
2.47 (b + c + d + e + g - 0.0333h + 2.5709) 11.8497
d=
1000
b + c 33.1661 d + e + g 0.0333h = 2.5709 (4)
BFW pump turbine:
Head developed = 70 bar
= 742.907 m H2O at 105°C (378 K)
(a + b + e + 16.5) 742.907 ´ 0.7355 ´ 1000
Power requirement =
3600 ´ 75 ´ 0.65
= 3.1134 (a + b + e + 16.5)
3.1134 (a + b + e + 16.5) 11.8497
=c
1000
a + b + e 27.1055 c = 16.5 (5)
CW pump turbine:
Enthalpy, given-up in SC = 2567.4 209.2
= 2358.2 kJ/kg steam
2358.2 (b + e)
CW requirement in SC =
10 ´ 4.1868
= 56.3246 (b + e) t/h or m3/h
Total CW requirement in the plant = 56.3246 (b + e) + 600 m3/h
Power requirement of CW pump

[56.3246 (b + e) + 600] 51 ´ 0.7355 ´ 1000
=
3600 ´ 75 ´ 0.6
= 02315 [ 56.3246 (b + e) + 600] kW
0.2315[56.3246 (b + e) + 600] 6.0376
b=
1000
656.1343 b 56.3246 e = 600 (6)
All six equations are solved by Mathcad. Assume h = 0.
HP steam generation,
Z = b + c + d + e + g + 2.571
= 3.771 + 2.193 + 1.649 + 33.273 + 12.875 + 2.571
= 56.332 t/h
Fig. 8.21 is the steam balance with all values.
Increased in HP steam generation over that
(56.332 - 53.618) 100
in Example 8.7 =
53.618
= 5.06 %
Energy absorption in 64 bar a boiler
= 56 332 (3273.3 440.17)
= 159 595 879 kJ/h
º 44 332.188 kW
Energy absorption in 115 bar a boiler (Example 8.6)
= 53 618 (3190.7 440.17)
= 147 477 918 kJ/h
º 40 966.088 kW
Increase in energy absorption in boiler
= 159 595 879 147 477 918
= 12 117 961 kJ/h
º 3366.1 kW
12 117 961 ´ 100
Increase in energy consumption in boiler = = 8.22%
147 477 918
12 117 961
Additional fuel requirement =
0.75 ´ 40 000
= 403.93 kg/h
EXERCISE 8.19
Refer Example 8.7. Its basis is used for following calculations.
LP steam header pressure = 4 bar a
Enthalpy of superheated steam at 4 bar a and 438 K (165°C) = 2785.1 kJ/kg
At 4 bar a, Ts = 416.77 K (143.62 °C)

h = 604.67 kJ/kg and H = 2737.6 kJ/kg
For letdown from MP to LP header, let x1 be kg of BFW injected.
3020.4 + 440.17 x1 = (1 + x1) 2737.6
x1 = 0.123 kg/kg MP steam
For production LP saturated steam from LP superheated steam, let x2 kg BFW is
injected.
2785.1 + 440.17 x2 = (1 + x2) 2737.6
x2 = 0.0207 kg/kg LP superheated steam
Steam ejectors for inter-after condenser and other LP ejectors will consume
10% more steam.
LP steam consumption to inter-after condenser
= 500 ´ 1.1 = 550 kg/h
LP steam consumption to other ejectors
= 2000 ´ 1.1 = 2200 kg/h
BF make-up will increase from 2000 to 2200 kg/h.
LP steam consumption in heaters will reduce by 1.75%.
Steam consumption in brine heater = 2000 ´ 0.9825
= 1965 kg/h
Steam consumption in first stage evaporator
= 9000 ´ 0.9825
= 8842 kg/h
Symbols of Example 8.6 are used.
LP steam header:
LP steam requirement = 8.842 + 1.965 + 2.2 + 0.55 + a
= 13.557 + a t/h
LP steam production = 1.0207 (c + d) + 1.123 g
1.0207 (c + d) + 1.123 g = 13.557 + a (1)
Deaerator:
a = 0.11 (b + e + 16.557)
a 0.11 b 0.11 e = 1.821 (2)
Power Turbine: No change in Eq. (3).
FD fan:
Enthalpy drop in turbine = 3020.4 2785.1
= 235.3 kJ/kg
3600
Specific steam consumption =
235.3 ´ 0.97
= 15.773 kg/kWh
2.47 ´ 15.773(b + c + d + e + g + 2.74 )

d=
1000
b + c 24.668 d + e + g = 2.74 (4)
BFW pump:
5.493 ´ 15.773( a + b + e + 16.95)
c=
1000
a + b + e 11.542 c = 16.95 (5)
CW pump turbine: No change in Eq. (6).
Solving by Mathcad
a = 4.674 t/h
b = 3.778 t/h
c = 4.776 t/h
d = 2.069 t/h
e = 29.718 t/h
g = 10.014 t/h
Z = 53.095 t/h
Refer Fig. 8.22 in the text for the steam balance. Ans.
EXERCISE 8.20
Refer solution of Example 8.7. In this example, cooling water pump turbine is
shown to be condensing. In this Exercise, this CW pump turbine is considered to
be a back pressure type.
Production of superheated LP steam = b + c + d t/h
Corresponding saturated LP stream = 1.022 (b + c + d) + 1.121 g t/h
1.022 (b + c + d) + 1.121 g = 13.5 + a
(1)
Deaerator:
Condensate from SC = e + 0.5 t/h
a = 0.11 (e + 16.5)
a = 0.11 e + 1.815
or a 0.11 e = 1.815 (2)
Equations, concerning power turbine and FD fan turbine remain unchanged.
Thus equations (3) and (4) of Example 8.6 are unchanged.
5.16 b + 5.16 c + 5.16 d +21.79 e + 5.16 g 5.50 h = 754.03 (3)
b + c 23.78 d + e + g 0.066 h = 2.74 (4)
BFW pump:
Total BFW = a + e + 16.5 t/h
c = 5.493 (a + e + 16.5) 16.34/1000
a + e 11.14 c = 16.5 (5)

CW pump:
CW requirement = 54.05 e + 600 m3/h
b = 0.2315 (54.05 e + 600) 16.34/1000
264.36 b 54.05 e = 600
(6)
Coefficient matrix of constraint equations:
Eq. No. a b c d g h e Constant
6 0 1 0 0 0 0 0.2045 2.2696
2 1 0 0 0 0 0 0.11 1.815
5 1 0 11.14 0 0 0 1 16.500
1 1 1.022 1.022 1.121 1.121 0 0 13.50
3 0 5.16 5.16 5.16 5.16 5.50 21.79 768.17
4 0 1 1 1 1 0.066 1 2.74
Mathcad solution
Matrix
LM-1 1.022 1.022 1.022 0 1121 . O
PP
MM 10 0516 .
0
5.16
0
5.16
-0.11 0
21.79 5.16 P
M: = M PP
MM 01 10 -1114 1
.
-23.78
0
1
1
1
0 PP
MN 0 264.36 0 0 -54.05 0 Q
LM 13.5 OP
MM 7541..815
03 P
P
v: = M
MM--162..574 PPP
MN 600 PQ
LM 5153 . OP
MM 48..668
474
PP
Solution = M
061 P
1
Solution = M × v
MM302..346 PP
MN 2.78 PQ
Refer Fig. 8.23 in the text for steam balance. Ans.
EXERCISE 8.21
Nomenclature will be same as that of Example 8.7.
Initial steam Final steam Enthalpy Actual energy Specific
conditions conditions available for conversion steam
energy (97%), consumption
conversion, kJ/kg in turbine
kJ/kg kg/kWh
115 bar a 39 bar a 170.3 165.2 21.79
713 K (440 °C) 593 K (320 °C)
3190.7 kJ/kg 3020.4 kJ/kg
36 bar a 4.4 bar a 396.5 384.6 9.36
673 K (400 °C) 458 K (185 °C)
3222.5 kJ/kg 2826.0 kJ/kg
115 bar a 12 kPa a 718.7 697.1 5.16
713 K (440 °C) 323 K (50 °C), 95% dry
3190.7 kJ/kg 2472.0 kJ/kg
36 bar a 12 kPa a 750.5 728.0 4.945
673 K (400 °C) 323 K (50 °C), 95% dry
3222.5 kJ/kg 2472.0 kJ/kg
BFW requirement for desuperheating LP steam:
Let x2 kg BFW is to be injected in the desuperheater per kg of LP superheated
steam at 458 K (185 °C)
2826.0 + 440.17 x2 = (1 + x2) 2741.9
x2 = 0.0365 kg/kg LP superheated steam
Rest BFW requirements for desuperheating will remain unchanged (refer Table
8.17). Assume h = 0. Saturated LP Steam Header:
1.0365 (c + d ) + 1.121 g = 13.5 + a
a + 1.0365 c + 1.0365 d + 1.121 g = 13.5 (1)
Dearerator: Balance is unchanged.
a 0.11 b 0.11 e = 1.815 (2)
Power Turbine: Balance is unchanged.
5.16 b + 5.16 c + 5.16 d + 21.79 e + 5.16 g = 754.03 (3)
FD Fan Turbine:
2.47( b + c + d + e + g + 2.74)9.36
d=
1000
b + c 42.254 d + e + g = 2.74 (4)
BFW Pump Turbine:
5.493( a + b + e + 16.5)9.36
c=
1000
a + b + e 19.45 c = 16.5 (5)
CW Pump Turbine:
0.2315(54.05b + 54.05e + 600 )4.945
b=
1000
819.49 b 54.05 e = 600 (6)
Mathcad solution:
a = 5.401 t/h
b = 2.704 t/h
c = 2.802 t/h
d = 1.214 t/h
e = 29.900 t/h
g = 13.148 t/h
Z = 52.508 t/h Ans.
(53.624 - 52.508)100
Saving in HP steam generation =
53.624
= 2.08%
(33.822 - 33104
. )100
Reduction in heat load of cooling tower =
33.822
= 2.12%
Refer Fig. 8.24 in the text for steam balance. Ans.
EXERCISE 8.22
Basis: 10 000 kg/h dry PP handling
Inlet n-hexane content = 35% on wet basis
Dry basis n-hexane content = 35 ´ 100/65
= 53.85%
n-Hexane removal rate = 10 000 (0.5385 0.02)
= 5185 kg/h
Antoine constants for n-hexane (Table 5.4)
A = 4.002 66, B = 1171.53 and C = 48.784
Nitrogen, ingoing to the spiral dryer has a dew point of T1 = 307.15 K (34°C).
1171.53
log10 p1 = 4.002 66
(307.15 - 48.784)
= 0.666 35
p1 = 0.294 bar º 29.4 kPa
29.4 86.1754
n-Hexane content = ´
(102 - 29.4) 28.0134
= 1.2457 kg n-hexane/kg dry N2
Nitrogen circulation rate = 10 000 ´ 0.18
= 1800 kg/h º 64.255 kmol/h
n-Hexane circulation in N2 = 1800 ´ 1.2457

= 2242.26 kg/h
º 26.02 kmol/h
Nitrogen-n-Hexane mixture is heated from 343.15 K (70°C) to 403.15 K (130 °C).
Heat input to nitrogen heater, f1 =
64.255 [29.5909 (403.15 343.15) 5.141 ´ 103 (403.152 343.152)/2
+ 13.1829 ´ 106 (403.153 343.153)/3 4.968 ´ 109 (403.154 343.154)/4]
+ 26.02 [ 4.4142 (403.15 343.15) + 581.9233 ´ 103 (403.152 343.152)/2
311.8584 ´ 106 (403.153 343.153)/3 + 64.9193 ´ 109 (403.154 343.154)/4]
= 64.255 ´ 1755.1 + 26.02 ´ 10 591.47
= 112 774 + 275 590
= 388 364 kJ/h
º 107.879 kW
lv of saturated steam at 0.4 MPa a = 2133.0 kJ/kg (Table AIV.2)
Steam requirement = 388 364/2133 = 182.1 kg/h Ans. (a)
For T2 = 363.15 K (90°C),
1171.53
log10 p2 = 4.002 66
(363.15 - 48.784)
= 0.276 02
p2 = 1.888 bar º 188.8 kPa
Pressure of N2-n-Hexane mixture, leaving the separator (i.e. the mixture entering
interchanger) = 110 kPa
n-Hexane content of the mixture = 2242.3 + 5185
= 7427.3 kg/h
Specific n-hexane content = 7427.3/1800
= 4.1263 kg/kg dry N2
If partial pressure of n-hexane is p3 after interchanger,
p3 86.1754
´ = 4.1263
110 - pa 28.0134
p3 = 63.02 kPa º 0.6302 bar
log10 p3 = 0.200 52
1171.53
= 4.002 66
(T3 - 48.784)
Saturation temperature T3 = 327.5 K (54.35°C)
Reference temperature To = 298.15 K (25°C)
Enthalpy of N2-n-hexane mixture, leaving the seperator
H2= 64.255 [29.5909 (363.15 298.15) 5.141 ´ 103 (363.152 298.152)/2
+ 13.1829 ´ 106 (363.153 298.153)/3 4.968 ´ 109 (363.154 298.154)/4]

+ (7411.6/86.1754) [ 4.4142 (363.15 298.15)
+ 581.9233 + 103 (363.152 298.152)/2
311.8584 ´ 106 (363.153 298.153)/3
+ 64.9193 ´ 109 (363.154 298.154)/4
f2 = 64.255 ´ 1895 + 86.188 ´ 10 150.6
= 121 763 + 874 860
= 996 623 kJ/h
º 276.840 kW
In the interchanger, N2-n-hexane mixture from the blower at 307.15 K (34°C) is
heated to 343.15 K (70°C).
n-Hexane content = 25.837 kmol/h
Heat added to the mixture, f3 = 64.255 [29.5909 (343.15 307)
5.141 ´ 103 (343.152 307.152)/2
+ 13.1829 ´ 106 (343.153 307.153)/3
4.968 ´ 109 (343.154 307.154)/4]
+ 26.02 [ 4.4142 (343.15 307.15)
+ 581.9233 ´ 103 (343.152 307.152)/2
311.8584 ´ 106 (343.153 307.153)/3
+ 64.9193 ´ 109 (343.154 307.154)/4
= 64.255 ´ 1049.1 + 26.02 ´ 5543.0
= 67 409.9 + 144 229
= 211 638.9 kJ/h
= 58.789 kW
Average heat capacity of N2-n-hexane mixture, leaving the separator
996 623
=
(64.255 + 86.188)(363.15 - 298.15)
= 101.92 kJ/(kmol × K)
If it is assumed that there is no condensation of n-hexane from this mixture in the
interchanger, drop in temperature
= [211 638.9/(150.443 ´ 101.92)]
= 13.8 K
Temperature of the mixture, leaving the interchanger
= 363.15 13.8 = 349.35 K or 76.2°C Ans. (c)
This temperature is more than the calculated dew point = 327.5 K (54.35 °C) and
hence no condensation will take place in the interchanger. Latent heat of evaporation
(lv) of n-hexane at 298.15 K (25°C) is calculated using Watson equation [Ref.
Eq. (5.25)].
0.98
é 507.6 - 298.15 ù
lv = ê ú ´ 28 850
ë 507.6 - 341.9 û
= 31 537 kJ/kmol n-hexane
Heat balance across spiral dryer:
Reference temperature To = 298.15 K (25 °C)
Enthalpy of ingoing N2-n-hexane gas mixture,
f4 = 64.255 [29.5909 (403.15 298.15)
5.141 ´ 103 (403.152 298.152)/2
+ 13.1829 ´ 106 (403.153 298.153)/3
4.968 ´ 109 (403.154 298.154)/4]
+ 26.02 [ 4.4142 (403.15 298.15)
+ 581.9233 ´ 103 (403.152 298.152)/2
311.8584 ´ 106 (403.153 298.153)/3
+ 64.9193 ´ 109 (403.154 298.154)/4
= 64.255 ´ 3066.2 + 26.02 ´ 17 000.0
= 197 019 + 442 340
= 639 359 kJ/h
º 177.6 kW
Enthalpy of outcoming N2-n-hexane gas mixture,
f2 = 996 623 kJ/h = 276.840 kW
Enthalpy of feed (wet PP),
f5 = 10 000 ´ 1.926 (338.15 298.15) + 5385 (338.15 298.15) ´ 2.512
= 770 400 + 541 085
= 1311 485 kJ/h
º 364.301 kW
Enthalpy of outgoing PP-n-hexane mixture,
f6 = 10 000 ´ 1.926 (353.15 298.15) + 200 ´ 2.512 (353.15 298.15)
= 1059 300 + 27 632
= 1086 932 kJ/h
º 301.926 kW
Heat required for evaporation,
f7 = 31 537 ´ 5185/86.1754
= 1897 518 kJ/h º 527.088 kW
Net heat input to jacket
= f2 + f7 + f6 f4 f5 = 276.840 + 527.088 + 301.926
177.600 364.301
= 563.953 kW
Steam requirement in jacket

= 563.953 ´ 3600/2133
= 951.8 kg/h Ans. (b)
EXERCISE 8.23
Basis: Dry nitrogen flow to AFD = 100 Nm3/h
100
Molar flow rate = = 4.4615 kmol/h
22.414
Solvent laden nitrogen comes out from the dryer at 105 kPa and 90°C (363.15 K)
with a DP = 10°C (283.15 K).
Refer Table 5.4 for Antoine constants for CH2Cl2.
1327.016
At 10°C, log10 pv1 = 4.53691 +
T - 20.474
T = 283.15 K
log pv1 = 4.536 91 5.50 191 = 0.515
pv1 = 0.3055 bar or 30.55 kPa
CH2Cl2 content of N2 from ldryer,
30.55
y1 = = 0.4103 kmol/kmol dry N2
(105 - 30.55)
.
CH2Cl2 in N2 stream from dryer, n1 = 4.4615 ´ 0.4103
= 1.8306 kmol/h
N2 stream from dryer is cooled from 90°C to 40°C in a cooler with cooling
water. Since DP = 10°C, no condensation will take place.
363.15 363.15
o
f1 = 4.4615 ò C pN2 dT + 1.8306 ò C pmc dT
313.15 313.15
= 4.4615 [29.5908 (363.15 313.15) 5.141 ´ 103 (363.152 313.152)/2

+ 13.1829 ´ 106 (363.153 313.153)/3 4.968 ´ 109 (363.154 313.154)/4]
+ 1.8306 [16.9092 (363.15 313.15) + 140.4533 ´ 103 (363.152
313.152)/2 94.028 ´ 106(363.153 313.153)/3 + 23.7905 ´ 109(363.154
313.154/4]
f1 = 4.4615 [1479.54 86.92 + 75.51 9.66] + 1.8306 [845.46 + 2374.71
538.56 + 46.25]
= 4.4615 ´ 1458.47 + 1.8306 ´ 2727.86
= 6507 + 4994
= 11 501 kJ/h º 3.195 kW
Solvent laden N2 enters cryo condenser at 40°C and leaves at 31°C (242.15 K).
1327.016
log10pv2 = 4.536 91 +
(242.15 - 20.474)
= 1.449 38
pv2 = 0.0355 bar or 3.55 kPa
CH2Cl2 content of saturated N2 stream, leaving cryo condenser,
3.55
y2 =
102 - 3.55
= 0.0361 kmol/kmol dry N2
.
CH2Cl2, leaving with N2, n2 = 4.4615 ´ 0.0361
= 0.1611 kmol/h
CH2Cl2 condensed in cryo condenser
. . .
n3 = n1 n2
= 1.8306 0.1611
= 1.6695 kmol/h
º 141.8 kg/h
Ideal Gas Heat Capacity Equation Constants for Incoming GAs Mixture
.
Component ni Equation constants
. . . .
kmol/h ai × n i bi × n i ´ 103 ci × n i ´ 106 di × n i ´ 109
N2 4.4615 132.02 22.94 58.82 22.16
CH2Cl2 1.8306 21.73 315.36 273.22 95.71
Total 6.2921 153.75 292.42 -214.40 73.55
Reference temperature, T0 = 298.15 K, T1 = 313.15 K
Enthalpy of N2-stream, entering cryo condenser,
f2 = 153.75 (313.15 298.15) + 292.42 ´ 103 (313.152 298.152)/2 214.40
´ 106 (313.153 298.153)/3 + 73.55 ´ 109 (313.154 298.154)/4
= 2306.25 + 893.78 300.51 + 31.52
= 2931.04 kJ/h º 0.814 kW
Ideal Gas Heat Equation Constants for Outgoing Gas Mixture
.
Component ni Equation constants
. . . .
N2 4.4615 132.02 22.94 58.82 22.16
CH2Cl2 0.1611 1.91 27.75 24.04 8.42
Total 4.6226 133.93 3.81 34.78 13.74
T2 = 242.15 K
enthalpy of N2-stream, leaving cryo condenser,
f3 = 133.93 (242.15 298.15) + 3.81 ´ 103 (242.152 298.152)/2 + 34.78 ´
106 (242.153 298.153)/3 13.74 ´ 109 (242.154 198.154)/4
= 7500.08 57.64 142.65 + 15.33
= 7685.04 kJ/h º 2.135 kW
Sensible heat load of cryo condenser
f ¢4 = 2931.04 (7685.04)
= 10 616.08 kJ/h º 2.949 kW
Average temperature of condensation
10 + (-31)
= = 10.5°C or 262.65 K
2
lv1 at TB (= 313 K) = 28.06 kJ/mol (Ref. Table 5.5)
Tc = 508.K
Using Watson equation,
0.38
é 508 - 262.65 ù
lv2 = 28.06 ê ú
ë 508 - 313 û
= 30.619 kJ/mol CH2Cl2
Condensation heat duty, f¢¢4 = 30 619 ´ 1.6695
= 51 118.42 kJ/h
º 14.20 kW
Total heat duty of cryo condenser
f4 = f¢4 + f¢¢4
= 61 734.5 kJ/h º 17.149 kW
(a) Conventional cryo condenser:
N2 vapour (as refrigerant) enters the coil at 5 bar a and 170°C (103.15 K) and
leaves at 4.8 bar a and 4°C (277.15 K).
Enthalpy available for refreigeration
= 408.41 220.23
= 185.16 kJ/kg N2
51 118.42
LN requirement = = 276.08 kg/h
185.16
(b) Modified cryo condenser:
Refrigeration in one coil = 408.53 220.23
= 188.03 kJ/kg
Enthalpy requirement in vaporizer for LN

= 220.23 35.21
= 185.02 kJ/kg
Enthalpy required for cooling gaseous N2 = 408.53 223.40
= 185.13 kJ/kg
Both values match closely and hence vaporization heat duty is satisfied by cooling
of N2 gas stream from the first coil on a mass to mass basis.
Refrigeration in 2nd coil = 408.53 223.40
= 185.13 kJ/kg
Total refrigeration available
= 188.18 + 185.3
= 373.48 kJ/kg LN
LN requirement for the modified system
51 118.42
= = 136.87 kg/h
373.48
(276.08 - 136.87) 100

Reduction in LN requirement =
276.08
= 50.42 % Ans.
EXERCISE 8.24
(a) Basis: 900 kg liquid chlorine at 303.15 K (30°C)
At 303.15 K, rl1 = 1378.83 kg/m3
lv1 = 245.5 kJ/kg
Volume of liquid chlorine V1 = 900/1378.83
= 0.652 73 m3
Length of container = 1.8 m
Cross-sectional area of chlorine filled circular surface = A1 = 0.652 73/1.8
= 0.362 63 m2
1 2
A1 = r a1
2
where a1 = angle in radians
2 p radians = 360°
6.283 18 radians = 360°
1 radian = 57.296°
r = 0.76/2 = 0.38 m
1
(0.38)2 a1 = 0.362 63
2
a1 = 5.022 58 radian
º 287.77°
Arc length of cylinder in contact with liquid chlorine, S = ra
S = 0.38 ´ 5.022 58
= 1.9086 m
Area in contact with liquid chlorine,
A¢1 = 1.9086 ´ 1.8
= 3.435 48 m2
Energy balance:
.
Chlorine withdrawl rate, m3 = 5.56 g/s
= 20.016 kg/h
.
m3 lv1 = UA¢1(T0 Ts)
T0 = 303.15 K
U = 11.4 W/(m2 × K)
= 41.04 kJ/(h × m2 × K)
41.04 ´ 3.435 48 (303.15 Ts) = 20.016 ´ 245.5
Ts = 268.3 K
Iteraction 2:
At this Ts = 268.3 K, r1 = 1483.68 kg/m3
lv1 = 270.82 kJ/kg
(245.5 + 270.82)
Average lv =
2
= 258.16 kJ/kg
V 1 = 900/1483.68
= 0.6066 m3
A 1 = 0.6066/1.8 = 0.337 m2
a1 = 0.337 ´ 2/(0.38)2
= 4.66759 radian
S = ra = 0.38 ´ 4.667 59
= 1.773 68 m
A¢1 = 1.773 68 ´ 1.8
= 3.192 62 m2
41.04 ´ 3.192 62 (303.15 Ts) = 20.016 ´ 258.16
Ts = 263.71 K
Iteration 3:
At Ts = 263.71 K, r1 = 1496.31 kg/m3
l 1 = 273.73 kJ/kg
Average lv = 272.27 kJ/kg
V 1 = 900/1496.31
= 0.601 48 m3
A 1 = 0.601 48/1.8 = 0.334 16 m2
a1 = 0.334 16 ´ 2/(0.38)2
= 4.628 25 radian
S = r a1 = 0.38 ´ 4.628 25 = 1.758 74 m
A¢ = 1.758 74 ´ 1.8
= 3.165 73 m2
41.04 ´ 3.165 73 (303.15 Ts) = 20.016 ´ 272.27
Ts = 261.20 K
Iteration 4:
At Ts = 261.20 K, r1 = 1503.1 kg/m3
lv1 = 275.28 kJ/kg
V 1 = 900/1503.1
= 0.598 76 m3
A 1 = 0.596 76/1.8 = 0.332 65 m2
a1 = 0.332 65 ´ 2/(0.38)2
= 4.607 28 radian
S = 4.607 28 ´ 0.38
= 1.750 77 m
A¢1 = 1.750 77 ´ 1.8
= 3.151 38 m2
41.04 ´ 3.151 38 (303.15 Ts) = 20.016 ´ 274.5
Ts = 260.67 K
Iteration 5:
At Ts = 260.67, r1 = 1504.53 kg/m3
lv1 = 275.6 kJ/kg
V 1 = 900/1504.53
= 0.598 19 m3
A 1 = 0.598.19/1.8 = 0.332 33 m2
a1 = 0.332 33 ´ 2/(0.38)2
= 4.6029 radian
S = 4.6029 ´ 0.38
= 1.749 10 m
A¢1 = 1.749 10 ´ 1.8
= 3.148 39 m2
41.04 ´ 3.148 39 (303.15 Ts) = 20.016 ´ 275.44
Ts = 260.48 K or 012.67°C
This Ts value is close enough to the value of iteration 4.
Steady state temperature, t/T = 12.67°C/260.48 K Ans.
Average latent heat between 303.15 K and 260.48 K
(245.5 + 275.44)
l= = 260.47 kJ/kg
2
Average heat transfer rate, f = 20.016 ´ 260.47
= 5213.6 kJ/h
º 1.448 kW
Initially the container has 900 kg liquid chlorine at 303.15 K. Its enthalpy = 62.64
kJ/kg (with reference enthalpy of saturated liquid chlorine at atmospheric (1.013
25 bar) and 33.98°C (239.17 K) = 0 kJ/kg). Enthalpy of liquid chlorine at
260.47 K is 20.68 kJ/kg. Thus for cooling down the mass of 900 kg liquid
chlorine, enthalpy equivalent to h = 900 (62.64 20.68) = 37 764 kJ needs to be
removed. This will take q = 37 764/5213.6 = 7.24 h for cooling. Thus it will
take approximately 7 h 14 min to attain the steady state conditions to
achieve 260.48 K.
In 7 h 14 min, chlorine consumption will be 144.92 kg which is substantial. Thus
surface area in contact with liquid chlorine (S) would be reduced to a definite
extent. This will mean heat pick-up from atmosphere will be lower. Thus in
actual practice, time required to achieve 260.45 K will be more than 7.24 h.
(b) Basis: 100 kg liquid chlorine at 303.15 K
(i) Dq1 = 0.2 h = 720 s
At 303.15 K, r1 = 1378.83 kJ/kg
lv1 = 245.5 kJ/kg
V 1 = 100/1378.83 = 0.072 53 m3
A 1 = 0.072 53/1.8 = 0.040 29 m2
a1 = 0.040 29 ´ 2/(0.38)2
= 0.55803 radian
Arc length, S1 = 0.38 ´ 0.558 03 = 0.212 05 m
A¢1 = 0.212 05 ´ 1.8

= 0.381 69 m2
Ts = 303.15 [20.016 ´ 245.5/(41.04 ´ 0.381 69)]
= 10.55 K - irrational answer
Therefore, transient material and energy balance is required.
Energy balance:
Heat input Heat output = Accumulation
. .
UA¢ (Ta T) mlv = (M0 mq) Cl (dT/dq) (1)
where M 0 = initial mass of liquid chlorine
= 100 kg at q = 0 h
Cl = Heat capacity of liquid chlorine
= 0.985 kJ/(kg ×K)
q = time, h
T = Temperature of liquid chlorine in the
container after time q, K
Integrating above equation
T2
q dq Cl dT
ò = ò (2)

0 ( M 0 - mq ) lv ]
T1 [UA ¢ (Ta - T ) - m
.
Let a = UA¢ (Ta T) mlv
da
= UA¢
dT
.
When T = T0, a = UA¢ (Ta T0) mlv = a0
.
Let b = Cl (M0 mq)
db .
= Cl m
dq
when q = 0, b = ClM0 = b0
Rewriting Eq. (2)
a da b db
ò = ò
a0 -UA¢ a
b0 - Cl mb
1 a = 1 ln b
ln
UA¢ a0 Cl m b0
UA¢ / C m
l
UA ¢ (Ta - T ) - m lv é C [ M 0 - m q ] ù
ln = ln ê l ú
UA ¢ (Ta - T0 ) - m lv ë Cl M 0 û
Simplifying, .
. . .
UA¢ (Ta T) mlv = (UA (Ta T0) mlv) (1 mq/M0)UA/Clm
Rearranging,
1
(UA ¢ Ta - m lv ) + [m lv = UA ¢ (Ta - T0 )] (1 - m q / M 0 )UA¢ / Cl m (3)

T=
UA ¢
Equation (3) can be utilized to know T after time q (is elapsed). Since surface
(A¢ ) in contact with liquid chlorine (of the container) varies as soon as some
mass is vaporized, it is advisable to adopt numerical integration.
Period-I : q1 = 0.2 h
Initially liquid in the container is at the ambient temperature, i.e., T1 = 303.15 K
Ta T1 = 0
Liquid density at T1, rl = 1378.83 kg/m3
Latent heat of vaporization at T1, l v = 245.50 kJ/kg
Inital mass M0 = 100 kg
Volume, V 1 = 100/1378.83 = 0.072 53 m3
Cross-section area of liquid of circular surface, A1 = 0.072 53/1.8 = 0.040 29 m2
Central angle, a1 = 0.040 29 ´ 2/(0.38)2
= 0.558 06 radian
Arc length of curved surfaqce in contact with liquid,
S1 = 0.558 06 ´ 0.38
= 0.212 06 m
Area in contact with liquid, A¢1 = 0.212 06 ´ 1.8 = 0.381 71 m2
.
mq/M0 = 20.016 ´ 0.2/100
= 0.040 03
.
1 mq/M0 = 1 0.040 03 = 0.959 97
.
UA¢1/mCl = 41.04 ´ 0.381 71/(20.016 ´ 0.985)
= 0.794 56
. .
(UA¢1/mCl)
[1 mq/M0] = (0.959 97)0.794 56
= 0.968 06
1
T2 = [ (41.04 ´ 0.38171 ´ 303.15 20.016 ´ 245.5)
(41.04 ´ 0.381 71)
+ {20.016 ´ 245.5 0} 0.968 06]
= 293.13 K
T2 is substantially lower (10.02 K) than T1.
Hence, liquid chlorine properties will change. Also, reduction in mass will be
4.0032 kg in 0.2 h which will change the surface area (A¢ ) in contact with liquid
chlorine.
Mass of chlorine after 0.2 h = 100 4.0032
= 95.9968 kg
Because of these variations, iterations will have to be performed till calculated T2
matches closely with assumed T1.
Density of chlorine at 293.13 K = 1410.59 kg/m3
lv at 293.13 K = 253.13 kJ/kg

Average mass of liquid chlorine for 0.2 h period,
(100 + 95.9968)
M0 = = 97.9984 kg
2
Using these values, T2 is recalculated as
T2 = 287.74 K
simlar iterations are performed 10 times.
Final T2 = 282.70 K after 0.2 h
During second period of 0.2 h,
M 0 = 95.9968 kg (initial value)
Nine iterations are performed and T3 = 260.90 K.
For the third period nine iterations are performed.
T3 = 238.40 K (34.75°C) Ans.
Spreadsheet Excel was used for calculations as attached.
EXERCISE 8.25
Basis: F = 100 kmol/h
Let D and B be kmol/h of distilled and bottom products.
D + B = 100
Benzene balance:
0.228 D = 2.2
or D = 9.63 kmol/h
B = 100 9.63 = 90.37 kmol/h
A check can be made for other components. Ans. (a)
Heat load of overhead condenser:
For finding the heat load of the condenser, bubble and dew points of the distillate
products are required to be found.
Component mole fraction Antoine constants (Ref. Table 5.4)
A B C
Benzene (1) 0.228 4.018 14 1203.835 53.226
Toluene (2) 0.722 4.078 27 1343.943 53.773
Ethylebenzene (3) 0.050 4.074 88 1419.315 60.539
Styrene (4) . 4.219 48 1525.059 56.379
Total pressure in the column, p = 21.3 kPa a = 0.213 bar a
Using, Antoine equation, i.e. Eq. (5.24):
T1b = saturation temp. of benzene at 21.3 kPa
= 309.92 K or 36.77°C
Excel outputs for Exercise 8.24

Basis: 100 kg liquid chlorine in the container
Chlorination rate, m = 20.016 kg/h
Interval q = 0.2 h Ambient temperature, ta/Ta = 30°C/303.15 K
First Interval q1, = 0.2 h
Mo = 100 kg (initial value)
Overall heat transfer coefficient, U = 11.4 W/(m*-K) = 41.04 kJ/(h-m*K)
Initial value of T Tin,K 303.15 293.13 287.91 285.29 283.98 283.33 283.00 282.84 282.76 282.72
Liquid density at T ri, kg/m3 1378.83 1410.59 1426.64 1434.53 1438.45 1440.40 1441.37 1441.85 1442.10 1442.22
Liquid latent lv, kJ/kg 245.50 253.36 257.28 259.19 260.13 260.60 260.83 260.95 261.01 261.04
heat of vap.
Average liquid density ri, kg/m3 1378.83 1394.71 1402.74 1406.68 1408.64 1409.62 1410.10 1410.34 1410.47 1410.53
Average latent lV, kJ/kg 245.50 249.43 251.39 252.34 252.81 253.05 253.16 253.22 253.25 253.27
heat of vap.
Average Mo Mo, kg 100 97.9984 97.9984 97.9984 97.9984 97.9984 97.9984 97.9984 97.9984 97.9984
Volume of liquid V1, m3 0.07253 0.07026 0.06986 0.06967 0.06957 0.06952 0.06950 0.06949 0.06948 0.06948
Cross-sectional area A1, m2 0.04029 0.03904 0.03881 0.03870 0.03865 0.03862 0.03861 0.03860 0.03860 0.03860
Central angle a1, radian 0.55806 0.54066 0.53757 0.53606 0.53531 0.53494 0.53476 0.53467 0.53462 0.53460
Arc length Si, m 0.21206 0.20545 0.20428 0.20370 0.20342 0.20328 0.20321 0.20317 0.20316 0.20315
Area in contact A¢1, m2 0.38171 0.36981 0.36770 0.36666 0.36615 0.36590 0.36578 0.36571 0.36568 0.36567
with liquid
m*q/Mo 0.04003 0.04085 0.04085 0.04085 0.04085 0.04085 0.04085 0.04085 0.04085 0.04085
1m*q/Mo 0.95997 0.95915 0.95915 0.95915 0.95915 0.95915 0.95915 0.95915 0.95915 0.95915
UA ¢1 15.6654 15.1771 15.0902 15.0479 15.0270 15.0166 15.0114 15.0089 15.0076 15.0069
To 303.15 298.14 295.53 294.22 293.57 293.24 293.08 293.00 292.95 292.93
UA¢1/mC1 0.79456 0.76979 0.76539 0.76324 0.76218 0.76166 0.76139 0.76126 0.76120 0.76116
(1-m*q/Mo)(UA 1¢ /mC1) 0.96806 0.96840 0.96858 0.96867 0.96871 0.96873 0.96874 0.96875 0.96875 0.96875
UATa 4748.968 4600.926 4574.608 4561.772 4555.434 4552.287 4550.718 4549.936 4549.545 4549.350
mlv (avg) 4913.851 4992.569 5031.750 5050.868 5060.306 5064.994 5067.329 5068.494 5069.076 5069.366
UA (Ta To) 0.000 76.030 115.025 134.372 144.006 148.813 151.212 152.411 153.010 153.309
4756.899 4761.195 4762.250 4762.454 4762.475 4762.465 4762.454 4762.448 4762.444 4762.442
Calculated T Tcal,K 293.13 287.91 285.29 283.98 283.33 283.00 282.84 282.76 282.72 282.70
Second interval q2 = 0.2 h
Initial value of T Tin.K 282.70 272.44 266.64 263.74 262.29 261.57 261.21 261.03 260.94
Liquid density at T ri, kg/m3 1442.27 1472.70 1488.13 1495.70 1499.44 1501.30 1502.23 1502.69 1502.92
Liquid latent heat of vap. lv, kJ/kg 261.05 268.26 271.85 273.59 274.44 274.87 275.08 275.18 275.23
Average liquid density ri, kg/m3 1442.27 1457.49 1465.20 1468.98 1470.86 1471.79 1472.25 1472.48 1472.60
Average latent heat of vap. lv, kJ/kg 261.05 264.65 266.45 267.32 267.75 267.96 268.06 268.12 268.14
Average Mo Mo, kg 95.9968 93.9952 93.9952 93.9952 93.9952 93.9952 93.9952 93.9952 93.9952
Volume of liquid V1, m3 0.06795 0.06383 0.06349 0.06333 0.06325 0.06321 0.06319 0.06318 0.06318
Cross-sectional area A1, m2 0.03775 0.03546 0.03527 0.03518 0.03514 0.03512 0.03511 0.03510 0.03510
Central angle a1, radian 0.52283 0.49111 0.48855 0.48731 0.48669 0.48639 0.48624 0.48616 0.48612
Arc length S1, m 0.19868 0.18662 0.18565 0.18518 0.18494 0.18483 0.18477 0.18474 0.18473
Area in contact with liquid A¢1 m2 0.35762 0.33592 0.33417 0.33332 0.33290 0.33269 0.33259 0.33254 0.33251
m*q/Mo 0.04085 0.04259 0.04259 0.04259 0.04259 0.04259 0.04259 0.04259 0.04259
1m*q/Mo 0.95915 0.95741 0.95741 0.95741 0.95741 0.95741 0.95741 0.95741 0.95741
UA ¢1 14.6766 13.7862 13.7144 13.6794 13.6622 13.6536 13.6494 13.6472 13.6462
To 282.70 277.55 274.64 273.20 272.47 272.11 271.93 271.84 271.80
UA¢1/mC1 0.74441 0.69925 0.69560 0.69383 0.69296 0.69252 0.69231 0.69220 0.69215

(1-m*q/Mo)(UA¢1/mC1) 0.96943 0.97003 0.97018 0.97025 0.97029 0.97031 0.97032 0.97032 0.97032
UATa 4449.216 4179.288 4157.508 4146.910 4141.686 4139.095 4137.806 4137.163 4136.842
mlv (avg) 5225.141 5369.526 5405.415 5422.821 5431.384 5435.627 5437.738 5438.790 5439.314
UA (Ta To) 300.137 352.985 390.938 409.763 419.126 423.790 426.115 427.274 427.852
4774.445 4866.171 4864.940 4863.939 4863.347 4863.031 4862.869 4862.787 4862.747
Calculated T Tcal,K 272.44 266.64 263.74 262.29 261.57 261.21 261.03 260.94 260.90
Third interval q2 = 0.2 h
Initial value of T Tin,K 260.92 250.22 244.44 241.55 240.11 239.39 239.03 238.85 238.76
Liquid density at T ri, kg/m3 1502.99 1531.84 1546.36 1553.45 1556.94 1558.67 1559.53 1559.96 1560.18
Liquid latent heat of vap. lv, kJ/kg 275.25 281.70 284.86 286.38 287.12 287.49 287.67 287.76 287.80
Average liquid density ri, kg/m3 1502.99 1517.42 1524.68 1528.22 1529.97 1530.83 1531.26 1531.48 1531.58
Average latent heat of vap. lv,kJ/kg 275.25 278.48 280.06 280.81 281.18 281.37 281.46 281.50 281.53
Average Mo Mo, kg 91.9936 89.9920 89.9920 89.9920 89.9920 89.9920 89.9920 89.9920 89.9920
Volume of liquid V1,m3 0.06121 0.05875 0.05847 0.05834 0.05827 0.05824 0.05822 0.05821 0.05821
Cross-sectional area A1 m2 0.03400 0.03264 0.03248 0.03241 0.03237 0.03235 0.03235 0.03234 0.03234
Central angle a1 radian 0.47097 0.45204 0.44991 0.44888 0.44837 0.44812 0.44799 0.44793 0.44790
Arc length S1 m 0.17897 0.17178 0.17097 0.17057 0.17038 0.17029 0.17024 0.17021 0.17020
Area in contact with liquid A¢1 m2 0.32214 0.30920 0.30774 0.30703 0.30669 0.30651 0.30643 0.30639 0.30636
m*q/Mo 0.04352 0.04448 0.04448 0.04448 0.04448 0.04448 0.04448 0.04448 0.04448
1m*q/Mo 0.95648 0.95552 0.95552 0.95552 0.95552 0.95552 0.95552 0.95552 0.95552
UA ¢1 13.2207 12.6895 12.6296 12.6006 12.5864 12.5793 12.5758 12.5741 12.5732
To 260.92 255.73 252.76 251.27 250.53 250.17 249.98 249.89 249.84
UA¢1/mC1 0.67056 0.64362 0.64058 0.63911 0.63839 0.63803 0.63786 0.63777 0.63772
(1-m*q/Mo)(UA¢1/mC1) 0.97061 0.97114 0.97127 0.97134 0.97137 0.97138 0.97139 0.97140 0.97140
UATa 4007.851 3846.812 3828.667 3819.875 3815.554 3813.416 3812.355 3811.826 3811.563
mlv (avg) 5509.428 5638.517 5670.126 5685.314 5692.743 5696.411 5698.230 5699.135 5699.585
UA (Ta To) 554.079 601.717 636.437 653.672 662.244 666.510 668.635 669.693 670.220
4809.693 4891.426 4889.079 4887.419 4886.470 4885.968 4885.711 4885.581 4885.516
Calculated T Tcal, K 250.22 244.28 241.31 239.83 239.09 238.72 238.54 238.45 238.40
Final temperature of liquid chlorine in container after 0.6 h (2160 s) = 238.40 K (34.75°C)
T1t = saturation temp. of toluene at 21.3 kPa

= 336.71 K or 63.56°C
T1e = saturation temp. of ethylbenzene at 21.3 kPa
= 359.56 K or 86.41°C
T1 = 309.92 ´ 0.228 + 336.71 ´ 0.722 + 359.56 ´ 0.05
= 331.7 K (58.55°C) first assumption for the bubble point and
dew point calculations
Bubble point: All pressures are in kPa.
Temperature, K
Component xi
T1 = 331.7 K T2 = 328.7 K T3 = 328.3 K
p si yi p si yi p si yi
Benzene(1) 0.228 49.606 0.531 44.512 0.477 43.826 0.469
Toluene (2) 0.722 17.497 0.582 15.496 0.525 15.233 0.516
Ethyl 0.050 6.932 0.016 6.059 0.014 5.946 0.014
benzene (3)
Total 1.000 1.129 1.016 0.999
Bubble point of distillate product TBB = 328.3 K (55.15 °C) Ans. (b i)
Dew Point: All pressures are in kPa.
Temperature, K
Component yi
T1 = 33.17 K T2 = 336 K T3 = 335 K T4 = 334.7 K
p si xi p si xi p si xi p si xi
Benzene(1) 0.228 49.606 0.098 58.011 0.084 56.030 0.087 55.112 0.088
Toluene(2) 0.722 17.497 0.879 20.852 0.738 20.050 0.767 19.693 0.781
Ethyl 0.050 6.932 0.154 8.420 0.126 8.065 0.132 7.906 0.135
benzene(3)
Total 1.000 1.131 0.948 0.986 1.004
Dew point of distillate product, TDP = 334.7 K (61.55°C) Ans. (b ii)
Average temperature of condensation = (TBB + TDP)/2
= (328.3 + 334.7)/2
= 331.5 K (58.35°C)
Consider reference temperature, T0 = 331.5 K
Use Watson equation [Eq. (5.26)] and data from Table5.5 for calculation of
enthalpy of vaporisation.
0.98
é 562.05 331.5 ù
lv1 = 30 720 ê ú = 31 902 kJ/kmol of benzene
ë 562.05 - 353.3 û
0.98
é 591.75 - 331.5 ù
lv2 = 33 180 ê ú = 36 133 kJ/kmol of toluene
ë 591.75 - 383.8 û
0.98
é 617.15 - 331.5 ù
lv3 = 35 570 ê ú = 40 138 kJ/kmol of ethylebenzene
ë 617.15 - 409.3 û
Since distillate product is leaving in saturated conditions,
its enthalpy = 0 kJ/kmol.
Heat load of condenser = 9.63 [0.228 ´ 31 902
+ 0.722 ´ 36 133 + 0.05 ´ 40 138] ´ (1 + 6)
= 2384 196 kJ/h
= 662.277 kW Ans.(c)
Enthalpy of bottom product:
Tower is considered to operate at near constant pressure
T1s = saturation temperature of styrene at 21.3 kPa
= 368.18 K or 95.03°C
T1 = 336.7 ´ 0.005 ´ 359.6 ´ 0.475 + 368 ´ 0.52 = 364 K (90.85°C)
Bubble Point: All pressures are in kPa
Temperature, K
Component xi
T1 = 364.0 K T2 = 363.0 K T3 = 363.55 K
Toluene(2) 0.005 52.350 0.012 54.078 0.013 54.935 0.013
Ethyl 0.475 23.304 0.520 24.154 0.539 24.594 0.548
benzene(3)
Styrene(4) 0.520 17.018 0.415 17.668 0.431 17.973 0.439
Total 1.000 0.947 0.983 1.000
T BB = 363.55 K (90.4°C)
Data on heat capacity constants:
Component xi liquid heat capacity (C°mp) equation constants

ai xi bi xi ´ 103 ci xi ´ 106 di xi ´ 109
Toluene(2) 0.005 0.009 4.061 7.563 8.150
Ethyl 0.475 2.049 427.583 688.774 680.960
benzene(3)
Styrene(4) 0.520 19.770 622.549 1441.738 1005.222
Total 1.000 17.712 1054.193 1838.075 1694.332
Enthalpy of bottom product = 90.37 [ 17.712 (363.55 331.5)
+ 1054.193 ´ 103 (363.552 331.52)/2
1838.075 ´ 106 (363.553 331.53)/3

+ 1694.332 ´ 109 (363.554 331.54)/4]
= 572 794 kJ/h
º 159.11 kW (liquid)
Enthalpy of feed:
T1 = 0.022 ´ 309.9 + 0.074 ´ 336.7 + 0.434 ´ 359.6 + 0.47 ´ 368
= 360.7 K (87.7°C)
Bubble Point: All pressures are in kPa.
Temperature, K
Component xi
T1 = 360.7 K T2 = 358.0 K T3 = 357.75 K
Benzene(1) 0.022 124.80 0.129 117.27 0.121 116.137 0.120
Toluene(2) 0.074 49.19 0.171 45.88 0.159 45.402 0.158
Ethyl 0.434 21.757 0.443 20.145 0.410 19.927 0.406
benzene(3)
Styrene(4) 0.470 15.838 0.349 14.614 0.322 14.424 0.323
Total 1.000 1.092 1.012 1.007
TBB = 357.75 K (84.75 °C)
Heat capacity data:
Lliquid heat capacity C°mp equation constants

Component xi
ai xi bi xi ´ 103 ci xi ´ 106 di xi ´ 109
Benzene(1) 0.022 0.160 16.952 36.26 41.755
Toluene(2) 0.074 0.134 60.105 111.93 120.621
Ethyl 0.434 1.872 390.676 629.322 622.182
benzene(3)
Styrene (4) 0.470 17.869 562.689 1031.956 908.566
Total 1.000 16.023 1030.422 1809.476 1693.124
Enthalpy of feed = 100.0[ 16.023 (357.75 331.5)

+ 1030.422 ´ 103 (357.752 331.52)/2
1809.475 ´ 106 (357.753 331.53)/3
+ 1693.124 ´ 109 (357.754 331.54)/4]
= 506 369 kJ/h
º 140.66 kW
Reboiler duty = Heat load of condenser + Enthalpy of distillate
+ Enthalpy of bottoms Enthalpy of feed

= 662.277 + 0 + 159.11 140.66
= 680.727 kW Ans. (d i)
Latent heat (lv) of steam at 0.2 MPa a = 2201.6 kJ/kg
Steam consumption in reboiler = 680.727 ´ 3600/2201.6
= 1113.1 kg/h Ans. (d ii)
EXERCISE 8.26
Basis: 40 000 Nm3/h offgas mixture at 0.25 bar g and 523.15 K (250°C)
40 000
Offgas mixture flow rate = = 1784.6 kmol/h
22.414
New basis: 100 kmol dry offgas mixture
Case I:
Element Balance of Offgas Mixture
Component kmol C, kmol H2, kmol O2, kmol
H2 15.3 15.3
N2 61.9
Ar 0.9
CH4 0.4 0.4 0.8
CO 17.2 17.2 8.6
CO2 3.9 3.9 3.9
C2H2 0.4 0.8 0.4
Total 100.0 22.3 16.5 12.5
Moisture in offgas mixture = 0.15 ´ 100 = 15 kmol
16.5
Theoretical O2 requirement = 22.3 + 12.5
2
= 18.05 kmol
Excess air = 10%
º 2726.76 kg
Moisture, entering with air = 94.548 ´ 0.017
= 1.607 kmol
Boiler Flue Gas Analysis

Component kmol Dry analysis, % Wet analysis
(Orsat) %
N2 + Ar 61.9 + 0.9 + 74.693 = 137.693 85.08 70.62
O2 19.855 18.05 = 1.805 1.12 0.93
CO2 22.300 13.80 11.45
H2O 16.5 + 15.0 + 1.607 = 33.107 17.00
Total 194.705 (wet) 100.00 100.00
161.598 (dry)
Heat Input to Boiler: (For nomenclature, refer Table 7.13).
Gross Calorific value of fuel:
H1 = 15.3 ´ 285.83 ´ 1000 + 17.2 ´ 282.98 ´ 1000
+ 0.4 ´ 890.65 ´ 1000 + 0.4 ´ 1301.0 ´ 1000
= 10 117 115 kJ/100 kmol offgas mixture
Heat of Offgas mixture at 523.15 K (250°C)
T0 = 298.15 K (25 °C)
Cºmp equation constants
Component kmol, ni
H2 15.3 437.741 15.600 – 2.258 11.628
N2 61.9 1831.676 – 318.230 816.022 – 307.519
Ar 0.9 18.695 — — —
CH4 0.4 7.700 20.845 4.789 – 4.527
CO 17.2 499.276 – 48.444 200.272 – 80.948
CO2 3.9 144.979 90.625 – 28.777 3.203
C2 H 2 0.4 9.002 36.050 – 25.494 7.146
H2O 15.0 487.382 1.194 198.161 – 68.211
Total 115.0 3436.451 – 202.360 1162.716 – 439.228
H2 = 3436.451 (523.15 298.15) 202.36 ´ 10 (523.15 298.152)/2
3 2
+ 1162.716 ´ 106 (523.153 298.153)/3 439.228 (523.154 298.154)/4

= 791 829 kJ
Heat of input (combustion) air at 313.15 K (40°C):
Cs = 1.006 + 1.84 ´ 0.017 = 1.037 kJ/(kg dry air × K)
H3 = 2726.76 ´ 1.037 (313.15 298.15)
= 42 415 kJ
Total heat input HI = H1 + H2 + H3
= 10 951 359 kJ/100 kmol offgas mixture
Heat Output:
Heat loss in flue gases at 448.15 K (175ºC):
Component kmol, ni Cºmp equation constants

N2 137.493 4068.542 706.852 1812.556 683.065
O2 1.805 46.976 21.218 4.228 1.015
CO2 22.300 476.451 1433.535 915.428 218.538
H2O 33.107 1075.716 2.635 437.367 150.5511
Total 194.705 5667.685 750.536 1330.267 616.093
3 2 2
H7 = 5667.685 (448 298.15) + 750.536 ´ 10 (448 298.15 )/2
+ 1330.267 ´ 106 (4483 298.153)/3 616.093 ´ 109 (4484 298.154)/4
= 914 392.4 kJ
Heat loss due to evaporation:
33107
. kmol
Humidity of flue gas = = 0.2047
161598
. kmol dry gas
p = 745 Torr = 99.3 kPa a
Let pw = saturation pressure of water in flue gas
pw1
= 0.2049
p - pw1
pw1 = 16.887 kPa
From Table 6.13, Ts = 329.55 K (56.4ºC)
From steam tables (Appendix AIV.1), lv = 2367 kJ/kg
Heat loss due to evaporation of moisture,
H8 = 16.5 ´ 18.0153 ´ 2367
= 703 597 kJ
Unaccounted heat loss, H13 = 10 278 006 ´ 0.015
= 119 833 kJ
Total heat loss = 914 392.4 + 703 597 + 119 833
= 1772 159 kJ
Heat utilised for production of superheated steam
H14 = 10 951 359 1772 159
= 9179 200 kJ/115 kmol wet incoming gas
Total heat available for steam production for original basis of 1784.6 kmol/h
offgas mixture
9179 200 ´ 1784.6
f14 =
115
= 142 445 220 kJ/h
º 39 568.117 kW
From steam tables:
Enthalpy of superheated steam at 43 bar a and 698.15 K (425ºC)
= 3269 kJ/kg
Enthalpy of BFW at 303.15 K (30ºC) = 121.41 kJ/kg
Heat required for production of superheated steam
= 3269 121.41 = 3147.59 kJ/kg
97 005 216.7
Production of superheated steam =
3147.59
= 45 255.3 kg/h Ans.
Case II:
Loss of offgas in CO2 processing plant = 1%
CO2 recovery in CO2 processing plant = 97%
CO2 recovery = 3.9 ´ 0.99 ´ 0.97
= 3.745 kmol/100 kmol dry offgas
mixture
CO2 in offgas mixture to boiler = 3.9 ´ 0.99 3.745
= 0.116 kmol
Pressure and temperature of offgas mixture at the outlet of CO2 absorber
= 0.1 bar g and 328 K
p = 0.1 bar g = 1.113 25 bar a
T = 328 K (55ºC), pw2 = 15.741 kPa
15.741 kmol
Humidity of offgas = = 0.1647
111325
. - 15.741 kmol dry gas
Element Balance of Offgas Mixture
H2 15.147 15.147
N2 61.281
Ar 0.891
CH4 0.396 0.396 0.792
CO 17.028 17.028 8.514
CO2 0.116 0.116 0.116
C2H2 0.396 0.792 0.396
Total 95.255 (dry) 18.332 16.335 8.630
Water, entering with gas mixture = 95.255 ´ 0.1647
= 15.688 kmol
16.335
2
= 17.87 kmol
N2, entering with O2 = 79 ´ 19.657/21
= 73.948 kmol
º 2699.568 kg
Moisture entering with air = 93.605 ´ 0.017
= 1.591 kmol
Boiler Flue Gas
Component kmol Dry analysis, % Wet
(Orsat) analysis %
N2 + Ar 61.281 + 0.891 + 73.948 = 136.12 87.06 71.65
O2 19.657 17.87 = 1.787 1.14 0.94
CO2 0.116 + 18.332 = 18.448 11.80 9.71
H2O 15.688 + 16.335 + 1.591 = 33.614 17.70
Total wet189.969 100.00 100.00
dry 156.355
Heat Input to Boiler:
Heat of offgas mixture to boiler at 328.15 K (55ºC):
C ºmp equation constants
Component kmol, ni
H2 15.147 433.363 15.441 2.236 11.648
N2 61.281 1813.360 315.046 807.861 304.444
Ar 0.891 18.508
CH4 0.396 7.623 20.637 4.741 4.482
CO 17.028 494.284 47.959 198.270 80.139
CO2 0.116 2.478 7.457 4.762 1.137
C2H2 0.396 8.912 35.689 25.239 7.074
H2O 15.688 509.736 1.249 207.249 71.340
Total 110.943 3288.264 282.532 1185.884 440.548
H2 = 3288.264 (328 298.15) 282.532 ´ 103 (3282 298.152)/2
+ 1185.884 ´ 106 (3283 298.153)/3 440.548 ´ 109 (3284 298.154)/4
= 101 870.5 kJ
Heat of input air at 313 K (40ºC):
H3 = 2699.6 ´ 1.037 ´ 15
= 41 992.3 kJ
GCV of offgas mixture,
H1 = 15.147 ´ 285 830 + 17.028 ´ 282.98 ´ 1000 + 0.396 ´ 890 650
+ 0.396 ´ 1301 000
= 10 015 660 kJ
Total heat input, HI = 10 015.660 + 101 870.5 + 41 992.3
= 10 159 523 kJ
Heat output:
Unaccounted heat loss, H13 = 10 159 523 ´ 0.015
= 152 393 kJ
Component kmol, ni C mp
N2 136.12 4027.913 699.793 1794.456 676.244

O2 1.787 46.508 21.006 4.186 1.005
CO2 18.448 394.151 1185.913 757.301 180.789
H2O 33.614 1092.189 2.676 444.064 152.856
Total 189.969 5560.761 509.802 1477.033 649.316
H7 = 5560.761 (448.15 298.15) + 509.802 ´ 10 (448.15 298.152)/2
3 2
+ 1477.033 ´ 106 (4483 298.153)/3 649.316 ´ 109 (448.154 298.154)/4

= 887 744.8 kJ
pw1 33.614 kmol
= = 0.215
p - pw 3 156.355 kmol dry gas
pw3 = 17.572 kPa
From Table 6.13, Ts = 330.45 K (57.3ºC).
From Steam Tables, l v = 2365.2 kJ/kg
H8 = 16.335 ´ 18.0153 ´ 2365.2
= 696 019.3 kJ
Total heat loss = 887 744.8 + 696 019.3 + 152 393
= 1735 157 kJ
Heat utilised for steam generation = 10 159 523 1735 137
= 8423 366 kJ
Total heat available for steam production for 40 000 Nm2/h offgas mixture,
8423 366 ´ 1784.6
¢ =
B14
115
= 130 715 991 kJ/h
º 36 310.0 kW
130 715 991
Steam generation = = 41 528.9 kg/h Ans. (i)
3147.59
1784.6
CO2 production = 3.745 ´ ´ 44.0098 ´ 0.95
115
= 2429.79 kg/h
º 51 315 kg/d
º 51.315 t/d Ans. (ii)
Case III:
Additional loss of gas in cryogenic separation plant = 1%
Pressure of gas at the outlet of cold box = 1 bar g
Temperature = 298.15 K (25ºC)
Moisture = Nil
Recovery of H2 in cryogenic plant = 90%
H2 recovery = 15.147 ´ 0.99 ´ 0.9 = 13.496 kmol
H2 in reject gas stream = 15.147 ´ 0.99 13.496
= 1.5 kmol
13.496
CO requirement for methanol production =
2
= 6.748 kmol
CO in reject gas stream = 17.028 ´ 0.99 6.748
= 10.11 kmol
Reject Gas to Boiler at 298.15 K (25ºC):
Element Balance of Reject Gas Stream:
H2 1.5 1.5
N2 60.668
Ar 0.882
CH4 0.392 0.392 0.784
CO 10.110 10.110 5.055
CO2 0.115 0.115 0.115
C2H2 0.392 0.784 0.392
H2O Nil
Total 74.059 11.401 2.676 5.170
2.676
2
= 7.569 kmol
Excess O2 = 8.326 7.569 = 0.757 kmol
º 1143.448 kg
Moisture, entering with air = 39.648 ´ 0.017 = 0.674 kmol
Boiler Flue Gas
Component kmol Dry analysis, % Wet analysis

(Orsat) %
N2 + Ar 60.668 + 0.882 + 31.322 = 92.872 88.42 85.69
O2 0.757 0.72 0.70
CO2 11.401 10.86 10.52
H2O 2.676 + 0.674 = 3.350 3.09
Total wet 108.380 100.00 100.00
dry 105.030
Heat Input to Boiler:
Since reject gas stream enters at 298.15 K,
H2 = 0
H1 = 1.5 ´ 285 830 + 10.11 ´ 282 980 + 0.392 ´ 890 650
+ 0.392 ´ 1301 000
= 4148 800 kJ
Enthalpy of input air, H3 = 1143.448 ´ 1.037 ´ 15
= 17 786.3 kJ
Total heat input, H1 = 4148 800 + 0 + 17 786.3
= 2426 683.6 kJ
Heat Output from Boiler:
Unaccounted heat loss, H13 = 4166 586 ´ 0.015
= 62 49.9 kJ
C mp
Component kmol, ni
N2 92.872 2748.166 477.455 1224.322 461.388
O2 0.757 19.701 8.899 1.773 0.426
CO2 11.401 243.588 732.903 468.016 111.729
H2O 3.350 108.848 0.267 44.256 15.234
Total 105.030 3120.303 264.614 798.787 465.319
H7 = 3120.303 (448.15 298.15) + 264.614 ´ 103 (448.152 298.152)/2
+ 798.787 ´ 106 (448.15 3 298.153)/3 465.319 ´ 109 (448.15 4
298.154)/4
= 495 488.1 kJ
3.35
Moisture in fine gas = = 0.0329 kmol/kmol dry gas
(105.03 - 3.35)
p = 1 bar g = 2.013 25 bar a

º 201.325 kPa
pw3
= 0.0329
p - pw3
p w = 6.413 kPa
DP of flue gas = 37.4°C or 310.55 K
lv of water at DP = 2413.14 kJ/kg
Heat loss due to evaporation = 2.676 ´ 18.0153 ´ 2413.15
= 116 335 kJ
Total heat loss = 66 499 + 116 335 + 495 488.1
= 674 322 kJ
Heat utilised for steam generation = 4166 586 674 322
= 3492 264 kJ
Total heat available for steam generation for 40 000 Nm3/h offgas mixture,
¢¢ = 3492 264 ´ 1784.6/115
B14
= 54 193 864 kJ/h
º 15 053.85 kW
Steam generation = 54 193 864/3147.59
= 17 217.6 kg/h Ans. (i)
CO2 production = 51 315 kg/d same as Case II Ans.(ii)
13.496 1784.6
Methanol (100%) production = ´ 0.9 ´
2 115
= 94.246 kmol/h
º 3019.8 kg/h
º 72 476 kg/d º 72.476 t/d Ans. (iii)
EXERCISE 8.27
Basis: 50 kmol/h of dry offgas mixture to first bed
Vapour pressure of water, fw = 7.375 kPa at 313.15 K (40ºC) (Table 6.13)
Total pressure, p = 2 bar g = 301.325 kPa a
7.375
Moisture content of offgases =
301325
. - 7.375
Offgas Mixture from Adipic Acid Plant
Component kmol Molar mass kg
N2O 30 44 1320
O2 8 32 256
CO2 3 44 132
N2 59 28 1652
H2O 2.5 18 45
Total 102.5 3405
3405
Average molar mass of wet offgas = = 33.22
102.5
3405 - 45
Average molar mass of dry offgas = = 33.60
100
3405 ´ 50
Flow of wet offgas mixture of first bed =
100
= 1702.5 kg/h
1
Reaction: N2O = N2 + O2
2
DHºf 82.05 0 0 kJ/mol at 298.15 K
Considering 100% conversion, following will be the composition of treated gas
mixture from the first bed.
Component kmol/100 kmol mole % Molar kg
offgas (dry) (dry) mass
N2O Nil 0 44 0
30
O2 8+ = 23 20.00 32 736
2
CO2 3 2.61 44 132
N2 59 + 30 = 89 77.39 28 2492
H2O 2.5 18 45
Total 117.5 100.00 3405
In 117.5 kmol wet treated gas mixture, 115 kmol dry gas mixture is present.
Thus for 1 kmol dry offgas mixture, production of treated dry gas mixture will
be 1.15 kmol.
Compositions of recycle gas mixture and treated gas mixtures will be same
as 100% conversion.
Offgas mixture:
Component kmol Cºmp equation constant
ni ni × ai ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109

N2O 0.30 6.962 19.101 – 12.702 3.121
O2 0.08 2.082 0.940 – 0.187 – 0.045
CO2 0.03 0.641 1.929 – 1.232 0.294
N2 0.59 17.459 – 3.033 7.778 – 2.931
H2O 0.025 0.812 0.002 0.330 – 0.114
Total 1.025 27.956 18.939 – 6.013 0.325
Treated gas mixture:

Component kmol Cºmp equation constant
ni ni × ai ni × bi ´ 103 ni × ci ´ 106 ni × di ´ 109

O2 0.2000 5.205 2.351 0.469 0.112
CO2 0.0261 0.558 1.678 1.071 0.256
N2 0.7739 22.900 3.979 10.202 3.845
H2O 0.0217 0.705 0.002 0.287 0.099
Total 1.0217 29.368 0.052 8.949 3.602
Base temperature, To = 298.15 K (25°C)
Based on Cºmp equation, following enthalpies are calculated.
Temperature, T Enthalpy at T over To, kJ/kmol dry gas

K (°C) Offgas mixture Treated gas mixture
313.15 (40) 497.9 451.8
323.15 (50) 831.7 753.5
353.15 (80) 1 842.3 1 661.6
373.15 (100) 2 523.4 2 269.5
443.15 (170) 4 952.7 4 414.1
483.15 (210) 6 371.4 5 652.3
723.15 (450) 15 308.3 13 302.6
913.15 (640) 22 830.1 19 654.0
973.15 (700) 25 274.5 21 715.3
Catalyst Bed I:
Let R kmol/h of dry treated gas mixture mixed (i.e. recycled) with 50 kmol/h of
dry offgas mixture at 373.15 K (100 ºC).
Total enthalpy of mixed gas at 723.15 K
= 15 308.3 ´ 50 + 13 302.6 R
= 765 415 + 13 302.6 R kJ/h
Heat of reaction at 298.15 K = 82.05 kJ/mol N2O (exothermic)
Heat generated in 1st bed = 50 ´ 0.3 ´ 82 050
= 1230 750 kJ/h
Enthalpy of total treated gas mixture = 1230 750 + 765 415 + 13 302.6 R
= 1996 165 + 13 302.6 R kJ/h at 973.15 K
Total flow of dry treated gas mixture from 1st bed
= 50 ´ 1.15 + R = 57.5 + R kmol/h
Since treated gas mixture leaves at 973.15 K from 1st bed,
21 715.3 (57.5 + R) = 1996 165 + 13 302.6 R
R = 88.86 kmol/h
Catalyst Bed II:

Flow of dry gas mixture, leaving 1st bed
= 57.5 + 88.86 = 146.36 kmol/h
Enthalpy of gas mixture, leaving 1st bed
= 21 715.3 ´ 146.36
= 3178 251 kJ/h º 882.848 kW
Let the flow of dry offgas mixture (i.e. quenching) to 2nd bed be F1 kmol/h
at 373.15 K. Mixed gas temperature is 723.15 K.
Heat balance of mixing:
3178 251 + 2523.4 F1 = 13 302.6 ´ 146.36 + 15 308.3 F1
F 1 = 96.31 kmol/h at 723.15 K
Enthalpy of total gas mixture, entering 2nd bed
= 3178 251 + 2523.4 ´ 96.31
= 3421 280 kJ/h
Heat generated in 2nd bed = 96.31 ´ 0.3 ´ 82 050
= 2370 671 kJ/h
Enthalpy of gas mixture, leaving 2nd bed
= 3421 280 + 2370 671
= 5791 951 kJ/h º 1608.875 kW
Flow of dry gas mixture, leaving 2nd bed
= 146.361 + (96.31 ´ 1.15)
= 257.12 kmol/h
If T1 is the temperature of gas mixture, leaving 2nd bed,
z
T1
257.12 C mp
º dT = 5791 951
298.15
Solving by Mathcad, T1 = 996.55 K or 723.4 ºC

Catalyst Bed III:
Let the flow of dry offgas mixture (i.e. quenching) to 3rd bed be F2 kmol/h at
373.15 K. Again mixed gas temperature is 723.15 K.
Heat balance of mixing:
5791 951 + 2523.4 F2 = 13 302.6 ´ 257.12 + 15 308.3 F2
F 2 = 185.50 kmol/h
Enthalpy of total gas mixture, entering 3rd bed
= 5791 951 + 2523.4 ´ 185.50
= 6260 042 kJ/h at 723.15 K
Heat generated in 3rd bed = 185.50 ´ 0.3 ´ 82 050
= 4566 083 kJ/h
Enthalpy off gas mixture, leaving 3rd bed

= 6260 042 + 4566 083
= 10 826 125 kJ/h º 3007.257 kW
Flow of dry gas mixture, leaving 3rd bed
= 257.12 + (185.50 ´ 1.15)
= 470.45 kmol/h
If T2 is the temperature off gas mixture, leaving 3rd bed
z
T2
470.45 Cºmp dT = 10 826 124

298.15
Solving by Matched T2 = 1010.52 K or 737.37 ºC

Total dry offgas flow treated = 50 + 96.31 + 185.50
= 331.81 kmol/h
96.31 ´ 100
Offgas mixture bypassed to 2nd bed = = 29.03%
331.81
185.50 ´ 100
Offgas bypassed to 3rd bed = = 55.91%
331.81
88.86 kmol
Recycle = = 0.233
(470.45 - 88.86) kmol gas emitted
Heat exchange E2:
Enthalpy of mixed feed gas, entering E2 = 50 ´ 2523.4 + 88.86 ´ 1661.6
= 273 820 kJ/h
Enthalpy of mixed feed gas, leaving E2 = 50 ´ 15 308.3 + 13 302.6 ´ 88.86
= 1947 484 kJ/h
Heat duty of E2, f1 = 1947 484 273 820
= 1673 664 kJ/h
º 464.91 kW
Enthalpy of reactor effluent stream, leaving E2
= 10 826 124 1673 664
= 9152 460 kJ/h
If T3 is the temperature of reactor effluent stream, leaving E2,
z
T3
470.45 C°mp dT = 9152 460

298.15
Solving by Mathcad, T3 = 907.3 K or 634.15 K

Heat exchanger E3:
Heat duty of E3, f2 = 9152 460 (470.45 ´ 5652.3)
= 6493 335 kJ/h
º 1803.7 kW
Enthalpy of saturated steam at 4.5 bar a
= 2742.6 kJ/kg
Enthalpy of feed water at 303.15 K (30°C) = 126 kJ/kg
6493 335
Steam generated in steam drum =
(2742.6 - 126)
= 2481.6 kg/h (saturated)
Heat exchanger E1:
Offgas (total) enters E1 at 313.15 K and leaves at 373.15 K
Heat duty of E1, f3 = 331.81 (2523.4 497.9)
= 672 081 kJ/h
º 186.69 kW
Enthalpy of reactor effluent stream, leaving E1
= 470.45 ´ 5652.3 672 081
= 1987 043 kJ/h or 4223.71 kJ/kmol
dry gas mixture
If T4 is the temperature of reactor effluent stream, leaving E1,
z
T4
470.45 Cºmp dT = 1987 043

298.15
Solving by Mathcad, T4 = 436.97 K or 163.82 ºC

Heat exchanger E4:
In this heat exchanger, 88.86 kmol/h (= R) dry gas mixture is cooled from 436.97
K to 323.15 K.
Heat duty of E4, f4 = 88.86 (4223.71 753.5)
= 308 363 kJ/h
º 85.66 kW
Assuming 5 K rise in cooling water temperature, cooling water flow
308 363
= = 14 730 kg/h
5 ´ 4.1868
º 14.7 m3/h
Heat exchanger E5:

Flow of dry gas, being emitted to atmosphere
= 470.45 88.86
= 381.59 kmol/h
Recycle dry gas (88.86 kmol/h) is heated in E5 from 341.15 K to 353.15 K.
z
353.15
Heat duty of E5, f5 = 88.86 Cºmp dT
341.15
= 32 327 kJ/h
º 8.98 kW
Enthalpy of emitted gas mixture to stack = 381.59 ´ 4223.71 32 327
= 1579 398 kJ/h º 438.722 kW
If T5 is the gas mixture to stack,
z
T5
381.59 Cºmp dT = 1579 398

298.15
Solving by Mathcad, T5 = 434.2 K or 161.05ºC. Ans.
EXERCISE 8.28
Basis: 1 kmol dry acid gas fed to the burner
Reactions taking place in burner:
H2S (g) + 3/2 O2 (g) = SO2 (g) + H2O (g) (1)
H2 (g) + ½ O2 (g) = H2O (g) (2)
æ mö
CnHm(g) + çè n + ÷ø O2(g) = n (CO2(g) + m H2O(g) (3)
2
In the burner, combustion reactions go to 100% completion.
H2S burnt = 0.3 kmol
H2 burnt = 0.01 kmol
O2 requirement for acid gas = 0.3 ´ 1.5 + 0.01 ´ 0.5 = 0.455 kmol
Let a kmol NG are required for firing in the burner. From Example 7.4,
2.064
O2 required = = 1.032 kmol/kmol NG
2
N2 entering in NG = 0.02 kmol/kmol NG
Total O2 required = 0.455 + 1.032a kmol
Excess O2 supply = 5% = 0.022 75 + 0.0516 a kmol
Actual O2 supply = 1.05 (0.455 + 1.032 a) = 0.477 75 + 1.0836 a kmol
78
N2 entering with O2 = (0.477 75 + 1.0836 a) = 1.7745 + 4.0248 a kmol
21
1
Ar entering with O2 = (0.477 75 + 1.0836 a)
21
= 0.022 75 + 0.0516 a kmol
Total dry air = 2.275 + 5.16 a kmol
Moisture entering with air = 0.02 (2.275 + 5.16 a)
= 0.0455 + 0.1032 a kmol
Acid gas enters saturated at 0.2 bar g and 50°C (323.15 K).
pw at 50°C = 12.335 kPa
p = 0.2 bar g = 1.21325 bar a = 121.325 kPa a
12.335
Moisture content of acid gas = (121.325 - 12.335)
Total moisture in the burner exit gas mixture
= 0.3 + 0.01 + 0.1132 + 0.0455 + 0.1032 a
+ 2.064 a
= 0.4687 + 2.1672 a kmol
CO2 produced by NG burning = 1.098 kmol/kmol NG
Composition of Gas Exit of Burner
Component kmol
SO2 0.03
CO2 0.69 + 1.098 a
Ar 0.022 75 + 0.0516 a
N2 1.7745 + 4.0248a + 0.02a = 1.7745 + 4.0448a
O2 0.02275 + 0.0516a
H2O 0.4687 + 2.1672a
Total 3.2787 + 7.4132 a wet
2.81 + 5.246 a dry
Heat effect:
D H ro1 = 296.83 241.82 (20.63)
= 518.02 kJ/mol H2S at 298.15 K (exothermic)
Similarly, D H ro2 = 241.82 kJ/mol H2 at 298.15 K (exothermic)
D H ro3 = 855.32 kJ/mol NG at 298.15 K (exothermic)
Enthalpy of feed (acid) gas:
Heat Capacity Equation Constants
Component kmol Heat capacity equation constants
n ai × ni bi × ni ´ 103 ci × ni ´ 106 di × ni ´ 109
H2S 0.30 10.357 5.294 20.300 15.974
CO2 0.69 14.472 44.356 28.325 6.762
H2 0.01 0.286 0.010 0.001 0.008
H2O 0.1132 3.678 0.009 1.495 0.515
Total 1.1132 29.063 39.081 6.531 9.719
Reference temperature, To = 298.15 K

Feed (acid) gas temperature, T1 = 323.15 K
39.081 ´ 10 -3
H1 = 29.063 (323.15 298.15) + (323.152 298.152)
2
-6.531 ´ 10 -9 9.719 ´ 10 -9
(323.153 298.153) (323.154 298.154)
3 4
= 726.6 + 303.5 15.8 7.3
= 1007.0 kJ/kmol dry acid gas
Enthalpy of Combustion air:
ni ai × ni bi × ni ´ 103 ci × ni ´ 106 di × ni ´ 109
O2 0.21 4.314 16.820 13.112 3.564
N2 0.78 23.081 4.100 10.283 3.875
Ar 0.01 0.208
H2O 0.02 0.650 0.002 0.264 0.091
Total 1.02 28.253 12.722 2.565 0.402
T2 = 313.15 K
12.722 ´ 10-3
H2 = 28.253(313.15 298.15) + (313.15 2 298.15 2 )
2
2.565 ´ 10-6 0.402 ´ 10-9

(313.153 298.153) (313.154 298.154)
3 4
= 423.8 + 58.3 3.6 0.2
= 478.3 kJ/mol dry air
Enthalpy (Sensible heat) of NG:
ni ni × ai bi × ni ´ 103 ci × ni ´ 106 di × ni ´ 109
CH4 0.894 17.209 46.589 10.704 10.118
C2H6 0.050 0.271 8.904 3.369 0.436
C3H8 0.019 0.080 5.819 3.014 0.611
i-C4H10 0.004 0.036 1.678 0.935 0.204
n-C4H10 0.006 0.017 2.743 0.147 0.286
CO2 0.007 0.150 0.450 0.287 0.069
N2 0.020 0.592 0.103 0.264 0.099
Total 1.000 18.089 66.080 5.086 8.413
T3 = 308.15
66.080 ´ 10-3
H3 = 18.089 (308.15 298.15) + (308.15 2 298.15 2 )
2
5.086 ´ 10-6 8.413 ´ 10-9

+ (308.153 298.153) (308.154 298.154)
3 4
= 180.9 + 209.3 + 4.7 2.3
= 383.6 kJ/kmol NG
Total enthalpy of product gas mixture,
exit of burner:
H4 = 518.02 ´ 0.3 ´ 1000 + 241.82 ´ 0.01 ´ 1000 + 855.32 ´ 1000 a + 1007.0
+ 478.3 (2.275 + 5.16 a) + 383.6 a
= 155 406 + 2418 + 855 320 a + 1007.0 + 1088.1 + 2468.0 a + 383.6 a
= 159 919.1 + 858 171.6 a kJ
Burner exit gas mixture enter reaction furnace where 60% of H2S is converted
to elemental sulphur.
2 H2S(g) + SO2(g) = 3 S(g) + 2 H2O(g) (4)
1
Acid gas bypassed and introduced to reaction furnace = ´ 0.6
0.4
= 1.5 mol
H2S entering furnace = 1.5 ´ 0.3 = 0.45 kmol
H2S reacted by Eq. (2) = 0.45 ´ 0.6 = 0.27 kmol
0.27
SO2 reacted = = 0.135 kmol
2
3
S produced = ´ 0.27 = 0.405 kmol
2
H2 reacted = 1.5 ´ 0.01 = 0.015 kmol
H2O produced = 0.015 + 0.27 = 0.285 kmol
H2O entering with acid gas = 1.5 ´ 0.1132 = 0.1698 kmol
Composition of Gas Mixture Exit of Reaction Furnace
Component kmol
H2S 0.45 0.27 = 0.180
SO2 0.3 0.135 = 0.185
CO2 0.69 + 0.69 ´ 1.5 + 1.098 a = 1.725 + 1.098 a
Ar 0.022 75 + 0.0516 a
N2 1.7745 + 4.0448 a
O2 0.022 75 + 0.0516 a (0.015/2) = 0.015 25 + 0.0516 a
S 0.405
H2O 0.4687 + 2.1672 a + 0.285 + 0.1698 = 0.9235 + 2.1672 a
Total 5.211 + 7.4132 a wet
4.2875 + 5.246 a dry
It is specified that gas mixture, leaving reaction furnace should have 1100°C
(1373.15 K).
Heat effect:
D H ro4 = 2(241.82) + 3(278.81) [2(20.63) 296.83]
= +690.88 kJ/2 mol H2S (endothermic)
= +345.44 kJ/mol H2S
Enthalpy of product gas mixture, leaving reaction furnace,
H5 = 159 919.1 + 858 171.6 a 345.44 ´ 0.27 ´ 1000 + 241.82 ´ 0.015 ´ 1000
+ 1.5 ´ 1007.0
= 159 919.1 + 858 171.6 a 932 688 + 3627.3 + 1510.5
= 767 631.1 + 858 171.6 a kJ
Enthalpy, H5 is the enthalpy of product gas at 1100°C (1373.15 K) over 25°C
(298.15 K).
Enthalpy (H ¢5) of the gas mixture, exit of reaction furnace, can be calculated
using heat capacity equation constants of Table 5.2. H ¢5 and H5 should match for
a given value of a. Thus it can be a trial and error method in which iterations are
to be performed by varying value of a. Such calculations can be done with ease
on Excel worksheet, attached herewith.
Trial-1: Assume a = 0.1 kmol NG/kmol dry acid gas fed to burner
For the exit gas mixture (from reaction furnace),
Cmo pmix (1) = 163.1492 + 110.2838 ´ 10 3 T 23.8516 ´ 10 6 T 2 6.5103
´ 109 T 3
1373.15
o
H 5¢ = ò Cmpmix
(1) dT
298.15
= 175 385.3 + 99 070.6 20 374.3 5773.6

= 248 308.0 kJ/kmol mixture
H5 = 767 631.1 + (858 171.6 ´ 0.1)
= 621 814 kJ/kmol mixture
H 5¢ ¹ H5
After several trails, for a = 1.6395 kmol NG/kmol dry acid gas
Cmo pmix (2) = 495.2154 + 193.5631 ´ 103 T + 27.9635 ´ 106 T 2 34.7041
´ 109 T 3
1373.15
H 5¢ = ò Cmo pmix (2) dT

298.15
= 532 356.5 + 173 882.3 + 23 886.7 30777.0

H5 = 767 631.1 + (858 171.6 ´ 1.6395)
H 5¢ = H5
Iterative Calculations for Claus Process
Case (a): Combustion Air Feed Temperature: 40°C (313.15 K)
Gas mixture at the exit of the reaction furnace
Trial 1: a = 0.1 kmol/kmol dry acid gas fed to burner
Component a kmol ai < a* n, bi b*n*E3 ci ci;*ni*E6 di di*n*E9
SO2 0.165 0.1 0 0.1650 24.7706 4.0871 62.9481 10.3864 44.2582 7.3026 11.1220 1.8351
H2S 0.18 0.1 0 0.1800 34.5234 6.2142 17.6481 3.1767 67.6664 12.1800 53.2454 9.5842
CO2 1.725 0.1 0.1098 1.8348 21.3655 39.2014 64.2841 117.9485 41.0506 75.3196 9.7999 17.9809
Ar 0.02275 0.1 0.00516 0.0279 20.7723 0.5798 0.0000 0.0000 0.0000
N2 1.7745 0.1 0.40448 2.1790 29.5909 64.4780 5.1410 11.2021 13.1829 28.7253 4.9680 10.8252
02 0.01525 0.1 0.00516 0.0204 20.5451 0.4193 80.0947 1.6347 62.4369 1.2743 16.9722 0.3464
S 0.405 0.1 0 0.4050 27.4597 11.1212 13.3278 5.3978 10.0657 4.0766 2.6624 1.0783
H20 0.9235 0.1 0.21672 1.1402 32.4921 37.0481 0.0796 0.0908 13.2107 15.0631 4.5474 5.1850
5.2110 5.9523 163.1492 110.2838 23.8516 6.5103
Enthalpy at 1373.15 Kover 298.15 K Total

H¢5 175385.3 99070.5820374.27 5773.56 248308.1kJ/kmol acidgas to burnerby integration
H5 621813.9kJ/kmol acidgas to burner Difference 870122 kJ
Final trial 1: a = 1.6395 kmol/kmol dryacid gas fed to burner
SO2 0.165 1.6395 0 0.1650 24.7706 4.0871 62.9481 10.3864 44.2582 7.3026 11.1220 1.8351
H2S 0.18 1.6395 0 0.1800 34.5234 6.2142 17.6481 3.1767 67.6664 12.1800 53.2454 9.5842
CO2 1.725 1.6395 1.800171 3.5252 21.3655 75.3170 64.2841 226.6124 41.0506 144.7104 9.7999 34.5463
Ar 0.02275 1.6395 0.084598 0.1073 20.7723 2.2299 0.0000 0.0000 0.0000
N2 1.7745 1.6395 6.63145 8.4059 29.5909 248.7396 5.1410 43.2150 13.1829 110.8148 4.9680 41.7608
02 0.01525 1.6395 0.084598 0.0998 20.5451 2.0514 80.0947 7.9973 62.4369 6.2342 16.9722 1.6946
S 0.405 1.6395 0 0.4050 27.4597 11.1212 13.3278 5.3978 10.0657 4.0766 2.6624 1.0783
H2O 0.9235 1.6395 3.553124 4.4766 32.4921 145.4549 0.0796 0.3563 13.2107 59.1393 4.5474 20.3570
5.2110 17.3649 495.2154 193.5631 27.9635 34.7041
Enthalpy at 1373.15 K over 298.15 K
Total

H5' 532356 .5 173882.3 23886.68 30777 699348.5kJ/kmol acidI gas to burnerby integration
H5 699341 .2kJ/kmol acidgas to burner Difference 7.308321 kJ
Gas mixtureat the exitof the burner
SO2 0.3 0 0 0.3 24.7706 7.43118 62.9481 18.88443 44.2582 13.27746 11.122 3.3366
CO2 2.49017 0 0 2.49017 21.3655 53.20373 64.2841 160.0783 41.0506 102.223 9.7999 24.40342
Ar 0.10735 0 0 0.10735 20.7723 2.229906 0 0 0
N2 8.40595 0 0 8.40595 29.5909 248.7396 5.141 43.21499 13.1829 110.8148 4.968 41.76076
O2 0.10735 0 0 0.10735 20.5451 2.205516 80.0947 8.598166 62.4369 6.702601 16.9722 1.821966
H2O 4.02182 0 0 4.02182 32.4921 130.6774 0.0796 0.320137 13.2107 53.131057 4.5474 18.28882
15.4326 15.43264 444.4873 144.6661 41.742822 30.4876
Enthalpy at 2918.26 K over 298.15 K
Total
1164606 609575.7 345437.2552728.5 1566890 kJ/kmol acid gas to burner Case (b): Combustion Air Feed Temperature: 250°C (523.15 K)
SO2 0.165 1.4106 0 0.1650 24.7706 4.0871 62.9481 10.3864 44.2582 7.3026 11.1220 1.8351
H2S 0.18 1.4106 0 0.1800 34.5234 6.2142 17.6481 3.1767 67.6664 12.1800 53.2454 9.5842
CO2 1.725 1.4106 1.548839 3.2738 21.3655 69.9472 64.2841 210.4558 41.0506 134.3930 9.7999 32.0833
Ar 0.02275 1.4106 0.072787 0.0955 20.7723 1.9845 0.0000 0.0000 0.0000
N2 1.7745 1.4106 5.705595 7.4801 29.5909 221.3427 5.1410 38.4552 13.1829 98.6093 4.9680 37.1611
02 0.01525 1.4106 0.072787 0.0880 20.5451 1.8087 80.0947 7.0513 62.4369 5.4968^ 16.9722 1.4942
S 0.405 1.4106 0 0.4050 27.4597 11.1212 13.3278 5.3978 10.0657 4.0766 2.6624 1.0783
H2O 0.9235 1.4106 0.145574 1.0691 32.4921 34.7365 0.0796 0.0851 13.2107 14.1232 4.5474 4.8615
5.2110 12.7566 351.2422 180.9490 18.2033 17.2725
Enthalpy at 1373.15 K over 298.15 KTotal
H5' 377585.3 162550.8 15549.4 15317.91 509268.8 kJ/kmol acid gas to burner
H5 509281 kJ/kmol acid gas to burnerDifference 12.17642 kJ
Hence, a = 1.6395 kmol NG/kmol dry acid gas fed to burner Ans. (ai)
Substitute a = 1.6395.
Gas Mixture, Exit of Gas Burner
Component kmol mole % mole %
(wet) (dry)
SO2 0.3 1.94 2.63
CO2 2.49017 16.14 21.82
Ar 0.10735 0.70 0.94
N2 8.40595 54.46 73.67
O2 0.10735 0.70 0.94
H2O 4.02182
Total 15.43264 (wet) 100.00 100.00
11.41082 (dry)
Using heat capacity equation constants,

C°mp (3) = 444.4873 + 144.6661 ´ 103 T + 41.7428 ´ 106 T2 30.4876
mix
´ 109 T 3
Enthalpy of the gas mixture,
H4 = 159 919.1 + (858 171.6 ´ 1.6395)
= 159 919.1 + 1406 972.3
= 1566 891.4 kJ
T
= ò Cmo pmix (3) dT

298.15
Solving by Mathcad, T = 2918.25 K or 2645.1°C
(b) Combustion air is preheated to 250°C (523.15 K).
Enthalpy of combustion air at 523.15 K
H 2¢ = 6256.9 + 1175.5 99.8 6.7
Enthalpy of product gas mixture, leaving reaction furnace,
H5 = 767 631.1 + 858 171.6a + (7425.9 478.3) (2.275 + 5.16a)
= 751 825.3 + 894 021.2 a kJ
For a = 1.4106
Cmo pmix (4) = 351.2422 + 180.9490 ´ 103 T 18.2033 ´ 106 T2 17.2725
´ 109 T3
1373.15
H ¢5 = ò Cmo pmix (4) dT

298.15
= 509 269/kmol mixture
H5 = 4\509 281 kJ/kmol mixture
H 5¢ = H5
Hence, a = 1.4106 kmol NG/kmol dry acid to burner Ans.(b)
A reduction of 13.96% NG can be realized by preheating combustion air.
EXERCISE 8.29
Basis: qr1 = 120 m3/h waste water feed to stripper
Benzene content = 200 mg/L
= 200 g/m3 waste water
.
Benzene entering in waste water, m1 = 120 ´ 200/100
= 24 kg/h
.
Molar flow rate of benzene, n1 = 24/78.1118
= 0.3073 kmol/h
Since waste water, leaving the stripper, has negligible benzene content, all benzene,
entering in feed, will be stripped.
Nitrogen flow rate, qv2 = 3400 m3/h
Nitrogen enters stripper at 0.2 bar g and 50°C (323.15 K).
0.08314 ´ 323.15
Specific volume of gas = (1.013 25 + 0.20)
= 22.144 m3/kmol
.
Molar flow rate of dry nitrogen, n 2 = 3400/22.144
= 153.54 kmol/h
Benzene in ingoing nitrogen = 20 ´ 106 ´ 3400
= 0.068 m3/h
º 0.0031 kmol/h
Benzene in outcoming nitrogen from stripper
= 0.0031 + 0.3073
= 0.3104 kmol/h
Specific benzene content of nitrogen stream, leaving stripper
0.3104
=
153.54
= 0.002 022 kmol/kmol
º 2022 ppm (v/v)
Nitrogen stream leaves stripper at 0.14 bar g, saturated with water at 50°C
(323.15 K)
Nitrogen leaves heater at 0.12 bar g and 45°C (318.15 K) and 40% RH.
Vapour pressure of water at 45°C, pv1 = 9.582 kPa
Partial pressure of water, p1 = 9.582 ´ 0.4
= 3.8328 kPa
Moisture content of nitrogen at heater outlet,
3.8328
H2 = (113.325 - 3.8328)
= 0.035 kmol/kmol dry nitrogen

Vapour pressure of water at 50°C = 12.335 kPa
Moisture content of nitrogen at stripper outlet,
12.335
H1 = (115.325 - 12.335)
= 0.1198 kmol/kmol dry nitrogen

Moisture, required to be condensed = H1 H2
= 0.1198 0.035
= 0.0848 kmol/kmol
Total moisture removal = 0.0848 ´ 153.54
= 13.02 kmol/h
º 234.56 kg/h
Since maximum moisture content of 0.035 kmol/kmol is desired of the nitrogen
stream from chiller, the stream should be cooled to a saturation level at a system
pressure of 0.13 bar g.
pv2
114.325 - p = 0.035
v2
pv2 = 3.866 kPa
From Table 6.13, saturation temperature
t2 = 28.4°C or T2 = 301.55 K
Thus nitrogen stream will leave stripper at 0.14 bar g and 50°C (323.15 K), will
be cooled to 301.55 K and 0.13 bars in chiller and then rehated to 45°C (318.15 K)
at 0.12 bar g.
Chiller:
Average condensation temperature in
50 + 28.4
chiller =
2
= 39.3°C or 312.35 K
lv at 39.2°C = 2408.8 kJ/kg
Gas stream entering chiller
.
. . . .
kmol/h ai ×n i bi ×n i ´ 103 ci × n i ´ 106 di × n i ´ 109
N2 153.54 4548.387 789.349 2024.102 762.787
H2O 18.39 597.530 1.464 242.945 83.628
C6H6 0.3104 11.791 152.227 99.759 24.635
Total 172.2402 5134.126 -635.658 2167.288 -821.779
Gas stream leaving chiller

.
. . . .
N2 153.54 4548.387 789.349 2024.102 762.787
H2O 5.37 174.483 0.427 70.941 24.420
C6H6 0.3104 11.791 152.227 99.759 24.635
Total 159.2204 4711.079 636.695 1995.284 762.572
Reference temperature, T0 = 298.15 K

Enthalpy of gas mixture, entering chiller
323.15
f1 = ò 5134.126 635.658 ´ 103 T + 2167.288 ´ 106 T2 821.779

298.15
´ 109 T3) dT
= 128 034 kJ/h
º 35.565
Enthalpy of gas mixture, leaving chiller
301.55
f2 = ò (4711.079 639.695 ´ 103 T + 1995.284 ´ 106 T2 762.572

298.15
´ 109 T3) dT
= 15 909 kJ/h
º 4.419 kW
Heat load of chiller,
fc = f1 f2 + 2409.8 ´ 234.56
= 128 034 15 909 + 565 008
= 677 133 kJ/h
º 188.093 kW º 53.52 TR
Heat load of heater,
318.15
fh = ò (4711.079 636.695 ´ 103 T + 1995.284 ´ 106 T 2 762.572

301.55
´ 109 T 3) dT
= 77.733 kJ/h
º 21.593 kW
Saturated steam at 2 bar a is used for heating
lv at 2 bar a = 2201.6 kJ/kg
77 733
Steam consumption in heater =
2201.6
= 35.3 kJ/h
Regeneration of adsorber is carried out in 4 hours at an uniform rate after heating
the bed for 3 hours. Flow rate of vapours to condenser
24 ´ 8
= 700 +
4
= 748 kg/h
During regeneration, pressure of about 0.1 bar g is maintained in the adsorber.
ts/Ts = 102.32°C/375.47 K
lv1 at 1.113 25 bar a = 2251.4 kJ/kg
0.38
é 562.05 - 375.47 ù
lv2 of benzene at 375.47 K, lv2 = 30720 ê ú
ë 562.05 - 353.3 û
= 29 437 kJ/kmol º 376.86 kJ/kg
Heat load of condensation = 700 ´ 2251.4 + 48 ´ 376.86

= 1575 980 + 18 089
= 1594 069 kJ/h
º 442.797 kW
Both liquids are cooled from 375.47 K to 318.15 K.
Cooling load of benzene
375.47
= 0.3073 ò (484.365 + 5056.235 ´ 103 T 14 292.204 ´ 106 T2

318.15
+ 14 419.754 ´ 109 T3) dT

= 0.3073 ´ 8704
= 2675 kJ/h
º 0.743 kW
Cooling load of water = 700 (428.8 188.4)
= 168 280 kJ/h
º 46.744 kW
Total heat load of condenser
fcd = 1594 069 + 2675 + 168 280
= 1765 024 kJ/h
º 490.284 kW Ans.
EXERCISE 8.30
Reaction pressure, p = 50 atm
= 50.6625 bar
Since the reaction take place at very high pressure, use of partial pressures may
lead to wrong answes. It is therefore necessary to consider gas-vapour mixture
to be non-ideal. Rewriting Eq. (8.1).
pv AA x AA g AA f sat
AA
yAA =
f AA p
sat
pvMe xMe g Me fMe
and yMe =
fMe p
where gi = activity coefficient of i-th component in solution (assumed for similar
compoinds)
fi = fugacity coefficient of i-th component in pure state
sat
fi = fugacity coefficient of i-th component in pure state at saturated conditions
From Ref 13, and Eq. (8.2)
é pri o ù
fi = exp ê ( Bi + w i × Bi1 ) ú
ë Tri û
é prisat o 1
ù
and fi sat
= exp ê T ( Bi + w i × Bi ) ú
ëê ri ûú
where pri = reduced pressure

p
= p
ci
and Tri = reduced temperature
T
=
Tei
pvi
prisat = p
ci
and w i = acentric factor for ith component
Boi and Bi1 are Pitzer correlation coefficients and are functions of temperature
only
0.422
Boi = 0.083 T 1.6
ri
pvi
p cisat =
pci
0.172
and Bi1 = 0.139 T 4.2
ri
Component Tci, K pci, bar wi pvi, bar Tri p ri

Acetic acid 590.7 57.8 0467 5 0.7645 0.8756
Methanol 512.64 80.92 0.564 27 0.884 0.626
Component psat
ri B 0i B1i fi fsat
i
Acetic acid 0.0864 0.5655 03923 0.4242 0.9189
Methanol 0.3337 0.431 0.1497 0.6942 0.8232
5 ´ 0.15 ´ 0.9189
yAA = 50.6625 ´ 0.4242 = 0.032
27 ´ 0.85 ´ 0.8232
yMe = 50.6625 ´ 0.6842 = 0.5372
For gas-vapour mixture,
yCO + yH2 + yAA + yMe = 1
yCO + yH2 = 1 0.032 0.5372
= 0.4308
nCO + nH 2 65 + 35
= =
nt nt
. 100 100
nt = = = 232.126 kmol/h
0.4308 0.4308
.
nMe = 0.5372 ´ 232.126 = 124.7 kmol/h
.
nAA = 0.032 ´ 232.126 = 7.43 kmol/h
If the gas-vapour mixture is considered ideal, vapour-liquid equilibrium will follow

Raoult's law.
x AA × pv AA 0.15 ´ 5
y¢AA = =
p 50 × 6625
= 0.0148
0.85 ´ 27
y¢Me =
50.6625
= 0.453
yCO2 + yH2 = 1 0.0148 0.453
= 0.5322
. 100
nt = = 187.899 kmol/h
0.5322
.
nMe = 0.453 ´ 187.899 = 85.12 kmol/h
.
nAA = 0.0148 ´ 187.899 = 2.78 kmol/h
Molar flow rates of acetic acid and methanol are significantly high with non-
ideality. Ans.
9
Stoichiometry and
Digital Computation
EXERCISE 9.1
a. by spreadsheet
Component y Mm y.Mm Tc, K y.Tc, K pc, Pa y.pc, Pa
H2 0.81 2.0159 1.6329 32.200 26.082 1.297E+06 1.051E+06
C2H6 0.02 30.0696 0.6014 305.420 6.108 4.880E+06 9.760E+04
C2H4 0.04 28.0538 1.1222 282.340 11.294 5.039E+06 2.016E+05
C3H8 0.01 44.0965 0.441 369.820 3.698 4.247E+06 4.247E+04
C3H6 0.02 42.0806 0.8416 364.850 7.297 4.601E+06 9.202E+04
N2 0.08 28.0135 2.2411 126.090 10.087 3.394E+06 2.715E+05
NH3 0.02 17.0306 0.3406 405.500 8.110 1.135E+07 2.270E+05
7.2207 72.676 1.983E+06
p 2.00E+06 Pa
T 333.15 K
pc 1.98E+06 Pa
Tc 72.68 K
R 8314 kJ/(kmol × K)
Mm 7.2207
e 0.00100
dV 0.10
a 77682.8
B 0.038093
Trial V F(V) dV new dV Test sp. vol.
0 0.1 0.22164 0.10000 0.10000 FALSE # N/A
1 0.20000 0.54072 0.10000 0.10000 FALSE # N/A
2 0.30000 0.70550 0.10000 0.10000 FALSE # N/A
3 0.40000 0.75247 0.10000 0.10000 FALSE # N/A
4 0.50000 0.73677 0.10000 0.10000 FALSE # N/A
5 0.60000 0.68813 0.10000 0.10000 FALSE # N/A
6 0.70000 0.62128 0.10000 0.10000 FALSE # N/A
Stoichiometry and Digital Computation 377
7 0.80000 0.54376 0.10000 0.10000 FALSE # N/A

8 0.90000 0.45963 0.10000 0.10000 FALSE # N/A
9 1.00000 0.37122 0.10000 0.10000 FALSE # N/A
10 1.10000 0.27992 0.10000 0.10000 FALSE # N/A
11 1.20000 0.18662 0.10000 0.10000 FALSE # N/A
12 1.30000 0.09188 0.10000 0.05000 FALSE # N/A
13 1.35000 0.04410 0.05000 0.02500 FALSE # N/A
14 1.37500 0.02012 0.02500 0.01250 FALSE # N/A
15 1.38750 0.00811 0.01250 0.00625 FALSE # N/A
16 1.39375 0.00210 0.00625 0.00313 FALSE # N/A
17 1.39688 0.00091 0.00313 0.00156 TRUE 0.19345
b. by Mathcad
FG
a (R, Tc, pc) := 27 × R2
Tc2 IJ
H 64 × pc K
Tc
b (R, Tc, pc) := R ×
8× pc
LMF p + a( R, T , p ) I ×(V - b( R, T , p ))OP (R × T)
NH K
c c
f (V, p, R, T, Tc, pc) :=
V 2
Q c c
Guess value of v
V := 1.358
V := root ( f (V, 2 × 106, 8314, 333.15, 72.676, 1.983 × 106),V)
V = 1.39593 m3/kmol
V
spvol :=
7.2207
spvol = 0.19332 m3/kg
EXERCISE 9.2
F aI
H vK
A(a0, a, v) := a0 × 1 -
B(b0, b, v) := b0 × F1 - I
b
H vK
c
e(c, T, v) :=
v×T 3
LM R× T ×(1 - A(c, T, v) ×(v + B(b0, b, v)OP
f(a0, b0, a, b, c, T, R, p, v) := p
N v 2
Q
A( a0, a, v )
+
v2
For Guess value of T use Ideal Gas Law.

T := T1
soln := root (f(a0, b0, a, b, c, T, R, p, v), T)
soln = 1
Solution of Exercise 2.37
T := 840
soln := root (f (0.588, 0.094, 0.05861, 0.01915, 90 × 104, T, 0.008314, 4.2, 1.6628), T)
soln = 835.183 K
EXERCISE 9.3
(a) Exercise 4.36 Case (a).
F := 100 x := 0.24 y := 0.1 z := 0.65 yf := 0.01
af := 24.75 M := 10 P := 8 a := 2
For equations refer the solution of Exercise 4.36.
Given
y × M × P = yf × F × (M 2 × x × a × (1 + z) M × z × (1 y) + 4 × a × z)
100 + (M 2 × x × a × (1 + z) M × z × (1 y) + 4 × a × z) P = M
(1 x) × a ×
LM P OP + a = a
N M - 2 × x × a × (1 + z ) - M × z (1 - y ) + 4 × a × z Q f
vec := Find (M, P, a)
LM455.293 OP
vec =
MMN 967..9789 P
4188PQ
M := vec0 P := vec1 a := vec2
M = 455.293 P = 7.9789 a = 96.4188
R := M F R = 355.293
R
rr := rr = 3.5539
F
nh3 := (2 × x × a + M × (1 y) 4 × a) × z nh3 = 45.7401
(b) Exercise 4.36 Case (b).
F := 100 x := 0.25 y := 0.1 z := 0.7 yf := 0.01
af := 24.75 M := 10 P := 8 a := 2
Given
y × M × P = yf × F × (M 2 × x × a × (1 + z) M × z × (1 y) + 4 × a × z)
100 + (M 2 × x × a × (1 + z) M × z × (1 y) + 4 × a × z) P = M
LM
(1 x) × a × 1 -
P OP+ af = a
N M - 2 × x × a × (1 + z ) - M × z × (1 - y ) + 4 × a × zQ
vec := Find (M, P, a)
LM432.801 OP
vec :=
MMN 927..8713 P
5826 PQ
M := vec0 P := vec1 a := vec2
M = 432.801 P = 7.8713 a = 92.5826
R := M F R = 332.801
R
rr := rr = 3.328
F
nh3 := (2 × x × a + M × (1 y) 4 × a) × z nh3 = 45.8374
EXERCISE 9.4
HP steam enthalpy = H1 kJ/kg
MP superheated steam enthalpy = H2 kJ/kg
LP superheated steam enthalpy = H3 kJ/kg
LP saturated steam enthalpy = H4 kJ/kg
15 bar saturated steam enthalpy = H5 kJ/kg
Surface condenser steam enthalpy = H6 kJ/kg
BFW enthalpy = H7 kJ/kg
Surface condenser condensate enthalpy = H8 kJ/kg
Let x1 kg BFW required to quench 1 kg of 39 bar MP superheated steam to 15
bar saturated steam.
H - H5
x1(H2, H5, H7) := 2
H5 - H7
3
Q1(H2, H5, H7) := t MP steam required/h
1 + x1 ( H2 , H5 , H7 )
Let x2 kg BFW required to quench 1 kg of 39 bar MP superheated steam to 4.4
bar saturated steam.
H - H4
x2(H2, H4, H7) := 2
H 4 - H7
Let x3 kg BFW required to quench 1kg of 4.4 bar superheated steam to 4.4 bar
saturated steam.
H - H4
x3(H3, H4, H7) := 3
H 4 - H7
Power Turbine:
Specific Steam consumption in Power Turbine from HP to MP steam:
3600
S1(H1, H2) :=
( H1 - H2 ) × 0.97
Steam consumption in turbine from MP to LP:

3600
S2(H2, H3) :=
( H2 - H3 ) × 0.97
Specific Steam consumption in Power turbine from HP to SC steam:
3600
S3(H1, H6) :=
( H1 - H6 ) × 0.97
Steam turbine from MP to surface condenser:
3600
S4(H2, H6) :=
( H2 - H6 ) × 0.97
Cooling water requirement in surface condenser:
H 6 - H8
Qcw(H6, H8) :=
10 × 4.1868
Guess
a := 1 b := 1 c := 1 d := 1 e := 1 g := 1
Given
13.5 + a = (1 + x3(H3, H4, H7)) × (b + c + d) + (1+ x2(H2, H4, H7)) × g
a = 0.11 × (e + 16.5)
(b + c + d + g + Q1 ( H2 , H5 , H7 )) e 6832
+ =
S1 ( H1 , H2 ) S3 ( H1 , H6 ) 1000
2.47 × (b + c + d + e + g + Q1(H2, H5, H7)) × S2(H2, H3) = 1000d
5.493 (a + e + 16.5) × S2(H2, H3) = 1000c
0.2315 [(Qcw(H6, H8) × e) + (600)] × S2(H2, H3) = 1000b
vec(H1, H2, H3, H4, H5, H6, H7, H8) := find(a, b, c, d, e, g)
Case I
vec(3190.7, 3020.4, 2793.3, 2741.9, 2800.8, 2472.0, 440.17, 209.2)
LM 5.1556 OP
MM 48..6702
4795
PP
=
MM 2.0625PP
MM302..3692 PP
a = Saturated LP steam input to deaerator = 5.156 t/h
N 7687 Q
b = MP steam input to CW pump turbine = 8.480 t/h
c = MP steam input to BFW pump turbine = 4.670 t/h
d = MP steam input to FD fan turbine = 2.063 t/h
e = Exhaust (under vacuum) from power turbine = 30.369 t/h
g = Letdown from MP steam to LP steam = 2.769 t/h
Z = Total HP steam production = 51.095 t/h
By substituting appropriate values of variables in vec(H1, H2, H3, H4, H5, H6,
H7,H8) for Cases II to V, values of a, b, c, d, e and g can be obtained. These are
tabulated in Table 9.7 in the text.
EXERCISE 9.5
E1 is Ethylene required for EO production:
28.0538
E 1(E) := ×E
44.0532
Ethylene reacted:
E ( E)
E2(E, yE) := 1
yE
Ethylene converted to CO2 and H2O:
Eb(E, yE) := E2(E, yE) E1(E)
Total ethylene mixed feed:
E2 ( E, yE )
E3(E, yE, xE) :=
x E × 28.0538
Total mixed feed in the reactor:
E3 ( E, yE , x E )
E4(E, yE, xE, yI1) :=
0.1
Inerts in mixed feed:
Imf (E, yE, xE, yI1) := E4(E, yE, xE, yI1) × yI1
Oxygen reacted by reaction 1:
E3 ( E, yE , x E ) × x E × yE
O21(E, yE, xE) :=
2
Oxygen reacted by reaction 2:
Eb ( E, yE ) × 3
O22(E, yE, xE) :=
28.0538
Total oxygen fed:
O23(E, yE, xE) := O21(E, yE, xE) + O22(E, yE, xE)
Inerts fed along with oxygen:
O23 ( E, yE , x E ) × yI 2
I1(E, yE, xE, yI2) :=
(1 - yI 2 )
CO2 and H2O in mixed feed:
E5(E, yE, xE, yI1) := E4(E, yE, xE, yI1) E3(E, yE, xE) O23(E, yE, xE) Im(E, yE,
xE, yI1)
CO2 and H2O produced:
O22 ( E, yE , x E ) × 4
E6(E, yE, xE) :=
3
Reactor outlet stream:
E7(E, yE, xE, yI1, yI2, x, P) := E3(E, yE, xE) × (1 xE) + (I1(E, yE, xE, yI2)
LM
+ O23(E, yE, xE) + E3 ( E, yE , x E ) × (1 - xE ) ×
P OP
Recycle stream 1 contains:
N R1 ( E, yE , xE , yI1 , x ) Q
R1(E, yE , xE, yI1, x) := E3(E, yE, xE) (1 xE) + Imf (E, yE, xE, yI1) + x
Recycle stream 2 contains:
R1(E, yE , xE, yI1, x, P) := R1(E, yE , xE , yI1, x) P
Given
x × R2 ( E, y E , x E , yI1 , x, P)
= E5(E, yE, xE, yI1)
R1 ( E, y E , x E , yI1 , x )
Imf ( E, yE , x E , yI1 ) × P yI 2 × O23 ( E, yE , x E )

=
R1 ( E, yE , x E , yI1, x ) (1 - yI 2 )
soln(E, yE, xE, yI1, yI2, x, P) := find (x, P)
x := 1600 P := 44
soln(3500, 0.7, 0.5, 0.1, 0.03, x, P) =

LM 1.707 × 10 OP 3
N39.58 Q
x := soln(3500, 0.7, 0.5, 0.1, 0.03, x, P)0
P := soln(3500, 0.7, 0.5, 0.1, 0.03, x, P)1
x = 1.707 × 103 P = 39.58 kmol/h
E := 3500 yE := 0.7 xE := 0.5 yI1 := 0.1 yI2 := 0.03
Recycle Stream R2 to Reactor:
R2(E, yE, xE, yI1, yI2, x, P) = 2.008.103 kmol/h
Fresh Ethylene feed:
FE := E3(E, yE, xE)
LM
E3 ( E, yE , xE ) × (1 - xE ) - E3 ( E, yE , xE ) ×
(1 - x E ) × P OP
N R1 ( E, yE , xE , yI1 , x ) Q
FE = 115.693 FE × 28.0538 = 3.246.103 kg/h
Inerts entering with oxygen :
I1(E, yE, xE, yI2) = 4.388
Oxygen fed :
O23(E, yE, xE) = 141.874
Total Fresh Feed = Fresh Ethylene Feed + Inerts with oxygen + oxygen fed :
F E := FE + I1(E, yE, xE, yI2) + O23(E, yE, xE)
F E = 261.955 kmol/h
Recycle ratio:
R2 ( E, yE , x E , yI1 , x, P)
ratio :=
FF
ratio := 7.666 kmol/kmol fresh feed
By substituting appropriate values of yI1, various parameters can be calculated.
Please refer Table 9.8 in the text for the answers.
EXERCISE 9.6
Double recycle system of ammonia synthesis loop
By varying values of inerts in mixed feed (i), ratio of H2 to carbon oxides (r) and
K, Tables 9.10, 9.11 and 9.12 are prepared.

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Dimensions and Units

In FPS units, pressure = 0.0981 ´ 106 ´ (1.450 377 ´ 104)

0.023( 737.28G ¢ )0.8 (0.5778k ¢ )0.67 (2.3885 ´ 10 -4 C p¢ )0.33

1 mol CS2 = 1 mol C

F p + 3.6 I (1.32  0.043) = 0.008 314 ´ 300 ´ 1000

Solving the equation, p = 1951.104 kPa

= 27(0.083 14)2(416.90)2/(64 ´ 79.77)

Density = 71/0.1536 = 462.24 kg/m3 Ans.

Simplifying and solving the equation by Newton-Raphson method,

Density = 30.0704/0.40045 = 75.092 kg/m3 Ans.

0.330 0.1385 0.0121 0.607 ´ 10 3

0.331 0.423 0.8 ´ 10 2

Gas Mole Molar Mass Critical temp Critical

Pseudo critical temperature, Tc = 164.195 K

Substituting the values in the equation,

Average molar mass = 27.587

Gas kmol Vapour pressure Partial pressure

Gas Solubility at Partial pr. Solubility at

(1 ´ 10-3 - 2 ´ 10-4 )25

Recovery of hydrogen = 66 ´ 0.85 = 56.1 kmol

Compound Formula molar mass, mass % kmol mole %

New Basis: 290 kg final solution, saturated at 298.15 K (25 ºC)

(159.5/249.5) ´ x + (152/278) ´ y = 59.78

y 65.05 64.84 64.63 64.43 64.22 64.01

n 69.7 67.7 65.7 63.7 61.7 59.7

n 65.83 65.5 65.17 64.83 64.50 64.17

Fig. E3.1 Solution of Exercise 3.13

Salt content of final solution = 11.46 ´ 0.06 = 0.69 kg

Water from H2SO4 = 19  18.1 = 0.9 kg

Fig. E3.2 Preparation of Mixed Acid

Let m = quantity of oleum used, kg

Fig. E3.3 Fortifying of Spent Acid

Total 100.0 1.2254 100.0

Note : All Percentages Are Mole %.

Fig. E3.4 Mixing of Benzene-Acetone-Cyclohexane

Mass of acetone = 127.9 kg Ans.

Tri-glyceride Fatty acid content, kg

Ca in effluents = 37.5 ´ 2/40 = 1.88 meq/L

Fig. E3.5 Decoking of catalyst

Area under the diagonal lines are as follows:

Area for air introduction (i.e. from 1800 to 3600 s)

0.6619 ´ 0.132 ´ 10-3

0.5495 ´ 0.42 ´ 10-3

= 3796 g/m3 or mg/L

SO2 absorbed = 17 ´ 0.75 = 12.75 kmol º 816 kg

Solids in outgoing gas mixture = 120 ´ (16.5  4.2)/106

Concentration of solids (bacterial and non-bacterial) in the total combined feed =

Ratio, c2/c1 = n1/n2

cross -sectional area of empty segment, A

Component kmol mole % on wet basis

Since H2 is 50% in the mixture, it is within the flammability envelope.

 (1/0.006) ln (1  0.021 G ) = 133.655

dG = (2090/0.165) dc/c = 12 667 ln (c1/c2)

Similar iterations can be performed.

Time suspended suspended Time suspended suspended

Time suspended suspended Time suspended suspended

Substitute r = p/p0 and R1 = p1/p0

Note: For a double acting compressor,

L OP of Exercise 3.45 can be solved by

= 0.060 41(1.010 00 + 4.084 36 + 2.063 84

N requirement for 81.4 kg DSN = 128 ´ 81.4/288 = 36.18 kg

CO 25.8 25.8  12.9

In FPS units, pressure = 0.0981 ´ 106 ´ (1.450 377 ´ 104)

F p + 3.6 I (1.32 0.043) = 0.008 314 ´ 300 ´ 1000

0.330 0.1385 0.0121 0.607 ´ 10 3

0.331 0.423 0.8 ´ 10 2

Water from H2SO4 = 19 18.1 = 0.9 kg

Solids in outgoing gas mixture = 120 ´ (16.5 4.2)/106

(1/0.006) ln (1 0.021 G ) = 133.655

CO 25.8 25.8 12.9

CHOOCH!# C # + 3 KOH = C#H !COOK + C%H !!COOK + C!H#(OH)!

Moisture in gas = 0.044 61 0.040 57

Unburnt FeS2 = 88 85.1 = 2.9 kg

recycle stream = 0.37 M + 1.95 a P

or R 4.348 R × yO2 = 575.381

From Eq. (2), yN 2 + yUC = 1.0 yO 2 = 0.9334

n-butylene in product mixture = 12.33 12.12

CO 0.0038 0.1103 0.0107 0.0443 0.0179

= 1.436 (533.15 453.15) + 0.002 18 (533.152 453.152)/2

1648.18 ´ 106 T2 + 1897.94 ´ 109 T 3)

1512.67 ´ 106 T 2+ 1630.01 ´ 109 T 3)

Balance length of pipe = 150 146 = 4 m

At Syi = 1.00. Bubble point, TBP = 362.75 K or 89.6°C Ans. (ai)

At Sx i = 1.00 dew point, TDP= 369 K or 95.85 °C Ans. (a ii)

= 484.365 (369.0 273.15)

+ 5056.235 ´ 103 (369.02 273.152)/2

V = 1 0.041 = 0.959 kmol and L = 0.041 kmol Ans.