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Dimensions and Units


EXERCISE 1.1
(a) Wave length 5500 = 5500 108 cm

1 m 10 +9 nm
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
40 lb dry air

or

kg moisture
kg dry air

1 kg moisture 1000 g

1 kg
40 kg dry air
= 25 g moisture/kg dry air

Ans.

Vacuum = 475 Torr


Absolute pressure = 760 475 = 285 Torr
285 101.325/760
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 1.2

EXERCISE 1.3
F
(5)2
4
= 19.635 cm2
Pressure = Force/Area = 192.6 104/(19.635 106)
= 0.0981 MPa 0.981 bar

Cross sectional area of piston =

2 Solutions ManualStoichiometry

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


= 14.228 psi

Ans.

EXERCISE 1.4
Weight = 500 lb 500 0.4536 226.8 kg
Volume = 29.25 L = 0.029 25 m3
Density of Fe, r = 226.8/0.029 25
= 7753.85 kg/m3 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
Pressure drop = 0.05

lbf min
(Pa. in 2 )

6894.759
(in 2 US gal)
lbf

m3
1
US gal
1 h

10
3
3
h
m
60 min
3.785 412 10

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

1000
7753.85
50
22.106
1
= 0.0134 cm/a
0.0053 in/year 5.3 mpy

Corrosion rate =

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)
log10 p + 0.8751 = 6.9057

1211.0
(T - 52.35)

log10 p = 6.0306

1211.0
(T - 52.35)

Ans.

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
0.133 68
2.54
Dp = 1.0227 102 v2 L

Ans.

4 Solutions ManualStoichiometry

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)
h=

3412.142 10-3
h = 0.1761 h
10.7639 1.8

G=

2.204 62 3600
G = 737.28 G
10.7639

Cp =

9.478 172 10 -4
= 2.2885 104 Cp
2.204 62 1.8

k=

3412.142 10-3
k = 0.5778 k
3.2808 1.8

D = 3.2808 D
m =

2.204 62 3600
m = 2419.11 m
3.2808

Substituting the values,


0.1761 h =

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


(3.2808 D )0.2 (2419.11m )0.47

or
h = 0.023 G0.8 k0.67 Cl0.33 / (D0.2 m0.47)
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 madeup 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 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

EXERCISE 2.5
Molar mass of CS2 = 12 + 2 32
= 76
76 g CS2 12 g C

Ans.

6 Solutions ManualStoichiometry

1 mol CS2 = 1 mol C


3.5 kmol C = 3.5 kmol CS2
3.5 76 266 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
SiO2
H2O

84.3
60
18

81
14
5

0.961
0.233
0.278

65.28
15.83
18.89

Total

100

1.472

100.00

Ans.

EXERCISE 2.9
Basis: 100 kg glass
Compound

Molar mass

Na2O
MgO
ZnO
Al2O3
B2O3
SiO2

62
40.3
81.4
102.0
69.6
60.0

Total

kg

kmol

mole %

7.8
7.0
9.7
2.0
8.5
65.0

0.1258
0.1737
0.1192
0.0196
0.1221
1.0833

7.65
10.57
7.25
1.19
7.43
65.91

1.6437

100.00

100

Ans.

Basic Chemical Calculations 7

EXERCISE 2.10
Concentration of solids = 35 000 ppm or mg /L
(35 000 100)/106 3.5%
For watery solutions, 10 000 ppm = 1% by mass

Ans.

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 Na2O + H2O
NaOH content of flakes =

2 Molar mass of NaOH 74.6


Molar mass of Na 2 O

2 40 74.6
62
= 96.26%

Ans.

8 Solutions ManualStoichiometry

EXERCISE 2.14
Basis: 1 kmol azeotropic mixture
Compound

kmol

Molar mass

kg

% by mass

H2O
HNO3

0.622
0.378

18
63

11.196
23.814

31.98
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
H2O

25
75

58.5
18

0.4274
4.1667

9.3
90.7

Total

100

4.5941

100.0

Ans.

EXERCISE 2.16
Basis: 100 g water
Component

mass, g

HCl
KCl
H2O

4.00
19.61
100.0

Total

123.61

mass %

Molar mass

mole

mole %

3.24
15.86
80.90

36.4609
74.5513
18.0153

0.1097
0.2630
5.5508

1.85
4.44
93.71

100.00

5.9235

100.00

Ans.

EXERCISE 2.17
Basis: 100 kg solution
Compound

kg

Nitrogen content
kg/kmol comp.

Molar mass

Nitrogen
Content kg

NH3
NH4NO3
NH2CONH2

19
65.6
6

14
28
28

17
80
60

15.647
22.960
2.800

Total

90.6

41.407

Nitrogen content of the solution = 41.41%

Ans.

Basic Chemical Calculations 9

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 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 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 H SO + NH +
NH4HSO4 NH4+ + HSO4
2
4
4
115

18

97

98

Chemically bound acid = 98 45/115


= 38.35 kg
Total acid content = 20 + 38.35 = 58.35 kg
or
58.35%

18

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.

10 Solutions ManualStoichiometry

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
mass % alcohol =

15.80 100
= 16.49
(15.80 + 80)

Ans.

EXERCISE 2.23
Component
CaCO3
Na2CO3
MgSO4
(a) Concentration of Na2CO3 =
=
(b) Concentration of MgSO4 =
=

Equivalent mass
100/2 = 50
106/2 = 53
120.3/2 = 60.15
50 800/53
754.7 ppm or mg/L as CaCO3
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
6N

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
0.0865 N
(c) Equivalent mass of H3PO4 = 98/3 = 32.67
Concn. of H3PO4 in solution = 5 N
5 32.67
163.35 g/L
(d) Equivalent mass of HCl
= 36.5
Concn. of HCl in solution = 54.75/36.5 = 1.5 g/L
1.5 N 1.5 M
(e) Molar mass of K2SO4
= 174
Concn. of K2SO4 in solution = 174 3
= 522 g/L

Ans.

Ans.

Ans.

Basic Chemical Calculations 11

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
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 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(129.2C). (Ref. Fig. 2.3)
Boiling point of pure water at atm. pressure = 100C (373.15 K)
Boiling point elevation = 402.2 373.2
= 29 K or 29C

Ans.

12 Solutions ManualStoichiometry

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
Urea present in solution =

25
= 0.4167 kmol
60

75
= 4.1667 kmol
18
Quantum of solution = 0.4167 + 4.1667 = 4.5834 kmol

Water present in solution =

4.1667
4.5834
= 0.9091
Since vapour pressure of urea at 60C (333.15 K) is negligible,
Vapour pressure of solution = 0.9091 19.92
= 18.11 kPa

Mole fraction of water in solution =

Ans.

EXERCISE 2.31
1 bar = 10.1972 m H2O
1000 m H2O = 98.066 bar
According to Henry's law,
mole fraction of solute =

Partial pressure of solvent


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.

Basic Chemical Calculations 13

EXERCISE 2.32
Mole fraction of NH3 in solution = 0.02
Roult's law:
yi p = xi pi
yi =
=

[Ref. Eq. (2.18)]

xi pi
p

11.58 0.02
1.01 325

= 0.2286

Henry's law:

pi =
=
=
=
yi =

Hi xi
0.861 0.02
0.01722 bar
1.722 kPa

[Ref. Eq. (2.44)]

pi 0.01722
=
p 1.013 25

= 0.017

Ans.

EXERCISE 2.33
Basis: 100 kmol gas
Gas

Formula

Molar mass

kmol

kg

mass %

Ethylene
Benzene
Oxygen
Methane
Ethane
Nitrogen

C2H4
C6H6
O2
CH4
C2H6
N2

28
78
32
16
30
28

30.6
24.5
1.3
15.5
25.0
3.1

856.8
1911.0
41.6
248.0
750.0
86.8

22.00
49.07
1.07
6.37
19.26
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.

14 Solutions ManualStoichiometry

EXERCISE 2.34
Basis: 100 kmol sewage gas
Gas

Formula

Molar mass

kmol

kg

mass %

Methane
Carbon
dioxide
Ammonia

CH4
CO2

16
44

68
30

1088
1320

44.55
54.05

NH3

17

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
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


19.51 bar

Ans.

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

Density =

Ans.

Basic Chemical Calculations 15

= 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
6.353 72
152 +
(V 0.054 314) = 0.083 14 503.15 = 41.831 89
V2
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:

FG
H

I
K



Density = 71/0.1536 = 462.24 kg/m3

Ans.

EXERCISE 2.37
Equation:

Pressure p = 73 bar, Temperature T = 423.15 K


p = [RT(1 e)/ v2] [V + b] A/v2
a
A = A0 1 = (5.88) [1 (0.058 61/V)]
V
b
= 0.094 [1 (0.019 15/V)]
B = B0 1 V

F
H
F
H

I
K
I
K

90 104
V (423.15)9
0.9
0.011 89
=
=
75.687V
V

e = c/VT3 =

Substituting the values.

0.011 89 2
/V
73 = 0.08314 423.15 1

[V + 0.094 (0.0018/V)] [5.88 (0.344 63/V)]/V2

16 Solutions ManualStoichiometry

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
Mathcad Solution:

Density = 30.0704/0.40045 = 75.092 kg/m3

Ans.

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
Tr =
f = 0.1445

T
353.15
=
= 0.8824
Tc
400.2

0.607 10 3
0.1385
0.0121
0.330

(0.8824)8
0.8824
(0.8824) 2
(0.8824)3

= 0.4262
f 1 = 0.0637 +

0.8 10 2
0.331
0.423

(0.8824)8
(0.8824) 2
(0.8824)3

= 0.148
B=

0.08314 400.2
[ 0.4262 + 0.192 ( 0.148)]
53.4

= 0.283 26

Basic Chemical Calculations 17

Z=1

( - 0.283 26)15
0.08314 353.15

= 1.1447
V=

ZRT
1.1447 0.08314 353.15
=
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)
V=

0.08314 923.15
RT
=
8.103 25
p

= 9.472 m3/kmol
Density = 27.587/9.472 = 2.912 kg/m3
(b) van der Waals equation:
a=

27 R 2Tc2
64 pc

and b = RTc / 8pc

where pc and Tc are pseudo critical properties.


Gas

Mole
fraction
ni

Molar
mass
Mi

Mass
kg
n Mi

N2
O2
H2O
NH3

0.705
0.188
0.012
0.095

28
32
18
17

19.740
6.016
0.216
1.615

Total

1.000

27.587

Critical temp
Tc, K

Critical
pressure
pc, bar

Tc

ni Tc

pc

88.893
29.061
7.718
38.523

33.94
50.42
221.2
113.50

126.09
154.58
643.30
405.50

164.195

ni pc
23.93
9.48
2.65
10.78
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

18 Solutions ManualStoichiometry

Substituting the values in the equation,


1.679
(V 0.036 43) = 0.083 14 923.15 = 75.7507
8.1 +
V2
Mathcad Solution:

F
H

I
K

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
(0.216/9.3626)106 23 071 mg/m3
23.071 27.587
2.9465 18
= 12000 ppm

In terms of ppm concentration =

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.

Basic Chemical Calculations 19

EXERCISE 2.42

Basis: 100 kmol flue gases


Gas
CO2
O2
N2
SO2

Molar mass
44
32
28
64

Total

Avg. molar mass =


Partial pressure of water =
=
Absolute humidity =
=

EXERCISE 2.43

kmol
10.00
7.96
82.00
0.04

kg
440.00
254.72
2296.00
2.56

100.00

2993.28

29.933 (of dry gas)


Vapour pressure of water at DP
10.612 kPa
(ref. Chapter 6)
[10.612 18]/[(100 10.612) 29.933]
0.071 39 kg/kg 71.39 g/kg
Ans.

Concentration of SO2 in flue gases = (0.04/100) 106 = 400 ppm (v/v)


= 2.56/2993.28
= 0.8552 103 kg/kg
855.2 mg/kg or ppm (by mass)
Volume of gas = 0.082 06 463.15 760/750
= 38.513 m3/kmol
mg
kmol
2.56 kg
1
106

kg
100 kmol
38.513 m 3
3
= 664.7 mg/m
Ans.

Concentration of SO2 =

EXERCISE 2.44

Basis: 733 kg mixture


Component

kg

Molar mass

CH3CH
Steam
Oxygen (from air)
Nitrogen (from air)

200
133

32
18

Component
O2
N2
CH3OH
H2O
Total

kmol
6.25
7.39
0.21 400/29 = 2.897
0.79 400/29 = 10.897

Total pressure = 68.6 kPa g


Absolute Pressure = 68.6 + 101.325 = 169.925 kPa
kmol
mole %
Partial pressures,
kPa
2.897
10.56
17.94
10.897
39.72
67.49
6.250
22.78
38.71
7.390
26.94
45.78
27.434
100.00
169.92
Ans.

20 Solutions ManualStoichiometry

EXERCISE 2.45
Basis: 1 kmol LPG mixture at 313.15 K (40 C).
Gas

kmol

Molar mass

kg

C3H8
n-C4H10
i-C4H10

0.30
0.45
0.25

44.0956
58.1222
58.1222

13.229
26.155
14.531

Total

1.00

53.915

Average molar mass = 53.915


Specific gravity =
Gas

kmol

C3H8
n-C4H10
i-C4H10

0.30
0.45
0.25

Total

1.00

Ans. (a)

53.915
= 1.861
28.97
Vapour pressure
bar
13.975
3.773
5.290

Pressure in LPG cylinder = 7.2129 bar

Ans. (b)
Partial pressure
bar
4.1925
1.6979
1.3225
7.2129

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,

Basic Chemical Calculations 21

Gas

Solubility at
0.1013 MPa a and
305.75 K/5 m3 soln.

N2
H2
Ar
CH4
Total

Partial pr.
at 6.77 MPa g

Solubility at
305.75 K and
6.77 MPa g/5 m3
solution

0.0675
0.0800
0.1375
0.1400

1.4473
4.3560
0.2881
0.7800

0.964
3.440
0.391
1.078

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 38.53C

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 18.1C

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 =
31315
. 1.013 25
= 14.657 Nm3
Volume of air in the receiver at 1 bar g and 313.15 K,
v2 =

2.013 25 2 27315
.
31315
. 1.013 25

= 3.466 Nm3
Volume of air pressurized = 14.657 3.466
= 11.191 Nm3 in 4 min
11191
.
60
4
= 167.9 Nm3/h

Capacity of air compressor =

Ans.

22 Solutions ManualStoichiometry

EXERCISE 2.50
qL =

(1 10-3 - 2 10-4 )25


7.5 60

= 4.444 105 (mbar L)/s

Ans.

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.

24 Solutions ManualStoichiometry

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%

EXERCISE 3.6
Basis: 100 kmol feed gas (vent stream)
H2 in vent stream = 66 kmol

Ans.

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
H2
CH4
Other components

kmol
66 56.1 = 9.9
33 1.14 = 31.86
1.00

Total

42.76

mole %
23.15
74.51
2.34
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 C)
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

26 Solutions ManualStoichiometry

Compound

Formula

molar
mass

mass,
kg

mass %

kmol

mole %

Magnesium
chloride
Water
Ethanol

MgCl2
H2O
C2H5OH

95.32
18
46

307.3
348.2
344.5

30.73
34.82
34.45

3.224
19.344
7.490

10.72
64.36
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 C)
Compound

Formula

Chloroacetic
acid (CAA)
Ether (E)

ClCH2COOH
(CH3CH2)2O

Total

molar
mass

kmol

mass

mass %

94.5
74.0

0.2
0.8

18.9
59.2

24.2
75.8

1.0

78.1

100.0

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


Compound

mass %

kmol

mole %

CAA
E

Mass
kg
190
100

65.52
34.48

2.01
1.35

59.82
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
Balance of CAA:
0.242 x + y = 0.6552 500 = 327.6
Solving the equations,
x = 227.44 kg
y = 272.56 kg

(1)
(2)
Ans.

EXERCISE 3.10
Basis: 100 kg mixture
Let
x = mass of CuSO4 5H2O in the mixture, kg
y = mass of FeSO4 7H2O in the mixture, kg
x + y = 100
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

(1)

Material Balances without Chemical Reaction 27

(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
+
100
100
If incorrect molar mass (14) of nitrogen is considered,
14 x
(100 - x ) y
= 18.74
+
100
100
Solving two equations,
x = 81 kmol
or 81% nitrogen
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
44 m + 32 n = 38.95 19 = 740.05
Solving Eqs. (3) and (4),
m = 11 kmol or 11% CO2
n = 8 kmol or 8% O2

(1)

(2)
Ans. (a)

(3)
(4)
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
Benzene balance:
0.81 x + 0.1 y = 74
Solving two equations,
x = 90.14 kg

(1)
(2)

28 Solutions ManualStoichiometry

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)

0.0962 x + 0.9303 y = 0.634 100 = 63.4

(2)

Acetic acid balance:


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
Let

Ans. (c)

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
Solving the equations,

(4)

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)

Eq. (2)

Eq. (3)

30

32

34

36

38

40

70

68

66

64

62

60

30

32

34

36

38

40

65.05

64.84

64.63

64.43

64.22

64.01

40

42

44

46

48

50

69.7

67.7

65.7

63.7

61.7

59.7

Material Balances without Chemical Reaction 29

Eq. (4)

40

42

44

46

48

50

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

Fig. E3.1 Solution of Exercise 3.13

EXERCISE 3.14
Basis: 100 kg spent lye
Glycerol content of lye =
Loss of glycerol by entertainment =
Glycerol content of final solution =
=
Quantity of final solution =

9.6 kg
9.6 0.045 = 0.432 kg
9.6 0.432
9.168 kg
9.168/0.8 = 11.46 kg

38

40

30 Solutions ManualStoichiometry

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
Rate of evaporation = 5000 0.7893 = 3946.5 kg/h

Ans. (b)
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
142
P2O5
94.2
K2O
98
H3PO4
HCl
74.6
17
NH3
Urea
60
(a)
Anhydrous NH3 requirement = 17 10/14 = 12.14 kg
2 kmol H3 PO4 1 kmol P2O5
Anhydrous H3PO4 requirement = 98 2 26/142 = 35.89 kg
2 kmol KCl 1 kmol K2O
100% pure KCl requirement = 74.6 2 26/94.2
= 41.18 kg
Total of three is 89.21 kg/h.
Balance is called 'filler'.
(b) Urea requirement
= (60/28) 10 = 21.43 kg
(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%

EXERCISE 3.16
Basis: 100 kg mixed acid
Quantity of 68.3% HNO3 required
Sulphuric acid requirement
Water in 68% HNO3
Water content of mixed acid

= 39/0.683 = 57.1 kg
= 100 57.1 = 42.9 kg
= 57.1 (1.000 0.683) = 18.1 kg
= 19 kg

Ans.
Ans.

Ans.

Material Balances without Chemical Reaction 31

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

30

2O

70
60

40

50

60

40
A

70

SO 4
H2

30

50

80

20

90

10

C
100%
HNO3

90

80

70

60
HNO3

50

40

30

20

10

100%
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.

32 Solutions ManualStoichiometry

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:
1
1 O
LM1
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
NQ
LMmOP LM532 OP
128.589 all in kg
MM np PP := MM339
P
N Q N .41 PQ
1

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.

Material Balances without Chemical Reaction 33

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.
Final acid after evaporation 10.75 units
=
original spent acid
17.75 units

Ans. (a)

Therefore final fortified acid = 10.75 1000/17.75


= 605.6 kg
Water can be evaporated = 1000 605.6 = 393.4 kg

Ans. (b)

34 Solutions ManualStoichiometry

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

1.2254

100.0

Total

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

30

70
D 60

40

50

50

40
30

60

70
E

20

80
90

10
B
BENZENE

90

80

70

60

50

40

30

20

C
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

Material Balances without Chemical Reaction 35

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
(rounded off values)

Palmitodistearin
Stearodipalmitin
Oleodistearin
Oleopalmitostearin
Palmirodiolein
Palmitic acid (C15H31COOH)
Stearic acid (C17H35COOH)
Oleic acid (C17H33COOH)

862
834
888
860
858
256
284
282

Mass, kg
3
2
2
11
82
?
?
?

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.

36 Solutions ManualStoichiometry

Tri-glyceride

Fatty acid content, kg


palmitic

stearic

oleic

Total

Palimitodistearin
Steorodipalmitin
Oleodistearin
Oleopalmitostearin
Palmitodiolein

0.891
1.228

3.274
24.466

1.977
0.681
1.279
3.633

0.635
3.607
53.902

2.867
1.909
1.914
10.514
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
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

Material Balances without Chemical Reaction 37

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
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).

Oxygen Concentration, vol. %

25

Air

Air in N2

N2

21

20

Oxygen consumed
from air

15

Effluent
oxygen
concentration

10
Oxygen consumed from
5 % mixture

Start 100 %
air feed

Stop
air
feed

Start 5 %
O2 in feed
0

600
1200
Decoking Time, s

1800

2400

3000

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

38 Solutions ManualStoichiometry

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


= 2.099 square units
Basis: Nitrogen supply @ 0.025 L/s at NTP.
Molar flow of nitrogen =

0.025 10-3
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
0.7496 square units
0.6619 0.132 10-3
0.7496
= 0.117 103 kmol
0.117 mol

O2 consumed =

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
2.099 square units
O2 consumed =

0.5495 0.42 10-3


4384.8

= 0.11 105 kmol


0.011 mol
Total oxygen consumed = 0.117 + 0.011
= 0.128 mol
4.096 g or 4.096 103 kg

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.

Ans.

Material Balances without Chemical Reaction 39

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)

40 Solutions ManualStoichiometry

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
=
F + R2
F=
R2/F =
R1 =

0.6 or

6.25
= 0.6
F + 1.25

9.17 m3/h
1.25/9.17 = 0.136 m3/m3
F P2 = 9.17 5 = 4.17 m3/h

Material Balances without Chemical Reaction 41

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

55
= 267 g/m3 or mg/L
0.015 6.25
= P2 xP + R2 xR

DS in P1, xP =
1

P1 xP

6.25 267 = 5 5 + 1.25 xR

xR = 1315 g/m3 or mg/L


2

(unchanged)

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
Concentration DS in MF =

40 158
10.42

= 3854 g/m3 or mg/L


DS in R1 = 4.17 9230
= 38 489 g
Rejection RO Module I =

38 489
100
40 158

= 95.84%
Rejection from Module I = 70%

Ans. (a)

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
Concentration of DS in MF =

33 900
(7.68 + 1.25)

42 Solutions ManualStoichiometry

= 3796 g/m3 or mg/L


DS in R1 = R1 xR = 2.68 12 026
1
= 32 230 g
Rejection in RO Module I =

32 230
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
CH4 balance:
.
.
0.985 n1 + 0.04 n2 = 3000 0.88
.
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.

(1)
(2)

Material Balances without Chemical Reaction 43

.
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
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
Feed rate to M-3,

CH4 concentration of R1 =

274.852 100
= 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
CH4 content of R2 =

288.179 100
= 67.93 %
424.238

Ans.

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.

44 Solutions ManualStoichiometry

SO2 absorbed = 17 0.75 = 12.75 kmol 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
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
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
Oxidation reactions:
CH3OH
+
1.5 O2
CO2 +
H2O
32

HCHO
30

1.5 32

O2

32

44

CO2 +

44

(1)

18

H2O
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
Solving the equations, x = 535 mg/L
y = 144 mg/L

EXERCISE 3.33
Basis: 16.5 Nm3/s of moist gas flow rate
Molar flow rate = 16.5/22.414
= 0.736 kmol/s 2650 kmol/h
Water vapours, present in moist gas = 4.2 Nm3/s
= 0.1874 kmol/s 674.6 kmol/h
Solids, present in the gas mixture = (16.5 4.2) 9000/106
= 0.1107 kg/s 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

(2)
Ans.

Material Balances without Chemical Reaction 45

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


= 1.476 103 kg/s 5.314 kg/h
Solids scrubbed = 398.5 5.314 = 393.186 kg/h
Vapour pressure of water at 348 K (75 C) = 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
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
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.
H2SO4 concentration =

69.43 100
= 0.18%
39 230

Make-up water = 9691 + 39 230 = 48 921


13.59 kg/s

Ans.

EXERCISE 3.34
Let the baterial suspended in total combined feed
Bacterial suspended solids in total combined feed
For minimum recycle ratio, xR
Bacterial suspended solids in fresh feed
Concentration of solids in clarifier overflow

= xR mg/L
= x0 mg/L
= 5x0
=0
=0

(1)

46 Solutions ManualStoichiometry

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
xR =

20 000 (1 + r ) - 485
r

(2)

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.

Material Balances without Chemical Reaction 47

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
= 1.25 m
2
h1
0.375
=
= 0.3
1.25
R
From Chemical Engineers' Handbook, Ed. R.H. Perry, 5th Ed., p, 1-22, 1973,

Radius of isotank, R =

48 Solutions ManualStoichiometry

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)


After first cycle of purging, c2 =

20.946
2.973 85

= 7.043 vol.%
7.043
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.

After second cycle of purging, c3 =

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 (35C)
At NTP, nitrogen requirement = 16.404 273.15/308.15
= 14.541 Nm3

EXERCISE 3.37
Basis: 100 kmol dry gas mixture at time of shutdown.
Steam present = 100 1.2 = 120 kmol

Ans.

Material Balances without Chemical Reaction 49

Component

kmol

mole % on wet basis

H2
CO
CO2
N2
Ar
H2O

56.0
15.0
7.0
21.7
0.3
120.0

25.45
6.82
3.18
9.86
0.14
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
= 0.210 08
p1/p2 =
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

50 Solutions ManualStoichiometry

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

1400

14

LM 100 OP + 7500LM x OP = 14 75 = 1050


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 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

Material Balances without Chemical Reaction 51

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
0.458 y
dy
(0.2856 0.006 q)
=
dG
( 44 - 12 y)
dG
-dy( 44 - 12 y)
=
(0.2856 - 0.006 G )
0.45 y

Rearranging,

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.
G

dG
(0.2856 - 0.006G ) =
0

0.2

( 44 - 12 y)dy
0.458 y

(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 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
=
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)

Pressure in the system =

EXERCISE 3.40
Basis: 1.65 kg/s 10% NaOH solution

52 Solutions ManualStoichiometry

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

c2

dG = (2090/0.165)

dc/c = 12 667 ln (c1/c2)

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
0.0118 kmol/kmol moist air
Total moisture in the inlet air = 6.332 0.0118
= 0.0747 kmol/h
1.345 kg/h
Dry air flow rate = 6.332 0.075 = 6.257 kmol/h
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

Material Balances without Chemical Reaction 53

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 = 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
G h

0
1
2
3
4
5
6
7
8
9
10
11

suspended
solids in
outlet
water from
filter, mg/L
10
10
10
10
10
10
10
10
10
9
9
9

suspended
solids in
CW at the
end of
G h, mg/L
50.0
48.667
47.378
46.131
44.927
43.763
42.637
41.549
40.598
39.448
38.433
37.452

Time
G h

12
13
14
15
16
17
18
19
20
21
22
23

suspended suspended
solids in
solids in
outlet
CW at the
water from
end of
filter, mg/L G h, mg/L
9
9
9
9
9
9
9
9
8
8
8
8

36.503
35.587
34.700
33.844
33.016
32.215
31.441
30.693
29.927
29.206
28.499
27.815

54 Solutions ManualStoichiometry

24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46

8
7
7
7
6
6
6
6
6
6
6
6
6
5
5
5
5
5
5
5
5
5
5

27.155
26.483
25.833
25.205
24.565
23.946
23.348
22.770
22.211
21.671
21.148
20.643
20.155
19.683
19.194
18.721
18.263
17.821
17.394
16.981
16.582
15.822
15.462

47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68

5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5

15.113
14.776
14.450
14.135
13.831
13.536
13.231
13.143
12.710
12.453
12.205
11.965
11.733
11.508
11.291
11.082
10.879
10.683
10.493
10.310
10.133
9.962

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
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

Material Balances without Chemical Reaction 55

Time
G h

suspended
solids in
outlet
water from
filter, mg/L

suspended
solids in
CW at the
end of
G h, mg/L

50.0

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37

10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
9
9
9
9
9
9
9
8
9
9
9
9
9
9
9
9
9
9
9
9
9

49.232
48.490
47.772
47.078
46.407
45.759
45.132
44.526
43.941
42.810
42.282
41.771
41.277
40.800
40.339
39.891
39.427
38.978
38.544
38.124
37.718
37.326
36.947
36.581
36.227
35.885
35.554
35.234
34.925
34.626
34.337
34.058
33.788
33.527
33.275
33.031
32.795

Time
G h

38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74

suspended suspended
solids in
solids in
outlet
CW at the
water from
end of
filter, mg/L G h, mg/L
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
7

32.567
32.347
32.134
31.929
31.730
31.537
31.352
31.172
30.998
30.831
30.668
30.511
30.359
30.213
30.071
29.900
29.736
29.577
29.423
29.274
29.130
28.991
28.857
28.727
28.601
28.480
28.363
28.249
28.140
28.034
27.931
27.832
27.737
27.644
27.555
27.468
27.351
(Contd.)

56 Solutions ManualStoichiometry

(Contd.)
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92

7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7

27.238
27.129
27.023
26.921
26.822
26.722
26.635
26.546
26.460
26.380
26.296
26.218
26.149
26.070
26.000
25.932
25.866
25.803

93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109

7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7

25.741
25.682
25.624
25.569
25.515
25.464
25.413
25.335
25.318
25.273
25.229
25.187
25.146
25.106
25.068
25.031
24.999

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
0 F CAG = V
When

DG 0,

DC
DG

F
dCA
=
dG
V
dCAG

Integrating on both the sides,

CAG

CA 0

dCA
F
=
dG
dCAG
V
F
q
V
CAG = CA0 e(FG/V)

ln CAG ln CAO =
or

EXERCISE 3.45
Basis: V m3 volume of the receiver
Input output = accumulation

Ans.

Material Balances without Chemical Reaction 57

Output = 0
Actual volume swept = v = v0 Dv

LM
MN

v = v0 1 + c -

Swept volumetric flow rate =

Input =

LM
MN

FG IJ OP
H K PQ

3600 s v0 p0
kmol/h
ZRT

RS UV OP in 1 h
T W PQ
1/ C

3600 s v0 p0
p
p
-c
1+ cZRT
100 p0
p0

After time G,

1/ C

p
p
-c
100 p0
p0

dn
dG
n = no. of kmol present at time G

Accumulation in the receiver =


where

=
Therefore,

V
dp

ZRT
dG

LM
MN
p
dp
3600 s v p L
=
1+ cM
V
100 p
dG
MN
L
RpU
p
dq = dp/ M1 + c - cS V
100 p
MN
Tp W

RS UV
T W
RpU
- cS V
Tp W
OP
PQ

3600 s v0 p0
p
p
V
dp

=
-c
1+ cZRT
dG
ZRT
100 p0
p0
0

or

3600 s v0 p0
V

Substitute

1/ C

z z

LM p LM1 + c - p
100 p
MN MN

p1

dG =

dp

p0

R1

LM
N

dr / 1 + c -

V
q =
3600 s v0

R1

RS p UV
Tp W

1/ C

-c
0

r = p/p0 and R1 = p1/p0


3600 s v0
q =
ZRT

or

OP
PQ
OP
PQ

1/ C

Integrating on both the sides,


3600 s v0
V

1/ C

r
- c(r )1 / C
100

OP
Q

dr
1 + c - (r /100) - c(r )1/ C

OP O
PQ PPQ

58 Solutions ManualStoichiometry

Note: For a double acting compressor,


V
q =
7200 s v0

R1

dr
1 + c - (r /100) - c(r )1/ C

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
The integral M
MN

R1

dr
1 + c - (r /100) - c(r )1 / C

OP of Exercise 3.45 can be solved by


PQ

Numerical integration using Simpsons rule:


r

[1 + c (r/100) c(r)1/C]

1.000 00
1.181 22
1.362 44
1.543 66
1.724 88
1.906 10
2.087 32
2.268 54
2.499 76
2.630 98
2.812 20

0.990 00
0.979 34
0.969 07
0.959 11
0.949 42
0.939 97
0.930 72
0.921 65
0.912 75
0.903 99
0.895 37

f = 1/[1 + c (r/100) c(r)1/C]


f1 =
f2 =
f3 =
f4 =
f5 =
f6 =
f7 =
f8 =
f9 =
f10 =
f11 =

1.010 00
1.021 09
1.031 92
1.042 63
1.053 27
1.063 86
1.074 44
1.085 01
1.095 59
1.106 20
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]

Material Balances without Chemical Reaction 59

= 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.
Therefore, q =
=

V
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
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.

Material Balances
Involving Chemical
Reactions
EXERCISE 4.1
Basis: 1000 kg ammonia production
Molar mass of ammonia = 17.0305
NH3 Production =

1000
= 58.7182 kmol
17.0305

3
58.7182
2
= 88.0773 kmol
CH4 requirement = 88.0773/4
= 22.0193 kmol
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
528.126 Nm3
Ans. (b)

H2 requirement =

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
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


= 1.0093 103 kg/s
1.6 31.9988
Mass of coke
Coke present in catalyst =
100
Mass of catalyst

Coke burnt =

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
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

(2)

62 Solutions ManualStoichiometry

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
DSN
H2SO4
H2O

19.53
85.45
128.64
12.37

7.94
34.74
52.29
5.03

Total

245.99

100.00

Ans.

EXERCISE 4.5
Basis: 100 kg product
Compound

mass, kg

SBP
Nitric acid
DNOSBP
DNPSBP

65
15
18
2

150
63
240
240

0.4333
0.2381
0.0750
0.0083

57.41
31.55
9.94
1.10

100

0.7547

100.00

Total

Molar mass

kmol

mole %

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

Material Balances Involving Chemical Reactions 63

450 2 46 2
342
= 242.105 kg
308.41 L

Theoretical ethyl alcohol production =

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
iC4H8
C3H6
H2
CH4

0.5
0.44
0.06
1.19
0.143

21.43
18.86
2.57
51.01
6.13

Total

2.333

100.00

Ans.

EXERCISE 4.8
Basis: 100 kmol creacked gas
Composition of cracked gas:
Component
H2
CH4
C2H4
C2H2
C3H6

kmol
56.5
5.2
0.3
7.5
0.5

Carbon
kmol

5.2
0.6
15.0
1.5

Hydrogen
kmol
56.5
10.4
0.6
7.5
1.5

Oxygen

64 Solutions ManualStoichiometry

CO
CO2
O2
Total

25.8
4.0
0.2

25.8
4.0

12.9
4.0
0.2

100.0

52.1

76.5

17.1

Entire carbon atom comes from methane.


Methane fed = 52.1 kmol
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
O2 used for water production = 27.7/2
= 13.85 kmol
O2 consumed = 13.85 + 17.1 = 30.95 kmol
Conversion of methane = (52.1 5.2) 100/52.1
= 90.02%
Yield of acetylene = 15 100 (52.1 5.2)
= 31.98%

Ans. (a)

Ans. (c)
Ans. (b)
Ans. (d)
Ans. (c)

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
Total alkalinity =

M N 50 000
mg/L as CaCO3
vol.of sample, mL

P = 35.4 mL and
1
M
2
Therefore, the solution contains hydroxide and carbonate alkalinies.
Normally of titrating acid, N = 0.012
(2P M) N 50 000
ppm as CaCO3
Hydroxide alkalinity =
vol. of sample in mL

M = 38 mL. Hence P >

(2 35.4 38)0.012 50 000


10
= 1956 ppm (mg/L) as CaCO3
38 0.012 50 000
Total alkalinity =
10

Material Balances Involving Chemical Reactions 65

= 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 0.1426 g 0.003 24 mol
Water in the flue gas = 0.0362 g
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
24.464 (x + y) = 1
Solving the equations, x = 0.003 87 mol, y = 0.037 mol
Component

mol

mole % (dry)

(1)
(2)

Molar mass

Mass, g

mass %

CO2
O2
N2
H2O

0.003 24
0.003 87
0.037
0.002 01

7.34
8.78
83.88

44
32
28
18

0.1426
0.1238
.1.036
0.0362

10.65
9.25
77.39
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)

MgCO3 + H2SO4 = MgSO4 +

(2)

100

84.3

98

98

136

120.3

18

44

H2O + CO2

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

66 Solutions ManualStoichiometry

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
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
2 kmol
Total CO2, escaped from reactor = 132 + 88 = 220 kg
5 kmol
Total H2O at the end of reactions = 4683.3 562 + 54 + 36
= 4219.1 kg
Compound
CaCO3
MgCO3
Inerts
H2SO4
H2O
CaSO4
MgSO4
Total

Mass of
reactants, kg
300.0
167.5
32.5
562.0
4121.3
Nil
Nil
5183.3

Mass of
products, kg
Nil
Nil
32.5
73.3
4211.3
408.0
239.0
4964.1

mass %
in product

0.65
1.48
84.84
8.21
4.82
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
HCl
O2

kmol
20.0
12.5

Ans.(d)

mole % (dry basis)


10.27
6.42

Material Balances Involving Chemical Reactions 67

Cl2
N2

40.0
122.3

20.53
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

Simplifying, nCO =

100( a - b)
100 + b

Q.E.S.

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.

68 Solutions ManualStoichiometry

( 4 - x )100
= 0.45
( 4 - x ) + (13 - 0.5 x ) + 83
400 - 100 x
=
100 - 1.5 x
400 100 x =
99.325 x =
x=
Conversion =
=

0.45
45 0.675x
355
3.574 kmol
3.574 100/4
89.35%

Ans.

EXERCISE 4.15
Basis: 100 kmol of outgoing gas mixture from reactor
(1)
Reactions are: CO2 + 4 H2 = CH4 + 2 H2O
(2)
CO2 + H2 = CO + H2O
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)
Ans. (b)
Yield of CH4 = 1.68 100/1.8 = 93.33%
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)

Material Balances Involving Chemical Reactions 69

CO2 content of exit gas mixture


O2 reacted as per reaction (2)
CH3CHO, reacted as per reaction (2)
O2 reacted as per reaction (1)
Acetic acid produced
Acetaldehyde, reacted as per reaction (1)
Total CH3CHO reacted
CH3CHO in exit gases
Total CH3CHO, entering the reactor
Conversion
Yield of acetic acid
air
29 87.41
=
acetic acid
30.58 44
Water, produced as per reaction (2)
CH3CHO in the exit gases
Acetic acid removed with water

Mass ratio,

= 4.85 kmol
= 5 4.85/4 = 6.06 kmol
= 2 4.85/4 = 2.43 kmol
= 15.81 6.06 = 9.75 kmol
= 2 9.75 = 19.5 kmol
= 19.50 kmol
= 2.43 + 19.50
= 21.93 kmol
= 8.65 kmol
= 21.93 + 8.65
= 30.58 kmol
= 21.93 100/30.58 = 71.7%
Ans. (a)
= 19.50 100/21.93 = 88.9%
Ans. (b)
= 1.884 kg/kg

Ans. (c)

= 4.85 kmol
= 14.90 kmol
= 19.50 14.90
= 4.60 kmol
Composition of gas mixture, leaving reactor:
Component
CO2
CH3CHO
CH3CHOH
O2
H2O
N2
Total

kmol

mole %

4.85
8.65
19.50
2.55
4.85
69.05

4.43
7.90
17.82
2.33
4.43
63.09

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.

70 Solutions ManualStoichiometry

Carbon balance:
Hydrogen balance:

a + b = 6.25
(1)
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
Solving the quadratic equation, a
b
c
d

=0
= 1.151 kmol CO2
= 6.25 1.151 = 5.099 kmol CO
= 5.556 1.151 = 4.405 kmol H2O
= 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

Material Balances Involving Chemical Reactions 71

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:

a a

CH OOCH !!C%

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


+ C #H !#COOK
CH OOCH ! C#
860

3 56

KOH requirement= 3 56 5/860 = 0.977 kg


Gycerine produced= 92 5/860 = 0.535 kg

92

72 Solutions ManualStoichiometry

(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

KOH required = 3.541 kg and glycerine produced = 1.939 kg


(v) Saponification of oleodilinolein:

92

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:
Fatty acid

kg

Molar mass

Palmitic acid
Stearic acid
Oleic acid
Linoleic acid
Linolenic acid

1.4
1.2
4.5
6.0
0.5

256.42
284.48
282.46
280.45
278.43

kmol
0.0055
0.0042
0.0159
0.0214
0.0018

H2 requirement,
kmol

0.0159
0.0428
0.0054

Material Balances Involving Chemical Reactions 73

Ricinoleic acid

86.4

Total

298.46

100.0

0.2895

0.2895

0.3383

0.3536

100
0.3383
= 295.6
Average molar mass of castor oil = 295.6 3 + 92.09 3 18.02
= 924.83

Average molar mass of castor fatty acids =

924.83 100
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)

Quantity of castor oil =

EXERCISE 4.23
Basis: 100 kg soybean fatty acids
Fatty acid

kg

Molar mass

kmol

Palmitic acid
Stearic acid
Oleic acid
Linoleic acid
Linolenic acid

46.04
5.60
21.94
23.22
3.20

256.42
284.48
282.46
280.45
278.43

0.1795
0.0197
0.0777
0.0828
0.0115

Total

100.0

0.3712

100
= 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
0.1237 kmol
Reaction :
CH3(CH2)14 COOH + CH3OH = CH3(CH2)14COOCH3 + H2O

Average molar mass of fatty acids =

Palmitic acid
256.42

Methanol
32.04

Methyl ester
270.44

Methyl ester produced equivalent to palmitic acid

Water
18.02

74 Solutions ManualStoichiometry

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
required, kg

Methyl ester
produced, kg

water produced
kg

Palmitic acid
Stearic acid
Oleic acid
Linoleic acid
Linolenic acid

46.04
5.60
21.94
23.22
3.20

5.75
0.62
2.49
2.65
0.37

48.56
5.88
23.03
24.38
3.36

3.23
0.34
1.40
1.49
0.21

Total

100.00

11.88

105.21

6.67

11.88
= 0.1135 kg/kg soybean oil
104.71
105.21
= 1.005 kg/kg soybean oil
Specific methyl ester production =
104.71

Specific methanol requirement =

Ans.

EXERCISE 4.24
Basis: 100 kg soybean fatty acids
Reaction:
CH3(CH2)14COOCH3 + 2 H2 = CH3(CH2)14CH2OH + CH3OH
FAME of
Palmitic acid

Hydrogen

FOH of
Palmitic acid

Methanol

Similar reactions can be written for other fatty acids.


FAME of

Palmitic acid
Stearic acid
Oleic acid
Linoleic acid
Linolenic acid

Molar mass
of FAME

kg
FAME*

270.44
298.50
296.48
294.83
292.81

48.56
5.88
23.03
24.38
3.36

Total

105.21

Molar mass
of corres-

ponding
242.43
270.49
268.47
266.82
264.80

kg
FOH

kg
CH3OH

43.53
5.33
20.85
22.06
3.04

5.75
0.63
2.49
2.65
0.36

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

Material Balances Involving Chemical Reactions 75

EXERCISE 4.25
Basis: Urea feed rate of 350 kg/h
.
350
= 5.833 kmol/h
Molar feed rate of urea, nu =
60
H2SO4 required =
SO3 required =
Actual H2SO4 charged =
=
H2O entering with H2SO4 =
=
Actual SO3 charged =
=
On completion of reaction,
H2SO4 consumed =
SO3 consumed by reaction (1) =
SO3 consumed by reaction (2) =

5.833 kmol/h 571.67 kg/h


5.833 kmol/h 466.64 kg/h
1.25 571.66
714.58 kg/h
2
714.58
98

14.58 kg/h
3.5 466.64
1633.24 kg/h
571.67 kg/h
466.64 kg/h
80
14.58
18

= 64.8 kg/h
H2SO4 produced by reaction (2) = 14.58 + 64.8
= 79.38 kg/h
194
350 = 1131.67 kg/h
60
.
mass, mi kg/h
714.58 571.67 + 79.38 = 222.29
1633.24 466.64 64.8 = 1101.80
1131.67

Sulphamic acid produced =


Component
H2SO4
SO3
Sulphamic acid
Total

2455.76

mass %
9.05
44.87
46.08
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.

76 Solutions ManualStoichiometry

Liquid Feed
Component

Molar
mass

C10H20
C11H22
C12H24
C13H26
C14H28

140
154
168
182
196

Total

kmol
kmol feed

kg

mass %

0.8
9.9
82.2
6.7
0.4

112.0
1 524.6
13 809.6
1 219.4
78.4

0.67
9.11
82.47
7.28
0.47

100.0

16 744.0

100.00

Average molar mass of liquid =

kg/h for
6.1 kg/h
feed
0.040
0.555
5.030
0.444
0.028

87
71
67
08
67

6.100 00

16 744
100

= 167.44
Tetramer feed rate =

6.1
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 50C (323.15 K)
= 12.335 kPa (Ref. Chatper 6)
Feed gas pressure = 0.35 bar-g
= 1.363 25 bar a
Moisture in gas =

0.123 35
(1.363 25 - 0.123 35)

= 0.0995 kmol/kmol dry gas


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
CO2
HC

0.967
0.013
0.020

0.039 23
0.000 53
0.000 81

Total

1.000

0.040 57

Material Balances Involving Chemical Reactions 77

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
C11H22
C13H26
C14 H28
C12H26S(DDM)

0.040 87
0.555 71
0.444 08
0.028 67
6.049 90

0.57
7.81
6.24
0.40
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
CO2
HC
BF3

0.039 23 0.029 95 = 0.009 28


0.000 53
0.000 81
0.001 56

76.19
4.35
6.65
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
Conversion of H2S = (0.029 95/0.039 23) 100
= 76.34 %

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

Ans. (c)
Ans.(d)

78 Solutions ManualStoichiometry

Gas

kmol

mole %

SO2
O2
N2

8.0
6.6
66.21

9.90
8.17
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:
Component
SO2
O2
N2
Total

kmol

mole %

0.76
(1.767 1.14) = 0.627
6.647

9.46
7.80
82.74

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:
Component

kmol

mole %

SO2
O2
SO3
N2

0.015
0.254
0.745
6.647

0.20
3.32
9.72
86.76

Total

7.661

100.00

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

Ans. (b)

Material Balances Involving Chemical Reactions 79

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%
Actual O2 supply = 2.02 2.5 = 5.05 kmol
N2 entering with O2 = 79 5.05/21 = 19.0 kmol
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
FeS2 unburnt
3.90
=
=
S- free cinder
0.667 x + 12
92.20
x = 85.1 kg

80 Solutions ManualStoichiometry

Unburnt FeS2
Quantity of cinder
Sulphur, lost in cinder
Total sulphur charged
% S, lost in the cinder
Actual FeS2 roasted
FeS2 roasted to SO2
FeS2 roasted to SO3
O2 consumed

= 88 85.1 = 2.9 kg
= 2.9 100/3.9 = 74.4 kg
Ans. (a)
= 74.4 0.026 = 1.93 kg
= 64 88/120 = 46.93 kg
= 1.93 100/46.93 = 4.11% Ans. (b)
= 85.1/120 = 0.709 kmol
= 0.709 0.92 = 0.652 kmol
= 0.709 0.652 = 0.057 kmol
= [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
SO3
O2
N2

1.304
0.114
3.043
19.000

5.56
0.49
12.97
80.98

5.59

13.03
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
CO2
O2
N2
Total

Molar
mass
44
32
28

Incoming gases
kmol
kg
12.8
563.2
6.1
195.2
81.1
2270.8
100.0

3029.2

Outgoing gases
kmol
kg
27.54
1211.76
6.10
195.20
81.10
2270.80
114.74

3677.76

Avg. molar mass of dry incoming gases= 30.29


Avg. molar mass of dry outgoing gases = 3677.79/114.74 = 32.05

mole %
24.00
5.32
70.68
100.00

Ans. (b)

Material Balances Involving Chemical Reactions 81

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:
nB,in = nB,out - A1 + 2A 4
Benzene balance:
nT,in = nT,out + A1 - A 2
nX,in = nX,out + A 2 - A 3

Toluene balance:
Xylene balance:
Pseudocumene balance:
Methane balance:

nP,in = nP,out + A 3
nCH4 , in = nCH4 ,out - A1 - A 2 - A3

nH2 , in = nH2 ,out + A1 + A 2 + A3 - A 4


nDP2 , in = nDP,out - A 4
Diphenyl balance:
Reaction performance equations:
nC,B nB,in = - A1 + 2A 4
nC,T nT,in = - A1 - A 2

Hydrogen balance:

nC,X nX,in = A 2 - A 3
nC,P nP,in = A3

These eleven equations can be represented in matrix form as under.

n
nB,in

1 0 0 0 0 0 0 -1 0 0 2 nB,0 nT,in

0 1 0 0 0 0 0 1 -1 0 0 T,0 n

0 0 1 0 0 0 0 0 1 -1 0 nX,0 X,in

0 0 0 1 0 0 0 0 0 1 0 nP,0 nP,in
0 0 0 0 1 0 0 -1 -1 -1 0 nCH ,0 nCH 4 ,in

0 0 0 0 0 1 0 -1 -1 -1 1 n 4 = nH ,in

0 0 0 0 0 0 1 0 0 0 -1 H2 ,0 n 2

0 0 0 0 0 0 0 -1 0 0 2 nDP,0 DP,in
f n
0 0 0 0 0 0 0 2 -1 0 0 A1
C,B B,in
0 0 0 0 0 0 0 0 1 -1 0 A 2
f C,T nT,in
0 0 0 0 0 0 0 0 0 1 0 A 3
f C,X nX,in

A 3
f C, nP,in
1
0
0
0
0
0
0
0
0
0
0

0
1
0
0
0
0
0
0
0
0
0

0
0
1
0
0
0
0
0
0
0
0

0
0
0
1
0
0
0
0
0
0
0

0
0
0
0
1
0
0
0
0
0
0

0
0
0
0
0
1
0
0
0
0
0

n

0 -1 0 0 2 B,0 1

n
T,0
0 1 -1 0 0
3.67

0 0 1 -1 0 nX,0 6
0 0 0 1 0 nP,0 7.34

0 -1 -1 -1 0 nCH4 ,0 0
0 1 1 1 -1 nH ,0 = 81.99

1 0 0 0 -1 n 2 0
0 -1 0 0 2 DP,0 0.2
2.5
0 2 -1 0 0 A1
1.02
0 0 1 -1 0 A 2

5.138
3
0 0 0 1 0
A 4

V0 = I
0 = V1 I

82 Solutions ManualStoichiometry

EXERCISE 4.32
Basis: Liberation of 127 g iodine
Electrochemical reactions: KI K + I 1
I - - e 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

Material Balances Involving Chemical Reactions 83

I 3600 3 126.9
= 127.0
96 485
I = 8.95 amperes.

Iodine liberated =

Ans.

EXERCISE 4.33

Basis: 2 m3 oxygen liberation at NTP


Molar liberation = 2/22.414 = 0.0892 kmol
2855.4 g
Electrochemical reactions:

AgNO3 Ag+ + NO 3Ag+ + e Ag


NO 3- e NO3

NO3 + H2O HNO3 + OH


2 OH 2e H2O + 1/2 O2
1 equivalent of oxygen = 2 equivalents of Ag
Ag deposited = 108 2855.4/8 = 38 548 g
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:

-3
(1500 1.25 103 ) + m

m
10
10 -4
1
1500 10 +
10 =
1.005
H 103
(1875 000 + m)
1.5 106 + 9.95 105 m =
10-7
H
pH of 0.1 N HCl solution = log (0.1) = 1
1
H =
w
i
Hi
1
H =
1875 000 1

1
m
1875 000 + m 1.25 + 1875 000 + m 1.005

1875 000 + m
1500 000 + 0.995 m

(1)

(2)

84 Solutions ManualStoichiometry

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)
N2 reacted, kmol/s
H2 reacted, kmol/s
NH3 produced, kmol/s
Total gas mixture, leaving
the converter, kmol/s
NH3 in outlet gas
mixture, kmol/s
NH3 separated, kmol/s
NH3 uncondensed, kmol/s
Composition of gas mixture,
leaving separator, kmol/s
Component
N2
H2
NH3
Inerts
Total

0.24 a
0.72 a
0.48 a
M 0.48 a

Case (b)
0.25 a
0.75 a
0.50 a
M 0.5 a

0.9 M 3.52 a

0.9 M 3.5 a

0.585 M 2.288 a
0.315 M 1.232 a

0.63 M 2.45 a
0.27 M 1.05 a

0.76 a
2.28 a
0.315 M 1.232 a
0.1 M

0.75 a
2.25 a
0.27 M 1.05 a
0.1 M

0.415 M + 1.808 a

0.37 M + 1.95 a

Material Balances Involving Chemical Reactions 85

Case (a):
Purge balance:

0.1 M P
= 1.0
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
Nitrogen balance:
Nitrogen lost in purge =

(3)

0.76 a P
kmol/s
(0.415 M + 1.808 a)

Nitrogen in recycle stream = 0.76 a


Hence 0.76 a

(2)

0.76 a P
kmol/s
(0.415 M + 1.808 a)

0.76 a P
+ 24.75 = a
(0.415 M + 1.808 a)

0.415 M + 1.808 a = 0.1 MP from Eq. (2)


0.76 a P
+ 24.75 = 1
0.75 a
0.1 M P
24.75 M
a=
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

(4)

Substitute

24.75 455.293
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

(5)

a=

Case (b)
Purge balance:

0.1 MP
= 1.0
0.37 M + 1.95 a

Ans.

(2)

86 Solutions ManualStoichiometry

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
kmol/s
Nitrogen lost in purge =
(0.37 M + 1.95 a)
0.75 a P
kmol/s
Nitrogen in recycle stream = 0.75 a
(0.37 M + 1.95 a)
Hence,
0.75 a

0.75 a P
+ 24.75 = a
(0.37 M + 1.95 a)

Substitute

(4)

0.37 M + 1.95 a = 0.1 M P from Eq. (2)


0.75 a

0.75 a P
+ 24.75 = a
0.1 M P
a=

24.75 M
unchanged from Example 4.14
0.25 M + 7.5

3.7 M + 19.5 a
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

From Eq. (2),

P=

a=

24.75 432.801
0.25 432.801 + 7.5

= 92.5826 kmol/s
3.7 432.801 + 19.5 92.5826
432.801
= 7.8713 kmol/s
Note: Exercise 9.3 is Mathcad exercise for this exercise.

P=

Ans.

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.

Material Balances Involving Chemical Reactions 87

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
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
Since fresh make-up has 88.5 % H2, reduction in make-up stream =
= 3341.71 Nm3/h

Ans.(a)

2957.42
0.885

88 Solutions ManualStoichiometry

% reduction =

3341.71
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.
Permeate II flow rate =

724.5
= 9056.25 Nm3/h
0.08

H2 recycled in Permeate II = 9056.25 724.5


= 8331.75 Nm3/h
Reduction in make-up stream =

8331.75
0.88

= 9414.41 Nm3/h
% reduction =

9414.41
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.

Material Balances Involving Chemical Reactions 89

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

(1 + x) (1 + y) = 1 +

H - M
C- H

I F1 + A - H I
KH M K

(C - M )( M + A - H )
(C - H ) M

(C - M )(C - H )
(C - H ) M

because M + A = C

C- M
M

because C M = A

A
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
Nitrogen, entering in air = 0.79 F
N2 in recycle stream = R yN 2
= R R yO2 R yUC

(3)

90 Solutions ManualStoichiometry

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
= 80.251 kmol/h

[from Eq. (3)]

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
R + F - 55194
.
Multiply Eq. (3) by

(4)

1.017 72
= 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
or

R 4.348 R yO2 = 575.381


R yO2 = 0.23 R 132.332

From Eq. (1),


F = 1339.37 1.0952 R
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
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

(6)
(7)

(8)

Material Balances Involving Chemical Reactions 91

From Eq. (2),

yN 2 + yUC = 1.0 yO 2 = 0.9334

UC Balance:
R yUC + 13.365
=
R + F - 55.194
R + F 55.194 =
=
809.9 yUC + 13.365 =

yUC

(9)

809.9 + 452.37 55.194


1207.076 kmol/h
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
Component
CH3OH
O2
N2
H2O
UC

kmol
125.00
148.81
452.37 0.79 + 809.9 0.8997 = 1086.04
452.3 0.017 72 + 809.9 0.1146 = 100.84
809.9 0.0337 = 27.30

Total

1487.99

mole %
(wet basis)
8.40
10.00
72.99
6.78
1.83
100.00

Composition of Gaseous Mixture Leaving Reactor


Component
CH3OH
HCHO
UC
O2
N2
H2O
Total

mole %

kmol

Wet

1.25
111.375
27.30 + 13.365 = 40.665
80.251
1086.04
100.84 + 129.937 = 230.779
1550.358

0.08
7.18
2.62
5.18
70.05
14.89
100.00

Dry tail gas

3.37
6.65
89.98

100.00

Purge stream must contain 13.365 kmol/h UC.


Total purge stream =

13.365
= 396.6 kmol/h (dry)
0.0337

Recycle stream 809.9


=
Purge stream
396.6

92 Solutions ManualStoichiometry

= 2.042 kmol/kmol
Recycle ratio =

Ans. (a)

Recycle stream
809.9 1.1146
=
452.37 1.017 72
Fresh air stream

= 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
1206.954
= 3.37%

Concentration of UC in tail gas =

(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.

Material Balances Involving Chemical Reactions 93

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)
(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:

P=

F 0.9a + 0.9b - 0.1c - 310 I P + 300 = (1 0.025) a


H a + b - 300 K

(4)

= 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.

94 Solutions ManualStoichiometry

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

EXERCISE 4.43
Basis: 3500 kg/h ethylene oxide (EO) production rate
Only first two reactions are considered.
Compound
Ethylene (C2H4)
Oxygen (O2)
Ethylene oxide (C2H4O)
Carbon dioxide (CO2)
Water (H2O)

Molar mass
28.0538
31.9988
44.0532
44.0098
18.0153

Ethylene required for EO production = 28.0538 3500/44.0532


= 2228.86 kg/h 79.45 kmol/h

Ans.

Material Balances Involving Chemical Reactions 95

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
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
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

CO2 produced =

Component
Ethylene
Oxygen
Inerts (N2 + Ar)
CO2 + H2O
Ethylene oxide
Total

Mixed feed to reactor


(M), kmol/h
227.000
141.875
227.000
1674.125
(by balance)
Nil
2270.00

Reactor effluent,
kmol/h
113.500
Nil
227.000
1674.125 + 68.10 2
= 1810.325
3500/44.0532 = 79.450
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.

96 Solutions ManualStoichiometry

x (340.5 + x - P)
(340.5 + x )
= 1674.125

CO2 + H2O in stream R2 =

Simplifying,
x2 1333.625 x x P 570 040 = 0

(1)

227.00 P
(340.5 + x )
= 4.39 kmol/h
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

Inerts in purge =

Streams, kmol/h
R2

(2)

Component

R1

Purge

Ethylene
Inerts
CO2 + H2O
Oxygen

113.50
227.00
1707.14
Nil

2.194
4.392
33.015
Nil

111.306
222.608
1674.125
Nil

Fresh feed
(M R2)
115.694
4.392
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
Ethylene
Water

kmol
0.85 C
0.85 0.65 C = 0.5525 C

Material Balances Involving Chemical Reactions 97

NRG

0.15 C

Total

1.5525 C

Conversion per pass


Ethylene reacted
Water reacted
Ethanol produced
Reactor outlet stream:
Component
Ethylene
NRG
Ethanol
Total

= 5%, based on ethylene


= 0.05 0.85 C = 0.0425 C kmol
= 0.0425 C kmol
= 0.0425 C kmol
kmol

(0.85 0.0425) C = 0.8075 C


(0.5525 0.0425) C = 0.51 C
0.15 C
0.0425 C
1.51 C

In the scrubber, it is assumed that all the water and alcohol are removed:
Scrubber outlet off-gases:
Component

Ethylene
NRG
Total

kmol

0.8075 C
0.1500 C
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)

98 Solutions ManualStoichiometry

Component

C2 H 4
H2O
NRG
C2H5OH

Gas mixture, incoming


to reactor
kmol
mole %
1489.41
54.83
968.12
35.64
258.92
9.53
Nil
Nil

Gas mixture, outgoing


from reactor
kmol
mole %
1414.94
53.56
893.65
33.82
258.92
9.80
74.47
2.82

Total

2716.45

2641.98

100.00

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

Material Balances Involving Chemical Reactions 99

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
mole %

i-butane
i-butylene
n-butylene
n-butane
1,3-butadiene
Total

Mixed feed

kmol

kmol

Recycle stream
kmol

mole %

1.5
Nil
Nil
98.5
Nil

0.297
Nil
Nil
19.533
Nil

3.84
6.94
25.29
63.59
0.34

3.543
6.940
25.290
44.057
0.340

4.42
8.66
31.55
54.95
0.42

100.0

19.830

100.00

80.17

100.00

Total n-butane consumed =


=
Total butadiene produced =
=

100 0.6359 143 0.3091


19.39 kmol
143 0.0878 0.34
12.215 kmol
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 (175C) 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
Na2CO3 + SO2 = Na2SO3 + CO2
Na2CO3 reacted = 106 276.66/64 = 458.22 kg/h

Reaction:

100 Solutions ManualStoichiometry

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 (50C), pw = 12.335 kPa
Water vapours in outgoing gases = 12.335/(106.6 12.335)
= 0.1309 kmol/kmol dry gas
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
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

Material Balances Involving Chemical Reactions 101

Equivalent Ca3(PO4)2 in rock = 75.43 kg


HCl fed = 3 100 = 300 kg of 25% concentration
= 75 kg 100% HCl
= H3PO4 + 3 CaCl2
Reaction: Ca3(PO4)2 + 6 HCl
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
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

102 Solutions ManualStoichiometry

= 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
NO
O2

kmol/h

H2O

x
275.4 [1.25x + 109.28 0.75 x] =
166.12 0.5x
1036.01 + 72.86 0.5x =
1108.87 0.5x
218.57 1.5x + 1.5x = 218.57

Total

1493.56

N2

% 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

Material Balances Involving Chemical Reactions 103

Composition of absorber outlet gas:


Component

kmol/h

NO
O2
N2

138.45 y
96.9 + 76.31 0.75 y = 173.21 0.75 y
1039.65 + 287.08 = 1326.73

Total

1638.39 1.75 y

(138.45 - y)100
1638.39 - 1.75 y
= 0.2
y = 135.65 kmol/h
NO consumed
100
Absorber efficiency =
NO fed

% NO in absorber outlet gases =


or

=
Combustion efficiency of reactor =
=
=
Overall efficiency =
=
=

135.65
100 = 98.0% Ans. (b)
138.45
NH 3 converted to NO
100
Total NH 3 fed
138.45
100
145.71
95.02%
Ans. (a)
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

104 Solutions ManualStoichiometry

= 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.

Energy Balances
EXERCISE 5.1
Basis: 10 000 Lph of thermic fluid
Energy balance:
E1 +

g
g
qm p1
q p
+ Z1 + Q + W = E2 + m 2 + Z 2

gc
gc
J r
J r

Z1 =
p1 =
p2 =
p2 p1 =

Z2
101.325 kPa a
100 + 101.325 = 201.325 kPa a
201.325 101.325 = 100 kPa
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


E2 E1 =

7500 ( -0.1) 1000


+ 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 41.7C
Outlet temperature of thermic fluid = 473.15 + 41.7
= 514.85 K (241.7C)
Ans.

EXERCISE 5.2
Basis: 1 kmol oxygen
T1 = 350 K and T2 = 1500 K
Ref. 7:

106 Solutions ManualStoichiometry

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

= 29.8832 (1500 350)

11.3842
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
Ref. 5:

T2

H2 =

Ans. (ii)

(26.0257 + 11.7551 103 T 2.3426 106 T 2

T1

0.5623 109 T 3) dT
117551
.
103 (15002 3502)
= 26.0257(1500 350) +
2
2.3426
0.5623
6
3
10 (1500 3503)
103 (15004 3504)

4
3
= 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

EXERCISE 5.3
Basis: 1 kmol SO2
T1 = 300 K and T2 = 1000 K
Ref. 7:

T2

H=

T1

(25.7725 + 57.8938 102 T 38.0844 106 T 2


+ 8.6063 109 T 3) dT

Ans. (iii)

Energy Balances 107

= 25.7725 (1000 300) +

57.8938
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
Ref. 9:

T2

H=

T1

Ans. (a)

(24.7706 + 62.9481 103 T 44.2582 106 T 2


+ 11.122 109 T3) dT

= 24.7726 (1000 300) +

62.9481
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:

T2

H=

(44.4586 + 10.634 103 T + 5.945 105/T 2) dT

T1

10.634
103 (10002 3002)
2
+ 5.945 105 [(1/1000) (1/300)]
= 30 420.6 + 4838.5 1387.2
= 33 871.9 kJ/kmol
Use of absolute enthalpies (Table 5.22):
H = 314 357 ( 347 921)
= 33 564 kJ/kmol

= 43.458 (1000 300) +

Ans. (c)

Ans. (d)

EXERCISE 5.4
Basis: 1 kmol dry gas mixture from absorber
T1 = 343 K and T2 = 618 K
equation constants
Cmp

Component kmol
ni
CH4

0.0025

ai ni

bi ni 103

ci ni 106

di ni 109

0.0481

0.1303

0.0299

0.0283

108 Solutions ManualStoichiometry

CO
CO2
H2
N2
Ar
H2O

0.0038
0.001
0.7462
0.2435
0.003
0.0126

0.1103
0.0214
21.3492
7.2054
0.0623
0.4094

0.0107
0.0643
0.7607
1.2518

0.0010

0.0443
0.0411
0.1101
3.2100

0.1665

0.0179
0.0098
0.5738
1.2097

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
Use data of Table 5.22.
Component

ni
kmol

A=
(Ho H0o + DH fo)1

CH4
CO
CO
CO2
H2
Ar
H2O

0.0025
0.0038
0.001
0.7462
0.2435
0.003
0.0126

55 311
103 981
382 381
+ 9 709
+ 9 902

27 751

Total

1.0126

ni A

+
+

138
395
382
7245
2411

2870
+ 5871

Ans. (a)

B=
(H H0o + DH of )2 ni B
42 622
95 802
307 401
+ 17 722
+ 18 029

218 133

107

364

370
+ 13 224
+ 4 390

2748
+ 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 (70C), 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
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 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 (46.5C)

Ans.

EXERCISE 5.6
Basis: 1 kg Diphyl DT

T2

Q=

(1.436 + 0.002 18 T) dT

T1

=
=
Mean heat capacity =
Q=
Error =
=

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


114.9 + 86 = 200.9 kJ/kg
Ans. (a)
(2.03 + 2.206)/2 = 2.118 kJ/(kg K)
2.118 (533.15 453.15) = 169.4 kJ/kg
(169.4 200.9) 100/200.9
15.7%
Ans.(b)

EXERCISE 5.7
For benzene:

C = a + bT
1.591 = a + 283b
2.018 = 1 + 338b
Solving the equations,
a = 0.6051, b = 0.007 76
For toluene:

(1)
(2)

C = a + bT

1.524 = a + 283b
2.236 = a + 358b
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 =

303

m1 Cl1 dT

(3)
(4)

110 Solutions ManualStoichiometry

0.007 76 2
(T 3032)
2
= 0.907 92 T 2 141.593 T 40 452

= 234 [ 0.6051 (T 303)] +

373

Heat lost by toluene =

m2 Cl2 dT

= 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 (63.45C)
Ans. (a)
(b) Use of data given in Table 5.3 (Ref. 7).
T1 = 303 K (30C)
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 (100C)

373

Heat given-up by toluene = 2

(1.8083 + 812.223 103 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 (61.1C)

Ans. (b)

EXERCISE 5.8
(a) From Table 5.4 for acetic acid,
log p = 4.682 06

1642.540
(T - 39.764)

T = 316.15 K
log p = 4.682 06

1642.540
(316.15 - 39.764)

= 1.260 86
or
p = 0.0548 bar or 5.48 kPa
(b) From Table 5.4, for sulphur trioxide,
log p = 4.205 15

Ans.

892.175
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,

LM
N

lv
T - To
= c
T
lv1
c - TB

OP
Q

0.38

0.38
lv
508.1 - 313.15
=

lv1
508.1 - 329.3
lv = 29.1 1.0334
= 30.072 kJ/mol
(b) From Table 5.5, for carbon disulphide,

552.0 - 413.15
lv
=

26.74
552.0 - 319.4

0.38

l v = 29.1 kJ/mol
1

112 Solutions ManualStoichiometry

l v = 26.74 0.821 97
= 21 98 kJ/mol

Ans.

EXERCISE 5.10
From Table 5.4, for chlorobenzene
1435.675
T - 55.124
1.013 25 bar
347.292
402.42 K or tB = 129.27C
404.9 K or tB = 131.75C

log p = 4.110 83

p=
T 55.124 =
T = TB =
Table 5.5 reports
TB =
Riedel equation:
1.092(ln pc - 5.6182 )
lv
=
0.930 - TBr
R TB
Read Tc and pc values from Appendix III.2
TBr = TB /Tc = 404.9/633.0
= 0.6396
pc = 4.53 MPa = 4530 kPa
lv =
Table 5.5 reports

8.31451 404.9 1.092 (ln 4530 - 5.6182)


(0.930 - 0.6396)

= 35 450 kJ/kmol
lv = 35 190 kJ/kmol

Ans.

EXERCISE 5.11
(a) Benzene:

Riediel equation:

pc = 4.895 MPa, Tc = 562.05 K, TB = 353.3 K


Tr = 353.3/562.05 = 0.6286 at TB
1.092 (ln 4895 - 5.6182)
l v1 = 8.314 51 353.3

(0.930 - 0.6286)

= 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 = 25C/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:

lv2 = 29 100 562.05 - 298.15


562.05 - 353.3

0.38

= 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:

1.092 (ln 4700 - 5.6182)


lv1 = 8.314 51 329.3

(0.930 - 0.6481)

= 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 = 25C/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:

lv2 = 29 100 508.1 - 298.15


508.1 329.3

0.38

= 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.

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)

114 Solutions ManualStoichiometry

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 (270C) 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
5712.29 kW
Total enthalpy of 10 000 kg/h superheated steam = 10 000 3004.5
= 30 045 000 kJ/h
8345.83 kW
Total enthalpy of mixed fluids = 5712.29 + 8345.83
= 14 058.12 kW
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 (216.0C) at 0.44 MPa a which is superheated.

EXERCISE 5.14
Basis: 100 kg superheated steam @ 0.5 MPa a and 523 K (250C)
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 (151.85C).
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 (134.65C),
h = 566.23 kJ/kg and l v = 2159.9 kJ/kg
At 101.3 kPa a, Ts = 373.15 K (100C),
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%

EXERCISE 5.16
Basis: 1 kmol dry gas mixture. T1 = 1473.15 K, T2 = 573.15 K

Ans.

116 Solutions ManualStoichiometry

Component

kmol
ni

equation constants
Cmp
ai ni

bi ni 103

ci ni 103

di ni 103

H2
CO
CO2
CH4
N2
H2O

0.557
0.345
0.028
0.005
0.065
1.850

15.936
10.015
0.598
0.096
1.923
60.110

0.568
0.972
1.800
0.261
0.334
0.147

0.082
4.017
1.149
0.060
0.857
24.440

0.428
1.624
0.274
0.057
0.323
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
9820 840 kJ/100 kmol dry gas mixture
Steam pressure p = 4.0 MPa g = 4.1013 MPa a
Ts = 524.8 K (251.8C)
(Ref. A IV.2)
Water enters WHB at 504.8 K (231.8C), 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 ( 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 ( 45.35 kW) of gas leaving 1st
stage.
Enthalpy of 100 kg liquid NH3 at 276 K = 100 213.92
= 21 392 kJ/h ( 5.94 kW)
Heat, removed in flash cooler = 163 268 21 392
= 141 876 kJ/h ( 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 (48C)
Enthalpy of saturated liquid at 1930.3 kPa a
= Enthalpy of saturated liquid at 276 K (3C) + Enthalpy
of saturated vapours at 276 K (3C)
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 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 40C (313.15 K) = 256.35 kJ/kg
Saturation temperature of R-134a at 101.325 kPa = 26C
Superheat = 10C
Temperature of R-134a gas, leaving chiller = 26 + 10 = 16C
Enthalpy of superheated R-134a gas at 101.325 kPa and 16C = 391.0 kJ/kg
(Ref. Table 5.71)
Heat picked up by R-134a in chiller = 391.0 256.35
= 134.65 kJ/kg

118 Solutions ManualStoichiometry

Evaporation rate = 60

kJ
1
kg

s 134.65 kJ

= 0.4456 kg/s
Ans.(a)
With the incorporation of the economizer, R-134a gas heats upto 10C 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 40C (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
Evaporation rate =

EXERCISE 5.20

65
= 0.4176 kg/s with
155.65
economizer
Ans. (b)

(a) Locate a point representing 273 K (0C) on p-H diagram for CO 2


(Fig. 5.11). Follow constant enthalpy line (i.e. vertical line) which intersects 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(40C) = 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
yi
CO2
O2
N2
H2

0.947
0.008
0.030
0.015

Total

1.000

Molar mass
Mi

ni M i

41.677
0.256
0.840
0.030

Critical
pressure
yi pci
p ci
MPa
7.375
6.983
5.042
0.040
3.394
0.102
1.297
0.019

Critical
temperature
Tci
yi Tci
K
304.12 288.00
154.59
1.24
126.09
3.78
33.2
0.48

44.01
31.9988
28.0134
2.016

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 (20.35C)
New Basis: 100 kmol dry gas
Component

kmol
ni

C
mp equation constants
ai ni

bi ni 103

ci ni 106

di ni 109

CO2
O2
N2
H2

94.7
0.8
3.0
1.5

2023.313
20.821
88.773
42.916

6087.704
9.404
15.423
1.529

3887.492
1.874
39.549
0.221

928.051
0.450
14.904
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

 

R
= Cmp

 

+ w CmRp

R
At pr = 2.8 and Tr = 1.22

C 
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 
R
mp

R
Cmp

= 7.222
= 5.681 + (0.225 7.222) = 7.306

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

120 Solutions ManualStoichiometry

= 897 783 kJ/h


249.38 kW
For p = 4.0 MPa a
pr = 4.0/7.144 = 0.56, Tri = 313.15/293.5 = 1.067
0

R
Cmp

= 1.2062
R
R
Cmp

From Fig. 5.1,

= 2.3857

R
Cmp

= 1.2062 + (0.225 2.3857) = 1.743


R
= 1.743 8.314 14 = 14.491
R
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 +5.32C (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
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

74.633
Uncondense CO 2
=
= 14.083 kmol / kmol
5.3
inerts
At T = 273.15 K, saturation pressure of CO2, pS1 = 3485.9 kPa
total pressure = 3000 kPa
Applying Raoult's law,

(Ref. 24)

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
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
5.3
Inerts

CO2 condensed = 20.555 kmol/h


At T = 275.15 K pS2 = 3673.3 kPa
3673.3
Moles of CO 2
=
= 11.244 no match
(4000
- 3673.3)
Moles of inerts
Trial 3: Assume
T3 = 276.15 K or t3 = 3C.
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
52.479 kW
(94.7 x) 9749.1 = 188 926
x = 75.322 kmol/h
Uncondensed CO 2 = 75.322
= 14.211
5.3
Inerts
Saturation pressure of CO2 at 276.15 K, p53 = 3768.5 kPa
3768.5
Uncondensed CO 2 =
= 16.279
(4000 - 3768.5)
Inerts
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 = 2.5C
lv = (225.05 + 221.53)/2

122 Solutions ManualStoichiometry

=
Heat given-up by gas =
=

(94.7 x) 9826.9 =
x=
Uncondensed CO 2 =
Inerts
At T4 =

223.29 kJ/kg 9826.9 kJ/kmol


(193 955 + 188 926)/2
191 441 kJ/h
53.178 kW
191 441
75.219 kmol/h
75.219
= 192
5.3
275.65 K, p54 = 3720.9 kPa
3720.9
Uncondensed CO 2 =
= 13.332
(4000 - 3720.9)
Inerts
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 2.5C (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 11C.
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
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)
30.767 kmol/h
Duty of water cooler = (30.767 191.441)/100
= 58 901 kJ/h
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 = 29C (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
676.25
1.0844
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,
C(K)

NH3 vapours,
kg

29 (244.15)
27 (246.15)
25 (248.15)
23 (250.15)
21 (252.15)
19 (254.15)
17 (256.15)

14.49
15.62
16.85
18.12
19.44
20.84
22.27

liquid NH3,
kg

total enthalpy,
kJ

31 985.51
31 984.38
31 983.15
31 981.88
31 980.56
31 978.16
31 377.73

2205 899.1
2493 097.8
2781 056.0
3069 691.4
3359 336.6
3649 276.3
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
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
K
From
to
244.15
246.15
246.15
248.15

Enthalpy change,
kJ
287 198.7
287 958.2

Heat transfer
rate, f, kJ/h

Time, h

261 576
252 216

1.098
1.142

124 Solutions ManualStoichiometry

248.15
250.15
252.15
254.15

250.15
252.15
254.15
256.15

288 635.4
289 645.2
289 939.7
291 146.5

Total

1734 523.7

242 856
233 496
224 136
214 776

1.189
1.240
1.294
1.356
7.319

Ans. (a)
244.15 + 256.15
= 250 K
2
f = 1.3 [298.15 250.15] + 3.76
= 66.16 kW 238 176 kJ/h
Time q = 1734 523.7/238 176 = 7.283 h

Average T =

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 (190C) = 575.8 W/m
[Ref. Fig. (5.35)]
Heat loss rate at 459.15 K (180C) = 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 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,
C(K)

Heat loss rate,


ref. Fig. (5.35), W/m

Avg. heat loss


rate, W/m

190 (463.15)
180 (453.15)
170 (443.15)
160 (433.15)
150 (423.15)
140 (413.15)
130 (403.15)
120 (393.15)
110 (383.15)
100 (373.15)

575.8
532.3
481.1
434.4
400.0
364.8
324.6
292.6
266.4
244.3

554.05
506.7
457.75
417.2
382.4
344.7
308.6
279.5
255.35

Total

Length of pipe
m

10.71
11.71
12.96
14.22
15.51
17.21
19.22
21.23
23.23
146.00

Energy Balances 125

Balance length of pipe = 150 146 = 4 m


Heat loss rate at 363.15 K (90C) = 216.4 W/m
Avg. heat loss rate between 373.15 K (100C) and 363 K(90C)
= (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 (98.45C)
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
ts2 = 110.62 C
ts1 = 80.1C
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
p si

0.6
0.4

147.653
59.416

1.0

T2 = 360
yi

p si

T3 = 364
yi

p si

T5 = 362.75
yi

p si

yi

0.8743 124.155
0.2346 48.928

0.7352 139.468
0.1932 55.737

0.8259 134.533 0.7966


0.2200 53.132 0.2121

1.1089

0.9284

1.0459

1.0087

At Syi = 1.00. Bubble point, TBP = 362.75 K or 89.6C

Ans. (ai)

Dew point:
Temperature, K
y1
0.6

T1 = 366
p si
xi
147.653

T2 = 368
p si
xi

0.4117 156.206

T3 = 370
p si
xi

0.3892 165.137

0.3681

p si

T4 = 369
xi

160.62 0.3785

126 Solutions ManualStoichiometry

0.4
1.0

59.416

0.6821

63.283

0.6405

1.0938

67.350

1.0297

0.6018

65.29 0.6208

0.9699

0.9993

At Sx i = 1.00 dew point, TDP= 369 K or 95.85 C


Enthalpy (sensible heat) of liquid mixture at T:
Reference temperature: T0 = 273.15 K (0 C)
H1 =

Ans. (a ii)

TBP

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
H2 =

TBP

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 :
l v1

562.05 369.0
=

562.05 353.3

0.38

30 720

= 29 820.7 kJ/kmol of benzene at TDP


591.75 369.0
l v2 =

591.75 383.8

0.38

33 180

= 34 058.3 kJ/kmol of toluene at TDP


H1 =

TDP

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
H 2 =

TDP

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 yi

= 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
Temperature

ni

CH4
CO2
C2 H 6
C3 H 3
i-C4H10
n-C4H10
C5H12
C6H14
C7H18

0.8957
0.0112
0.0526
0.0197
0.0068
0.0047
0.0038
0.0031
0.0024

Total

1.0000

Ki
2.70
0.90
0.38
0.098
0.038
0.024
0.0075
0.0019
0.0007

Values of Li for trial value of L


L = 0.5

0.1

0.01

0.041

0.2421
0.0059
0.0381
0.0179
0.0065
0.0046
0.0038
0.0031
0.0024

0.0354
0.0012
0.0019
0.0105
0.0051
0.0039
0.0035
0.0030
0.0024

0.0033
0.0001
0.0014
0.0019
0.0014
0.0014
0.0022
0.0026
0.0022

0.0140
0.0005
0.0053
0.0060
0.0036
0.0030
0.0032
0.0030
0.0024

0.3244

0.0769

0.0165

0.041

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

Ans.

128 Solutions ManualStoichiometry

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

H2
CH4
C2H6
N2

0.750
0.200
0.045
0.005

49.73
0.057
9.45 105
1.158

1.000

L1 =
0.5
0.0148
0.1892
0.0450
0.0022

L2 =
0.25
0.0050
0.1708
0.0450
0.0011

L3 =
0.22
0.0042
0.1664
0.0450
0.0010

L4 =
0.215
0.0041
0.1655
0.0450
0.0010

V
0.7459
0.0345
Nil
0.0040

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:
ni
kmol/h

Molar

( m i )

Hi , kJ/kg

mi Hi

mass

kg/h

at 2.75 MPa a
and 300.15 K

kW

H2
CH4
C2H6
N2

626.4
167.03
37.58
4.18

2
16
30
28

1252.8
2672.5
1127.4
117.0

3972.1
888.43
607.82
305.67

1382.29
659.54
190.35
9.93

Total

835.19

components

5169.8

2242.11

Product gas stream:


component

kmol/h
ni

Molar
mass

kg/h
( m i )

H2
CH4
C2H8
N2

622.98
28.81
Nil
3.34

2
16
30
28

1246.0
461.0
Nil
93.5

Total

655.13

Hi, kJ/kg
at 2.75 MPa a,
and 297.65 K
3935.7
883.44
604.90
303.17

1800.5

mi Hi
kW
1362.19
113.13
Nil
7.83
1483.19

Tail gas stream:


component

H2

ni
kmol/h
3.42

Molar

( m i )

Hi, kJ/kg

mi Hi

mass

kg/h

at 140 KPa a,
and 297.15 K

kW

6.8

3917.6

7.40

Energy Balances 129

CH4
C2H6
N2

138.22
37.58
0.84

Total

180.06

16
30
28

Net heat change, f1 =


=
Heat infiltration, f2 =
Refrigeration requirement, f3 =

Recovery of hydrogen =
Purity of product hydrogen stream =
=

2211.5
1127.4
23.5

907.34
665.26
308.14

557.38
208.34
2.01

3369.3

775.13

775.13 + 1483.19 2242.11


16.21 kW (endothermic)
20.9 kW
20.9 16.21 = 4.69 kW
1.334 TR
(622.98 100)/626.4 = 99.45%
622.98 100/655.13
95.1%
Ans.

EXERCISE 5.27
(a) C7H16(g) + 11 O2(g) 7 CO2(g) + 8 H2O(g)
Heat of combustion of n-heptane (g), DHc = 4501.46 kJ/kmol
7 C(s) + 7 O2(g) 7 CO2(g)
Heat of combustion of carbon (s), DHc = 393.51 kJ/kmol
8 H2(g) + 4 O2(g) 8 H2O(g)
Heat of combustion of hydrogen (g), DHc (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
DHf = 7 393.51 8 241.82 + 4501.46
= 187.67 kJ/kmol
Ans.
From Table AV.2 DHf = 187.78 kJ/kmol
(b) C2H5OH (g) 2 CO2(g) + 3 H2O(g)
Heat of combustion of ethyl alcohol (g), DHc = 1277.53 kJ/kmol
2 C(s) + 2 O2(g) 2 CO2(g)
3 H2(g) + 1.5 O2(g) 3 H2O(g)
D Hf of C2H5OH (g) = 2 393.51 3 241.82 + 1277.53
= 234.95 kJ/kmol
D
H
From Table AV.2,
= 234.95 kJ/kmol
f
(c) C4H6(l) + 5.5 O2 (g) 4 CO2(g) + 3 H2O(g)
Heat of combustion of butadiene (1,3), DHc = 2386.69 kJ/kmol
4 C(s) + 4 O2(g)
4 CO2(g)
3 H2(g) + 1.5 O2(g) 3 H2O(g)
D Hf of C4H6(l) = 4 393.51 3 241.82 + 2386.69

Ans.

130 Solutions ManualStoichiometry

= 87.19 kJ/kmol
From Table AV.2, D Hf = 87.19 kJ/kmol

Ans.

EXERCISE 5.28
(a)

(b)

DHc (g) for hydrogen =


lv at 298.15 for water =

D Hf (l) =

241.82 kJ/kmol
2442.5 kJ/kg
44.002 kJ/mol
241.82 44.002

= 285.82 kJ/mol
D Hf (g) for methanol = 200.94 kJ/mol

Ans.

Watson equation:
512.5 298.15
lv at 298.15 K for methanol = 35 210

512.5 337.7
= 38 048 kJ/kmol
D Hf (l) = 200.94 38.05 = 238.99 kJ/mol

0.38

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
DHf (l) = 200.94 37.485
= 238.43 kJ/mol
(c)

Ans.

D Hf (g) for CS2 = 117.36 kJ/mol

Watson equation:
552 298.15
l v = 26 740

552 319.04
= 27 627 kJ/kmol

0.38

D Hf (l) = 117.36 27.64


= 89.72 kJ/mol
Ans.
NIST equation:
Tc = 552.0 K
For CS2, pc = 73.00 bar
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
DHf (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
+ 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
Ans.
= 807.15 kJ/kg NaHCO3

EXERCISE 5.30

D H ro = D Hfo

products

D Hfo

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-

mass

ture K(C)

ni

(H DHo + DHf )i ni (H DHo


+ DHf ), kJ

kJ/kmol

100
100
100

16
32
18

6.250
3.125
5.55

698 (425)
698 (425)
1253 (980)

38 416
+ 2 102
192 447

240 100
+ 65 691
1068 081

Total 300

14.925

1242 490

CH4
O2
H2O

Outlet Heat balance:


Molar kmol

Tempera- (H DHo DHf )i ni (H DHo

mass

ni

ture K(C)

kJ/kmol

H2
27.3
H2O 79.2
CO 149.8
CO2 50.7

2
18
28
44

13.65
4.40
5.10
1.15

1198 (925)
1198 (925)
1198 (925)
1198 (925)

+ 35 134
194 882
76 942
339 706

+ 479 579
857 481
392 404
390 662

Total 300.0

24.30

1160 968

Gas

kg

Heat of reaction,

+ DHf )i, kJ

D H r = 1160 968 (1242 490)


= 81 522 kJ (endothermic)

Ans.

132 Solutions ManualStoichiometry

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)
DHf
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
CH3OH

.
ni
kmol/h

Heat capacity (Cmpr2 ) equation constants


.
.
.
.
ai ni
bi ni 103 ci ni 106
di ni 109

1.415

35.2

72.0

83.0

63.9

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

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

HCHO

(CH3)2O

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),

523.15

Heat duty of heat exchanger f6 = (1395.1/1363.1)

Cmpa

308.15

Energy Balances 133

= 8935 667 kJ/h


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,

T1

(93/125)

T1

Cmpme dT = (1395.1/1363.1)

351. 47

Cmpa dT

523.15

Solving by Mathcad, T1 = 504.9 K or 231.75 C


Enthalpy of reactor input stream over 298.15 K,

504.9

f2 = (93/125)

504.9

Cmpme dT + (1395.1/1363.1)

298.15

Cmpa

298.15

= 9546 895 kJ/h


2651.92 kW
Heat of reactions at 298.15 K in RI,
D HrI = 20320 839 92.07/123.75

= 15118 704 kJ/h


4199.64 kW
Heat Capacity Data for RI Exit Gas stream
.
Component ni, kmol/h

.
ai ni

Heat capacity (Cpmr1


) equation constants
.
.
.
bi ni 103
ci ni 106 di ni 109

CH3OH
HCHO

0.93
92.07

23.1
4437.7

47.3

54.5

42.0

CO2
CO
H2
CH4
(CH3)2O
O2

6.537
0.737
1.474
0.460
0.737
236.865

139.7
21.4
43.2
8.9
48.5
6164.6

420.2
2.1
1.5
24.0

2784.4

268.3
8.6
0.2
5.5

554.9

64.1
3.5
1.1
5.2

133.2

N2
H2O

1082.930
120.974

32 044.9
3930.7

5567.3
9.6

14 276.2
1598.2

5380.0
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,

134 Solutions ManualStoichiometry

613.15

f 3 =

Cmpr1

dT

298.15

= 15 260 251 kJ/h 4238.96 kW


Heat transfer in RI = 9546 895 + 15 118 704 15 260 251
= 9405 348 kJ/h
2612.60 kW
Enthalpy of additional methanol vapours added to RI exit stream
140.548
f 3 =
125

351. 47

Cmpa
dT

298.15

= 344 999 kJ/h


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,

613.15

f4 =

Cmpr2 dT

298.15

= 18 246 584 kJ/h 5068.50 kW


140.063
20 320 639
123.75
= 22 999 351 kJ/h

Heat of reaction in RII =

6388.71 kW
Heat transfer in RII = 15 260 251 + 22 999 351 18 246 584
= 20 013 018 kJ/h
5559.17 kW
RII exit gases leave the gas heat exchanger at 383.15 K (110C).
Heat transfer in BFW heater and heat exchanger

613.15

Cmpr2 = 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
1241.24 kW
Total heat transfer taken place for steam generation
= 9405 348 + 20 013 018 + 4468 455
= 33 886 821 kJ/h
9413.01 kW
Steam generated =
=
Total methanol evaporated =
=
Heat duty of evaporator f1 =
=

33 886 821
2629.3
12 888.2 kg/h
93 + 140.548
233.548 kmol/h
233.548 4551 263
125
8503 506 kJ/h
2362.01 kW

8503 506
2119.7
= 4011.7 kg/h

Steam consumption in evaporator, ms =

Ans.

EXERCISE 5.34
(a) Basis: 1 kmol CH4
Reaction: CH4 + C2H4 = C3H8 (gaseous)
Gas

D Hf
kJ/kmol

CH4
C2H4
C3H8

74 520
+ 52 550
104 680

Constants of Cmp equation


a
19.2494
4.1261
4.2227

b 103

c 106

d 109

52.1135
155.0213
306.264

11.973
81.5455
158.6316

11.3173
16.9755
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

136 Solutions ManualStoichiometry

DHo = D HRT DaT (Db/2)T 2 (Dc/3)T 3 (Dd/4)T 4

For T = 298.15 K, D H rT = 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 HrT = 78 154 27.598 T + 49.565 103 T2 29.686 106 T 3

+ 6.622 109 T4 Ans.


CO(g) + H2O(g) = CO2(g) + H2(g)

(b)
D Hf

110.53

241.82

393.51

all in kJ/mol

D Hr = 393.51 ( 110.53 241.82)

= 41.16 kJ/mol
Gas

Constants of Cmp equation


b 103

a
CO2
H2
CO
H2O

21.3655
28.6105
29.0277
32.4921

64.2841
1.0194
2.8165
0.0796

c 103

d 103

41.0506
0.1476
11.6437
13.2107

9.7999
0.769
4.7063
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
(c) Basis = 1 kmol CO consumed or CH3OH produced
CO(g) + 2 H2(g) = CH3OH(g)

Ans.

Energy Balances 137

Gas

DHf
kJ/mol

CH3OH
CO
H2

200.94
110.53
O

Constants of C mp
equation
a
24.8692
29.0277
28.6105

b 103

c 103

d 103

50.8755
2.8165
1.0194

58.6278
11.6437
0.1476

45.1266
4.7063
0.769

DHr = 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
DH0 = 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
DHrT = 74 741 61.38 T + 25.827 103 T2 + 15.76 106 T3
10.49 109 T 4
Ans.
At T = 593.15 K
DHrT = 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
105
1075
.
+ 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
=

138 Solutions ManualStoichiometry

EXERCISE 5.36
Basis: 100 kmol outgoing gas mixture
Gas

kmol ni
incoming

outgoing

CO2
H2
CH4
CO

58.9
47.94

57.10
41.10
1.68
0.12

Total

107.84

100.00

Constants of Cmp equation

a
21.3655
28.6105
19.2494
29.0277

b 103

c 106

d 109

64.2841
1.0194
52.1135
2.8165

41.0506
0.1476
11.973
11.6437

9.7999
0.769
11.3173
4.7063

T1 = 298.15 K, T2 = 588.15 K
H1 =

T2

(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)
DHr1 = 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 r2 = 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.
H1 =

T3

(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 396.46C
Ans.

EXERCISE 5.37
Basis: 100 kmol dry gas mixture, entering the shift converter.
Refer Exercise 5.32 (b).
T1 = 618.15 K
DH rT1 = 41 160 7134 + 12 993 5197 + 723
= 39 775 kJ/kmol CO
T2 = 783.15 K
DH rT2 = 41 160 9039 + 20 857 10 570 + 1863
= 38 049 kJ/kmol CO
Average heat of reaction, DHrT = [ 39 775 + ( 38 049)]/2
= 38 912 kJ/kmol CO
Gas
CO
H2
CO2
N2
Ar
H2O

(H H + DHf ), kJ/kmol
618 K

783 K

95 804
17 723
370 400
18 029

218 133

90 644
22 585
362 262
23 126

211 933

Average Cmp between


618 K and 783 K,
31.273
29.467
49.321
30.891
39.946 (constant)
37.576

Partial oxidation of NG:


Sni Cmpi = ( 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)

140 Solutions ManualStoichiometry

Partial oxidation of FO:


Sni Cmpt = ( 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 Cmpt = (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 Cmpt = (3063.7 + 3139.5 + 3146.8)/3
= 3116.7 kJ/(100 kmol dry gas K)
For steam, accompanying the gas mixture,
ni Cmpt = 37.576 100 x
= 3757.6 x kJ/(100 kmol K)
Rise in temperature in shift converter,
DT =

38912 a
12.485 a
=
K
3116.7 + 3757.6 x
1 + 1.206 x
12.5 a
K
1 + 1.2 x

Ans.

EXERCISE 5.38
Basis: Flowrate of offgases from uranium oxide dissolver
= 38.3 Nm3/h
Flow rate = 919.2 Nm3/day 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)
DHf : kJ/mol
45.94
33.18
0
o
DH r = 241.82 12 (45.94 8 + 6 33.18)
= 2733.4 kJ/6 mol NO2
455 567 kJ/kmol NO2 (exothermic)
Total heat generated = 455 567 1.025
= 466 956 kJ/d 5.405 kW
Theoretical NH3 required = 4 1.025/3 = 1.367 kmol/d
Actual NH3 fed = 2 Nm3/h 0.089 kmol/h
2.141 kmol/d
Excess NH3 = [(2.141 1.367)/1.367]/100
= 56.6%

+ 12 H2O(g)
241.82

Ans. (a)

Energy Balances 141

Reactants:
Component

.
n i, kmol/d

N2
O2
NO2
H2O
NH3

11.278
2.051
1.025
26.656
2.141

.
n i a i
337.73
53.38
24.17
866.11
54.92

Total

41.099

1336.31

Constants of Cmp equation


.
.
.
n i bi 103
n i ci 106
n i di 109
57.98
148.68
56.03
24.11
4.80
1.15
54.93
32.28
6.70
2.12
352.14
121.22
71.68
0.75
6.6
94.86

464.49

178.3

Enthalpy of reactants at 393.15 K (120C) over 298.15 K (25C):


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 1.558 kW
Total enthalpy of product gas mixture
= f1 + DHr
= 134 652 + 466 956
= 601 608 kJ/d 6.963 kW
Products:
Component

.
n i, kmol/d

N2
O2
H2O
NH3

12.474
2.051
28.706
0.774

.
n i a i
369.12
53.38
932.72
19.85

Total

44.005

1375.07

Constants of Cmp equation


.
.
.
n i bi 109
n i ci 106
n i di 109
64.13
164.44
61.97
24.11
4.80
1.15
2.28
379.23
130.54
25.91
0.27
2.39
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 6.963 kW
By trial and error or by Mathcad, T = 703.78 K or 430.63C
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

142 Solutions ManualStoichiometry

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 7.566 kW
Reactants:
.
Components n i kmol/d

.
n i a i

Constants of Cmp
.
.
n i bi 103
n i ci 106

.
n i di 109

N2
O2
NO2
H2O
NH3

10.868
2.051
1.435
26.656
2.141

321.59
53.38
33.84
866.11
54.92

55.87
24.11
76.91
2.12
71.68

143.27
4.80
45.19
352.14
0.75

53.99
1.15
9.38
121.22
6.6

Total

43.151

1329.84

118.95

446.17

173.58

Enthalpy of reactants at 393.15 K (120C) over 298.15 K (25C),


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 1.558 kW
This enthalpy does not include enthalpy of nitrogen (x kmol/d) at 303.15 K (30C).
Total enthalpy of product gas mixture (excluding that of N2 stream),
f1 = 134 638 + 653 739
= 788 377 kJ/d 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

.
n i a i

Constants of Cmp equation


.
.
n i bi 103
n i ci 106

.
n i di 109

N2
O2
H2O
NH3

12.544
2.051
29.526
0.228

371.13
53.38
959.36
5.85

64.48
24.11
2.35
7.63

165.34
4.80
390.06
0.08

62.31
1.15
134.27
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,
f2 = 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 7.905 kW
Enthalpy carried by extra nitrogen in feed stream
f1 f2 = 788 377 683 014
= 105 363 kJ/d 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
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 (25C)
= 0.125 328 690 + 0.005 377 200
= 42 972 kJ
Inlet gas mixture is at 448.15 K (175C):

144 Solutions ManualStoichiometry

Constants of Cmp equation


Components kmol
ni
C7H8
1.0
2.0
O2
N2
7.524
Total

10.524

mole %

niai

nibi 103

9.5
19.0
71.5

35.19
52.05
222.64

563.18
23.51
38.68

349.80
4.69
99.19

82.59
1.12
37.38

548.01

255.30

44.09

100.0

239.500

nici 106

nidi 109

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 (195C):
Constants of Cmp equation
Components kmol
ni
C7H8
0.87
O2
1.83
7.524
N2
C7H8O
0.125
0.035
CO2
H2O
0.020
Total

10.404

mole %

n i a i

ni bi 103

ni ci 106

ni di 109

8.36
17.59
72.32
1.20
0.34
0.19

30.62
47.63
222.64
16.25
0.75
0.65

489.97
21.51
38.68

2.25

304.32
4.29
99.19

1.44
0.26

71.85
1.03
37.38

0.34
0.09

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
Conversion = 80%
S2 reacted = 0.8 kmol

Ans. (a)

Energy Balances 145

CS2 produced = 0.8/2 = 0.4 kmol


Ratio =

CS2 produced
76 0.4
=
= 30.4 kg/kmol
S2 fed
1

Ans.(b)

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 %

CH4
S2
N2

1.20
1.00
0.80

40.0
33.3
26.7

Total

3.00

100.0

(H Ho + DH f )i,
kJ/kmol at 720 K
(427C)
38 305
22 951
20 537

ni (H H o + DHf)i,
kJ
45 966
22 951
16 430

6 585

Products:
Gas

kmol, ni

mole %

CH4
S2
CS2
H2S
N2

0.8
0.2
0.4
0.8
0.8

26.67
6.67
13.33
26.66
26.67

Total

3.0

100.00

(H Ho + DHf ),
at 977 K (704 C)
20 257
+ 33 118
+ 32 118
45 137
+ 29 322

ni (H Ho + DHf ), kJ
16 206
+ 6 624
+ 12 843
36 110
23 458
9 391

Heat change in the reactor = 9391 ( 6585)


= 2806 kJ/kmol S2
Antoine constants for CS2
A = 6.0677, B = + 1169.1 and C = 31.55 at T = 298.15 K
Log p = 4.066 83
p = 0.481 bar
or p = 48.1 kPa

Ans. (c and d)

1168.62
(298.15 - 31.616)

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
(2)
SO2(g) + 2 H2S(g) = 3 S(l) + 2 H2O(g)

146 Solutions ManualStoichiometry

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
O2
N2
H2O

kmol
2.1 1.5 = 0.6
0.333 + 7.9 = 8.233
1.0

Total

9.833

mole %
6.11
83.73
10.16
100.00

Ans. (a)
Heat balance across furnace boiler:
DHr
= 241.82 296.83 ( 20.63)
= 518.02 kJ/mol H2S
Since the reactants are at 298.15 K (25 C), DHRectants = 0
Product stream from furnace boiler:
Component

ni kmol mole %

Constants of Cmp equation

O2
H2O
SO2
N2

0.6
1.0
1.0
8.233

5.54
9.23
9.23
76.00

n i a i
15.615
32.492
24.771
243.622

Total

10.833

100.00

316.500

ni bi 103
7.053
0.08
62.948
42.326
27.755

ni ci 106 ni di 109
1.406
0.337
13.211
4.547
44.258
11.122
108.535 40.902
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)
10 869.5 kW

Ans. (c)

EXERCISE 5.43
Basis: 100 kmol fresh ethylene feed (96% pure)
Heat capacity constants for combined (mixed) feed:
Component

ni kmol

Constants of Cmp

ni ai

ni bi 103

ni ci 106

ni di 109

C2H4
H2O
N2

0.5483
0.3564
0.0953

2.262
11.58
2.82

84.998
0.028
0.49

44.711
4.708
1.256

9.308
1.621
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]
H = 2716.45 12 800.7 = 34 772 462 kJ
Real gas enthalpy,
H = 34 772 462 + 2716.45 962 = 37 385 687 kJ
DHr = 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
equation

Component

ni kmol

C2 H 4
H2O
N2
C2H5OH

0.5356
0.3382
0.0980
0.0282

2.210
10.989
2.9
0.294

83.029
0.027
0.504
5.908

43.676
4.468
1.292
2.326

9.092
1.538
0.487
0.111

1.0000

16.393

88.46

40.242

7.178

Total

ni ai

ni bi 103

ni ci 106

ni di 109

148 Solutions ManualStoichiometry

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 331.87C
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),
DHr = 479.8 92.31 (484.2) 0 (Appendix AIV.2)
= 87.91 kJ/mol reactant
Average temperature = (40 + 100)/2 = 70C
Mean Heat Capacity at 100C (373.15 K)
Component

State

Acetic acid
Hydrogen chloride
MCA
Chloride

Liquid
Gas
Liquid
Gas

Cpmi, kJ/(kg K)
1.686
0.7977
1.88
0.45

Cpmi values are calculated using, equations given in Tables 5.1 and 5.3.
DHr at 100C (373.15 K)
= 87.99 1000 + (1.88 + 0.7977 1.686 0.485) (373.15 298.15)
= 87 842 kJ/kmol reacant
87.842 kJ/mol reactant
Ans.(a)
.
Let
nt = Molar flow rate of gas-vapour mixture, leaving the reactor, kmol/h
Basis: 100 kg/h MCA production rate molar production rate =
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

1000
= 10.582
94.5

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 100C (373.15 K),

log pvAA = 4.682 06

1642.540
373.15 - 39.764

pvAA = 0.569 14 bar


426.9 Torr
log pvMCA = 4.690 87

pCl

pvMCA =

pt =
=
+ pHCl =

pCl2 + pHCl
pt

1733.960
373.15 - 92.154

0.0331 bar
24.8 Torr
1.1 atm = 836 Torr
pCl + pHCl + 0.5 426.9 + 0.5 24.8
2
610.15

nCl2 + nHCl
nt

10.582 + 2.1164
610.5
=
nt
836
nt = 17.3888 kmol/h

nAA =

426.9 0.5 17.3888


= 4.4398 kmol/h
836

nMCA =

24.8 0.5 17.3888


= 0.2579 kmol/h
836

This gas-vapour mixture, is cooled to 40C (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.
xAA = Mole fraction of AA in the condensed liquid
=

4.4398
= 0.9451
(4.4398 + 0.2579)

xMCA = 1 0.9451 = 0.0549

150 Solutions ManualStoichiometry

Assume a pressure drop of 50 Torr in the heat exchanger. Gases leave the overhead
condenser at
pt = 836 50 = 786 Torr and 40C
At
T = 40 + 273.15 = 313.15 K,
pvAA = 0.0472 bar
35.4 Torr
pvMCA = 0.0007 bar
0.52 Torr
786 = pHCL + pCl + 0.9451 35.4 + 0.0549 0.52
2
pCL + pHCl = 752.51 Torr
2

10.582 + 2.1164
752.51
=
nt
786
t = 13.2635 kmol/h
n
AA =
n
MCA =
n

13.2635 0.9451 35.4


= 0.5646 kmol/h
786
0.0549 0.52 13.2635
786

= 0.482 103 kmol/h


Trial II: For this trial, composition of the condensed liquid is calculated as follows.
4.4398 - 0.5646
xAA = (4.4398 - 0.5646) + (0.2579 - 0.482 10-3 )

=
xMCA =
pCl + pHCl =
2
=
t =
n

0.9387
0.0613
786 0.9387 35.4 0.0613 0.52
752.74 Torr
(10.582 + 2.1164) 786
752.74

= 13.2595 kmol/h
AA =
n
MCA =
n

13.2595 0.9387 35.4


= 0.5606 kmol/h
786
13.2595 0.0613 0.52
= 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
x
MCA = 0.0623

Both these values are close enough to xAA and xMCA 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
lAA + m MCA
lMCA  + m AA
ClAA + m MCA
ClMCA  DTL
m Cl2 = 2.1164 71 = 150.26 kg/h
m HCl = 10.528 36.5 = 386.24 kg/h
4.4398 + 0.5646
60
m AA =
2

= 150.13 kg/h
m MCA

(0.2579 + 0.538 10-3 ) 94.5


=
2

= 12.21 kg/h
 AA = 232.75 kg/h
m
 MCA = 24.32 kg/h
m

 AA =
m
 MCA =
m

0 + 232.75
= 116.38 kg/h
2
0 + 24.32
= 12.16 kg/h
2

Specific Heats of Liquids and Gases at 70C (143.15 K)


Component
Chlorine
Hydrogen chloride
Acetic acid
MCA

Cpi, kJ/(kg C)
0.4864
0.7977
1.2254
1.0467

CLi, kJ/(kg C)

1.7
1.9

152 Solutions ManualStoichiometry

AT 70C (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 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 214.713 kW
Ans.(c)

EXERCISE 5.45
The rate of chemical reaction is
R =

dM
= 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 =
=
M1 =
=
=

250 {e ( 0.080 73 535 - 40.1841) } /183 672


0.027 52 kg
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
s

Mass of reactants,
kg

Rate of recion,
kg/s

Reaction temperature,
K

250

0.027 52

535.04

249.972 48

0.027 60

535.08

249.944 88

0.027 69

535.12

249.917 19

0.027 77

535.16

249.889 42

0.027 86

535.204

249.861 56

0.027 96

535.245

249.833 60

0.028 05

535.286

249.805 55

0.028 14

535.327

249.777 41

0.028 23

535.368

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.

154 Solutions ManualStoichiometry

EXERCISE 5.46
Heat of crystallisation is just opposite the heat to solution.
Heat of crystallisation = 17.58 kJ/mol (exothermic)
17 580/280.7
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) CuSO4 5 H2O(s)

771.36

5 ( 285.83)

DHf

D Hr = 11.95 = (DHf of CuSO4 5 H2O) ( 771.36 5 285.83)


DHf 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
5.56 18 100.08 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
(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
(c) Integral heat of solution of 40% soln. = + 157 kJ/kg NaClO3
Integral heat of solution of 20% soln. = + 190 kJ/kg NaClO3

Ans.

Ans.

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
3
3.5
4
4.5
5
6
8
10
12
15
20
25
30
40
50
75
100
150
200

110.1515
119.1592
128.1668
137.1745
146.1821
164.1974
200.2280
236.2586
272.2892
326.3351
416.4116
506.4881
596.5646
776.7176
956.8706
1407.2531
1857.6356
2758.4006
3659.1656

0.5093
0.4708
0.4378
0.4090
0.3838
0.3417
0.2802
0.2375
0.2061
0.1719
0.1347
0.1108
0.0940
0.0722
0.0586
0.0399
0.0302
0.0203
0.0153

0.2500
0.2222
0.2000
0.1818
0.1667
0.1429
0.1111
0.0909
0.0769
0.0625
0.0476
0.0385
0.0323
0.0244
0.0196
0.0132
0.0099
0.0066
0.0050

424.764
469.462
471.302
472.955
474.503
475.712
477.093
478.775
479.725
480.306
480.825
481.189
481.302
481.369
481.461
481.520
481.595
481.637
481.700
481.742

44.698 11174.50
46.538 10341.78
48.191 9638.20
49.739 9043.45
50.948 8491.33
52.329 7475.57
54.011 6001.22
54.961 4996.45
55.542 4272.46
56.061 3503.81
56.425 2686.90
56.538 2174.54
56.605 1825.97
56.697 1382.85
56.756 1112.86
56.831 747.78
56.873 563.10
56.936 377.06
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

156 Solutions ManualStoichiometry

Another plot of HEvs 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
KOH, wi

HE, Excess
enthalpy,
kJ/kg solution

0.5093
0.4708
0.4378
0.4090
0.3838
0.3417
0.2802
0.2375
0.2061
0.1719
0.1347
0.1108
0.0940
0.0722
0.0586
0.0399
0.0302
0.0203
0.0153

101.45
86.79
75.20
65.93
58.09
45.53
29.97
21.15
15.69
10.74
6.45
4.29
3.06
1.78
1.16
0.53
0.30
0.14
0.08

Usong above data, following diagram is prepared.


Heat of dilution, kJ/kg solution

Heat of dilution chart for KOH-H2O system


0
20

0.1

0.2

0.3

40
60
80
100
200

mass fraction of KOH

0.4

0.5

0.6

Energy Balances 157

EXERCISE 5.51
(a) Locate two points on Fig. 5.16. One point corresponds to 60% NaOH at
373 K (100C). Another point corresponds to pure water (i.e. 0% NaOH)
at 308 K (35C). Draw a line joining the two points. The line intersects
vertical axis of 10% NaOH at 335 K (62C).
(b) H1 = Enthalpy of 10% NaOH soln. at 335 K (62C)
= 231.3 kJ/kg solution
(from Fig. 5.16)
H2 = Enthalpy of 10% NaOH soln. at 298.15 K (25C)
= 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 (62C) and 298.15 K (25C) 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
NH4NO3 dissolved =

80.0434 8.675
2 14,0067

= 24.787 kg 0.3097 kmol 309.7 mol


H2O in solution = 100 50 24.787
= 25.213 kg
Associated urea = 1.1758 0.3097
= 0.3641 kmol
21.869 kg

o
m = 0.3097 1000/25.213
= 12.2833 molality of NH4NO3 1.1758 NH2CONH2
Additional urea dissolved =

50
0.3641
60.0553

= 0.8326 0.3641

158 Solutions ManualStoichiometry

= 0.4685 kmol 468.5 mol


Water = 25.213 kg = 1.3995 kmol
For additional urea dissolution,
Waber
1.3995
=
= 2.99, say 3
Urea
0.4685

DHf of urea crystals = 333.51 kJ/mol urea


DHf 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,
o
o 2
o 3
HE2 = 40.3044 2.5962 m
+ 0.1582 (m
) 3.4782 (m
)
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 0.3748 kmol
N from NH4NO3 =

28.0134 30
80.0434

= 10.5 kg
Required N from urea = 20 10.5
= 9.5 kg
Urea dissolved =

9.5
= 20.364 kg
0.4665

0.3391 kmol
H2O in solution = 100 30 20.364
= 49.636 kg
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.


Associated NH4NO3 =
o
=
m

0.3391
= 0.2884 kmol 288.4 mol
1.1758

0.2884 1000
= 5.81
49.636

Additional NH4NO3 dissolved = 0.3748 0.2884


= 0.0864 kmol 86.4 mol
Water
2.755
NH 4 NO3 = 0.0864 = 31.887, say 30

DHf of NH4NO3 crystals = 365.56 kJ/mol NH4NO3


DHf 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
fraction of
C2H5OH

0.05

Mass of
C2H5OH

mole
fraction

Mass of
CH3COOC2H5

per kmol
of
per kmol
mixture CH3COOC2H5 mixture
(m1) kg
(m2) kg
2.3

0.95

83.6

Mass
fraction
of
ester
0.973

Internal heat
of solution
kJ/kmol kJ/kg
soln.
ester
(H)
(H/m2)
326.6

3.907
(Contd.)

160 Solutions ManualStoichiometry

(Contd.)
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
0.95

4.6
9.2
13.8
18.4
23.0
27.6
32.2
36.8
41.4
43.7

0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.05

79.2
70.4
61.6
52.8
44.0
35.2
26.4
17.6
8.8
4.4

0.945
0.884
0.817
0.742
0.657
0.561
0.451
0.324
0.175
0.091

596.1
1032.3
1319.8
1467.0
1486.1
1385.8
1176.3
859.1
531.3
245.8

7.527
14.663
21.425
27.784
33.775
39.369
44.557
48.813
60.375
55.864

Integral heat of mixing (in kJ/kg ester) and mass fraction of ester are plotted
below.
Ans.
70.0

INTERGRAL HEAT OF MIXING kJ/kg ESTER

60.0

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

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:
H1 = 0.18

318.15

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

0.973

Energy Balances 161

Enthalpy of 0.82 kmol n-hexane at 318 K over 273 K:


H2 =

318.15

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
= 7515.2 kJ/kmol
Ans.

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
(Acid)

68. 3 % HNO3
97.9% H2SO4
Mixed acid

(Ref. Fig. 5.21)


Enthalpy at
273 K (0 C)
kJ/kg
191.8
10.5
226.9

(Ref. Fig. 5.20)


specific heat
kJ/(kg K)
2.6
1.42
2.05

Enthalpy
at 303 K
(0 C)
kJ/kg
113.8
+ 32.1

Enthalpy
at 313 K
(0 C)
kJ/kg

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
Basis: 100 kg spent acid
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)

162 Solutions ManualStoichiometry

Amount,
kg
mi

Acid

spent acid
69% HNO3
98% H2SO4
fortified mixed acid

(Ref. Fig. 5.21)


Enthalpy at
273 K (0 C), hi
kJ/kg

100
44.11
22.84
166.95

215.8
191.8
10.5
284.7

mi hi
kJ

21 580
8 460
600
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 (33C).
Locate another point representing water (w = 0) at 298 K (25C).
Join both the points. Line crosses 4.5% NH3 at 305 K (32C) having an enthalpy
value of 93.16 kJ/kg solution.
Enthalpy of 4.5% NH3 at 298.15 K(25C) = 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
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 ( 33C). From Fig. 5.22,
Enthalpy of anhydrous NH3 at 298.15 K (25C) = 464.9 kJ/kg NH3
Enthalpy of anhydrous NH3 at 240 K ( 33C) = 211.1 kJ/kg NH3
Heat evolved by cooling anhydrous NH3 = 464.9 211.1
= 253.8 kJ/kg
4322.5 kJ/kmol NH3
D Hf at 298.15 K (25C) 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)
0.33

LM
N

OP
Q

0.33

107.5
405.5 298.15
lv
=
=

165.8
405.5 239.8
23.325
l v = 23.35 0.848 = 19 775 kJ/kmol at 298.15 K
D Hf of liquid NH3 at = 46 110 4322.5 19 775
= 70 207.5 kJ/kmol

Energy Balances 163

D Hf 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
8.8075 kmol
From Table 5.59,
D Hf at 298.15 K (25C) 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
(25C) and 4.5% (mass) NH3 at 298.15 K (25C). 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
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
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 (45C) and leaves from the top at
303.15 K (30C).
Total pressure at absorber top = 6.85 kPa g
= 108.175 kPa a

164 Solutions ManualStoichiometry

Vapour pressure of water at 303 K (30C), pw = 4.2415 kPa


[Table 6.13]
Moisture content of gas mixture, leaving the absorber
= 4.2415/(108.175 4.2415)
= 0.0408 kmol/kmol dry gas
Total water leaving the absorber in the gas mixture
= 0.0408 (1 0.2445) 100
= 3.082 kmol/h 55.5 kg/h
HCl absorbed = 24.45 kmol/h
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
426.449 kW
Feed gas temperature = 318.15 K (45C)
Component

ni
kmol/h

heat capacity equation constants


.

ni bi 103
2803.71
1922.50

ni ci 106
644.15
867.44

ni di 109
608.87
143.86

CH4
CH3Cl

53.80
18.30

ni ai
1035.62
247.83

CH2Cl2
CHCl3
CCl4
HCl

2.65
0.65
0.15
24.45

44.81
19.67
7.52
741.05

372.20
98.20
22.15
186.04

249.17
77.14
19.79
324.23

63.04
21.55
5.90
105.96

100.00

2096.50

5032.72

245.16

480.48

Total

Outgoing gas-mixture from absorber: Temp. = 30 K (30C)

Energy Balances 165

Component

ni
kmol/h

ni ai

heat capacity equation constants

ni bi 103

ni ci 106

ni di 109

CH4
CH3Cl
CH2Cl3
CHCl3
CCl4
H2O

53.80
18.30
2.65
0.65
0.15
3.082

1035.62
247.83
44.81
19.67
7.52
104.93

2803.71
1922.50
372.20
98.20
22.15
29.74

644.15
867.44
249.17
77.14
19.79
101.70

608.87
143.86
63.04
21.55
5.90
63.02

Total

78.632

1460.38

5189.02

467.76

437.54

Reference temperature, T0 = 298.15 K (25C)


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
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
4.12 kW
Enthalpy of feed water f4 = 2135.5 4.1868 (303.15 298.15)
= 44 705 kJ/h
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

166 Solutions ManualStoichiometry

Enthalpy of feed water f4 = 16 994 4.1868 (303.15 298.15)


= 355 752 kJ/h
98.82 kW
Heat evolved due to absorption at 298.15 K = 165.0 ( 92.31)
= 72.69 kJ/mol HCl
f1 = 72 690 24.45 = 1777 271 kJ/h
493.686 kW
Enthalpy of outgoing acid (5% cocn.) = f1 + f2 f3 + f4
= 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 (54.3C)
Ans. (b)

EXERCISE 5.61

HE = H Hid
[Eq. (5.74)]
Hid = x1 H1 + x2 H2
Reference temperature, t0/T0 = 0C/273.15 K
Enthalpy of cyclohexane (1) at 50C over 0C,
H1 = 155.78 (323.15 273.15)
= 7789 kJ/kmol
Enthalpy of cyclohexanone (2) at 50C over 0C,
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
(endothermic)

Hid

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0

0
300.81
551.95
746.00
881.66
959.18
975.61
920.21
769.70
483.70
0

8842.0
8736.8
8631.5
8526.2
8420.9
8315.6
8210.2
8104.9
7999.6
7894.3
7789.0

8842.0
9037.6
9183.5
9272.2
9302.6
9274.8
9185.8
9025.1
8769.3
8378.0
7789.0

All enthalpy values are in kJ/kmol.

Energy Balances 167

H1 = H + x2

dH
dx1

Similarly, H 2 = H x1

(1)
dH
dx1

(2)

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
Substituting x2 = 1 x1, H and

dH
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
(4)
H 2 = 15 539.2x15 19 353.6 x14 + 8275.6 x13 + 1635.6 x12 + 8842.1
Using Eq. (3) and Eq. (4), following table is prepared
x1

H1

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0

8842.0
9037.6
9183.5
9272.2
9302.6
9274.8
9185.8
9025.1
8769.3
8378.0
7789.0

10 591.5
10 126.2
9 688.5
9 310.6
8 988.0
8 697.4
8 415.8
8 139.0
7 900.3
7 789.0

H2
8 842.0
8 865.0
8 947.7
9 093.7
9 297.1
9 561.5
9 918.6
10 447.0
11 290.6
12 677.7

Following is the plot of H vs x1, H1 and H 2 are evaluated at x1 = 0.4 and x1 = 0.7.

168 Solutions ManualStoichiometry


10 500
H2 at x1 = 0.7
10 000
9500

Enthalpy (H)
kJ/kg solution

H2 at x1 = 0.4

H1 at x1 = 0.4

9000

H1 at x1 = 0.7

8500
8000
7500

0.2

0.4

x1

0.6

0.8

Enthalpy of cyclohexane (x1)-Cyclohexanone (x2) Solutions at 50C (325.15 K)

EXERCISE 5.62
t0/T0 = 0C/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
4
3
H = 490.664 x1 + 645.318 x1 3309.315 x12 + 2628.911 x1 + 3770.75
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
(endothermic)

H1

H2

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0

282.97
502.94
662.01
761.11
800.01
777.24
690.24
535.19
307.67

3770.75
4001.14
4168.54
4275.03
4321.56
4307.88
4232.54
4092.96
3885.34
3604.74
3245.0

5787.15
5262.08
4810.23
4420.92
4087.00
3804.84
3574.35
3398.97
3285.69
3245.0

3770.75
3802.70
3895.15
4045.66
4255.32
4528.75
4874.10
5303.05
5830.83
6476.20

All enthalpy values are in kJ/kmol.

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.
H2 at x1 = 0.7

5400
5000
4600

Enthalpy (H)
kJ/kg solution

H2 at x1 = 0.4
4200

H1 at x1 = 0.4

3800

H1 at x1 = 0.7

3400
3000

0.2

0.4

x1

0.6

0.8

Enthalpy of Benzene(1)-Cyclohexane(2) Solutions at 25C (298.15 K)

EXERCISE 5.63

t0/T0 = 0C/273.15 K
Enthalpy of 1,2-dichloroethane(1) at 40C (313.15 K) over 0C (273.15 K)
H1 = 123.9 (313.15 273.15) = 4956 kJ/kmol
Enthalpy of dimethyl carbonate(2) at 40C (313.15 K) over 0C (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
(exothermic)

H1

H2

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0

0
56.25
112.95
160.87
193.30
205.99
197.21
167.71
120.76
62.11
0

6933.2
6679.24
6424.82
6179.18
5949.04
5738.69
5549.69
5381.47
5230.70
5091.64
4956.03

4375.81
4413.95
4507.54
4624.41
4739.87
4836.71
4905.23
4943.20
4955.88
4956.03

6933.2
6935.17
6927.54
6895.59
6832.12
6737.39
6619.16
6492.69
6380.70
6313.41

All enthalpy values are in kJ/kmol.

170 Solutions ManualStoichiometry

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


0.6.

Enthalpy (H)
kJ/kg solution

7000
H2 at x1 = 0.3
H2 at x1 = 0.6 6500
6000
5500
5000
4500

0.2

0.4

x1

0.6

0.8

H1 at x1 = 0.3
H1 at x1 = 0.6

Enthalpy of 1,2-Dichlorothane(1) - Dimethyl Carbonate(2) solution at 40C


(313.15 K)

EXERCISE 5.64
Basis: 100 Nm3/h vent stream
Molar flow rate =

100
= 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
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 0.0223 kmol/h
Aqueous solution rate =

5.357
= 107.14 kg/h
0.05

Water in solution = 107.14 5.357


= 101.783 kg/h
5.650 kmol/h
Water produced = 0.0558 kmol/h
2 NaOH(sol) + Br2(g) = NaOBr(sol) + NaBr(sol) + H2O(l)
DHf
470.11
30.91
334.3
361.665
285.83
DHr = 334.3 361.665 285.83 + 30.91]
DHr = 72.485 kJ/mol Br2

Energy Balances 171

Heat generated = 72.485 1000 0.0558


= 4044.66 kJ/h
1.1235 kW
Component

kmol/h

mole %

kg/h

mass %

NaOBr
NaBr
NaOH
H2O
Total

0.0558
0.0558
0.0223
5.7058
5.8397

0.96
0.96
0.38
97.70
100.00

6.634
5.741
0.893
102.792
116.060

5.72
4.95
0.77
88.56
100.00

Solid concentration of solution = 100 88.56


= 11.44% by mass

Ans.(a)

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 175C (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
9275.6 kg/h
Composition of solution purged from system
Component

kg/h

mass %

kmol/h

mole %

Na2SO3
Na2CO3
H2O
Total

544.67
305.48
9 776.73
10 626.88

5.13
2.87
92.00
100.00

4.3213
2.8822
542.6904
549.8939

0.79
0.52
98.69
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 32C (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,

172 Solutions ManualStoichiometry

0.038 86
H2O
=
= 13.73 kmol/kmol
0.002 83
NaOH
In the circulating solution,
H2O
98.69
Na 2SO3 = 0.79 = 124.92 say 125
H2O
98.69
=
= 189.79 say 190
Na 2 CO3
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)
DHf
1157.38
296.83
1115.87
393.51
DHr = 1115.87 393.51 [1157.38 296.83]
= 55.17 kJ/mol SO2 reacted
SO2 reacted = 276.66 kg/h
4.3185 kmol/h
Heat generated, f1 = 55.17 1000 4.3185
= 238 252 kJ/h
66.181 kW
Enthalpy of water at 32C (305.15 K), same as that of make-up solution
= 134.0 kJ/kg
Enthalpy of water vapour at 50C (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
6333.689 kW
Mean heat capacity of flue gas,
Cmp = 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
7634.717 kW
Reference temperature,
t0/T0 = 32C/305.15 K

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 50C (323.15 K).
Enthalpy of purge solution at 50C (323.15 K) over 32C (305.15 K),
f4 = 10 626.88 4 (323.15 305.15)
= 765 135 kJ/h
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 8C (8 K).
Required cooling water flow =

1154.671 3600
4 8

= 129 900 kg/h


129.9 m3/h

Ans.

EXERCISE 5.66
Refer solution of Exercise 5.44. Final vent gases have following composition
Component

kmol/h

mole %

Cl2
HCl
Acetic acid (AA)
Total

2.1164
10.5820
0.5646
13.2630

15.96
79.79
4.25
100.00

kg/h

mass %

150.065
385.829
33.905
569.799

26.34
67.71
5.95
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.
DHr1 = (347.3) + (407.27) + (285.83) 2[470.11]
= 100.18 kJ/mol Cl2

174 Solutions ManualStoichiometry

DHr2 = 407.27 285.83 [470.11 92.31]


= 130.68 kJ/mol HCl
DHr3 = 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)
460.155 kW
Total NaOH consumed for all three reactions
= 2 2.1164 + 10.582 + 0.5646
= 15.3794 kmol/h
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
Solution introduced at top =

676.69
0.1

= 6766.9 kg/h
Water in the solution = 6766.9 676.69
= 6090.2 kg/h
NaOCl produced = 2.1164 kmol/h
157.55 kg/h
Water produced by reactions (2) and (3)
= 10.582 + 0.5646 + 2.1164
= 13.263 kmol/h
238.937 kg/h
NaCl produced = 10.582 + 2.1164 kmol/h = 12.6984 kmol/h
724.13 kg/h
CH3COONa produced = 0.5646 kmol/h
= 46.32 kg/h

Energy Balances 175

Component

kg/h

mass %

NaOCl
NaCl
CH3COONa
H2O
Total

157.55
742.13
46.32
6329.14
7275.14

2.16
10.20
0.64
87.00
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 32C (305.15 K).
Temperature of outgoing solution = 32.5 + 65.06
= 97.56C say 97.6C or 370.75 K Ans.

EXERCISE 5.67

Basis: 100 kg 19.1% H2SO4


SO3 in the acid = 15.6 kg 0.195 kmol (ref. Table 5.64)
H2O in the acid = 100 15.6 = 84.4 kg
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 0.718 kmol
SO3 in resultant acid = 15.6 + 57.46
= 73.06 kg
0.913 kmol
H2O from oleum = 66.05 57.46 = 8.59 kg
0.477 kmol
H2O in resultant acid = 166.05 73.06 = 92.99 kg
5.166 kmol

176 Solutions ManualStoichiometry

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 (18C) = 2.404 kJ/(kg K)
heat capacity of 53.8% acid at 373 K (100C) = 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 (132C). 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)
1.115 kmol
Water content of oleum = 100 89.2 = 10.8 kg 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.
Overall material balance:
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

Equating Eq. (2) and Eq. (3),

ax
= dM

1 + (a - 1) x

ax
M x (M dM) (x dx) = dM

1 + (a - 1) x
Neglecting second order term dM dx,

ax
x dM + M dx= dM

1 + (a - 1) x
Dividing Eq. (5) by dM and substituting value of dM from Eq. (1),
M lv d x

ax
x
=

1 + (a - 1) x
Q dq
Eq. (1) can be rewritten as M = M0 (Q q/lv)
Substituting this value of M in Eq. (6),

Q q l d x
ax
x - M0
=

l v Q dq

1 + (a - 1) x

(3)

(4)

(5)

(6)
(7)
(8)

Qq d x
M 0 lv
ax
=
x
1
M
l
Q
d
1
(
q
+
a - 1) x
0 v

(a - 1)(1 - x) x
1 + (a - 1) x

(9)

Let K = Q/(M0lv) a constant


dx
(a - 1)(1 - x) x
1
[1 Kq]
=
K
dq
1 + (a - 1) x

(10)

dq
[1 + (a - 1) x] d x
=
(1
Kq )
(a - 1)(1 - x) x K

(11)

dq
[(1 - x) + x + (a - 1) x]d x
=
(1
Kq)
(a - 1)(1 - x) x K

(12)

dq
dx
dx
dx
+
+
=
(1 - Kq )
K (a - 1) x
K (a - 1)(1 - x)
K (1 - x)

(13)

dx a dx
dq
1
+
=
(1 - Kq )
K (a - 1) x (1 - x)

(14)

178 Solutions ManualStoichiometry

Integrating Eq. (14),


1
K (a - 1)

x dx
q
x dx
dq
x + a (1 - x ) = (1 - K q )
x
0
x0

(15)

x
ln(1 - Kq )
(1 - x)
1
a ln
ln
=
K
(1 - x0 )
K (a - 1) x0

(16)

x (1 - x0 )a
1
ln
= ln (1 K q)
(a - 1)
x0 (1 - x)a

(17)

or (1 Kq)(a 1) =

x (1 - x0 )a
x0 (1 - x)a

for Kq < 1

Q.E.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
Constant K =

Q
0.5 3600
=
= 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
x0 (1 - x)a

Therefore (1 Kq)(a 1)
(1 Kq)
Kq
q
Overall material balance:

0.3(1 - 0.5) 2.16


= 0.290 08
0.5(1 - 0.3) 2.16

= 0.290 08
[Ref. Eq. (17) of Exc. 5.70]
= 0.290 08(1/1.16) = 0.3441
= 1 0.3441 = 0.6559
= 0.6559/1.1506 = 0.57 h
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)
0.5
(1 - x) 2.16

= 0.447 57

x
(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)
DHf , kJ/mol
DHr1 = 6(241.82) + 4(+90.25) [4(46.11)]
= 905.48 kJ/4 mol NH3
226.37 kJ/mol NH3

180 Solutions ManualStoichiometry

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
8705.813 kW
Reaction (2):
4 NH3 + 3 O2 =
2 N2
+
6 H2O
4 ( 46.11)
3 (0)
2 (0)
6( 241.82)
DHf, kJ/mol
DHr2 = 6 ( 241.82) 4 ( 46.11)
= 1266.48 kJ/4 mol NH3
316.62 kJ/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
NH3
O2
N2
H2O
Total

ni

Heat capacity equation constants


.

kmol/h

ai n i

bi n i 103

145.71
275.40
1 036.01
33.805
1 490.925

3 737.5
5 658.1
30 656.5
1 098.4
41 150.5

4 878.5
22 058.1
5326.1
2.7
21 613.2

ci n i 106

di n i 109

51.3
17 195.1
13 657.6
446.6
3 039.6

449.3
4 674.1
5 146.9
153.7
9 218.0

Cmp = 37 413.0 + 16 734.7 103 T 3090.9 106 T2 + 9667.3 109 T 3


air
Cmp = 3737.5 + 4878.5 103 T + 51.3 106 T2 449.3 109 T 3
am

Air is preheated to 260C (533.15 K) and introduced to the reactor.


Reference temperature, t0/T0 = 25C/298.15 K
Enthalpy of air at 533.15 K over 298.15 K,
f3 =

553.15

Cmp dT

298.15

air

= 11 416 807.1 kJ/h


= 3171.335 kW

Energy Balances 181

Product stream from reactor


.

Component

ni

Heat capacity equation constants


.

kmol/h
NO
O2
N2
H2O
Total

n i ai

138.450
96.895
1039.645
252.375
1 527.365

4 082.4
1 990.7
30 764.0
8 200.2
45 037.3

n i bi 103

n i ci 106

n i di 109

284.2
7 760.8
5 344.8
20.1
2 151.9

1 569.7
6 049.8
13 705.5
3 334.1
12 559.5

667.3
1 644.5
5 165.0
1 147.7
5 335.5

Product stream temperature is to be limited to 910C (1183.15 K).


Enthalpy of reactor exit gas stream at 1183.15 K over 298.15 K.

f4 =

1183.15

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
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
=
Solving by mathcad,

Comp

298.15

am

dT

T = 378.45 K or t = 105.3C

Ans.

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
Molar feed rate, F =

1200 2800
+
46
18

= 26.087 + 155.556
= 181.643 kmol/h
Ethanol with NBP = 78.25 C (351.4 K) is a more volatile component.
Ethanol content in feed, zF =

26.087
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 ethanolwater binary is prepared as under.
95

P = 1.01 325 bar a

373
368

90

363

85

358

80

353

Temperature, K

Temperature, C

100

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
49000
48900
48800
48700

Enthalpy of Liquid, kJ/kmol Mixture

48600
10200

48500

9800

48400

9400

48300

9000

48200

8600

48100

8200

48000

Enthalpy of Vapour, kJ/mol Mixture

P = 1.01 325 bar a

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

184 Solutions ManualStoichiometry

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 1060.01 kW
Enthalpy of feed,
fF = 181.643 69 15
= 1256 061 kJ/h
348.906 kW
Ethalpy of bottom product,
fB = 149.763 7550
= 1130 711 kJ/h
314.086 kW
Enthalpy of distillate product,
fD = 31.88 9000
= 286 920 k/h
79.7 kW
Heat duty of reboiler, fRB = fC + fB + fD fF
= 286 920 + 1130 711 + 3816 036 1256 061
= 3977 606 kJ/h
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.
Overall material balance:
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
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

Stoichiometry and Unit Operations 185

Heat (latent heat only) duty of the condenser,


f2 = 8617 (1572.6 372.2)
= 10 343 847 kJ/h
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 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:
Component
Toluene
MCH
Phenol
Total

kg/h

mass %

4750 + 297 = 5 047


48
32 703

13.35
0.13
86.52

37 798

100.00

186 Solutions ManualStoichiometry

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 %

46
78
18

22.8
53.0
23.3

1048.8
4204.2
419.4

18.48
74.12
7.40

100.0

5672.4

100.00

C2H5OH
C6H6
H2O
Total

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
Overhead vapour =

0.04(100 + V3 )
= 54.054 + 0.540 54 V3
0.074

Material balance across C 2:


Entire benzene of D1 comes out in V2.
Benzene balance:

Ethanol balance:
Ethanol in

0.751 V2 = 0.11 D1
D1 = 6.827 V2
W2 = 0.53 D1 0.125 V2

Stoichiometry and Unit Operations 187

= 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
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
Solving Eq. (1) and Eq. (2),
V 2 = 1.887 kg and V3 = 6.8669 kg
Component

V3

W3

(1)

(2)

W2

kg

mass %

kg

mass %

kg

mass %

C2H5OH
H2O

6.5922
0.2747

96.00
4.00

0
4.000

0
100.00

6.5922
4.2747

60.66
39.34

Total

6.8669

100.00

4.0000

100.00

10.8669

100.00

Component

V2

D1

kg

mass %

0.2359
1.4171

12.50
75.10

H2O

0.2340

12.40

Total

1.8870

100.00

C2H5OH
C6H6

kg

V1
mass %

kg

mass %

6.8281
1.4171

53.54
11.11

10.6751
42.8160

18.48
74.12

4.5087

35.35

12.7539

100.00

4.2747
57.7658

Reflux R = V1 + V2 D1
= 57.7658 + 1.887 12.7539
= 46.8989 kg/100 kg fresh feed

7.40
100.00

188 Solutions ManualStoichiometry

Composition of Reflux
Component

kg

mass %

C2H5OH
C6H6
H2O

4.0829
42.8160
0

8.71
91.29
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
or

xR =

( R + P) xE - Pxp
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
xD =

FP xE - P xP
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
xE =

FP xE - P xP
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,

Stoichiometry and Unit Operations 189

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.
Mole fraction of ACN in feed =

0.0122
(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
= 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.

Quantity of bottom product from CII =

30.5 + 0.6 R
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

Quantity of D1 =

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.
Quantity of R =

(13.393 + 0.2696 R )
0.4

= 33.4825 + 0.674 R
R = 102.7 kmol/100 kmol fresh feed

Ans.

190 Solutions ManualStoichiometry

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
HCl content of outgoing dry gas mixture =

0.053 100
(2.457 + 0.053)

= 2.11%
Vapour pressure of H2O at 308 K (35 C) = 5.6216 kPa

Ans. (b)
(Table 6.13)

kmol
5.6216
= 0.0596
kmol dry gas
100 - 5.6216
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)
Water content of gas mixture =

D Hf of 3.9% HCl solution = 165.36 kJ/mol HCl


(Ref. Table 5.79)
D Hf 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
25.770 kW
Heat balance:
Component

Inlet kmol

Cmp equation constants


ni ai

ni bi 10

ni ci 106

ni di 109

N2
HCl

2.457
1.323

72.705
40.099

12.631
10.067

32.39
17.544

12.206
5.733

Total

3.780

112.804

22.698

49.934

17.939

Stoichiometry and Unit Operations 191

HCl absorbed = 1.27 kmol/h = 46.355 kg/h


Final solution flow =

46.355
= 1188.59 kg/h
0.039

Assume water input at 25C (298.15 K).


Component Outlet kmol
ni

C mp
equation constants
ni ai

ni bi 103

ni ci 106

ni di 109

N2
H2O
HCl

2.457
0.15
0.053

72.705
4.874
1.606

12.631
0.012
0.403

32.39
1.982
0.703

12.206
0.682
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 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 0.108 kW
Heat content of final solution, f4
= 2200.6 + 92 774 390.5
= 94584.1 kJ/h 26.273 kW
94 584.1
1188.59 4.19
= 19 K over 298.15 K

Rise in temperature of final solution =

Final temperature = 298.15 + 19


= 317.15 K or 44C

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

192 Solutions ManualStoichiometry

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
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.

AR2
Quantity of mixture (represented by) S
5.6 units
=
=
7 units
Quantity of mixture (represented by) A
SR2
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

OD

AL
CU
RV R1
ILLA
E
TION
BOU
NDA
0.5
RY

TIF

0.5

C9

R2

6.0

LIN

1.0

LIN

Ac20

s%

0.5

1.0

0.1
BINODAL CURVE

Mass % HOAc
Fig. E6.3 Solutionof Exercise 6.8

A
S

6.0

HOAc

Stoichiometry and Unit Operations 193

0.

6.0

as

0.3

0.3
0.7

TIF

s%

Ac

2O

DIST

as
M

194 Solutions ManualStoichiometry

AD is a tieline, drawn in proportion to other sideby tielines, which intersects top


binodal curve at R1

AD1
Quantity of mixture (represented by) D
9.7 units
=
=
2.7 units
Quantity of mixture (represented by) A
R1 D
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
AcOH
0.372
0.47

R1
D

Composition, mass fraction


Ac2O
C9
0.072
0.559
0.108
0.422

Join ND. Point M lies on ND.


Quantity of N
76 units
DM
=
=
107.8 units
Quantity of D
NM

DM
76
DM
76
=
=
=
76 + 107.8 1838
.
DM + TN
ND
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 C). However, the actual
conditions are 1.6 MPa g and 473.15 K(200 C).
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 C).
CO2 in inlet gas mixture = 8333.3 0.165 = 1375 m3/h
(H2 + inerts) = 8333.3 1375 = 6958.3 m3/h

Stoichiometry and Unit Operations 195

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 C), 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 C)
Actual flow rate at 4 bar g and 523.15 K (250 C)
= 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 C).
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
535.1/24.465 21.87 kmol/h
Ans. (b)
Change in CO2 content of DAPOL solution
= 5800 2200 = 3600 mL/L
Flow rate of aqueous DAPOL solution
=

5351
. 106
60 3600

= 2477.3 L/min
41.3 L/s

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

Ans. (c)

196 Solutions ManualStoichiometry

Gas enters the absorber at 101.3 kPa a and 333.15 K (60 C).
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 C) = 9.582 kPa (Ref. Table 6.13)
Moisture content of outgoing gas mixture = 9.582/(90 9.582)
= 0.119 kmol/kmol dry gas
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
94.27 kg/h
Inlet gas mixture:
Component

ni
kmol

Cmp equation constants

N2
H2
CO
CO2
CH4
H2O

8.50
25.51
0.19
3.98
0.12
9.37

ni ai
251.52
729.85
5.52
85.03
2.31
304.45

Total

47.67

1378.68

ni bi 103
43.70
26.00
0.54
255.85
4.25
0.75
244.61

ni ci 106
112.05
3.77
2.21
163.38
1.44
123.78
72.33

ni bi 109
42.23
19.62
0.89
39.00
1.36
42.61
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 14.216 kW
Outlet gas mixture:
Component kmol
ni
N2

8.50

Cmp
equation constants
ni ai
251.52

ni bi 103
43.70

ni ci 106
112.05

ni bi 109
42.23

(contd.)

Stoichiometry and Unit Operations 197

(contd.)
H2
CO
CO2
CH4
H2O

25.51
0.19
1.61
0.12
4.14

729.85
5.52
34.40
2.31
139.07

26.00
0.54
103.50
6.25
0.34

3.77
2.21
66.09
1.44
56.54

19.62
0.89
15.78
1.36
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
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
62.218 kW
Enthalpy of feed solution = 2250 4.19 (318.15 298.15)
= 188 550 kJ/h
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 84.75C
Ans.

EXERCISE 6.13
Basis: 25 000 m3/h feed gas

198 Solutions ManualStoichiometry

Molar
Mole feed rate = 25 000/22.414
= 1115.4 kmol/h
Gas

Molar mass

kmol/h

kg/h

H2
HCl
N2
CCl4

2
36.5
28
154

921.3
12.3
129.4
52.4

1 842.6
449.0
3 623.2
8 069.6

Total

1115.4

13 984.4

13 984.4
1115.4
= 12.54
HCl absorbed = 12.3 0.999 = 12.29 kmol/h
Reaction: HCl (g) + NaOH(ai) = NaCl(ai) + H2O(l)
DHf
92.31
470.11
407.27
285.83
DHR = 407.27 285.83 ( 92.31 470.11)
= 130.68 kJ/mol HCl
NaOH required = 12.29 kmol/h
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 (38C) at the top.
Total pressure = 338 kPa a
Vapour pressure of H2O at 311.15 K (38C), pw = 6.624 kPa
(Table 6.13)
Water content of outgoing gas mixture = 6.624/(439.325 6.624)
= 0.0153 kmol/kmol dry gas
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
303.8 kg/h
Composition of solution, leaving the absorber:

Average molar mass of gas mixture =

Component
NaCl
NaOH
H2O
Total

kg/h

mass %

12.29 58.5 = 719.0


3930 0.15 491.6 =
97.9
12.29 18 + 3930 0.85 303.8 = 3257.9

17.65
2.40
79.95

4074.8

100.00

Ans. (a)

Stoichiometry and Unit Operations 199

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 (38C).
Locate another point, representing 0% NaOH at 327 K (30C). Join the points.
The line interesects 15% axis at 327 K (54C).
Enthalpy of 15% solution at 327 K (54C) = 187.5 kJ/kg soln.
Enthalpy of 15% solution at 311 K (38C) = 118.8 kcal/kg soln.
Total heat to be removed = (187.5 118.8)3930
= 269 991 kJ/h 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


kmol/h

mole %

Dry outlet gas


kmol/h

mole %

NO
O2
N2

138.45
96.9
1039.65

10.86
7.60
81.54

2.80
71.47
1326.73

0.20
5.10
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 40C = 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
693.1 kg/h
Pressure of outgoing gas mixture = 10 kPa g
= 111.325 kPa a
Vapour pressure of H2O at 323 K (50C) = 12.335 kPa
Water content =

12.335
= 0.1246 kmol/kmol dry gas
- 12.335)
(111325
.

Water, accompanying outgoing gas = 0.1246 1401


= 174.56 kmol/h
3142.2 kg/h

200 Solutions ManualStoichiometry

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
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 (40C)
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
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)
DHf

2 90.309

286.021

2 ( 174.213)

DHr = 2 (174.213) (2 90.309 286.021)


= 243.023 kJ/2 mol NO
Heat of reaction at 298.15 K (25 C) = 243.023 135.65 1000/2
= 16 483 035 kJ/h (exothermic)
4578.62 kW
Air introduced at 311 K (40 C) = 363.39 kmol/h (secondary)
O2 feed = 76.31 kmol/h
N2 feed = 287.08 kmol/h
Base temperature T0 = 298.15 K (25 C)
Enthalpy of water vapour at 313 K (40 C) over 298.15 K (25 C)
= 2574.4 104.77 = 2469.63 kJ/kg
Enthalpy of water vapour at 323 K (50C) over 298.15 K (25C)
= 2592.2 104.77 = 2487.43 kJ/kg

Stoichiometry and Unit Operations 201

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 (40C)
Component

C mp
equation constants

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
155.142 kW
Enthalpy of moist air at 313.15 K over 298.15 K
=

313.15

o
Cmpair dT

298.15

(use data from Exercise 5.72

= 186 690 kJ/h

(by Mathcad)

51.858 kW
Absorber outlet gas enthalpy:
Temperature of outlet gas = 323.15 K (50C)
C mp
equation constants
ni ai

ni bi 103

ni ci 106

NO
O2
N2

ni
kmol
2.80
71.47
1326.73

82.6
1 860.1
39 259.1

5.7
840.1
6820.7

31.7
167.4
17 490.2

13.5
40.2
6591.2

Total

1400.00

41 201.8

5986.3

17 354.5

6644.9

Component

ni di 109

Enthalpy of outgoing gas mixture, f2 = 41 201.8 (323.15 298.15)


5586.3 103 (323.152 298.152)/2

202 Solutions ManualStoichiometry

+ 17 354.5 106 (323.153 298.153)/3


6644.9 109 (323.154 298.154)/4
= 1020 458 kJ/h 283.461 kW
Heat of dilution : Ref. Table 6.25
DHf of 58% HNO3 liquid = 197.00 kJ/mol HNO3 (by interpolation)
DHf 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 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 162.078 kW
Heat evolved at 313.15 K (40C) (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 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 (25C)
+ Heat of dilution at 313 K (40C)
= 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
3809.029 3600
Cooling water circulation rate =
8 4.1868 1000

= 409.6 m3/h

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

Ans.

Stoichiometry and Unit Operations 203

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
425

FG 0.4 IJ + 665 0.015 = 583 y


H 0.4 + 0.025 K

+ 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.

204 Solutions ManualStoichiometry

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)

Stoichiometry and Unit Operations 205

= 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 6.59 kW
Mechanical energy = 17 kW
Total heat gained by water = 1.92 3600 4.1868 5.8
= 167 847 kJ/h
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%

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

Ans.

206 Solutions ManualStoichiometry

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%
Biuret content of urea crystals =

0.07 100
(64.06 + 0.07)

= 0.11%

Ans.

EXERCISE 6.21
Basis: 1000 kg mixture
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

Stoichiometry and Unit Operations 207

=
NaCl remaining undissolved =
=
NaCl in saturated solution at 373 K =
=
NaCl crystallized out =
Total NaCl separated =
Additional salt which can be treated =
=

204.1 kg
40 306.1/60
204.1 kg
10.77 2666.7/100
287.2 kg
380.3 287.2 = 93.1 kg
204.1 + 93.1 = 297.2 kg
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
Isoconcs of nitrogen
Phase boundaries

100%
H2O
5C
A

O
4N

40%N
100%
CO(Nh2)2

C
C

0
0

1
C

26.5C

0C

35%N

30%N

20C

C
20

H
2O

20%N
25%N

NH

10C
ICE (H2O)

C
1020C
C
30
NH4NO3

CO(Nh2)2

CO(Nh2)2

100%
B
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
100
BC
2.031 units
=
100
1.285 units
= 158.05 kg

Requirement of NH4NO3 =

208 Solutions ManualStoichiometry

Salt-out temperature is read as 17.9C (291.05 K).


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
Refer given below figure.

Ans.

Solubility isotherms
Isoconcs of nitrogen
Phase boundaries

100%
H2O
5C

35%N
40%N
100%
D
CO(Nh2)2

C
C

0
0

1
C

26.5C

0C

30%N

20C

C
20

25%N

H
2O

20%N

O3
4N
NH

10C
ICE (H2O)

C
10 0C
2 C
30
NH4NO3

CO(Nh2)2

CO(Nh2)2

100%
NH4NO3

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
100
DF
1.578 units
= 1.574 units 100
= 100.25 kg
Salt-out temperature is read as 24.4C (297.55 K)
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

Requirement of urea =

Ans.

Stoichiometry and Unit Operations 209

(c) Let mc kg aqueous ammonium nitrate solution of 50% strength is required


to be mixed with 100 kg of 70% urea solution.
Refer given below figure.
Solubility isotherms
Isoconcs of nitrogen
Phase boundaries

100%
H 2O
5C

C
0

26.5C

35%N

40%N
100%
CO(Nh2)2

0C

30%N

20C

25%N

C
20

H
2O

20%N

O3
4N
NH

10C
ICE (H2O)

C
1020C
C
30
NH4NO3

CO(Nh2)2

CO(Nh2)2

100%
NH4NO3

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.
NH4NO3 required =

HI
100
GI

1.104 units
= 1.155 units 100

mc = 95.58 kg
Salt-out temperature is read as 8.3C (264.85 k)
Algebraic method:
Nitrogen balance:
100 0.7 0.4596 + mc 0.5 0.35= (100 + mc) 0.25
mc = 95.6 kg

Ans.

EXERCISE 6.23
In example 5.48, solution contains 42.02 kg NH4NO3, 37.63 kg urea and 20.35
kg H2O.

210 Solutions ManualStoichiometry

Point representing this concentration on Fig. 6.32 reads salt out temperature to
be -7.9C (265.25 K)
Ans(a)
When the above solution is cooled to 20C, it will cool on the phase boundary
line between NH4NO3 and urea. At 20C, 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
= 61.67 kg
0.33

Final solution =
NH4NO3 in final solution =
Urea in final solution =
Water in final solution =
NH4NO3 crystallized out =
=
Urea crystallized out =
=
Total crystallized mass =
NH4NO3 in the mass =
=
Urea in the mass =

61.67 0.37 = 22.82 kg


61.67 0.3 = 18.50 kg
61.67 22.82 18.5 = 20.35 kg
42.02 22.82
19.2 kg
37.63 18.50
19.13 kg
19.2 + 19.13 = 38.33 kg
(19.2 100)/38.33
50.09%
100 50.09 = 49.91 %
Ans.

EXERCISE 6.24

(a)

Moisture content = 5 ppm (v/v)


= 5 moles/106 moles
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 = 65.5C (207.65 K)
(b)

Total pressure = 0.8 MPa = 0.8 106 Pa


p
5
= 6
6
0.8 10
10

Or p = 4 Pa

From Table 6.12, DP = 48.05C (225.1 K)

Ans

Stoichiometry and Unit Operations 211

EXERCISE 6.25
Purge gas rate = 8000 Nm3/h
= 356.9198 kmol/h
Vapour pressure of ice at 40C,
p w = 12.841 Pa
Total pressure = 45 bar a
= 45 105 Pa
Basis:

Moisture in purge gas =

(dry)
(Ref. Table 6.12)

12.841
(45 105 - 12.841)

= 2.8536 106

kmol
kmol dry gas

Moisture, condensed in cold box in 300 days


= 356.9198 24 300 2.8536 106
= 7.3332 kmol
132.1 kg
Ans.

EXERCISE 6.26
Vapour pressure of water of 308.15 K (35C) = 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 (31C)= 4.4911 kPa
(Table 6.13)
Hence DP of air is 304.15 K (31 C).
Ans. (b)
Absolute humidity H =

18
4.4973

29
(100 4.4973)

= 0.0292 kg/kg dry air


Saturation humidity Hs =

Ans. (a)

18
5.6216

29
(100 5.6216)

= 0.036 97 kg/kg dry air


Saturation = (0.0292 100)/0.036 97 = 79.0%
Humid heat, CH = 1.006 + (1.84 0.0292)
= 1.06 kJ/(kg K)
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. (c)
Ans. (d)

Ans. (e)

212 Solutions ManualStoichiometry

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 (25.5C)
At 303 K DB and 50% RH, H2 = 13.2 g/kg dry air
and DP2 = 291.2 K (18.2C)
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
676.67 kW 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
225.32 kW
Latent of evaporation of water at 400 kPa a, lv = 2133 kJ/kg
Steam consumption = 811 168/2133 = 380.3 kg/h
(c) Desired NCL = 10 g moisture/kg dry air
At this humidity level let vapour pressure of water be pv.

(Table AIV.2)
Ans. (b)

Stoichiometry and Unit Operations 213

pv
0.622 =
(101.325 - pv )
pv =
From Table 6.13,
DP =
i2 at 14.02C =
Cooling load for NCL =

0.01

1.604 kPa
14.02C (287.17 K)
39 kJ/kg dry air
87.5 39 + (0.0207 0.01)
(307.15 287.17) 4.186 8
= 48.5 + 0.9
= 49.4 kJ/kg dry air
Total cooling load = 66 704.8 49.4
= 329 522 kJ/h
915.34 kW
260.45 TR
At H = 0.01 kg/kg dry air and RH = 50%, DB requirement can be read as 25.2C
(298.35 K) from Fig. 6.15.
CHs = 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
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
Absolute humidity, H =

7.375
18.015

(117.3 7.375)
44.01

= 0.0275 kg/kg dry CO2

Ans.

EXERCISE 6.29
Vapour pressure of water 291.15 K (18C) = 2.0624 kPa
Absolute humidity in chlorine gas =

2.0624
18.015

(101.325 2.0624) 70.906

= 0.005 279 kg/kg dry Cl2

214 Solutions ManualStoichiometry

On wet chlorine basis,


humidity =

18.015
2.0624

= 0.005 171 kg/kg wet Cl2


70.906
101.325

5171 ppm by mass

Ans.

EXERCISE 6.30
Basis: 4 kmol HCl gas
Based on Table 5.53, following data are tabulated.
Component
HCl
O2

Cl2
N2
H2O
Total

kmol

Molar mass

kg

0.8
0.55

36.5
32

29.2
17.6

1.6
5.079
(1.6)

71
28
18

113.6
142.21
(28.8)

302.61

(331.41)

8.029 (9.629)

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
=
8.029 0.8
Average of both molar mass =
=
Vapour pressure of water at 323 K (50C) =
Water vapours in the outgoing gas mixture

37.821
(37.69 + 37.821)/2
37.756
12.335 kPa
(Table 6.13)

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
3.284 kg/kmol HCl fed
HCl in aqueous acid = 13.134 8.8
= 4.334 kg

Stoichiometry and Unit Operations 215

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 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
3.39 kg/kmol HCl feed
close to previous value
HCl absorbed = 9.09 0.333/0.667 = 4.538 kg
0.124 kmol
Components ni kmol

Cmp equation constants


ni bi 103

ni ai

ni ci 106

ni di 109

HCl

0.68

20.610

5.174

9.017

2.947

O2
Cl2
H2O
N2

0.55
1.60
1.09
5.079

14.314
45.674
35.416
150.292

6.465
38.207
0.087
26.111

1.288
34.181
14.400
66.956

0.309
10.356
4.96
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,
DHf of 33% aqueous acid = 152.9 kJ/mol HCl
DHf 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)

216 Solutions ManualStoichiometry

Enthalpy of inlet gas at 599.5 K


= 91.520.2 kJ
Enthalpy to be removed in Trombone cooler

(Ref. Example 5.39)

= 91 520 + 21 660.6 + 7270.8 6877.9 886


= 112.688 kJ/4 kmol HCl fed
28 172 kJ/kmol HCl

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 80C (353.15 K).
Antoine equation for SO3:

892.175
log p = 4.205 15 T - 103.564
At T1 = 353.15 K,
log p1 = 4.205 15

892.175
(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 30C (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

Ans.

Stoichiometry and Unit Operations 217

= 8.6918 kmol/h
695.344 kg/h
Latent heat removal, f3 = 695.344 42.55
= 29 587 kJ/h
8.219 kW
Gas mixture ingoing to condenser
.
Component
ni
Heat capacity equation constants
kmol/h
ni ai
ni bi 103 ni ci 106 ni di 109
CO2
SO3

5.8330
9.1234

124.62
201.06

374.97
1109.62

239.45
838.14

57.16
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,


f1 =

353.15

298.15

(325.68 + 1484.59 103 T 1077.59 106 T2 + 279.49

109 T 3) dT
= 38 737 kJ/h
10.760 kW
Gas mixture outcoming from condenser
.
Component
ni
Heat capacity equation constants
kmol/h
ni ai
ni bi 103 ni ci 106 ni di 109
CO2
SO3

5.8330
0.4316

124.62
9.51

374.97
52.49

239.45
39.65

57.16
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,


f2 =

303.15

298.15

(134.13 + 427.46 10 3 T 279.10 10 6 T 2 + 67.68

109 T 3) dT
= 1196.4 kJ/h 0.332 kW
Heat load of condenser,
fc = 38 737 + 29 587 1196.4
= 67 127.6 kJ/h
18.647 kW

Ans.

218 Solutions ManualStoichiometry

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
log p = 4.022 91

1221.781
(313.15 45.739)

or pv = 0.2844 bar 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
28.44

1050.7
=
1130 28.44

= 27.127 kmol/h
CCl4 condensed = 52.4 27.127 = 25.273 kmol/h
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 (40C) = 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 (10C) = 6.06 kPa (Calculated)
Benzene content of outgoing gas mixture = 6.06/(101.325 6.06)
= 0.0636 kmol/kmol dry gas
Benzene unadsorbed = 0.0636 597.1 = 37.976 kmol
Benzene removal in adsorber = 182.9 37.976 = 144.924 kmol
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

Stoichiometry and Unit Operations 219

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 (60C), 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 (60C) = 52.187 kPa (calculated)
Let total pressure after compression be p kPa. After compression and cooling to
333 K (60C), benzene concentration should be 38.03 kmol/597.2 kmol dry N2.
52.187
37.976
=
597.1
p - 52.187

or p = 872.7 kPa a

Ans. (c)

EXERCISE 6.34
Basis: 1 kg bone dry soybean flakes
C6H14 removed = 0.61 0.025 = 0.585 kg/kg BD flakes
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)
293.15 (20)
343.15 (70)

0.1009 (10.09)
0.1616 (16.16)
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
116 326 kg

220 Solutions ManualStoichiometry

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 (70C),
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
=
101.325
p

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 (21C) = 2.485 kPa
(Ref. Table 6.13)
Moisture content of incoming air = 2.485/(114 2.485)
= 0.022 28 kmol/kmol dry air
0.0218 kmol/kmol wet air
Specific volume of air at 114 kPa and 373.15 K(100C),
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

Stoichiometry and Unit Operations 221

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 (34.85C)
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
0.7401 atm
0.75 bar
At t/T = 60C/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


Basis: Ejector pulling out 25 m /h at 310 Torr and 40C (313.15 K)
Specific volume of ideal gas at 310 Torr (0.4133 bar) and
3

313.15 K = 22.414

313.15 760

273.15 310

= 62.9974 m3/kmol
Gas mixture being ejected from the cooler (with cooling water) =

25
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

222 Solutions ManualStoichiometry

n-Hexane loss = 0.9015 0.3968


= 0.3577 kmol/h
30.7635 kg/h
Specific n-Hexane loss =

30.7635 24
200

= 3.692 kg/t soya flakes


5.723 L/t soya flakes
Ans.(a)
After incorporation of the chiller, temperature of gas mixture, leaving the chiller
is 10C (263.15 K).
Vapour pressure of n-hexane at 263.15 K = 0.0293 bar
0.0293
0.3968
0.4133
= 0.0281 kmol/h
2.419 kg/h
58.061 kg/d
0.2903 kg/t soya flakes
0.45 L/t soya flakes

n-Hexane loss =

Ans.(b)

Enthalpy balance:
(a) System with only cooler:
Gas mixture leaving cooler
.
Component
ni
Heat capacity equation constants
kmol/h
ni ai
ni bi 103 ni ci 106 ni di 109
O2
N2
n-C6H14

0.0082
0.0309
0.3577

0.2134
0.9144
1.5793

0.0964
0.1589
208.1540

0.0192
0.4074
111.5517

0.0046
0.1535
23.2216

Total

0.3968

0.4515

208.0915

111.1635

23.0625

t0/T0 = 25C/298.15 K
Enthalpy of gas mixture, leaving cooler, at 313.15 K,
f2 =

313.15

298.15

(0.4515 + 208.0915 103T 111.1635 106 T 2 + 23.0625

109T 3) dT
= 6.8 + 954.05 155.81 + 9.9
= 801.34 kJ/h 0.223 kW
n-Hexane in gas mixture entering condenser = (21.388 0.0391)
= 0.8363 kmol/h
Gas mixture entering condenser

Stoichiometry and Unit Operations 223

Component

.
ni

Heat capacity equation constants


ni bi 103

ni ci 106

ni di 109

kmol/h

ni ai

O2
N2
n-C6H14

0.0082
0.0309
0.8363

0.2134
0.9144
3.6924

0.0964
0.1589
487.0695

0.0192
0.4074
259.7882

0.0056
0.1535
52.6225

Total

0.8754

2.5646

487.0070

259.4000

52.4634

Eenthalpy of gas-mixture entering condenser at 333.15 K


f1 =

333.15

298.15

(2.5646 + 487.007 10 3 T 259.4 10 6 T 2 + 52.4634

109 T 3) dT
= 89.8 + 5380.3 905.5 + 57.9
= 4442.9 kJ/h
1.234 kW
n-Hexane condensed = 0.8363 0.3577
= 0.4786 kmol/h
Average temperature of condensation =
Latent heat of n-hexane at 323.15 K,

40 + 60
= 50C or 323.15 K
2
0.38

507.6 - 323.15
lv2 = 28.85

507.6 - 341.9
= 30.05 kJ/mol
Heat given up during condensation
f3 = 0.4786 30.050
= 14 381.9 kJ/h 3.995 kW
Heat duty of cooler = f1 + f3 f2
= 4442.3 + 14 381.9 801.3
= 18 022.9 kJ/h
5.006 kW
(b) System with cooler and chiller:
Gas mixture, leaving chiller
.
Component
ni
Heat capacity equation constants
kmol/h
ni ai
ni bi 103 ni ci 106 ni di 109
O2
N2
n-C6H14

0.0082
0.0309
0.0281

0.2134
0.9144
0.1241

0.0964
0.1589
16.3520

0.0192
0.4074
8.7632

0.0056
0.1535
1.8242

Total

0.0692

1.0039

16.2895

8.3750

1.6651

224 Solutions ManualStoichiometry

Enthalpy of gas mixture at 263.15 K over 298.15 K


f4 =

263.15

298.15

(1.0039 + 16.2895 103 T 8.3750 10 6 T2 + 1.665

109 T 3) dT
= 35.1 160.0 + 23.1 1.3
= 173.3 kJ/h 0.048 kW
40 - ( -10)
2
= 25C or 298.15 K

Average temperature of condensation =

0.38

507.6 - 298.15
lv = 28.85

3
507.6 - 341.9
= 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
3.158 kW
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)

Stoichiometry and Unit Operations 225

EXERCISE 6.38
Basis: 1000 kg/h dried product
X1 =

0.3
= 0.4286 kg moisture/kg dry solid
1 - 0.3

0.02
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
Reference temperature, t0/T0 = 0C/273.15 K
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 300C (573.15 K)
Hso = 2776.3 kJ/kg at 150C (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)
Solving Eq. (1) and Eq. (2),
.
msi = 8130.15 kg/h
.
mso = 8530.15 kg/h
Ans.

X2 =

226 Solutions ManualStoichiometry

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)
X1 =

0.75
= 3 kg moisture/kg dry solid at inlet
(1 - 0.75)

X2 =

0.03
= 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 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 0C (273 K),
is1 = Cs (ti 0) + X1 CL (ti 0)
= 1.4 (60 0) + 3 4.1868 (60 0)
= 837.6 kJ/kg dry solid
Enthalpy of solid at outlet above 0C (273 K)
is2 = Cs(t0 0) + X2CL(t0 0)
= 1.4 (70 0) + 0.030 93 (70 0)
= 100.165 kJ/kg dry solid
Enthalpy of at inlet of dryer above 0C (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 35C (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)
= 390.26 kJ/kg dry air
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

Stoichiometry and Unit Operations 227

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)
= 366.02 kJ/kg dry air
.
From Eq. (1), ma (0.107 87 0.036) = 0.2
.
ma = 2.7828 kg/s 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 = 54C 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
= 127.56 kJ/kg dry air
f = 2.7828 (390.26 - 127.56)
= 731.042 kW
731.357
Fuel oil consumption = 41 300 0.7

= 0.025 29 kg/s
91.03 kg/h

Ans.(c)

228 Solutions ManualStoichiometry

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.
Flow of 75% solution =

25 000
= 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 = 51.1C (324.25 K)
Boiling point of 75% solution = 51.1 + 81
= 132.1C 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 132.1C
(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 8.63 kg/s
Water evaporated
Steam consumed
16 666.67
= 31 083 = 0.5362 kg/kg
Note: High boiling point elevation results in lower economy.

Economy of evaporator =

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

Stoichiometry and Unit Operations 229

= 1272 436.4 kg/d


Evaporation = 4665 600 1272 436.4
= 3393 163.6 kg/d
141 381.8 kg/h
Steam economy = 141 381.8/28 500
= 4.961 kg evaporation/kg steam

Ans. (a)
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,
K (C)

saturation
pressure, kPa a

latent heat of
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 (121C)
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)

230 Solutions ManualStoichiometry

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
No.

temperature,
K(C)

saturation
pressure, kPa a

1st
2nd
3rd
4th

362 (89.0)
347.5 (74.5)
337.5 (64.5)
324.6 (51.6)

67.5
37.6
24.5
13.3

latent heat of
evaporation, kJ/kg
2287.4 (lv1)
2323.0 (lv2)
2347.6 (lv3)
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)

Stoichiometry and Unit Operations 231

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

232 Solutions ManualStoichiometry

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
in washed cake = 9.227/0.183
Salt
= 50.421
Liquor in washed liquor = 50.421 b

Ratio =

133.0 + 50.421 b = 133.61 +

F 133.61 I a
H 12.307 K

a + 4.644 b = 0.0562
Solving the equations, a = 0.249 kg/s
b = 0.066 kg/s

(2)

(12.307 0.249)
100
12.307
= 97.98% say 98%

Efficiency of 1st stage =

(0.249 0.183)
100
0.249
= 26.51%

Efficiency of 2nd stage =

(12.307 0.183)
100
12.307
= 98.51 %

Efficiency (overall) =

EXERCISE 6.45
Basis: 100 00 kg/h feed to the fractionator
Overall material balance:
F+S=W+Q+O

Ans.

Stoichiometry and Unit Operations 233

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


Components
CH2Cl2
CH3OH
H2O
Total

Upper layer (Q)

Lower layer (O)

Molar
mass

kg/h

kmol/h

mole %

kg/h

kmol/h

85
32
18

92.28
194.22
922.87

1.086
6.069
51.271

1.86
10.39
87.75

75.71
7.76

0.891
0.243

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
CH2Cl2
CH3OH
H2O
Total

kmol/h

mole %

1.086 + 29.78 0.186 + 0.891 = 2.531


6.069 + 29.78 0.1039 + 0.243 = 9.400
51.271 + 29.78 0.8775 = 77.403
89.34

kg/h

2.83
10.53
86.64

215.14
300.94
1393.25

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

234 Solutions ManualStoichiometry

Latent heat of evaporation:


Components

Antoine constants
(Ref. Table 5.4)

CH2Cl2
CH3OH
H2O
H2O

A
B
C
4.536 91 1327.016 20.474
5.204 09 1581.341 33.500
4.6543
1435.264 64.848
From Appendix (A IV.2)

Calculated
Saturation
Temperature

Latent heat of
evaporation (lv)

K (C)
kJ/kmol kJ/kg
238.75 (34.4C)
31.72 373.5
289.55 (16.4C)
38.62 1205.3
369.52 (96.37C)

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
1000.571 kW
Heat content of bottom product = W (373 318) 4.1868
= 259.58 W kJ/h 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)

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
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 9578 Btu/lb
Dlongs 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

236 Solutions ManualStoichiometry

= 5.88 + 48.96 + 1.11 = 55.96%


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%
Oxygen requirement:

Ans. (d)

Ans. (e)

Element

Mass,
kg

Molar
Mass

kmol

O2 requirement
kmol

Carbon
Hydrogen
Sulpher
Oxygen

59.04
3.36
0.38
17.86

12
2
32
32

4.92
1.68
0.012
0.558

4.92
0.84
0.012
() 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
SO2
O2
N2
H2O

4.92
0.012
3.128
31.445
1.911

11.88
0.03
7.55
75.92
4.62

12.48

7.92
79.60

Total

41.416 (wet)
39.505 (dry)

100.00

100.00

Ans.(g)

EXERCISE 7.3
Basis: 100 kg fuel oil
(Carbon + Hydrogen) content of fuel oil =
=
Carbon in the fuel oil =
=

100 1.37
98.63 kg
9.33 98.63/10.33
89.08 kg

Combustion

237

Hydrogen in fuel oil = 98.63 89.08


= 9.55 kg
4.775 kmol
H2O produced by combustion = 4.775 kmol 85.95 kg
[Ref. Eq. (7.1)]
NCV = GCV 2442.8 (H2O production)
= 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
(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.

Ans.

EXERCISE 7.5
NCV of CH4 = 802.62 kJ/mol at 298.15 K
(a) Specific energy consumption
= 22.0193 802.62 103/106
= 17.673 GJ/t NH3
(b) Specific energy consumption
= 25.9715 802.62 103/106
= 20.845 GJ/t NH3

(Ref. Appendix V.2)


Ans.
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

238 Solutions ManualStoichiometry

NCV of ethanol liquid =

1234.97 1000
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
CO2 generated by motor spirit alone

Ans.

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
44 050
= 70.65 kg/GJ

CO2 generated by motor spirit =

2.9919 106
42 325.7
= 70.68 kg/GJ
In both cases, CO2 generated are practically same on heat release basis.
CO2 generated by blend =

EXERCISE 7.8
Basis: 1 mol associated gas
Component mol
ni

Molar
mass
Mi

ni Mi
g

Calorific values
ni GCVi ni NCVi
kJ/mol
kJ
GCVi
NCVi
890.65
1560.69
2219.17
2868.20
2877.40
3528.83
3535.77

CH4
C2 H 6
C3 H 8
i-C4H10
n-C4H10
i-C5H12
n-C5H12
N2
CO2

0.744
0.084
0.074
0.017
0.020
0.005
0.004
0.043
0.009

16.0425
30.0690
44.0956
58.1222
58.1222
72.1488
72.1488
28.0135
44.0095

11.936
2.526
3.263
0.988
1.162
0.361
0.289
1.205
0.396

Total

1.000

22.126

802.62
1428.64
2043.11
2648.12
2657.32
3264.73
3271.67

GCV = 1096.05 1000/22.126 = 49 536.7 kJ/kg


NCV = 995.93 1000/22.126 = 45 011.8 kJ/kg

662.64
131.10
164.22
48.76
57.55
17.64
14.14

597.15
120.01
151.19
45.02
53.15
16.32
13.09

1096.05

995.93

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
H2
CH4
C2H6
C3H8
n-C4H10
n-C5H12
Total

mole ni

ni Mi, kg

ni GCVi, kJ

ni NCVi, kJ

74.0
13.5
7.4
3.6
1.2
0.3

148
216
222
158.4
69.6
21.6

21 151.4
12 023.8
11 549.1
7 989.0
3 452.9
1 060.7

17 894.7
10 835.4
10 571.9
7 355.2
3 188.8
981.5

100.0

835.6

57 226.9

50 827.5

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
H2
N2
Ar
CH4

mol,
ni
69.0
23.0
2.7
5.3

Total

100.0

Molar
mass, Mi
2
28
40
16

ni Mi, g
138
644
108
84.8

ni GCVi
kJ
19 722.3

4 720.4

ni NCVi
kJ
16 685.6

4 253.9

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
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)

Ans. (a)

240 Solutions ManualStoichiometry

Specific dry air requirement = 214.76 29/974.8


= 6.39 kg/kg purge gas
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

Ans.(b)

mole % (dry)

5.3
2.7
203.59 + 23.0 = 226.59
54.12 45.1= 9.02

CO2
Ar
N2
O2
Total

2.18
1.11
93.01
3.70

243.61 100.00

Ans.(c)

EXERCISE 7.11
Basis: 100 mol SNG
Component

ni
mol
96.59
1.29
0.22
2.00

CH4
H2
CO
CO2
Total

100.00

GCV =
NCV =
or GCV =
NCV =

Molar mass
Mi
16
2
28
44

ni Mi g
1545.44
2.58
6.16
88.00

ni GCVi ,
kJ
86 027.9
368.7
62.3

ni NCVi ,
kJ
77 525.1
311.9
62.3

1642.18

86 458.9

77 899.3

864.589 1000/16.4218 = 52 649 kJ/kg


778.993 1000/16.4218 = 47 437 kJ/kg
864.589/22.414 = 38 574 kJ/Nm3
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
CO2
CO
H2
CH4
(CH3)2O
O2
N2
H2O
Total

ni
kmol
1.17
0.13
0.26
0.08
0.13
11.28
76.67
10.28
100.00

(GCV)i
kJ/kmol

282 980
285 830
890 650
2107 400

ni GCVi
kJ

36 787.4
74 315.8
71 252.0
273 962.0

456 317.2

(NCV)i
kJ/kmol

282 980
241 820
802 620
1931 380

ni (NCV)i
kJ

36 787.4
62 873.2
64 209.6
251 079.4

414 949.6

Combustion

GCV = 456 317.2(22.414 100) = 203.6 kJ/Nm3


NCV = 414 949.6(22.414 100) = 185.1 kJ/Nm3

241

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
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
=
= 14.86 kg/kg Ans. (a)
Ratio
Coal
100
(100 + 4.304)63.805
Flue gas quantity =
127.2
= 52.32 kmol (wet)
For 100 kmol dry flue gas basis:
Component

Molar mass, Mi

ni Mi, kg

CO2
O2
N2
H2O

kmol, ni
10.6
8.7
80.7
4.304

44
32
28
18

466.4
278.4
2259.6
77.5

Total

104.304

3081.9

Average molar mass = 3081.9/104.304 = 29.547 (wet)


Ratio

flue gas 52.32 29.547


=
= 15.46 kg/kg fuel (wet basis)
coal
100

Ans.(b)

Hydrogen burnt = 4.304 2 63.805/127.2


= 4.32 kg/100 kg coal
Hydrogen content of coal = 4.32%

Ans. (c)

242 Solutions ManualStoichiometry

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
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

CO2
C2H4
C6H6
O2
CO
H2
CH4
N2

3.4
3.7
1.5
0.3
17.4
36.8
24.9
12.0

Theoretical O2
requirement, kmol

+ 11.10
+ 11.25
0.30
+ 8.70
+ 18.40
+ 49.80

Total

100.00

+ 98.95

Total carbon,
kmol
3.4
7.4
9.0

17.4

24.9

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

62.1

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
O2
N2

62.1
36.68
522.18

10.00
5.91
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
CO
O2
N2

12.4
3.1
5.4
79.1

12.4
3.1

12.4
1.55
5.40

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.

244 Solutions ManualStoichiometry

EXERCISE 7.17
Comparison of the fuels is to be made on NCV basis.
(A): Basis 100 kmol bottled LPG
Gas
C2 H 6
C3 H 2
i-C4H10
n-C4H10
Total

kmol
ni
1.2
25.2
23.9
49.7

Molar mass
Mi
30
44
58
58

100.0

Mass, ni Mi
kg
36.0
1108.8
1386.2
2882.6

LCVi,
kJ/kmol
1428 640
2043 110
2648 120
2657 320

5413.6

ni LCVi
kJ
1 714 368
51 486 372
63 290 068
132 068 800
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

CH4
C2 H 8
C3 H 8
n-C4H10
i-C4H10

0.866
0.086
0.039
0.007
0.002

Total

1.000

LCVi, kJ/kmol

ni LCVi, kJ

802
1428
2043
2657
2648

695
122
79
18
5

620
640
110
320
120

069
863
681
601
296

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

H2
CO
CO2
N2

3.2
26.2
13.0
57.6

Total

100.0

Molar mass
Mi
2
28
44
28

Mass
ni Mi kg
6.4
733.6
572.0
1612.8

O2 requirement,
kmol
1.6
13.1
Nil
Nil

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 (18C) WB
= 10.2 g/kg dry air
(Ref. Fig. 6.15)
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

CO2
O2
N2
H2O

26.2 + 13.0 = 39.2


2.94
66.36 + 57.6 = 123.96
3.2 + 1.378 = 4.578

Total

170 678 (wet)


166 100 (dry)

Actual analysis
(wet) mole %
22.97
1.72
72.63
2.68

Orsat analysis
mole %
23.60
1.77
74.63

100.00

100.00

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 (25C)
Enthalpy of fuel gas:
Component

ni, kmol

C
mp constants

H2
CO
CO2
N2

3.2
26.2
12.0
57.6

ai ni
91.554
760.526
256.386
1704.436

Total

100.0

2812.902

ni bi 103
32.621
73.792
771.409
296.122

ni ci 106
0.472
305.065
492.607
759.335

ni di 109
2.461
123.305
117.599
286.157

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

246 Solutions ManualStoichiometry

= 98 452 + 4794 + 200 319


= 103 127 kJ
Enthalpy of flue gases (total) = 8187 900 + 103 127 = 8291 027 kJ
Flue gas:
Heat capacity
constants

CO2

O2

N2

H2O

Total

ni, kmol

39.2

2.94

123.96

4.578

170.678

148.749
115.175
0.364
97.428
60.479
24.447
20.818
2.209

1771.791
2372.181
2431.683
1148.769
1239.730
347.821
242.652
37.857

(ni ai)1
(ni ai)2
(ni bi)1 103
(ni bi)2 103
(ni ci)1 106
(ni ci)2 106
(ni di)1 109
(ni di)2 109

837.528 76.516
1457.221 54.193
2519.937 34.560
910.894 63.849
1609.184 6.887
289.249 24.416
384.156 1.653
32.195
3.398

708.998
745.592
123.178
76.598
315.862
9.709
119.033
0.055

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 2509.56C

Ans.

Combustion

247

EXERCISE 7.19
Basis: 100 kg coal
Carbon content of coal = 46.21 kg
(refer Exercise 7.1)
3.85 katom or kmol
Sulphur content of coal = 0.7 kg
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
0.567 kmol
Absolute humidity of air at 307 K (34C) DB and 297 K(24C) WB
= 14.8 g/kg dry air
(Ref. Fig. 6.15)
0.0239 kmol/kmol dry air
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)

CO2
SO2
O2

3.85
0.022
4.05

7.85
0.04
8.27

Orsat analysis
8.80

9.20

248 Solutions ManualStoichiometry

N2
H2O

36.078
4.995

Total

48.995 (wet)
44.000 (dry)

73.65
10.19

82.00

100.00

100.00

Partial pressure of water vapours in flue gases, p


= 0.1019 100 = 10.19 kPa
From Table 6.13, dew point = 46.2C (319.35 K)
Temperature of water, entering the economiser is 311.15 K(38C) 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
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
12 436.11 kW
Heat gain:
Economiser: Heat gained by water, f4 = 12 150 (368 311)4.1868
= 2899 568 kJ/h
805.436 kW
Boiler pressure: At 0.9 MPa g, i.e. 10.013 bar a
Ts = 453 K (180C), 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
8026.8 kW

Superheater:
Enthalpy of steam at 0.9 MPa g and 473 K (180C) = 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 169.763 kW
Total moisture, evaporated in the boiler = 0.567 + 3.336
= 3.903 kmol/100 kg coal
0.7031 kg/kg coal
Total moisture evaporated = 0.7031 2500
= 1757.75 kg/h
lv at DP [46.2C)] = 2392.8 kJ/kg
Heat lost in evaporation, f8 = 1757.75 2392.8
= 4205 944 kJ/h 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
289.58 kW
Heat loss in flue gas:
Basis: 100 kg coal
Cmp equation constants
Component

ni kmol

ai ni

ni bi 103

ni ci 106

ni di 109

CO2
O2
N2
H2O

3.872
4.050
36.078
4.995

82.727
117.932
1067.581
162.333

248.908
4.031
185.477
0.398

158.948
49.647
475.613
66.027

37.945
162.503
179.236
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
[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

f7 =

250 Solutions ManualStoichiometry

= 6208 875 kJ/h


1724.688 kW
enthalpy, kW
Heat input, burning of fuel
Heat output:
1. Useful heat gain:
Economiser
Boiler
Superheater
2. Heat loss in flue gases
3. Heat loss due to evapn.
4. Heat loss in refuse
5. Unaccounted heat loss
Total

12 436.11

%
100.0

805.44
8 026.80
169.76
1 724.688
1 168.318
289.58
251.524

6.48
64.54
1.37
13.87
9.39
2.33
2.02

12 436.11

100.00

(805.44 + 8026.8 + 169.76)


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

Boiler efficiency =

EXERCISE 7.20
Basis: 100 kg fuel oil
Component
Carbon
Hydrogen
Sulphur
Oxygen
Nitrogen
Total

Mass, kg

kmol

O2 requirement, kmol

84.0
12.7
0.4
1.2
1.7

7.000
6.350
0.013
0.038
0.061

7.000
3.175
0.013
() 0.038

100.0

13.462

10.15

N2 entering with O2 = 79 10.15/21 = 38.183 kmol


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)
0.025 kmol/kmol dry air
Incoming moisture = 48.333 0.025 = 1.208 kmol

Combustion

251

Composition of flue gases with theoretical air:


Gas
CO2
SO2
H2O
O2
N2
Total

kmol
7.00
0.013
6.35 + 1.208 = 7.558
Nil
38.183 + 0.061 = 38.244
52.815 (wet)
45.257 (dry)

mole % (dry basis)


15.50 (Orsat)

84.50
100.00

Theoretical CO2 in flue gases = 15.50%


Ans.(c)
Total dry gas gases = 45.257 kmol/100 kg fuel oil
0.4526 kmol/kg fuel oil
Ans. (b-i)
10.14 Nm3/kg fuel oil
Total wet flue gases = 52.815 kmol/100 kg fuel oil
0.528 16 kmol/kg fuel oil
Ans. (b-ii)
11.84 Nm3/kg fuel oil
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
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
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
Ans. (d-ii)
= 62.047 m3/kg fuel oil
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 (41.2C)
(Ref. Table 6.13)
Ans. (e)

252 Solutions ManualStoichiometry

Component

ni kmol

Cmp equation constants


ai ni

ni bi 103

ni ci 106

ni di 109

CO2
O2
N2
H2O

7.013
13.118
87.595
9.120

149.836
381.982
2592.015
296.328

450.824
13.550
450.326
0.726

287.888
160.808
1154.756
120.482

68.727
526.348
435.172
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
Carbon
Sulphur
Hydrogen
Total

Mass, kg

kmol

O2 requirement, kmol

85.65
3.00
11.35

7.138
0.094
5.675

7.138
0.094
2.838

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 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
Total dry air = 13.802 + 51.923 = 65.725 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

Gas

kmol, ni

Molar mass,
Mi
44
64
18
32
28

CO2
SO2
H2O
O2
N2

7.138
0.094
8.238
3.732
51.923

Total

71.125 (wet)
62.887 (dry)

253

ni Mi,
kg
314.07
6.02
148.29
119.42
1453.84

mole %
(wet basis)
10.04
0.13
11.58
5.25
73.00

Orsat
analysis, %
11.50

5.93
82.57

2041.64

100.00

100.00

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 (198.4C), 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 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, f12 = 1000(482.5 343.31)
= 139 190 kJ/h 38.66 kW
f5 = (2790.0 482.5) 12 192 = 28 133 040 kJ/h 7814.73 kW
Heat lost in blow-down, f12 = (844.7 482.5) 1000
= 362 200 kJ/h 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 (280C)
= 2993.7 kJ/kg
f6 = (2993.7 2790) 12 192
= 2483 510 kJ/h
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

254 Solutions ManualStoichiometry

f7 = 2041.68 1060.8 1.15(550.15 298.15)/100


= 6276 529 kJ/h 1743.48 kW (approximate calculations)
Component

ni kmol

CO2
O2
N2
H2O
Total

Cmp equation constants


ai ni

ni bi 103

ni ci 106

ni di 109

7.232
3.732
51.923
8.238

154.515
108.672
1536.448
267.670

464.903
3.714
266.936
0.656

296.878
45.749
684.496
108.830

70.873
149.743
257.953
37.461

71.125

2067.305

202.337

405.699

74.798

1060.8
[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
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 (48.7C) = 2388.4 kJ/kg
Heat loss due to evaporation of moisture = f8
= 1084.18 2388.4 = 2589 456 kJ/h 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 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 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

Heat lost in flue gas, f7 =

= 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
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 (25C)
(Ref. Table AV.2)
Excess air = 40%
Actual O2 supply = 1.4 1.5 = 2.1 kmol
Excess O2 = 2.1 1.5 = 0.6 kmol
Actual N2 supply = 79 2.1/21 = 7.9 kmol
Component
dry

kmol
wet

Orsat analysis
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 (25C), their enthalpies are
0 kJ/kmol at reference temperature.
Heat capacity
constants
ni kmol
(ni ai)1*
(ni ai)2*

CO2
1.0
21.366
37.174

N2
7.9
233.768
245.834

O2
0.6
15.615
11.060

H2O

Total

2.0
64.984
50.317

11.5
335.733
344.385

256 Solutions ManualStoichiometry

(ni bi)1 103


(ni b)2 103
(ni ci)1 106
(ni ci)2 106
(ni di)1 109
(ni di)2 109

64.284
23.237
41.051
7.379
9.8
0.821

40.614
25.256
104.145
3.201
39.247
0.018

7.053
13.030
1.405
4.983
0.337
0.693

0.159
42.564
26.421
10.680
9.095
0.965

30.882
104.087
88.109
26.243
38.879
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 1560.12C)

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
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

CH4
H2
CO
CO2

96.59
1.29
0.22
1.90

96.59

0.22
2.00

193.18
1.29

kmol H2

kmol O2

0.11
1.90

Total

100.00

98.71

194.47

2.01

194.47
0.22
2.01 +
2
2
194.045 kmol
194.045 1.1
213.345 kmol
213.345 194.045 = 19.4 kmol
79 213.345/21
802.584 kmol
0.018 (213.345 + 802.584)
18.287 kmol
213.345 + 802.584 + 18.287
1034.186 kmol

Theoretical O2 requirement = 98.71 +

=
Actual O2 supply =
=
Excess O2 =
N2, entering through air =
=
Moisture entering with air =
=
Total moist air =
=
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

CO2
O2
N2
H2O

98.710
19.400
802.584
212.757

Total

1133.451 (wet)
920.694 (dry)

Wet gas analysis


mole %
8.71
1.71
70.81
18.77
100.00

Take reference temperature, T0 = 298.15 K (25C)

Orsat
gas analysis
mole %
10.72
2.11
87.17

100.00

258 Solutions ManualStoichiometry

Heat capacity
equation constants
ni
(ni ai)1*
(ni ai)2*
(ni bi)1 103
(ni bi)2 103
(ni ci)1 106
(ni ci)2 106
(ni di)1 109
(ni di)2 109

CO2
0.0871
1.861
3.238
5.599
2.024
3.576
0.643
0.854
0.072

N2

O2

H2O

Total

0.7081

0.0171

0.1877

1.0000

20.953
22.035
3.640
2.264
9.335
0.287
3.518
0.002

0.445
0.315
0.201
0.371
0.040
0.142
0.010
0.020

6.099
4.722
0.015
3.995
2.480
1.002
0.854
0.091

29.358
30.310
2.175
8.654
8.199
2.074
3.528
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 1882.1C

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
98.71
802.584 4.138 a
212.757 0.0943 a + b
19.400 0.1 a
200 a b from recycled flue gas

CO2
N2
H2O
O2
CO2 + N2
Total

1333.451 5.3323 a

19.4 0.1 a
a
=
200
1333.451 5.3323 a
5.3323 a2 1353.451 a + 3880 = 0
Solving for a, a = 2.9 kmol (only positive root)
1.45% in flue gas
H2O balance:
b
212.757 0.0943 a + b
=
200
1333.451 5.3323 a
Substituting value of a,
O2 balance:

b
212.484 + b
=
200
1317.987

260 Solutions ManualStoichiometry

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
Actual O2 supply = 191.145 1.1 = 210.260 kmol
Excess O2 = 210.260 191.145 = 19.115 kmol
79
210.260
N2 entering alongwith O2 =
21
= 790.978 kmol
Total dry air = 210.260 + 790.978 = 1001.238 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
CO2
O2
N2
H2O

kmol
98.71 + 17.66 = 116.37
19.115
790.978 + 141.43 = 932.408
250.502

Total

Recycle ratio =
Heat Capacity Data:
Heat capacity
constants
ni, kmol
(ni ai)1*
(ni ai)2*
(ni bi)1 103
(ni bi)2 103
(ni ci)1 106
(ni ci)2 106
(ni di)1 109
(ni di)2 109
*

1318.395 (wet)
1067.893 (dry)

Wet analysis
mole %
8.83
1.45
70.72
19.00

Dry analysis
mole %
10.90
1.79
87.31

100.00

100.00

kmol
200
= 0.1517
kmol
1318.398

Ans. (a)

CO2

N2

O2

H2O

Total

0.0883
1.887
3.282
5.676
2.052
3.625
0.652
0.865
0.073

0.7072
20.927
22.007
3.636
2.261
9.323
0.287
3.513
0.002

0.0145
0.377
0.267
0.170
0.315
0.034
0.120
0.008
0.017

0.1900
6.173
4.780
0.015
4.044
2.510
1.015
0.864
0.092

1.0000
29.364
30.336
2.225
8.672
8.174
2.074
3.520
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
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 1662.15C
Ans. (c)
Combustion air requirement
1019.26
1001.238 +18.022
=
=

100
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
CO
CO2
N2
O2
CH4

48.5
44.2
2.3
2.4
1.0
1.6

44.2
2.3

1.6

22.1
2.3

1.0

48.5

3.2

100.0

48.1

25.4

51.7

Total

262 Solutions ManualStoichiometry

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
4.352 kg
Carbon content of gas = 48.1 kmol 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)
=
coal charged
768.283
= 1.16 kg/kg
Dry blue gas produced = 100 100/768.283
= 13.02 kmol/100 kg coal

Ratio,

Ans. (b)
Ans. (a)

EXERCISE 7.26
Basis: 100 kmol dry blue gas
Gas

kmol

kmol C

kmol O2

kmol H2

H2
CH4
CO
CO2
N2

49.0
0.8
41.0
4.7
4.5

0.8
41.0
4.7

20.5
4.7

49.0
1.6

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
=
= 0.48 kmol/kmol
Ratio,
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
Gas

kmol

kmol C

kmol O2

kmol H2

H2
CH4
CO
CO2
C3H6
O2
N2

37.0
14.0
30.5
5.6
7.0
0.4
5.5

14.0
30.5
5.6
21.0

15.25
5.6

0.4

37.0
28.0

21.0

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

264 Solutions ManualStoichiometry

= 12.202 kmol
219.64 kg

additional steam decomposed


= 219.64/100
dry carburetted gas
= 2.196 kg/kmol
dry carburetted water gas
100
Ratio,
=
dry blue water gas
57.03
= 1.754 kmol/kmol
fuel oil used for carburetion
768.5
Ratio,
=
dry blue gas
57.03
= 13.48 kg/kmol

Ratio,

Ans. (c)

Ans. (b)

Ans. (a)

EXERCISE 7.27
Basis: 100 kmol producer gas
Gas

kmol

kmol C

kmol O2

kmol H2

H2
CH4
C2H 4
CO
CO2
N2

10.5
2.1
0.4
22.0
7.7
57.3

2.1
0.8
22.0
7.7

11.0
7.7

10.5
4.2
0.8

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 1.38 kmol
O2 from coal = 643.64 0.093 = 59.86 kg 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
(Table 6.13)
Vapour pressure of water 298.15 K (25C), pw = 3.166 kPa
Humidity of producer gas = 3.166/(106.7 3.166)
= 0.0306 kmol/kmol dry gas
Water vapours with producer gas = 0.306 100

Combustion

265

= 3.06 kmol
H2 from fuel = 15.5 3.94 = 11.56 kmol 23.12 kg
Check from fuel analysis:
H2 from fuel = 643.64 0.036 = 23.17 kg
Moist producer gas:
Molar mass, Mi

mass, kg (ni Mi)

H2
CH4
C2H4
CO
CO2
N2
H2O

Gas

kmol, ni
10.5
2.1
0.4
22.0
7.7
57.3
3.06

2
16
28
28
44
28
18

21.0
33.6
11.2
616.0
338.8
1604.4
55.08

Total

103.06

2680.08

moist producer gas


2680.08
=
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 (38C) DB and 299 K (26C) WB,
= 16.4 g/kg dry air (Ref. Fig. 6.15)
0.0263 kmol/kmol dry air
Moisture from air = 16.4 2041.28/1000
= 33.477 kg 1.86 kmol
moist air
(2041.28 + 33.477)
=
= 3.223 kg/kg
Ratio,
coal
643.64
Ans. (b)
Steam supplied = 3.94 + 3.06 1.86 = 5.14 kmol
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 (25C)
Enthalpy of steam at 4 bar a and 623 K (350C) = 3170 kJ/kg
(Ref. Table AV.3)
Enthalpy of steam over 298.15 K (25C) = 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)

Ratio

266 Solutions ManualStoichiometry

Enthalpy of coal = 22 657 643.64


= 14 582 951 kJ
Component

kmol ni

Cmp equation constants

H2
CH4
C2 H 4
CO
CO2
N2
H2O

10.5
2.1
0.4
22.0
7.7
57.3
3.06

ni ai
206.407
40.424
1.650
638.609
164.514
1695.559
99.426

Total

103.06

2846.589

ni bi 103
103.978
109.438
62.009
61.963
494.988
294.579
0.244
414.115

ni ci 106
ni di 109
3036.805 7786.180
25.143
23.770
32.618
6.790
256.161
103.539
316.090
75.459
755.380
284.666
40.425
13.915
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
CH4
C2H4
CO

10.5
2.1
0.4
22.0

285.83
890.65
1411.2
282.98

3001 215
1870 365
564 480
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
Hydrogen
Sulphur
Oxygen
Water

7.5
0.5
5.7
12.5
58.8

0.625
0.250
0.178
0.391
3.267

0.625
0.125
0.178
() 0.391
.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

CH4
C2H8
C3H8
C4H10 (total)
CO2

89.4
5.0
1.9
1.0
0.7

Total

98.0

O2 requirement
kmol
178.8
17.5
9.5
6.5

CO2 production
kmol
89.4
10.0
5.7
4.0
0.7

212.3

109.8

H2O production
kmol
178.8
15.0
7.6
5.0

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
0.625 + 1.098 x = 0.625 + 1.098 x
3.267 + 0.25 + 2.064 x = 3.517 + 2.064 x
0.178
0.02 x + 2.3234 + 9.1849 x = 2.3234 + 9.2049 x
0.0806 + 0.3185 x

CO2
H2O
SO2
N2
O2
Total

6.7240 + 12.6854 x

Absolute enthalpies: (Ref. Table 5.22 from text)


Component

(H Ho + DHf ), kJ/kmol at
1200 K

CO2
H2O
SO2
N2
O2

339 593
194 796
303 331
+ 36 699
+ 38 399

475 K

298.15 K

376 906
223 245
340 659
+ 13 745
+ 13 900

384 158
229 252
347 992
+ 8 613
+ 8 597

Absolute enthalpy
different, kJ
1200 K 475 K
37 313
28 449
37 328
22 954
24 499

1200 K 298.15
44 565
34 456
44 661
28 086
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

268 Solutions ManualStoichiometry

+ (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
7.522 Nm3 NG/100 kg waste liquor
Flue gas analysis: Substituting the value of x, following table is obtained.
Component
CO2
H2O
SO2
N2
O2
Total

kmol
0.9935
4.2097
0.1780
5.4126
0.1875
10.9813 (wet)
6.7716 (dry)

Wet gas
analysis, %
9.05
38.34
1.62
49.29
1.70
100.00

Furnace pressure p =
Partial pressure of water, pH O =
2
=
From Steam Tables (Table 6.13),
Water dew point =
A = ln (pH O) =
2
Partial pressure of SO2, pSO =
2
=
B = ln (pSO ) =
2

Dry gas
analysis, %
14.67

2.63
79.93
2.77
100.00

Orsat
analysis, %
17.30

79.93
2.77
100.00

103.5 kPa
103.5 0.3834
39.682 kPa
348.85 (75.7C)
ln (39.682) = 3.6809
103.5 0.0162
1.6767 kPa
ln (1.6767) = 0.5168

Ans. (bi)

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 72.4C
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
= 153C
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 (77C) = 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
3429.82 kW
Boiler efficiency = 85%
12 347 350 100
= 4969.5 kg/h
Waste liquor firing rate =
292 311 0.85
Ans. (a-i)
Stabilizing fuel (NG) firing rate = 0.3356 49.695
= 16.6775 kmol/h
373.81 Nm3/h
Ans. (a-ii)

EXERCISE 7.29
Combustion reaction:

F
H

Cn Hm + n +
Basis: 1 mol fuel

I
K

m
m
O2 = n CO2 +
H2O
2
4

m
mol
4
m
Let actual oxygen supply = n +
+ y mol
4

Theoretic oxygen required = n +

F
H

Total N2 = 3.762 n +

I
K

m
+ y from air and CO2 = n mol
4

==

y
4.762 y + [n + (m /4)]3.762 + n

y=

=
(1 - 4.762 = )

% excess air =

100 y
[n + ( m / 4)]

Where excess O2 = y mol


Solving the equation for y,

By definition,

LMF n + m I3.762 + nOP


NH 4 K
Q
LM
N

19.048 + 3.762r
100 =
4+r
(1 - 4.762 =)

OP
Q

270 Solutions ManualStoichiometry

where

r = m/n
4
For methane,
r = = 4 and = = 5/100 = 0.05
1
Substituting the values in the equation,
% excess air =
=

LM
N

19.048 + 3.762 4
100 0.05
4+4
[1 - ( 4.762 0.05)]
5(19.048 + 15.048)
= 27.97%
(1 - 0.2381)8

Ans.

EXERCISE 7.30
Basis: 1 mol fuel
Inerts content of fuel = a mol
Combustibles = (1 a) mol
Combustion reaction:

F
H

(1 a)Cn Hm + (1 a) n +

I
K

m
m
O2 = (1 a)n CO2 + (1 a)
H2O
2
4

F
H

Theoretical O2 required = (1 a) n +
In flue gases,

I
K

m
+ y mol
4

O2 = y mol i.e. excess oxygen

F
H

I
K

m
+ y mol
4
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
Solving the equation for y,

Total N2 = 3.762(1 a) n +

y=

F
H

% excess air =

I
K

=
m
[3.762 (1 a) n +
+ n(1 a) + a]
(1 - 4.762 =)
4

By definition,

100 y
(1 - a)[n + ( m / 4)]

LM
N

100=
19.048 + 3.762 r
4a
+
(1 - 4.762=)
(4 + r )
n(1 - a)( 4 + r )

100=
(1 - 4.762=)

LM19.048 + 3.762r + c OP
Q
N (4 + r )

where cf = correction factor

OP
Q

OP
Q

Combustion

=
Now when a =
cf =
% excess air =
=
=

4a
n(1 a)( 4 + r )
0.05
4 0.05/(1 0.95 8) = 0.0263
5
19.048 + 15.048
+ 0.0263
(1 - 0.2381)
8
5 34.307/(0.7619 8)
28.14

LM
N

OP
Q

EXERCISE 7.31
Basis: 1 mol fuel
Combustion reactions can be written as under:
m
m
x1 Cn Hm + x1 n1 + 1 O2 = x1 n1 CO2 + x1 1 H2O
1
1
2
4
m2
m
x2 Cn Hm + x2 n2 +
O2 = x2 n2 CO2 + x2 1 H2O
2
2
2
4
mi
mi
O2 = xi ni CO2 + xi
H2O
x1 Cni Hmi + xi ni +
4
2
mj
i
mol
Theoretical O2 required = xj n j +
4
1
mj
i
Actual O2 supply = xj n j +
+ y mol
4
1
Mole fraction of O2 in flue gases,
=
y
==
( 4.762 y + 3.762) i
i
mj
+ xj + xjnj
x j n j +

4
1
1
Solving the equation for y,

F
H
F
H
F
H

I
K

I
K

I
K

FG
H
FG
H

IJ
K
IJ
K

mj i

=
+ xi n j
3.762 x j n j +

(1 - 4.762=)
4 1

By definition,

y=

% excess air =

271

100 y
mj

xj nj +
4

1
i

Substituting the value of y and solving the equation,


i

xjnj

100=
1
% excess air =
3.762 + i

i
(1 - 4.762=)
nj xj + xjmj
1
1

Ans.

272 Solutions ManualStoichiometry

LM
N

19.048 + 3.762 rm
100=
4 + rm
(1 - 4.762=)
i

where, rm =

x m
j

1
i

OP
Q

x j n j rj
1

xjnj

xjnj

and rj = mj / nj

EXERCISE 7.32
Basis: 1 mol fuel
Combustion reactions can be written as follows:
m
x1(1 a1) Cn Hm + x1 (1 a1) n1 + 1 O2
1
1
4
m1
= x1 (1 a1)n1 CO2 + x1 (1 a1)
H2O
2
m
x2(1 a2) Cn Hm + x2 (1 a2) n2 + 2 O2
2
2
4
m2
= x2 (1 a2)n2 CO2 + x2(1 a2)
H2O
2
m
xi (1 ai)Cni Hmj + xi (1 ai) n4 + i O2
4
m
= xi (1 ai) ni CO2 + xi (1 a2) i H2O
2

F
H

I
K

F
H

I
K

F
H

I
K

Theoretical O2 required = x j (1 aj) [nj + (mj /4)] mol


1
i

Let actual O2 supply = x j (1 aj) [nj + (mj /4)] + y mol


1

Mole fraction of O2 in flue gases,


==

Solving for y,
y=

4.762 y + 3.762 x j (1 - a j )[n j + (m j /4)]


1

1
i

+ (1 - a j )n j x j + x j a j

i
1

3.762 x j (1 - a j )[n j + (m /4)]

(1 - 4.762=)
1

i
i

+ x j nj (1 aj) + x j a j
1

Combustion

273

By definition,
100 y

% excess air =

x j (1 - a j )[n j + (m j /4)]
1

Substituting the value of y and solving the equation,


% excess air

i
i

x j n j (1 - a j ) x j a j

=
1
1
=
3.762 + i

(1 - 4.762= )
x j (1 - a j )[n j + (m j /4)]

1
i

xjaj

=
1
1
=
+ i
3.762 +

(1 - 4.762= )
1 + rm

+
x
a
n
m
(1
)[
(
/4)]
j
j
j
j

1
3.762 rm + 19.048
=
+ c fm
=
4 + rm
(1 - 4.762=)

LM
N

where rm =

x j m j (1 - a j )
i

x j n j + (1 - a j )
1

and cfm = i 4 x a
j j
1

OP
Q

x j n j rj (1 - a j )
1

x j n j (1 - a j )
1

[n j x j ][(1 - a j )(4 + rj )]
1

EXERCISE 7.33
Fuels Firing in Reformer Furnace
Fuel
Firing rate
kmol/h
mole fraction xi
Natural gas
375
0.590
Tail gas
158
0.249
Naphtha
102.3
0.161
rm =
=
Cfm =

ai
0.028
0.820
0.005

ri
2.75
5.55
1.75

[(1 - 0.28) 0.59 2.75 + (1 - 0.82) 0.249 5.55 + (1 - 0.005) 0.161 1.75]
[(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]
[0.59 (1 - 0.028)(4 + 2.75) + 0.249 (1 - 0.82) (4 + 5.55)
+ 0.161 (1 - 0.005) (4 + 1.75)]

274 Solutions ManualStoichiometry

(0.0661 + 0.8167 + 0.0032) 0.886


=
(3.871 + 0.428 + 0.9211)
5.2201
= 0.1697

Excess air =

(19.048 + 3.762 2.695)

100 0.035
+ 0.1697

(1 - 4.762 0.035)
(4 + 2.695)

3.5 29.1866

+ 0.1697

0.8333 6.695

= 19.02 %

Ans.

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

276 Solutions ManualStoichiometry

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 (46.3C)
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

CO2
O2
N2
H2O
Total

Cmp equation constants

14.0
3.0
83.0
11.4

ai
299.12
78.08
2456.04
370.41

bi 103
899.98
35.27
426.70
0.91

111.4

3203.65

509.46

ci 106
574.71
7.03
1094.18
150.60

di 109
137.20
1.69
412.34
51.84

663.04

328.67

Combustion Air
Component

kmol

O2
N2
Ar
H2O
Total

Cmp equation constants


ai

bi 103

ci 106

di 109

0.21
0.78
0.01
0.0216

5.47
23.08
0.21
0.70

2.47
4.01

0.49
10.28

0.29

0.12
3.87

0.10

1.0216

29.46

1.54

10.08

4.09

Reference temperature, T0 = 298.15 K (25C)


Enthalpy of flue gas, entering RAH;

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),

433.15

H2 =

(3203.65 + 509.46 103 T + 663.04 106 T 2 328.67 109 T 3) dT

298.15

= 467 501 kJ/100 kmol dry flue gas from boiler


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,

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,

433.15

H4 =

(29.46 1.54 103 T + 10.08 106 T 2 4.09 109 T 3) dT

298.15

= 4057.17 kJ/kmol dry air

278 Solutions ManualStoichiometry

Heat transferred in RAH to combustion air


H5 = H1 H2 12 (H4 H3)
= 788 175 467 501 12 (4057.17 447.21)
= 277 354 kJ/100 kmol dry flue gas from boiler
2773.5 kJ/kmol dry flue gas, entering RAH

Ans. (b)

100
1.045
= 95.694 kmol wet air
93.67 kmol dry air
Let T be the temperature of combustion air after RAH.

Combustion air required =

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 123.8C

Ans. (c)

12 100
93.67
= 12.81%
Ans. (d)
Instead of RAH, a tubular heater is used,
heat transfer duty, H5 = 788 175 467 501
= 320 674 kJ/100 kmol dry flue gas

Increase in capacity of air blower =

(93.67)

(29.46 1.54 10

T + 10.08 106 T2 4.09 109 T3) dT = 320 674

298.15

Solving by Mathcad, T = 412.25 K or 139.1C

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

Stoichiometry and Industrial Problems 279

Yield of butadiene = 74.07 100/112.85 = 65.64%


Total H2 produced = 112.85 + 74.07 = 186.92 kmol/h

Offgas analysis:

.
n i, kmol/h

mole %

H2
C2H4

186.92
77.56

70.67
29.33

Total

264.48

100.00

Component

Composition of hot gases, leaving reactor:


.
Component
n i, kmol/h
Butene-1
426.96
1, 3-Butadiene
74.07
Hydrogen
186.92
Ethylene
77.56
Total

mole %
55.77
9.68
24.42
10.13

765.51

100.00

Ans. (a)
Enthalpy of reactants:
Component

kmol/h
.
ni

Temp.,
K (C)

n-Butane
Butene-1

112.85
426.95

920 (647)
920 (647)

Total

539.80

(H Ho+ DHf )i
kJ/kmol

.
n i (H Ho + DHf )i
kW

24 494
131 000

767.82
15 536.24

16 304.06

Enthalpy of products:
Component

kmol/h
.
ni

Temp.,
K (C)

(H Ho+ DHf )i
kJ/kmol

.
n i (H Ho + DHf )i
kW

Butene-1
1, 3-Butadiene
Hydrogen
Ethylene

426.96
74.07
186.92
77.56

810 (537)
810 (537)
810 (537)
810 (537)

110 850
204 386
23 386
105 220

13 146.50
4 205.24
1 214.25
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
lv = 22 470

. I
F 425 27315
H 425 268.7 K

0.38

280 Solutions ManualStoichiometry

= 22 223 kJ/kmol
(H Ho + DHf ) 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)

Stoichiometry and Industrial Problems 281


Slow Rinse

Acid Entry
60000
54000
48000

36000
30000

e
urv

12000

FM
AC

18000

e Curve

24000

Chlorid

Concentration in mg/L

42000

6000
0

10

20

30

40

50
60
70
Time in minutes
Fig. E8.1 Solution of Exercise 8.3

80

90

100

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

282 Solutions ManualStoichiometry

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
2450.3 kg
Average concentration of chlorides in concentrated stream
= 2450 298/49.8
= 49 203 g/m3 or ppm
Ans. (ci)
Weak stream:
Acid introduction step:
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
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
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:
Acid introduction step:
Area under FMA curve during acid introduction step = 36.232 sq. units

Chlorides, eluted in 20 min =

Stoichiometry and Industrial Problems 283

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
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 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
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)

284 Solutions ManualStoichiometry

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.
c1 =

1.263 25
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.
Similar calculations can be made for other hydrocarbons.
Gas

Ans. (a)

Concentration after 4 cycles

Ethane
Propane
Butane

0.02
0.42
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
1.263 25
27315
.

156.728
308.15 1.013 25
173.2 Nm3
Ans.(c)

Stoichiometry and Industrial Problems 285

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
V m1 =
Total gas inside the bullet =

0.083 14 308.15
= 25.284 57 m3/kmol
1.013 25

22
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)

286 Solutions ManualStoichiometry

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 (25C)
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 (132.4C) 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 (137C)
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

Stoichiometry and Industrial Problems 287

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(200C)
ps = 15.55 bar a of water
However, the vapours are produced at 101.325 kPa a and 473 K (200C).
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 (100C), 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)

288 Solutions ManualStoichiometry

In the second case, water is partially evaporated till the invariant composition is
reached at 373.15 K (100C).
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 (100C) 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 (0C), 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(0C),
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

Stoichiometry and Industrial Problems 289

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 (0C) 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

290 Solutions ManualStoichiometry

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)
DHf
601.7 285.83 601.7 2 92.31
DHr = 601.7 2 92.31 [ 641.32 285.83]
= +140.83 kJ/mol MgCl2 at 298.15 K (25C) (endothermic)
+ 70.415 kJ/mol HCl at 298.15 K (25C) (endothermic)
+ 1931.25 kJ/kg HCl at 298.15 K (25C) (endothermic)
Change in DHr 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 25C (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 = fi


1

= 3745.6 + 592.98 + 269.95 + 2637.84


+ 20.53 + 218.25 + 17.74 + 58.15
= 7561.04 kW
Ans.(b)

Stoichiometry and Industrial Problems 291

.
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 (525C) and 573 K (300C).
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
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

292 Solutions ManualStoichiometry

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 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
0.2024 kmol 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)

Stoichiometry and Industrial Problems 293

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
12.942 kg
Current efficiency =

actual Fe liberation
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.

294 Solutions ManualStoichiometry

Now as per Daltons law,


pi = p yi and yi = ni /n

(e / n) p ( d / n ) p
edn 2
= 3 2 = 2.5207 105
Therefore, Kp1 =
3
a bp
(b / n) p [(a / n) p]
System pressure, p = 2.0 MPa a = 19.7385 atm a
Kp1 =

edn 2
= 2.5207 105
a b (19.7385) 2
3

edn 2
= 9.8209 103
(5)
3
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.

or

Kp2 =

( a / n) (c / n) p 2
= 0.4465
(b / n) ( d / n) p 2

ac
= 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),

or

or

1.05 d (300) 2
= 9.8209 103
a 3b
1.05 (300 ) 2 10 3
d
d
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;
b = 77.22 kmol,

a = 163.38 kmol
c = 25.06 kmol

ac/ad = 1.5149 # 0.4465

Stoichiometry and Industrial Problems 295

d, kmol
(assumed)
30
35
37
39
39.5
39.1

a, kmol

b, kmol

c, kmol

168.88
163.88
161.88
159.88
159.88
159.78

59.93
77.22
83.94
91.83
93.88
92.23

42.35
25.06
18.34
10.45
8.40
10.05

ac /ad
3.978
1.5149
0.9559
0.4665
0.361
0.4453

>
>
>
>
<
<

0.4465
0.4465
0.4465
0.4465
0.4465
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
= 9.8209 102
3
a b
or
b = 10.2018 106 d/a3
Iteration:
d, kmol
(assumed)
39.1
38
37.8
37.85

a, kmol

b, kmol

c, kmol

159.74
160.84
161.04
160.99

97.862
93.17
92.335
92.544

4.398
9.09
9.925
9.716

ac / ad
0.1841
0.4130
0.4579
0.44655

< 0.4465
< 0.4465
> 0.4465
; 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.

296 Solutions ManualStoichiometry

Analysis of exit gas mixture:


Component
H2
CO
CO2
H2O
CH4
N2
Ar

dry gas
kmol
160.990
92.544
9.716

1.070
1.950
1.929

Total

268.199

mole %
60.03
34.50
3.62

0.40
0.73
0.72
100.00

kmol
160.990
92.544
9.716
37.850
1.070
1.950
1.929

wet gas
mole %
52.60
30.24
3.17
12.37
0.35
0.64
0.63

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
CH4
C2H6
C3 H8
n-C4H10
N2
O2
Ar
Total

kmol
ni
93.25
3.32
0.88
0.20
1.95
74.91
1.929

Temperature
K
422
422
422
422
422
400
400

176.439

Enthalpy, kJ/kmol
(H Ho + DHf )i
52 247
49 736
56 164
64 005
12 187
12 277

ni (H Ho DHf )i
kJ
4 871 996
165 123
49 424
12 801
+ 23 765
+ 919 673

4 155 906

Enthalpy of products: Ref. Table 5.22


Temperature of product stream = 1395 K
Component
H2
CO
CO2
H2O
CH4
N2
Ar

kmol
ni
160.99
92.544
9.716
37.85
1.07
1.95
1.929

Total

306.049

Temperature
K
1395
1395
1395
1395
1395
1395
1395

Enthalpy, kJ/kmol
(H Ho + DHf )i
+ 41 315
70 120
328 410
186 030
+ 12 386
+ 43 372

ni (H Ho DHf )i
kJ
+ 6 651 282
6 489 197
3 190 833
7 041 238
+ 13 253
+ 84 576

Enthalpy, supplied to argon = 20.7723 (1395 400) 1.929


= 39 869 kJ

9 972 157

Stoichiometry and Industrial Problems 297

Enthalpy change during reactions, DH


= 9972 157 (4155 906) + (39 869)
= 5856 120 kJ (exothermic) per 100 kmol
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
Basis: 100 kg spent acid
Let x kg be the fuel oil required for decomposition.
Reactions:
H2SO4 = H2O + SO3
SO3 = SO2 + 1/2 O2
2 NH4HSO4 + 1/2 O2 = N2 + 5 H2O + 2 SO2
C + O2 = CO2
H2 + 1/2 O2 = H2O
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
H2SO4
NH4HSO4
Cm Hn C
H
H2O
Total

kg
20
45
4.18
0.82
30.0
100.00

Molar mass
98
115
12
2
18

kmol

(A)
(B)
(C)
(D)
(E)

O2 requirement, kmol

0.2041
0.3913
0.3483
0.4100
1.6667

0.1021
+ 0.0978
+ 0.3483
+ 0.2050

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

298 Solutions ManualStoichiometry

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

Stoichiometry and Industrial Problems 299

LHV of organics =
Heat liberated by combustion =
=
Total air requirements =
=
Combustion air requirements =
=
Enthalpy of dry air =

41 870 kJ/kg
1791.67 41 870/3600
20 838.12 kW
(9.5775 + 0.1975)
9.775 kmol/100 kg spent acid
9.775 358.333
3502.7 kmol/h (moist)
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)
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
(Ref. Table 5.64)
H 1 = 2.093 kJ/mol H2O
(Ref. Table 5.64)
H 2 = 135.65 kJ/mol SO3
At 100% concentration, = H 1 = H 2 = 44.34 kJ/mol
Dehydration:
Dilute acid + Heat of mixing = 100% acid + water

300 Solutions ManualStoichiometry

( 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 (18C) = 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)
DHr1 = 241.82 296.83 ( 813.99)
= + 275.34 kJ/mol H2SO4 2807.3 kJ/kg H2SO4 (endothermic)
Reaction 2: 4 NH4HSO4(s) + O2(g) = 2 N2(g) + 10 H2O(g) + 4 SO2(g)
DHr2 = [10 ( 241.82) + 4 ( 296.83)] [4 ( 1026.96)]
= + 502.32 kJ/4 kmol NH4HSO4
+ 125.58 kJ/mol NH4HSO4 (endothermic)
+ 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 = 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

Stoichiometry and Industrial Problems 301

= 386.8 kg/13.8682 kmol


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 (922.47C)
This temperature is lower than the desired decomposition temperature of about
1275 K (1002C).
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
= 10.033 kmol/100 kg spent acid
SO2 in exit gas mixture = 0.5954 100/(6.6071 + 0.4724 7.9197)
= 5.75%
Mositure, entering with air = 10.033 0.0206
= 0.2067 kmol/100 kg spent acid
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
= 4.0154 kmol/100 kg spent acid
Flow rate of exit gas mixture = 6.6071 + 0.4724 7.9197 + 4.0154
= 14.3638 kmol/100 kg spent acid
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

302 Solutions ManualStoichiometry

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
= 0.2138 kmol/100 kg spent acid
Total moisture in exist gas mixture
= 3.2591 + 0.0694 8.6 + 0.2138
= 4.0697 kmol/100 kg spent acid
CO2 in exit gas mixture = 0.3483 + 0.0718 8.6
= 0.9658 kmol/100 kg spent acid
N2 in exit gas mixture = 4.9489 + 0.4006 8.6
= 8.3941 kmol/100 kg spent acid
Component

kmol
ni

Heat capacity Cmp equation constants

SO2
CO2
O2
N2
H2O

0.5954
0.9658
0.7145
8.3941
4.0697

ai ni
17.748
20.635
18.595
248.389
132.233

Total

14.7395

434.600

ni bi 103
37.479
62.086
8.399
43.154
0.324
65.134

ni ci 106
26.351
39.647
1.674
110.659
53.764
96.751

ni di 109
6.622
9.465
0.402
41.702
18.507
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
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 988.54C
This temperature is lower than 1275 K.

Stoichiometry and Industrial Problems 303

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
ni

Dry
gas
mole %

Heat capacity Cmp equation constants


ai ni

ni bi 103

ni ci 106

ni di 109
6.622
9.675
0.402
42.289
18.616

SO2
CO2
O2
N2
H2O

0.5954
0.9873
0.7145
8.5122
4.0937

5.51
9.13
6.61
78.75

14.748
21.094
18.595
251.884
133.013

37.479
63.468
8.399
43.761
0.326

26.351
40.529
1.674
112.215
54.081

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
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 1001.13C
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
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

304 Solutions ManualStoichiometry

+ 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 219.84 Torr
A = ln (pH2O) = 3.3779
Water dew point = 341.6 K (68.6C) (Ref. Table 6.13) Ans. (ii)
pSO = 0.5954 106.7/14.9031 = 4.263 kPa 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 (66.3C)
Therefore air must be introduced at about 345 K (72C). a 5 K margine.
Enthalpy of air 345 K (72C)
= 10.53 (1.006 + 1.84 0.0128) 358.33 (345 298.15)/3600
= 50.72 kW
Enthalpy of air at 723 K (450C) = 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
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

Stoichiometry and Industrial Problems 305

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 (184.1C), 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, %
Relative Profit Function

50
0.686

66
0.776

70
0.780

75
0.790

85
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

100

0.80

99

98

0.76

97

0.72

96

n
rsio
nve
Co
V/S

tV

/S

Co

0.74

ld
Yie

nv
e

r si

on

96.55

95

0.70

0.68

94

50

60

70

76

80

Conversion
Fig. E8.2 Solution of Exercise 8.11

90

100

93

Yield, %

0.78

Pr
ofi

Relative Profit Function

Max. Profit

306 Solutions ManualStoichiometry

0.82

Stoichiometry and Industrial Problems 307

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

308 Solutions ManualStoichiometry

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
H2
CH4
C6H6
C7H8
C12H10
Total

vapour phase
kmol
6.093 3
6.087 7
0.005 363
0.000 3258
0

12.186 589

liquid phase

kg
12.186 6
79.062 4
0.410 5
0.029 97
0

mole %
50.00
49.95
0.043
0.007
0

kmol

kg

0
0
1.052 63
0.325 7742
0.021 67

82.105 14
29.971 23
3.337 18

71.14
25.97
2.89

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

mass %

Stoichiometry and Industrial Problems 309

Toluene column:
Diphenyl in bottom product = 0.021 67 0.75
= 0.016 25 kmol
2.502 89 kg
Toluene in fresh feed = 1.3586 0.325 7742
= 1.032 858 kmol
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
H2 produced =

5.9
= 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
O2 consumed as per reaction (vi) =

3
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

310 Solutions ManualStoichiometry

100
(56.7 0.5d)=
79
H2O, entering with air =
=
NO production by reaction (i) =
=
H2O produced by reaction (i) =
=
Total H2O accounted =
=
=
Substituting value of a, d =
Total dry air, entering Reactor I =
=
H2O, entering Reactor I with air =
=

Total dry air =

71.7722 0.6329 d

0.024 (71.7722 0.6329)d


1.7225 0.0152 d kmol/h
NO consumed by reaction (ii)
5.9 kmol/h
1.5 5.9
8.85 kmol/h
5.9 + 2a + 1.5d + 8.85 + 1.7225 0.0152d
16.4725 + 2a + 1.4848 d
25.1
3.4365 kmol/h
71.7722 3.4365 0.6325
69.5972 kmol/h
1.7225 0.0152 3.4365
1.6699 kmol/h
21
(56.7 0.5d)
O2, entering Reactor I in air =
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
.
.
.
.
kmol/h
ni ai ni bi 103 ni ci 106 ni di 109
NH3
10.9365
13.30
280.52
366.16
3.85
33.72
14.6154
17.78
380.38
171.81
34.24
8.22
O2
54.9818
66.89
1626.96
282.66
724.82
273.15
N2
1.6699
2.03
54.26
0.13
22.06
7.59
H2O
Total

82.2036

100.00

2342.12

Exit Gas Stream From Reactor I


.
Component
ni
mole %
Heat
.
kmol/h
ni ai
NH3
5.0365
6.02
129.19
7.2404
8.65
188.44
O2
54.9818
65.71
1626.96
N2

255.44

716.49

322.68

.
capacity (n i Cop2) equation constant
.
.
.
ni bi 103 ni ci 106 ni di 109
168.63
85.11
282.66

1.77
16.96
724.82

15.53
4.07
273.15

Stoichiometry and Industrial Problems 311

NO
H2O

5.9000
10.5199

7.05
12.57

173.97
341.81

12.11
0.84

66.89
138.98

28.44
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
.
.
.
.
kmol/h
ni ai ni bi 103 ni ci 106 ni di 109
NH3
5.0365
5.43
129.19
168.63
1.77
15.53
7.2404
7.80
188.44
85.11
16.96
4.07
O2
54.9818
59.26
1626.96
282.66
724.82
273.15
N2
NO
5.9000
6.36
173.97
12.11
66.89
28.44
10.5199
11.34
341.81
0.84
138.98
47.84
H2O
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
.
.
.
.
kmol/h
ni ai ni bi 103 ni ci 106 ni di 109
NH3
1.6
1.6
41.04
53.57
0.56
4.93
56.7
56.7
1677.80
291.49
747.47
281.69
N2
HCN
5.9
5.9
192.89
133.29
25.78
2.41
25.1
25.1
815.55
2.00
331.59
114.14
H2O
2.0
1.2
42.73
128.57
82.10
19.60
CO2
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 = 900C (1173.15 K) over 25C
(298.15 K),
f1 =

1173.15

o
(ni C p1 ) dT

298.15

= 244 0897 kJ/h 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 226.37 kJ/mol NH3
Heat produced = 226.37 1000 5.9
f2 = 1335 583 kJ/h 371.0 kW
Enthalpy of Reactor I outlet stream over 25C (298.15 K):

312 Solutions ManualStoichiometry

f3 = f1 + f2 = 2440 897 + 1335 583


= 3776 480 kJ/h 1049.022 kW
=

T2

o
(ni C p2 ) dT

298.15

Solving by Mathcad, T2 = 1595.4 K or t2 = 1322.25C


Ans. (c)
Reactor II:
Reaction (ii)
DH or2 = 241.82 + 135.14
= (74.52 + 90.25)
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
316.52 kJ/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 735.643 kW
Enthalpy of exit stream from Reactor II at 1100C (1373.15 K) over 25C
(298.15 K),
f5 =

1373.15

o
(ni C p4 ) dT

298.15

= 3774 010 kJ/h 1048.336 kW


Enthalpy of gas stream, enteries Reactor II,
f6 = f5 f4
= 3774 010 2648 315
= 1125 695 kJ/h 312.693 kW
=

T3

o
( Sni C p3 ) dT

298.15

Solving by Mathcad
T3 = 671.80 K or t3 = 398.65C

Stoichiometry and Industrial Problems 313

Methane is introduced at 35C (308.15 K).


Enthalpy of methane at 35C (308.15 K) over 25C (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 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 311.812 kW
T2

o
( Sni C p2 ) dT

298.15

T 2 = 724.15 K or t2 = 451.0C
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 737.21 kW
Enthalpy of mixed feed, entering Reactor I, at 35C (308.15 K) over 25C
(298.15 K):
308.15

o
(ni C p1 ) dT

f10 =

298.15

= 247 642 kJ/h 6.879 kW


Enthalpy required to raise mixed feed, entering Reactor I, to 900C (1173.15 K)
from 35C (308.15 K),
f11 =

1173.15

o
(ni C p1 ) dT

298.15

= 2416 134 kJ/h 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 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 451.0C (724.15 K)
T3

o
(ni C p2 ) dT = 1360 346

298.15

Solving by Mathacad, T3 = 809.05 K or t3 = 535.9C


Since exit gas stream from Reactor I is specified to be 1100C (1373.15 K),
there will be a heat loss from the system.

314 Solutions ManualStoichiometry

Heat loss = 1360 346 1122 524


= 237 822 kJ/h 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
10.9315

Ans. (a)

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
CO
CO2
H2
CH3OH
H2O
Inerts

kmol/s
ax
by
2.1a + 3.15b 2x 3y
0.015 57 a + 0.020 85b + x + y
y
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
(3.461 75a + 4.634 28b - 2 x - 2 y )

Let c kmol/s of methanol are condensed alongwith y kmol/s of water.

(1)

Stoichiometry and Industrial Problems 315

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
Overall material balance:
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
T

(4)

Inerts balance:
(0.346 18a + 0.463 43b) P = 1
(5)
T
Reaction equilibrium of water gas reaction at 275C (584.15 K) in converter exit
gas mixture:

K=

(b - y ) (2.1a + 3.15 b - 2 x - 3 y )
(a - x) y

= 69
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)
CO
CO2

(6)

Converter outlet

kmol/s

mole %

kmol/s

mole %

133.849
140.201

12.02
12.60

117.596
129.675

11.10
12.24

316 Solutions ManualStoichiometry

H2
Inerts
CH3OH
H2O
Total

722.716
111.308
5.009
Nil

64.93
10.00
0.45
Nil

658.632
111.308
31.788
10.526

62.16
10.51
3.00
0.99

1113.083

100.00

1059.525

100.00

Composition of Gas Streams


Gas mixture after
condensation
CO
CO2
H2
Inerts
CH3OH
Total

kmol/s

mole %

117.596
129.675
658.632
111.308
5.055
1022.266

Purge steam
kmol/s

mole %

11.50
12.69
64.43
10.89
0.49

1.056
1.165
5.917
1.000
0.045

11.50
12.69
64.43
10.89
0.49

100.00

9.184

100.00

Compositions of Gas Streams


Recycle (R) stream
Component
CO
CO2
H2
Inerts
CH3OH
Total

kmol/s

Fresh feed (M-R)

mole %

kmol/s

mole %

116.540
128.510
652.715
110.308
5.010

11.50
12.69
64.43
10.89
0.49

17.309
11.691
70.000
1.000
Nil

17.31
11.69
70.00
1.00
Nil

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
133.849
= 12.14% per pass

Conversion of CO =

Stoichiometry and Industrial Problems 317

10.526 100
140.201
= 7.51% per pass

Conversion of CO2 =

(16.253 2 + 10.526 3) 100


722.716
= 8.87% per pass

Conversion of H2 =

Recycle ratio =

1013.083
= 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
140.201
2995.5
9012.7
5755.4
1374.0
CO2
722.716
20 677.3
736.7
106.7
555.8
H2
Ar
33.392
693.6

CH4
77.916
1499.8
4060.5
932.9
881.8
5.009
124.6
254.8
293.7
226.0
CH3OH
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
129.675
2770.6
8336.0
5323.2
1270.8
CO2
658.632
18843.8
671.4
97.2
506.5
H2
Ar
33.392
693.6

77,916
1499.8
4060.5
932.9
881.8
CH4
31.788
790.5
1617.2
1863.6
1434.5
CH3OH
H2O
10.526
342.0
0.8
139.1
47.9
Total

1059.525

28 353.8

14 354.7

1115.5

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)

1140.3

318 Solutions ManualStoichiometry

= 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 275C (548.15 K) over 298.15 K,
f3 =

548.15

298.15

(28.353.8 + 14 354.7 103 T 1115.5 106

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

298.15

(29876.1 + 13 687.7 103 T 3077.0 106


T 2 + 192.1 109 T 3) dT

Solving by Mathacad
Ans.
T1 = 486.47 K or t1 = 213.32C
Thus ingoing gas stream is to be heated from 66C (339.15 K) to 213.32C
(486.47 K).
Heat exchange in the heat exchanger (HE-1),
f4 =

486.47

339.15

(29876.1 + 13 687.7 103 T 3077.0 106


T2 + 192.1 109 T 3) dT

= 5157 753 kJ/h


1432.709 kW
If temperature of reactor exit gas stream after cooling in HE-1 is T 2,
248.15

T2

(28 353.8 + 14 354.7 10 3 T 1115.5 10 6


T2 1140.3 109 T 3) dT = 5157 753 kJ/h

Solving by Mathcad, T 2 = 399.86 K or t2 = 126.71C

Ans.

Stoichiometry and Industrial Problems 319

EXERCISE 8.16
Heat duty of chiller, fch = 1500 kW
.
Let mch be the mass flow rate of chilled water.
.
fch = mch CL Dt
.
mch =

1500
= 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 6C (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 45.83C (318.98 K)
Enthalpy of water at 6C = 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

320 Solutions ManualStoichiometry

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
38 775.83 + 36 449.28
+
1.842 (48.9 40)

Heat duty of generator,

= 1158 621.9 + 5787 060.5 + 616 612.7


= 7562 295.1 kJ/h
2100.638 kW
fg = Sensible heat change of WA from 75C
(348.15 K) to 88.9C (362.05 K) + Sensible
heat change from 88.9C (362.05 K) to
101.6C (374.75 K) + Heat of concentration
of LiBr solution + Latent heat of vaporization
of water at 45.83C (318.98 K)
= 38 775.83 1.842 (88.9 75)

38 775.83 + 36 449.28
+
1.842 (101.6
2

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 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
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
1614.865 kW

Stoichiometry and Industrial Problems 321

Cooling water enters at 32C (305 K) into absorber coils and leave at 40C
(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
399.3 m3/h
Rise in CW temperature across absorber
=

2100.638
= 4.523C or K
110.929 4.1868

Rise in CW temperature across condenser = 8 4.523 = 3.477C 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,
Condensate or
MPa a
BFW
Steam
4.6
Steam
0.95
Steam
0.95
Steam
0.1013
Steam
0.1013
Steam
0.014
Steam
0.014
Condensate
0.014
Condensate
0.014
Condendsate 0.014
BFW
4.9

Temperature,
K (C)
673
553
450.8
473
373
325.7
325.7
325.7
373
450.8
394

(400)
(280)
(177.7)
(200)
(100)
(52.6)
(52.6)
(52.6)
(100)
(177.7)
(121)

Condition

Enthalpy
kJ/kg

Superheated
Superheated
Saturated
Superheated
Saturated
0.955 DF
0.867 DF
Saturated
Saturated
Saturated
Subcooled

3205.3
3010.5
2774.2
2875.3
2676.0
2489.7
2280.6
220.0
419.1
752.8
508.0

Turbine A:
Heat transfer in turbine = 3205.3 3010.5 = 194.8 kJ/kg
1426 3600
= 27 740.2 kg/h
Steam requirement in turbine =
0.95 194.8
Let x1 kg/h BFW is introduced in steam at 0.95 MPa a and 553 K (280C).
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

322 Solutions ManualStoichiometry

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
(200C).
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 498.7 kW
Enthalpy removal in condensing part
= 2589.5 498.7 = 2090.8 kW
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 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

Stoichiometry and Industrial Problems 323

Total steam requirement @ 46 bar a and 673 K (400C)


= 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
Steam
Conditions

Final
steam
conditions

Enthalpy
available
for energy
conversion,
kJ/kg

Actual
energy
conversion
(97%),
kJ/kg

Soevific
steam
consumption
in turbine,
kg/kWh

64 bar a
440C
(713 K)
3273.3 kJ/kg

39 bar a
385C
(658 K)
3182.1 kJ/kg

91.2

88.464

40.6945

303.804

11.8497

684.723

5.2576

596.259

6.0376

Final steam conditions

BFW

39 bar a
4.4 bar a
313.2
385C
205C
(658 K)
(478 K)
3182.1 kJ/kg 2868.9 kJ/kg
64 bar a
12 kPa a
705.9
440C
50C (323 K)
(713 K)
99% dry
3273.4 kJ/kg 2567.4 kJ/kg
39 bar a
12 kPa a
614.7
385C
50C (323 K)
(658 K)
99% dry
3182.1 kJ/kg 2567.4 kJ/kg
BFW Requirements for Desuperheating
Initial steam conditions
Pressure
bar a

Temp.
C(K)

Enthalpy
kJ/kg

Pressure
bar a

64
39
39
4.4

440 (713)
385 (658)
385 (658)
205 (478)

3273.3
3182.1
3182.1
2868.9

39
15
4.4
4.4

Temp.
C (K)
385 (658)
Satd.
Satd.
Satd.

Enthalpy
kJ/kg
3182.1
2789.9
2741.9
2741.9

requirement,
kg/kg initial
Steam
0.0333
0.1669
01912
0.0552

324 Solutions ManualStoichiometry

Nomenclature will be same as that followed in Example 8.7.


Saturated 15 bar a steam requirement = 3 t/h
Equivalent MP steam =

3
= 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
Deaerator:
Equation remains unchanged
a 0.11 b 0.11 e = 1.815
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
FD fan turbine:

d=

(1)
(2)

(3)

2.47 (b + c + d + e + g - 0.0333h + 2.5709) 11.8497


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 105C (378 K)
Power requirement =

(a + b + e + 16.5) 742.907 0.7355 1000


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
CW pump turbine:
Enthalpy, given-up in
SC = 2567.4 209.2
= 2358.2 kJ/kg steam

CW requirement in

SC =

2358.2 (b + e)
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

(5)

Stoichiometry and Industrial Problems 325

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
1000
656.1343 b 56.3246 e = 600
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

b=

(6)

(56.332 - 53.618) 100


53.618
= 5.06 %
Energy absorption in 64 bar a boiler
= 56 332 (3273.3 440.17)
= 159 595 879 kJ/h
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
40 966.088 kW
Increase in energy absorption in boiler
= 159 595 879 147 477 918
= 12 117 961 kJ/h
3366.1 kW

in Example 8.7 =

Increase in energy consumption in boiler =


Additional fuel requirement =

12 117 961 100


= 8.22%
147 477 918
12 117 961
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 (165C) = 2785.1 kJ/kg

326 Solutions ManualStoichiometry

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
Specific steam consumption =

3600
235.3 0.97

= 15.773 kg/kWh

Stoichiometry and Industrial Problems 327

2.47 15.773(b + c + d + e + g + 2.74 )


1000
b + c 24.668 d + e + g = 2.74
(4)
BFW pump:

d=

5.493 15.773( a + b + e + 16.95)


1000
a + b + e 11.542 c = 16.95
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.

c=

(5)

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

328 Solutions ManualStoichiometry

a + e 11.14 c = 16.5

CW pump:

(5)

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.

6
2
5
1
3
4

0
1
1
1
0
0

1
0
0
0
0
11.14
1.022
1.022
5.16
5.16
1
1

Constant

0
0
0
1.121
5.16
1

0
0
0.2045
2.2696
0
0
0.11
1.815
0
0
1
16.500
1.121
0
0
13.50
5.16 5.50
21.79
768.17
1
0.066
1
2.74

Mathcad solution
Matrix

. O
LM-1 1.022 1.022 1.022 0 1121
PP
-0.11 0
0
0
MM 10 0516
.
5.16
5.16
21.79 5.16 P
M: = M
PP
-23.78
1
1
1
MM 01 10 -1114
.
0
1
0
PP
MN 0 264.36 0
-54.05 0
0
Q
LM 13.5 OP
MM 7541..815
P
03 P
v: = M
MM--162..574 PPP
MN 600 PQ
.
OP
LM 5153
474
PP
MM 48..668
Solution = M v
Solution = M
061 P
PP
MM302..346
MN 2.78 PQ
1

Refer Fig. 8.23 in the text for steam balance.

Ans.

Stoichiometry and Industrial Problems 329

EXERCISE 8.21
Nomenclature will be same as that of Example 8.7.
Initial steam
conditions

Final steam
conditions

Enthalpy
available for
energy
conversion,
kJ/kg
170.3

Actual energy Specific


conversion
steam
(97%),
consumption
kJ/kg
in turbine
kg/kWh
165.2
21.79

115 bar a
713 K (440 C)
3190.7 kJ/kg

39 bar a
593 K (320 C)
3020.4 kJ/kg

36 bar a
673 K (400 C)
3222.5 kJ/kg

4.4 bar a
458 K (185 C)
2826.0 kJ/kg

396.5

384.6

9.36

115 bar a
713 K (440 C)
3190.7 kJ/kg

12 kPa a
323 K (50 C), 95% dry
2472.0 kJ/kg

718.7

697.1

5.16

36 bar a
673 K (400 C)
3222.5 kJ/kg

12 kPa a
323 K (50 C), 95% dry
2472.0 kJ/kg

750.5

728.0

4.945

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)

330 Solutions ManualStoichiometry

CW Pump Turbine:
0.2315(54.05b + 54.05e + 600 )4.945
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.

b=

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 (34C).
1171.53
log10 p1 = 4.002 66
(307.15 - 48.784)
= 0.666 35
p1 = 0.294 bar 29.4 kPa
29.4
86.1754

28.0134
(102 - 29.4)
= 1.2457 kg n-hexane/kg dry N2
Nitrogen circulation rate = 10 000 0.18
= 1800 kg/h 64.255 kmol/h

n-Hexane content =

Stoichiometry and Industrial Problems 331

n-Hexane circulation in N2 = 1800 1.2457


= 2242.26 kg/h
26.02 kmol/h
Nitrogen-n-Hexane mixture is heated from 343.15 K (70C) 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
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 (90C),
log10 p2 = 4.002 66

1171.53
(363.15 - 48.784)

= 0.276 02
p2 = 1.888 bar 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 0.6302 bar


log10 p3 = 0.200 52
= 4.002 66

1171.53
(T3 - 48.784)

Saturation temperature T3 = 327.5 K (54.35C)


Reference temperature To = 298.15 K (25C)
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

332 Solutions ManualStoichiometry

+ 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
276.840 kW
In the interchanger, N2-n-hexane mixture from the blower at 307.15 K (34C) is
heated to 343.15 K (70C).
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 76.2C 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 (25C) is calculated using Watson equation [Ref.
Eq. (5.25)].

Stoichiometry and Industrial Problems 333


0.98

507.6 - 298.15
lv =
28 850

507.6 - 341.9
= 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
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
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
301.926 kW
Heat required for evaporation,
f7 = 31 537 5185/86.1754
= 1897 518 kJ/h 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

334 Solutions ManualStoichiometry

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
Molar flow rate =

100
= 4.4615 kmol/h
22.414

Solvent laden nitrogen comes out from the dryer at 105 kPa and 90C (363.15 K)
with a DP = 10C (283.15 K).
Refer Table 5.4 for Antoine constants for CH2Cl2.
At 10C, log10 pv1 = 4.53691 +

1327.016
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
= 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 90C to 40C in a cooler with cooling
water. Since DP = 10C, no condensation will take place.

y1 =

f1 = 4.4615

363.15

363.15

313.15

313.15

o
C pN2 dT + 1.8306 C pmc dT

= 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 3.195 kW

Stoichiometry and Industrial Problems 335

Solvent laden N2 enters cryo condenser at 40C and leaves at 31C (242.15 K).
log10pv2 = 4.536 91 +

1327.016
(242.15 - 20.474)

= 1.449 38
pv2 = 0.0355 bar or 3.55 kPa
CH2Cl2 content of saturated N2 stream, leaving cryo condenser,
y2 =

3.55
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
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
1.8306
21.73
315.36
273.22
95.71
CH2Cl2
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 0.814 kW
Ideal Gas Heat Equation Constants for Outgoing 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
0.1611
1.91
27.75
24.04
8.42
Total

4.6226

133.93

3.81

34.78

13.74

336 Solutions ManualStoichiometry

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 2.135 kW
Sensible heat load of cryo condenser
f 4 = 2931.04 (7685.04)
= 10 616.08 kJ/h 2.949 kW
Average temperature of condensation
=

10 + (-31)
= 10.5C
2

lv1 at TB (= 313 K) = 28.06 kJ/mol


Tc = 508.K
Using Watson equation,

or 262.65 K

(Ref. Table 5.5)

508 - 262.65
lv2 = 28.06

508 - 313

0.38

= 30.619 kJ/mol CH2Cl2


Condensation heat duty, f4 = 30 619 1.6695
= 51 118.42 kJ/h
14.20 kW
Total heat duty of cryo condenser
f4 = f4 + f4
= 61 734.5 kJ/h 17.149 kW
(a) Conventional cryo condenser:
N2 vapour (as refrigerant) enters the coil at 5 bar a and 170C (103.15 K) and
leaves at 4.8 bar a and 4C (277.15 K).
Enthalpy available for refreigeration
= 408.41 220.23
= 185.16 kJ/kg N2
51 118.42
= 276.08 kg/h
185.16
(b) Modified cryo condenser:
Refrigeration in one coil = 408.53 220.23
= 188.03 kJ/kg

LN requirement =

Stoichiometry and Industrial Problems 337

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
=
Reduction in LN requirement =

51 118.42
= 136.87 kg/h
373.48
(276.08 - 136.87) 100
276.08

= 50.42 %

Ans.

EXERCISE 8.24
(a) Basis: 900 kg liquid chlorine at 303.15 K (30C)
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
A1 =
where

1 2
r a1
2

a1 = angle in radians
2 p radians = 360
6.283 18 radians = 360
1 radian = 57.296
r = 0.76/2 = 0.38 m

338 Solutions ManualStoichiometry

1
(0.38)2 a1 = 0.362 63
2

a1 = 5.022 58 radian
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,
A1 = 1.9086 1.8
= 3.435 48 m2
Energy balance:
.
Chlorine withdrawl rate, m3 = 5.56 g/s
= 20.016 kg/h
.
m3 lv1 = UA1(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
Average lv =

(245.5 + 270.82)
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
A1 = 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

Stoichiometry and Industrial Problems 339

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
Average lv = 274.5 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
A1 = 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
Average lv = 275.44 kJ/kg
V 1 = 900/1504.53
= 0.598 19 m3
A 1 = 0.598.19/1.8 = 0.332 33 m2

340 Solutions ManualStoichiometry

a1 = 0.332 33 2/(0.38)2
= 4.6029 radian
S = 4.6029 0.38
= 1.749 10 m
A1 = 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 012.67C
This Ts value is close enough to the value of iteration 4.
Steady state temperature,
t/T = 12.67C/260.48 K
Average latent heat between 303.15 K and 260.48 K
l=

Ans.

(245.5 + 275.44)
= 260.47 kJ/kg
2

Average heat transfer rate, f = 20.016 260.47


= 5213.6 kJ/h
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 33.98C (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

Stoichiometry and Industrial Problems 341

A1 = 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
Cl dT
dq
=
 lv ]

T1 [UA (Ta - T ) - m
0 ( M 0 - mq )
.
a = UA (Ta T) mlv
da
= UA
dT
.
T = T0, a = UA (Ta T0) mlv = a0
.
b = Cl (M0 mq)
.
db
= Cl m
dq
q = 0, b = ClM0 = b0

Let

When
Let

when
Rewriting Eq. (2)

a0

(2)

b
da
db
=

-UA a
b0 - Cl mb

a = 1 ln b
1
ln
Cl m
b0
UA a0

UA / C m

l
C [ M 0 - m q ]
UA (Ta - T ) - m lv
ln
= ln l

UA (Ta - T0 ) - m lv
Cl M 0

Simplifying,
.
.
.
.
UA (Ta T) mlv = (UA (Ta T0) mlv) (1 mq/M0)UA/Clm
Rearranging,

T=

1

(UA Ta - m lv ) + [m lv = UA (Ta - T0 )] (1 - m q / M 0 )UA / Cl m (3)
UA

342 Solutions ManualStoichiometry

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,
A1 = 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
.
UA1/mCl = 41.04 0.381 71/(20.016 0.985)
= 0.794 56
.
.
(UA1/mCl)
[1 mq/M0]
= (0.959 97)0.794 56
= 0.968 06
T2 =

1
[ (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

Stoichiometry and Industrial Problems 343

lv at 293.13 K = 253.13 kJ/kg


Average mass of liquid chlorine for 0.2 h period,
M0 =

(100 + 95.9968)
= 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 (34.75C)
Spreadsheet Excel was used for calculations as attached.

Ans.

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
Benzene (1)
Toluene (2)
Ethylebenzene (3)
Styrene (4)

mole fraction
0.228
0.722
0.050
.

Antoine constants (Ref. Table 5.4)


A
4.018 14
4.078 27
4.074 88
4.219 48

B
1203.835
1343.943
1419.315
1525.059

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 36.77C

C
53.226
53.773
60.539
56.379

Initial value of T
Tin,K
303.15
Liquid density at T
ri, kg/m3 1378.83
Liquid latent
lv, kJ/kg
245.50
heat of vap.
Average liquid density ri, kg/m3 1378.83
Average latent
lV, kJ/kg
245.50
heat of vap.
Average Mo
Mo, kg
100
0.07253
Volume of liquid
V1, m3
Cross-sectional area
A1, m2
0.04029
Central angle
a1, radian 0.55806
Arc length
Si, m
0.21206
0.38171
Area in contact
A1, m2
with liquid
m*q/Mo
0.04003
1m*q/Mo
0.95997
UA 1
15.6654
303.15
To
UA1/mC1
0.79456
(1-m*q/Mo)(UA 1 /mC1)
0.96806
UATa
4748.968
4913.851
mlv (avg)
UA (Ta To)
0.000
4756.899
Calculated T
Tcal,K
293.13

293.13
1410.59
253.36

287.91
1426.64
257.28

285.29
1434.53
259.19

283.98
1438.45
260.13

283.33
1440.40
260.60

283.00
1441.37
260.83

282.84
1441.85
260.95

282.76
1442.10
261.01

282.72
1442.22
261.04

1394.71
249.43

1402.74
251.39

1406.68
252.34

1408.64
252.81

1409.62
253.05

1410.10
253.16

1410.34
253.22

1410.47
253.25

1410.53
253.27

97.9984
0.07026
0.03904
0.54066
0.20545
0.36981

97.9984
0.06986
0.03881
0.53757
0.20428
0.36770

97.9984
0.06967
0.03870
0.53606
0.20370
0.36666

97.9984
0.06957
0.03865
0.53531
0.20342
0.36615

97.9984
0.06952
0.03862
0.53494
0.20328
0.36590

97.9984
0.06950
0.03861
0.53476
0.20321
0.36578

97.9984
0.06949
0.03860
0.53467
0.20317
0.36571

97.9984
0.06948
0.03860
0.53462
0.20316
0.36568

97.9984
0.06948
0.03860
0.53460
0.20315
0.36567

0.04085
0.95915
15.1771
298.14
0.76979
0.96840
4600.926
4992.569
76.030
4761.195
287.91

0.04085
0.95915
15.0902
295.53
0.76539
0.96858
4574.608
5031.750
115.025
4762.250
285.29

0.04085
0.95915
15.0479
294.22
0.76324
0.96867
4561.772
5050.868
134.372
4762.454
283.98

0.04085
0.95915
15.0270
293.57
0.76218
0.96871
4555.434
5060.306
144.006
4762.475
283.33

0.04085
0.95915
15.0166
293.24
0.76166
0.96873
4552.287
5064.994
148.813
4762.465
283.00

0.04085
0.95915
15.0114
293.08
0.76139
0.96874
4550.718
5067.329
151.212
4762.454
282.84

0.04085
0.95915
15.0089
293.00
0.76126
0.96875
4549.936
5068.494
152.411
4762.448
282.76

0.04085
0.95915
15.0076
292.95
0.76120
0.96875
4549.545
5069.076
153.010
4762.444
282.72

0.04085
0.95915
15.0069
292.93
0.76116
0.96875
4549.350
5069.366
153.309
4762.442
282.70

344 Solutions ManualStoichiometry

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 = 30C/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)

Second interval q2 = 0.2 h

Calculated T

Tin.K
ri, kg/m3
lv, kJ/kg
ri, kg/m3
lv, kJ/kg
Mo, kg
V1, m3
A1, m2
a1, radian
S1, m
A1 m2

282.70

Tcal,K

282.70
1442.27
261.05
1442.27
261.05
95.9968
0.06795
0.03775
0.52283
0.19868
0.35762
0.04085
0.95915
14.6766
277.55
0.74441
0.96943
4449.216
5225.141
300.137
4774.445
272.44

272.44
1472.70
268.26
1457.49
264.65
93.9952
0.06383
0.03546
0.49111
0.18662
0.33592
0.04259
0.95741
13.7862
274.64
0.69925
0.97003
4179.288
5369.526
352.985
4866.171
266.64

266.64
1488.13
271.85
1465.20
266.45
93.9952
0.06349
0.03527
0.48855
0.18565
0.33417
0.04259
0.95741
13.7144
273.20
0.69560
0.97018
4157.508
5405.415
390.938
4864.940
263.74

263.74
1495.70
273.59
1468.98
267.32
93.9952
0.06333
0.03518
0.48731
0.18518
0.33332
0.04259
0.95741
13.6794
272.47
0.69383
0.97025
4146.910
5422.821
409.763
4863.939
262.29

262.29
1499.44
274.44
1470.86
267.75
93.9952
0.06325
0.03514
0.48669
0.18494
0.33290
0.04259
0.95741
13.6622
272.11
0.69296
0.97029
4141.686
5431.384
419.126
4863.347
261.57

261.57
1501.30
274.87
1471.79
267.96
93.9952
0.06321
0.03512
0.48639
0.18483
0.33269
0.04259
0.95741
13.6536
271.93
0.69252
0.97031
4139.095
5435.627
423.790
4863.031
261.21

261.21
1502.23
275.08
1472.25
268.06
93.9952
0.06319
0.03511
0.48624
0.18477
0.33259
0.04259
0.95741
13.6494
271.84
0.69231
0.97032
4137.806
5437.738
426.115
4862.869
261.03

261.03
1502.69
275.18
1472.48
268.12
93.9952
0.06318
0.03510
0.48616
0.18474
0.33254
0.04259
0.95741
13.6472
271.80
0.69220
0.97032
4137.163
5438.790
427.274
4862.787
260.94

260.94
1502.92
275.23
1472.60
268.14
93.9952
0.06318
0.03510
0.48612
0.18473
0.33251
0.04259
0.95741
13.6462
0.69215
0.97032
4136.842
5439.314
427.852
4862.747
260.90

Stoichiometry and Industrial Problems 345

Initial value of T
Liquid density at T
Liquid latent heat of vap.
Average liquid density
Average latent heat of vap.
Average Mo
Volume of liquid
Cross-sectional area
Central angle
Arc length
Area in contact with liquid
m*q/Mo
1m*q/Mo
UA 1
To
UA1/mC1
(1-m*q/Mo)(UA1/mC1)
UATa
mlv (avg)
UA (Ta To)

Initial value of T
Liquid density at T
Liquid latent heat of vap.
Average liquid density
Average latent heat of vap.
Average Mo
Volume of liquid
Cross-sectional area
Central angle
Arc length
Area in contact with liquid
m*q/Mo
1m*q/Mo
UA 1
To
UA1/mC1
(1-m*q/Mo)(UA1/mC1)
UATa
mlv (avg)
UA (Ta To)

Tin,K
ri, kg/m3
lv, kJ/kg
ri, kg/m3
lv,kJ/kg
Mo, kg
V1,m3
A1 m2
a1 radian
S1 m
A1 m2

260.92
250.22
244.44
241.55
1502.99
1531.84
1546.36
1553.45
275.25
281.70
284.86
286.38
1502.99
1517.42
1524.68
1528.22
275.25
278.48
280.06
280.81
91.9936
89.9920
89.9920
89.9920
0.06121
0.05875
0.05847
0.05834
0.03400
0.03264
0.03248
0.03241
0.47097
0.45204
0.44991
0.44888
0.17897
0.17178
0.17097
0.17057
0.32214
0.30920
0.30774
0.30703
0.04352
0.04448
0.04448
0.04448
0.95648
0.95552
0.95552
0.95552
13.2207
12.6895
12.6296
12.6006
260.92
255.73
252.76
251.27
250.53
0.67056
0.64362
0.64058
0.63911
0.97061
0.97114
0.97127
0.97134
4007.851 3846.812 3828.667 3819.875
5509.428 5638.517 5670.126 5685.314
554.079
601.717
636.437
653.672
4809.693 4891.426 4889.079 4887.419
Calculated T
Tcal, K
250.22
244.28
241.31
239.83
Final temperature of liquid chlorine in container after 0.6 h (2160 s) = 238.40 K (34.75C)

240.11
1556.94
287.12
1529.97
281.18
89.9920
0.05827
0.03237
0.44837
0.17038
0.30669
0.04448
0.95552
12.5864
250.17
0.63839
0.97137
3815.554
5692.743
662.244
4886.470
239.09

239.39
1558.67
287.49
1530.83
281.37
89.9920
0.05824
0.03235
0.44812
0.17029
0.30651
0.04448
0.95552
12.5793
249.98
0.63803
0.97138
3813.416
5696.411
666.510
4885.968
238.72

239.03
1559.53
287.67
1531.26
281.46
89.9920
0.05822
0.03235
0.44799
0.17024
0.30643
0.04448
0.95552
12.5758
249.89
0.63786
0.97139
3812.355
5698.230
668.635
4885.711
238.54

238.85
1559.96
287.76
1531.48
281.50
89.9920
0.05821
0.03234
0.44793
0.17021
0.30639
0.04448
0.95552
12.5741
249.84
0.63777
0.97140
3811.826
5699.135
669.693
4885.581
238.45

238.76
1560.18
287.80
1531.58
281.53
89.9920
0.05821
0.03234
0.44790
0.17020
0.30636
0.04448
0.95552
12.5732
0.63772
0.97140
3811.563
5699.585
670.220
4885.516
238.40

346 Solutions ManualStoichiometry

Third interval q2 = 0.2 h

Stoichiometry and Industrial Problems 347

T1t = saturation temp. of toluene at 21.3 kPa


= 336.71 K or 63.56C
T1e = saturation temp. of ethylbenzene at 21.3 kPa
= 359.56 K or 86.41C
T1 = 309.92 0.228 + 336.71 0.722 + 359.56 0.05
= 331.7 K (58.55C) first assumption for the bubble point and
dew point calculations
Bubble point: All pressures are in kPa.
Component

xi

Benzene(1)
0.228
Toluene (2)
0.722
Ethyl
0.050
benzene (3)
Total

Temperature, K
T1 = 331.7 K
p si
49.606
17.497
6.932

1.000

T2 = 328.7 K

yi
0.531
0.582
0.016

p si
44.512
15.496
6.059

T3 = 328.3 K

yi
0.477
0.525
0.014

1.129

p si
43.826
15.233
5.946

1.016

0.999

Bubble point of distillate product TBB = 328.3 K (55.15 C)


Dew Point: All pressures are in kPa.
Component

yi

yi
0.469
0.516
0.014

Ans. (b i)

Temperature, K
T1 = 33.17 K
p si
xi

T2 = 336 K
p si
xi

T3 = 335 K
p si
xi

T4 = 334.7 K
p si
xi

Benzene(1) 0.228 49.606 0.098 58.011


Toluene(2) 0.722 17.497 0.879 20.852
Ethyl
0.050 6.932 0.154 8.420
benzene(3)

0.084
0.738
0.126

56.030 0.087 55.112


20.050 0.767 19.693
8.065 0.132 7.906

0.088
0.781
0.135

Total

0.948

0.986

1.004

1.000

1.131

Dew point of distillate product, TDP = 334.7 K (61.55C)


Ans. (b ii)
Average temperature of condensation = (TBB + TDP)/2
= (328.3 + 334.7)/2
= 331.5 K (58.35C)
Consider reference temperature, T0 = 331.5 K
Use Watson equation [Eq. (5.26)] and data from Table5.5 for calculation of
enthalpy of vaporisation.
562.05 331.5
lv1 = 30 720

562.05 - 353.3

0.98

= 31 902 kJ/kmol of benzene

348 Solutions ManualStoichiometry

591.75 - 331.5
lv2 = 33 180

591.75 - 383.8

0.98

= 36 133 kJ/kmol of toluene


0.98

617.15 - 331.5
= 40 138 kJ/kmol of ethylebenzene
lv3 = 35 570

617.15 - 409.3
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 95.03C
T1 = 336.7 0.005 359.6 0.475 + 368 0.52 = 364 K (90.85C)

Bubble Point: All pressures are in kPa


Component

Temperature, K

xi

T1 = 364.0 K
p si
yi

Toluene(2)
0.005
Ethyl
0.475
benzene(3)
Styrene(4)
0.520
Total

T2 = 363.0 K
p si
yi

T3 = 363.55 K
p si
yi

52.350
23.304

0.012
0.520

54.078
24.154

0.013
0.539

54.935
24.594

0.013
0.548

17.018

0.415

17.668

0.431

17.973

0.439

1.000

0.947

0.983

1.000

T BB = 363.55 K (90.4C)
Data on heat capacity constants:
Component

xi

liquid heat capacity (Cmp) equation constants


bi xi 103
4.061
427.583

ci xi 106
7.563
688.774

di xi 109
8.150
680.960

Toluene(2)
Ethyl
benzene(3)
Styrene(4)

0.005
0.475

ai xi
0.009
2.049

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

Stoichiometry and Industrial Problems 349

1838.075 106 (363.553 331.53)/3


+ 1694.332 109 (363.554 331.54)/4]
= 572 794 kJ/h
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 (87.7C)
Bubble Point: All pressures are in kPa.
Component

Temperature, K

xi

T1 = 360.7 K
p si
yi

T2 = 358.0 K
p si
yi

T3 = 357.75 K
p si
yi

Benzene(1)
Toluene(2)
Ethyl
benzene(3)
Styrene(4)

0.022
0.074
0.434

124.80
49.19
21.757

0.129
0.171
0.443

117.27
45.88
20.145

0.121
0.159
0.410

116.137
45.402
19.927

0.120
0.158
0.406

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:
Component

xi

Lliquid heat capacity Cmp equation constants


ai xi

bi xi 103

ci xi 106

di xi 109

Benzene(1)
Toluene(2)
Ethyl
benzene(3)
Styrene (4)

0.022
0.074
0.434

0.160
0.134
1.872

16.952
60.105
390.676

36.26
111.93
629.322

41.755
120.621
622.182

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
140.66 kW
Reboiler duty = Heat load of condenser + Enthalpy of distillate

350 Solutions ManualStoichiometry

+ 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 (250C)
Offgas mixture flow rate =

40 000
= 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
N2
Ar
CH4
CO
CO2
C2H2

15.3
61.9
0.9
0.4
17.2
3.9
0.4

0.4
17.2
3.9
0.8

15.3

0.8

0.4

8.6
3.9

Total

100.0

22.3

16.5

12.5

Moisture in offgas mixture = 0.15 100 = 15 kmol


16.5
12.5
2
18.05 kmol
10%
18.05 1.1 = 19.855 kmol
79 19.855/21 = 74.693 kmol
19.855 + 74.693 = 94.548 kmol
2726.76 kg
94.548 0.017
1.607 kmol

Theoretical O2 requirement = 22.3 +


=
=
=
=
=

Moisture, entering with air =


=
Excess air
Actual O2 supply
N2, entering with O2
Total dry air

Stoichiometry and Industrial Problems 351

Boiler Flue Gas Analysis


Component
N2 + Ar
O2
CO2
H2O

kmol

Dry analysis, %
(Orsat)

Wet analysis
%

85.08
1.12
13.80

70.62
0.93
11.45
17.00

194.705 (wet) 100.00


161.598 (dry)

100.00

61.9 + 0.9 + 74.693 = 137.693


19.855 18.05 = 1.805
22.300
16.5 + 15.0 + 1.607 = 33.107

Total

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 (250C)
T0 = 298.15 K (25 C)
Component

kmol, ni

Cmp equation constants


ni ai

ni bi 103

H2
N2
Ar
CH4
CO
CO2
C2 H 2
H2O

15.3
61.9
0.9
0.4
17.2
3.9
0.4
15.0

437.741
1831.676
18.695
7.700
499.276
144.979
9.002
487.382

15.600
318.230

20.845
48.444
90.625
36.050
1.194

Total

115.0

3436.451

202.360
3

ni ci 106

ni di 109

2.258
816.022

4.789
200.272
28.777
25.494
198.161

11.628
307.519

4.527
80.948
3.203
7.146
68.211

1162.716

439.228

H2 = 3436.451 (523.15 298.15) 202.36 10 (523.15 298.152)/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 (40C):
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

352 Solutions ManualStoichiometry

Heat Output:
Heat loss in flue gases at 448.15 K (175C):
Component

kmol, ni

Cmp equation constants


ni ai

ni bi 103

ni ci 106

ni di 109

1812.556
4.228
915.428
437.367

683.065
1.015
218.538
150.5511

N2
O2
CO2
H2O

137.493
1.805
22.300
33.107

4068.542
46.976
476.451
1075.716

706.852
21.218
1433.535
2.635

Total

194.705

5667.685

750.536
3

1330.267
2

616.093
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:
Humidity of flue gas =

kmol
33107
.
= 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 (56.4C)
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

Stoichiometry and Industrial Problems 353

39 568.117 kW
From steam tables:
Enthalpy of superheated steam at 43 bar a and 698.15 K (425C)
= 3269 kJ/kg
Enthalpy of BFW at 303.15 K (30C) = 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 (55C),
pw2 = 15.741 kPa
kmol
15.741
Humidity of offgas =
= 0.1647
111325
.
- 15.741
kmol dry gas
Element Balance of Offgas Mixture
Component
H2
N2
Ar
CH4
CO
CO2
C2H2

kmol
15.147
61.281
0.891
0.396
17.028
0.116
0.396

C, kmol

0.396
17.028
0.116
0.792

H2, kmol
15.147

0.792

0.396

O2, kmol

8.514
0.116

Total
95.255 (dry)
18.332
16.335
Water, entering with gas mixture = 95.255 0.1647
= 15.688 kmol
16.335
Theoretical O2 requirement = 18.332 +
8.63
2
= 17.87 kmol
Actual O2 supply = 17.87 1.1 = 19.657 kmol
N2, entering with O2 = 79 19.657/21
= 73.948 kmol
Total dry air = 19.657 + 73.948 = 93.605 kmol

8.630

354 Solutions ManualStoichiometry

2699.568 kg
Moisture entering with air = 93.605 0.017
= 1.591 kmol
Boiler Flue Gas
Component
N2 + Ar
O2
CO2
H2O

kmol
61.281 + 0.891 + 73.948 =
19.657 17.87 =
0.116 + 18.332 =
15.688 + 16.335 + 1.591 =

Total

Dry analysis, %
(Orsat)
136.12
87.06
1.787
1.14
18.448
11.80
33.614

wet189.969
dry 156.355

100.00

Wet
analysis %
71.65
0.94
9.71
17.70
100.00

Heat Input to Boiler:


Heat of offgas mixture to boiler at 328.15 K (55C):
Component

kmol, ni

C mp equation constants
ni ai

ni bi 103

ni ci 106

ni di 109

H2
N2
Ar
CH4
CO
CO2
C2H2
H2O

15.147
61.281
0.891
0.396
17.028
0.116
0.396
15.688

433.363
1813.360
18.508
7.623
494.284
2.478
8.912
509.736

15.441
315.046

20.637
47.959
7.457
35.689
1.249

2.236
807.861

4.741
198.270
4.762
25.239
207.249

11.648
304.444

4.482
80.139
1.137
7.074
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 (40C):
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

Stoichiometry and Industrial Problems 355

Heat output:
Unaccounted heat loss, H13 = 10 159 523 0.015
= 152 393 kJ
Heat loss in flue gases at 448.15 K (175C):
Component

kmol, ni

C mp
equation constants
ni ai

ni bi 103

ni ci 106

ni di 109

1794.456
4.186
757.301
444.064

676.244
1.005
180.789
152.856

1477.033

649.316

N2
O2
CO2
H2O

136.12
1.787
18.448
33.614

4027.913
46.508
394.151
1092.189

699.793
21.006
1185.913
2.676

Total

189.969

5560.761

509.802
3

H7 = 5560.761 (448.15 298.15) + 509.802 10 (448.15 298.152)/2


+ 1477.033 106 (4483 298.153)/3 649.316 109 (448.154 298.154)/4
= 887 744.8 kJ
pw1
kmol
33.614
=
= 0.215
p - pw 3
kmol dry gas
156.355

pw3 = 17.572 kPa


From Table 6.13,
From Steam Tables,

Ts = 330.45 K (57.3C).
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
36 310.0 kW
130 715 991
Steam generation =
= 41 528.9 kg/h
Ans. (i)
3147.59
1784.6
44.0098 0.95
CO2 production = 3.745
115
= 2429.79 kg/h
51 315 kg/d
51.315 t/d
Ans. (ii)

356 Solutions ManualStoichiometry

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 (25C)
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 (25C):
Element Balance of Reject Gas Stream:
Component
H2
N2
Ar
CH4
CO
CO2
C2H2
H2O
Total

kmol
1.5
60.668
0.882
0.392
10.110
0.115
0.392
Nil

C, kmol

0.392
10.110
0.115
0.784

H2, kmol
1.5

0.784

0.392

O2, kmol

5.055
0.115

74.059

11.401

2.676

5.170

Theoretical O2 requirement = 11.401 +


=
Actual O2 supply =
Excess O2 =
N2, entering with O2 =
Total dry air =

Moisture, entering with air =


Boiler Flue Gas

2.676
5.17
2

7.569 kmol
7.569 1.1 = 8.326 kmol
8.326 7.569 = 0.757 kmol
79 8.326/21 = 31.322 kmol
8.326 + 31.322 = 39.648 kmol
1143.448 kg
39.648 0.017 = 0.674 kmol

Stoichiometry and Industrial Problems 357

Component
N2 + Ar
O2
CO2
H2O

kmol

Dry analysis, %
(Orsat)
60.668 + 0.882 + 31.322 = 92.872
88.42
0.757
0.72
11.401
10.86
2.676 + 0.674 = 3.350

Total

wet 108.380
dry 105.030

Wet analysis
%
85.69
0.70
10.52
3.09

100.00

100.00

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
Heat loss in flue gases at 448.15 K (175C):
Component

kmol, ni

C mp
equation constants
ni ai

ni bi 103

ni ci 106

ni di 109

N2
O2
CO2
H2O

92.872
0.757
11.401
3.350

2748.166
19.701
243.588
108.848

477.455
8.899
732.903
0.267

1224.322
1.773
468.016
44.256

461.388
0.426
111.729
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
Moisture in fine gas =

3.35
= 0.0329 kmol/kmol dry gas
(105.03 - 3.35)

358 Solutions ManualStoichiometry

p = 1 bar g = 2.013 25 bar a


201.325 kPa
pw3

= 0.0329
p - pw3
p w = 6.413 kPa
DP of flue gas = 37.4C 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
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
3019.8 kg/h
72 476 kg/d 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 (40C)
Total pressure, p = 2 bar g = 301.325 kPa a
7.375
Moisture content of offgases =
301325
.
- 7.375
= 0.025 kmol/kmol dry gas
Offgas Mixture from Adipic Acid Plant
Component
N2O
O2
CO2
N2
H2O

kmol
30
8
3
59
2.5

Total

102.5

Molar mass
44
32
44
28
18

(Table 6.13)

kg
1320
256
132
1652
45
3405

Stoichiometry and Industrial Problems 359

Average molar mass of wet offgas =

3405
= 33.22
102.5

Average molar mass of dry offgas =

3405 - 45
= 33.60
100
3405 50
100

Flow of wet offgas mixture of first bed =

= 1702.5 kg/h
Reaction:

N2O =

N2

1
2

O2

DHf
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
offgas (dry)

N2O

20.00

32

736

CO2
N2
H2O

Nil
0
30
8+
= 23
2
3
59 + 30 = 89
2.5

2.61
77.39

44
28
18

132
2492
45

Total

117.5

100.00

O2

mole %
(dry)

Molar
mass

44

kg

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
ni

Cmp equation constant


ni ai

ni bi 103

ni ci 106

ni di 109

N2O
O2
CO2
N2
H2O

0.30
0.08
0.03
0.59
0.025

6.962
2.082
0.641
17.459
0.812

19.101
0.940
1.929
3.033
0.002

12.702
0.187
1.232
7.778
0.330

3.121
0.045
0.294
2.931
0.114

Total

1.025

27.956

18.939

6.013

0.325

360 Solutions ManualStoichiometry

Treated gas mixture:


Component

kmol

Cmp equation constant

O2
CO2
N2
H2O

ni
0.2000
0.0261
0.7739
0.0217

ni ai
5.205
0.558
22.900
0.705

Total

1.0217

29.368

ni bi 103
2.351
1.678
3.979
0.002
0.052

ni ci 106
0.469
1.071
10.202
0.287
8.949

ni di 109
0.112
0.256
3.845
0.099
3.602

Base temperature, To = 298.15 K (25C)


Based on Cmp equation, following enthalpies are calculated.
Temperature, T
K (C)
313.15
323.15
353.15
373.15
443.15
483.15
723.15
913.15
973.15

(40)
(50)
(80)
(100)
(170)
(210)
(450)
(640)
(700)

Enthalpy at T over To, kJ/kmol dry gas


Offgas mixture
497.9
831.7
1 842.3
2 523.4
4 952.7
6 371.4
15 308.3
22 830.1
25 274.5

Treated gas mixture


451.8
753.5
1 661.6
2 269.5
4 414.1
5 652.3
13 302.6
19 654.0
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 C).
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

Stoichiometry and Industrial Problems 361

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 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 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,

T1

257.12

C mp
dT = 5791 951

298.15

Solving by Mathcad, T1 = 996.55 K or 723.4 C


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

362 Solutions ManualStoichiometry

Enthalpy off gas mixture, leaving 3rd bed


= 6260 042 + 4566 083
= 10 826 125 kJ/h 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

T2

470.45

Cmp dT = 10 826 124

298.15

Solving by Matched T2 = 1010.52 K or 737.37 C


Total dry offgas flow treated = 50 + 96.31 + 185.50
= 331.81 kmol/h
Offgas mixture bypassed to 2nd bed =
Offgas bypassed to 3rd bed =
Recycle =

96.31 100
= 29.03%
331.81
185.50 100
= 55.91%
331.81

88.86
kmol
= 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
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,

T3

470.45

Cmp dT = 9152 460

298.15

Stoichiometry and Industrial Problems 363

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
1803.7 kW
Enthalpy of saturated steam at 4.5 bar a
= 2742.6 kJ/kg
Enthalpy of feed water at 303.15 K (30C) = 126 kJ/kg
Steam generated in steam drum =

6493 335
(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
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,

T4

470.45

Cmp dT = 1987 043

298.15

Solving by Mathcad, T4 = 436.97 K or 163.82 C


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
85.66 kW
Assuming 5 K rise in cooling water temperature, cooling water flow
=

308 363
= 14 730 kg/h
5 4.1868

14.7 m3/h

364 Solutions ManualStoichiometry

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.

353.15

Heat duty of E5, f5 = 88.86

Cmp dT

341.15

= 32 327 kJ/h
8.98 kW
Enthalpy of emitted gas mixture to stack = 381.59 4223.71 32 327
= 1579 398 kJ/h 438.722 kW
If T5 is the gas mixture to stack,

T5

381.59

Cmp dT = 1579 398

298.15

Solving by Mathcad, T5 = 434.2 K or 161.05C.

Ans.

EXERCISE 8.28
Basis: 1 kmol dry acid gas fed to the burner
Reactions taking place in burner:
(1)
H2S (g) + 3/2 O2 (g) = SO2 (g) + H2O (g)
(2)
H2 (g) + O2 (g) = H2O (g)
m

CnHm(g) + n + 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
= 1.032 kmol/kmol NG
O2 required =
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

Stoichiometry and Industrial Problems 365

1
(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 50C (323.15 K).
pw at 50C = 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)
= 0.1132 kmol/kmol dry gas
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

Ar entering with O2 =

Component

kmol

SO2
CO2
Ar
N2
O2
H2O

0.03
0.69 + 1.098 a
0.022 75 + 0.0516 a
1.7745 + 4.0248a + 0.02a = 1.7745 + 4.0448a
0.02275 + 0.0516a
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)
D H ro2 = 241.82 kJ/mol H2 at 298.15 K (exothermic)
Similarly,
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

ai ni

bi ni 103

ci ni 106

di ni 109

H2S
CO2
H2
H2O

0.30
0.69
0.01
0.1132

10.357
14.472
0.286
3.678

5.294
44.356
0.010
0.009

20.300
28.325
0.001
1.495

15.974
6.762
0.008
0.515

Total

1.1132

29.063

39.081

6.531

9.719

366 Solutions ManualStoichiometry

Reference temperature, To = 298.15 K


Feed (acid) gas temperature, T1 = 323.15 K
H1 = 29.063 (323.15 298.15) +

39.081 10 -3
(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:


Heat Capacity Equation Constants
Component

kmol
ni

ai ni

Heat capacity equation constants


bi ni 103
ci ni 106
di ni 109

O2
N2
Ar
H2O

0.21
0.78
0.01
0.02

4.314
23.081
0.208
0.650

16.820
4.100

0.002

13.112
10.283

0.264

3.564
3.875

0.091

Total

1.02

28.253

12.722

2.565

0.402

T2 = 313.15 K
H2 = 28.253(313.15 298.15) +

12.722 10-3
2

(313.15 2 298.15 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:


Heat Capacity Equation Constants
Component

kmol
ni

Heat capacity equation constants


bi ni 103
ci ni 106
di ni 109

ni ai

CH4
C2H6
C3H8
i-C4H10
n-C4H10
CO2
N2

0.894
0.050
0.019
0.004
0.006
0.007
0.020

17.209
0.271
0.080
0.036
0.017
0.150
0.592

46.589
8.904
5.819
1.678
2.743
0.450
0.103

10.704
3.369
3.014
0.935
0.147
0.287
0.264

10.118
0.436
0.611
0.204
0.286
0.069
0.099

Total

1.000

18.089

66.080

5.086

8.413

Stoichiometry and Industrial Problems 367

T3 = 308.15
H3 = 18.089 (308.15 298.15) +

66.080 10-3
(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.
(4)
2 H2S(g) + SO2(g) = 3 S(g) + 2 H2O(g)

1
0.6
0.4
= 1.5 mol
1.5 0.3 = 0.45 kmol
0.45 0.6 = 0.27 kmol
0.27
= 0.135 kmol
2
3
0.27 = 0.405 kmol
2
1.5 0.01 = 0.015 kmol
0.015 + 0.27 = 0.285 kmol
1.5 0.1132 = 0.1698 kmol

Acid gas bypassed and introduced to reaction furnace =


H2S entering furnace =
H2S reacted by Eq. (2) =
SO2 reacted =
S produced =
H2 reacted =
H2O produced =
H2O entering with acid gas =

Composition of Gas Mixture Exit of Reaction Furnace


Component

kmol

H2S
SO2
CO2
Ar
N2
O2
S
H2O

0.45 0.27 = 0.180


0.3 0.135 = 0.185
0.69 + 0.69 1.5 + 1.098 a = 1.725 + 1.098 a
0.022 75 + 0.0516 a
1.7745 + 4.0448 a
0.022 75 + 0.0516 a (0.015/2) = 0.015 25 + 0.0516 a
0.405
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

368 Solutions ManualStoichiometry

It is specified that gas mixture, leaving reaction furnace should have 1100C
(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 1100C (1373.15 K) over 25C
(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

H 5 =

298.15

o
Cmp
(1) dT
mix

= 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 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 =

298.15

Cmo pmix (2) dT

= 532 356.5 + 173 882.3 + 23 886.7 30777.0


= 699 348.5 kJ/kmol mixture
H5 = 767 631.1 + (858 171.6 1.6395)
= 699 341.2 kJ/kmol mixture
H 5 = H5

Iterative Calculations for Claus Process


Case (a): Combustion Air Feed Temperature: 40C (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,
SO2
H2S
CO2
Ar
N2
02
S
H20

0.165
0.18
1.725
0.02275
1.7745
0.01525
0.405
0.9235
5.2110

0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1

0
0
0.1098
0.00516
0.40448
0.00516
0
0.21672

0.1650
0.1800
1.8348
0.0279
2.1790
0.0204
0.4050
1.1402
5.9523

24.7706
34.5234
21.3655
20.7723
29.5909
20.5451
27.4597
32.4921

4.0871
6.2142
39.2014
0.5798
64.4780
0.4193
11.1212
37.0481
163.1492

bi

b*n*E3

ci

ci;*ni*E6

1.6395
1.6395
1.6395
1.6395
1.6395
1.6395
1.6395
1.6395

0
0
1.800171
0.084598
6.63145
0.084598
0
3.553124

0.1650
0.1800
3.5252
0.1073
8.4059
0.0998
0.4050
4.4766
17.3649

24.7706
4.0871
34.5234
6.2142
21.3655 75.3170
20.7723
2.2299
29.5909 248.7396
20.5451
2.0514
27.4597 11.1212
32.4921 145.4549
495.2154

di

di*n*E9

62.9481 10.3864 44.2582 7.3026 11.1220


1.8351
17.6481 3.1767 67.6664 12.1800 53.2454 9.5842
64.2841 226.6124 41.0506 144.7104
9.7999 34.5463
0.0000
0.0000
0.0000
5.1410 43.2150 13.1829 110.8148 4.9680 41.7608
80.0947
7.9973 62.4369 6.2342 16.9722
1.6946
13.3278 5.3978 10.0657
4.0766 2.6624 1.0783
0.0796
0.3563 13.2107 59.1393 4.5474 20.3570
193.5631
27.9635
34.7041

Stoichiometry and Industrial Problems 369

0.165
0.18
1.725
0.02275
1.7745
0.01525
0.405
0.9235
5.2110

di*n*E9

62.9481 10.3864 44.2582 7.3026 11.1220


1.8351
17.6481 3.1767 67.6664 12.1800 53.2454 9.5842
64.2841 117.9485 41.0506 75.3196
9.7999 17.9809
0.0000
0.0000
0.0000
5.1410 11.2021 13.1829 28.7253 4.9680 10.8252
80.0947
1.6347 62.4369 1.2743 16.9722
0.3464
13.3278 5.3978 10.0657
4.0766 2.6624 1.0783
0.0796
0.0908 13.2107 15.0631 4.5474 5.1850
110.2838
23.8516
6.5103

Enthalpy at 1373.15 Kover 298.15 K Total


H5 175385.3 99070.5820374.27 5773.56 248308.1kJ/kmol acidgas to burnerby integration
621813.9kJ/kmol acidgas to burner
Difference
870122 kJ
H5
Final trial 1: a = 1.6395 kmol/kmol dryacid gas fed to burner
Component
a
kmol
ai
< a* n,
bi
b*n*E3
ci
ci;*ni*E6
SO2
H2S
CO2
Ar
N2
02
S
H2O

di

SO2
CO2
Ar
N2
O2
H2O

0.3
2.49017
0.10735
8.40595
0.10735
4.02182
15.4326

0
0
0
0
0
0

0
0
0
0
0
0

.5 173882.3 23886.68
30777 699348.5kJ/kmol acidI gas to burnerby integration
.2kJ/kmol acidgas to burner
Difference 7.308321
kJ

0.3
2.49017
0.10735
8.40595
0.10735
4.02182
15.43264

ai
24.7706
21.3655
20.7723
29.5909
20.5451
32.4921

< a* n,
7.43118
53.20373
2.229906
248.7396
2.205516
130.6774
444.4873

bi

b*n*E3

ci

ci;*ni*E6

62.9481 18.88443 44.2582 13.27746


64.2841 160.0783 41.0506 102.223
0
0
5.141 43.21499 13.1829 110.8148
80.0947 8.598166 62.4369 6.702601
0.0796 0.320137 13.2107 53.131057
144.6661
41.742822

di

di*n*E9

11.122
3.3366
9.7999 24.40342
0
4.968 41.76076
16.9722 1.821966
4.5474 18.28882
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: 250C (523.15 K)
Component
a
kmol
ai
< a* n,
bi
b*n*E3
ci
ci;*ni*E6
di
di*n*E9
SO2
H2S
CO2
Ar
N2
02
S
H2O

0.165
0.18
1.725
0.02275
1.7745
0.01525
0.405
0.9235
5.2110

1.4106
1.4106
1.4106
1.4106
1.4106
1.4106
1.4106
1.4106

0
0
1.548839
0.072787
5.705595
0.072787
0
0.145574

0.1650
0.1800
3.2738
0.0955
7.4801
0.0880
0.4050
1.0691
12.7566

24.7706
4.0871
34.5234
6.2142
21.3655 69.9472
20.7723
1.9845
29.5909 221.3427
20.5451
1.8087
27.4597 11.1212
32.4921 34.7365
351.2422

62.9481 10.3864 44.2582 7.3026 11.1220


1.8351
17.6481 3.1767 67.6664 12.1800 53.2454 9.5842
64.2841 210.4558 41.0506 134.3930
9.7999 32.0833
0.0000
0.0000
0.0000
5.1410 38.4552 13.1829 98.6093 4.9680 37.1611
80.0947
7.0513 62.4369 5.4968^ 16.9722
1.4942
13.3278 5.3978 10.0657
4.0766 2.6624 1.0783
0.0796
0.0851 13.2107 14.1232 4.5474 4.8615
180.9490
18.2033
17.2725

Enthalpy at 1373.15 K over 298.15 KTotal


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
H5

370 Solutions ManualStoichiometry

Enthalpy at 1373.15 K over 298.15 K


Total
532356
H5'
699341
H5
Gas mixtureat the exitof the burner
Component
a
kmol

Stoichiometry and Industrial Problems 371

Hence,
a = 1.6395 kmol NG/kmol dry acid gas fed to burner
Substitute a = 1.6395.
Gas Mixture, Exit of Gas Burner
Component
SO2
CO2
Ar
N2
O2
H2O
Total

Ans. (ai)

kmol

mole %
(wet)

mole %
(dry)

0.3
2.49017
0.10735
8.40595
0.10735
4.02182

1.94
16.14
0.70
54.46
0.70

2.63
21.82
0.94
73.67
0.94

100.00

100.00

15.43264 (wet)
11.41082 (dry)

Using heat capacity equation constants,


Cmp (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

298.15

Cmo pmix (3) dT

Solving by Mathcad, T = 2918.25 K or 2645.1C


(b) Combustion air is preheated to 250C (523.15 K).
Enthalpy of combustion air at 523.15 K
H 2 = 6256.9 + 1175.5 99.8 6.7
= 7425.9 kJ/kmol dry air
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 =

298.15

Cmo pmix (4) dT

= 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.

372 Solutions ManualStoichiometry

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 50C (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
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
2022 ppm (v/v)
Nitrogen stream leaves stripper at 0.14 bar g, saturated with water at 50C
(323.15 K)
Nitrogen leaves heater at 0.12 bar g and 45C (318.15 K) and 40% RH.
Vapour pressure of water at 45C, 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 50C = 12.335 kPa
Moisture content of nitrogen at stripper outlet,

Stoichiometry and Industrial Problems 373

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
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 = 28.4C or T2 = 301.55 K
Thus nitrogen stream will leave stripper at 0.14 bar g and 50C (323.15 K), will
be cooled to 301.55 K and 0.13 bars in chiller and then rehated to 45C (318.15 K)
at 0.12 bar g.
Chiller:
Average condensation temperature in
50 + 28.4
chiller =
2
= 39.3C or 312.35 K
lv at 39.2C = 2408.8 kJ/kg
Gas stream entering chiller
.
Component
ni
Heat capacity equation constants
.
.
.
.
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
18.39
597.530
1.464
242.945
83.628
H2O
0.3104
11.791
152.227
99.759
24.635
C6H6
Total

172.2402

5134.126

-635.658

2167.288

-821.779

Gas stream leaving chiller


.
Component
ni
Heat capacity equation constants
.
.
.
.
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
5.37
174.483
0.427
70.941
24.420
H2O
0.3104
11.791
152.227
99.759
24.635
C6H6
Total

159.2204

4711.079

636.695

1995.284

762.572

374 Solutions ManualStoichiometry

Reference temperature, T0 = 298.15 K


Enthalpy of gas mixture, entering chiller
323.15

f1 =

298.15

5134.126 635.658 103 T + 2167.288 106 T2 821.779

109 T3) dT
= 128 034 kJ/h
35.565
Enthalpy of gas mixture, leaving chiller
301.55

f2 =

298.15

(4711.079 639.695 103 T + 1995.284 106 T2 762.572

109 T3) dT
= 15 909 kJ/h
4.419 kW
Heat load of chiller,
fc = f1 f2 + 2409.8 234.56
= 128 034 15 909 + 565 008
= 677 133 kJ/h
188.093 kW 53.52 TR
Heat load of heater,
318.15

fh =

301.55

(4711.079 636.695 103 T + 1995.284 106 T 2 762.572

109 T 3) dT
= 77.733 kJ/h
21.593 kW
Saturated steam at 2 bar a is used for heating
lv at 2 bar a = 2201.6 kJ/kg
77 733
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

Steam consumption in heater =

24 8
4
= 748 kg/h
During regeneration, pressure of about 0.1 bar g is maintained in the adsorber.
ts/Ts = 102.32C/375.47 K
lv1 at 1.113 25 bar a = 2251.4 kJ/kg

= 700 +

0.38

562.05 - 375.47
lv2 of benzene at 375.47 K, lv2 = 30720

562.05 - 353.3
= 29 437 kJ/kmol 376.86 kJ/kg

Stoichiometry and Industrial Problems 375

Heat load of condensation = 700 2251.4 + 48 376.86


= 1575 980 + 18 089
= 1594 069 kJ/h
442.797 kW
Both liquids are cooled from 375.47 K to 318.15 K.
Cooling load of benzene
375.47

= 0.3073

318.15

(484.365 + 5056.235 103 T 14 292.204 106 T2

+ 14 419.754 109 T3) dT


= 0.3073 8704
= 2675 kJ/h
0.743 kW
Cooling load of water = 700 (428.8 188.4)
= 168 280 kJ/h
46.744 kW
Total heat load of condenser
fcd = 1594 069 + 2675 + 168 280
= 1765 024 kJ/h
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).
yAA =
and

yMe =

pv AA x AA g AA f sat
AA
f AA p
sat
pvMe xMe g Me fMe

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)
pri o

( Bi + w i Bi1 )
fi = exp
Tri

and

fi

sat

prisat o

1
= exp T ( Bi + w i Bi )
ri

376 Solutions ManualStoichiometry

where

pri = reduced pressure


p
= p
ci
Tri = reduced temperature
T
=
Tei

and

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

p cisat =

pvi
pci

0.172
Bi1 = 0.139 T 4.2
ri

and
Component

Tci, K

pci, bar

wi

pvi, bar

Tri

Acetic acid
Methanol

590.7
512.64

57.8
80.92

0467
0.564

5
27

Component

psat
ri

B 0i

B1i

fi

Acetic acid
Methanol

0.0864
0.3337

0.5655
0.431

03923
0.1497

0.4242
0.6942

0.7645
0.884

p ri
0.8756
0.626
fsat
i
0.9189
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
nt

65 + 35
nt

100
100
=
= 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

.
nt =

Stoichiometry and Industrial Problems 377

If the gas-vapour mixture is considered ideal, vapour-liquid equilibrium will follow


Raoult's law.
yAA =

x AA pv AA
p

0.15 5
50 6625

= 0.0148
0.85 27
50.6625
= 0.453
+ yH2 = 1 0.0148 0.453
= 0.5322

yMe =

yCO2

100
= 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 nonideality.
Ans.

.
nt =

Stoichiometry and
Digital Computation
EXERCISE 9.1
a. by spreadsheet
Component

H2
C2H6
C2H4
C3H8
C3H6
N2
NH3

0.81
0.02
0.04
0.01
0.02
0.08
0.02

Mm
2.0159
30.0696
28.0538
44.0965
42.0806
28.0135
17.0306

y.Mm

Tc, K

1.6329
0.6014
1.1222
0.441
0.8416
2.2411
0.3406

32.200
305.420
282.340
369.820
364.850
126.090
405.500

7.2207
p
T
pc
Tc
R
Mm
e
dV
a
B

2.00E+06
333.15
1.98E+06
72.68
8314
7.2207
0.00100
0.10
77682.8
0.038093

y.Tc, K
26.082
6.108
11.294
3.698
7.297
10.087
8.110

pc, Pa
1.297E+06
4.880E+06
5.039E+06
4.247E+06
4.601E+06
3.394E+06
1.135E+07

72.676

y.pc, Pa
1.051E+06
9.760E+04
2.016E+05
4.247E+04
9.202E+04
2.715E+05
2.270E+05
1.983E+06

Pa
K
Pa
K
kJ/(kmol K)

Trial

F(V)

dV

new dV

Test

sp. vol.

0
1
2
3
4
5
6

0.1
0.20000
0.30000
0.40000
0.50000
0.60000
0.70000

0.22164
0.54072
0.70550
0.75247
0.73677
0.68813
0.62128

0.10000
0.10000
0.10000
0.10000
0.10000
0.10000
0.10000

0.10000
0.10000
0.10000
0.10000
0.10000
0.10000
0.10000

FALSE
FALSE
FALSE
FALSE
FALSE
FALSE
FALSE

# N/A
# N/A
# N/A
# N/A
# N/A
# N/A
# N/A

Stoichiometry and Digital Computation 377

7
8
9
10
11
12
13
14
15
16
17

0.80000
0.90000
1.00000
1.10000
1.20000
1.30000
1.35000
1.37500
1.38750
1.39375
1.39688

0.54376
0.45963
0.37122
0.27992
0.18662
0.09188
0.04410
0.02012
0.00811
0.00210
0.00091

b. by Mathcad

FG
H

a (R, Tc, pc) := 27 R2


b (R, Tc, pc) := R
f (V, p, R, T, Tc, pc) :=

0.10000
0.10000
0.10000
0.10000
0.10000
0.10000
0.05000
0.02500
0.01250
0.00625
0.00313

Tc2
64 pc

Tc
8 pc

0.10000
0.10000
0.10000
0.10000
0.10000
0.05000
0.02500
0.01250
0.00625
0.00313
0.00156

FALSE
FALSE
FALSE
FALSE
FALSE
FALSE
FALSE
FALSE
FALSE
FALSE
TRUE

# N/A
# N/A
# N/A
# N/A
# N/A
# N/A
# N/A
# N/A
# N/A
# N/A
0.19345

IJ
K

LMF p + a( R, T , p ) I (V - b( R, T , p ))OP (R T)
K
V
NH
Q
c
2

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
7.2207
spvol = 0.19332 m3/kg

spvol :=

EXERCISE 9.2

F aI
H vK
b
B(b0, b, v) := b0 F1 - I
H vK
A(a0, a, v) := a0 1 -

e(c, T, v) :=

c
vT 3

f(a0, b0, a, b, c, T, R, p, v) := p

LM R T (1 - A(c, T, v) (v + B(b0, b, v)OP


v
N
Q
2

A( a0, a, v )
v2

378 Solutions ManualStoichiometry

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
OP + a = a
P
2
(
1
)
(
1
)
4
M
x
a
z
M
z
y
a
z

N
Q
f

vec := Find (M, P, a)

LM455.293 OP
vec =
MMN 967..9789
P
4188PQ

M := vec0
M = 455.293
R := M F

P := vec1
P = 7.9789
R = 355.293

a := vec2
a = 96.4188

R
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

rr :=

LM
N

(1 x) a 1 -

OP
Q

P
+ af = a
M - 2 x a (1 + z ) - M z (1 - y ) + 4 a z

Stoichiometry and Digital Computation 379

vec := Find (M, P, a)

LM432.801 OP
vec :=
MMN 927..8713
P
5826 PQ
M := vec0
M = 432.801
R := M F

P := vec1
P = 7.8713
R = 332.801

a := vec2
a = 92.5826

R
rr = 3.328
F
nh3 := (2 x a + M (1 y) 4 a) z

rr :=

nh3 = 45.8374

EXERCISE 9.4
HP steam enthalpy =
MP superheated steam enthalpy =
LP superheated steam enthalpy =
LP saturated steam enthalpy =
15 bar saturated steam enthalpy =
Surface condenser steam enthalpy =
BFW enthalpy =
Surface condenser condensate enthalpy =

H1
H2
H3
H4
H5
H6
H7
H8

kJ/kg
kJ/kg
kJ/kg
kJ/kg
kJ/kg
kJ/kg
kJ/kg
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
Q1(H2, H5, H7) :=

3
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

380 Solutions ManualStoichiometry

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
+
=
S3 ( H1 , H6 ) 1000
S1 ( H1 , H2 )
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)

a
b
c
d
e
g
Z

LM 5.1556 OP
4795
MM 48..6702
PP
=
MM 2.0625PP
MM302..3692
PP
7687
N
Q

= Saturated LP steam input to deaerator = 5.156 t/h


= MP steam input to CW pump turbine = 8.480 t/h
= MP steam input to BFW pump turbine = 4.670 t/h
= MP steam input to FD fan turbine = 2.063 t/h
= Exhaust (under vacuum) from power turbine = 30.369 t/h
= Letdown from MP steam to LP steam = 2.769 t/h
= Total HP steam production = 51.095 t/h

Stoichiometry and Digital Computation 381

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
E 1(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:
E3(E, yE, xE) :=
Total mixed feed in the reactor:
E4(E, yE, xE, yI1) :=

E2 ( E, yE )
x E 28.0538
E3 ( E, yE , x E )
0.1

Inerts in mixed feed:


Imf (E, yE, xE, yI1) := E4(E, yE, xE, yI1) yI1
Oxygen reacted by reaction 1:
O21(E, yE, xE) :=
Oxygen reacted by reaction 2:
O22(E, yE, xE) :=

E3 ( E, yE , x E ) x E yE
2
Eb ( E, yE ) 3
28.0538

Total oxygen fed:


O23(E, yE, xE) := O21(E, yE, xE) + O22(E, yE, xE)
Inerts fed along with oxygen:
I1(E, yE, xE, yI2) :=

O23 ( E, yE , x E ) yI 2
(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:
E6(E, yE, xE) :=

O22 ( E, yE , x E ) 4
3

Reactor outlet stream:


E7(E, yE, xE, yI1, yI2, x, P) := E3(E, yE, xE) (1 xE) + (I1(E, yE, xE, yI2)

382 Solutions ManualStoichiometry

LM
N
Recycle stream 1 contains:

+ O23(E, yE, xE) + E3 ( E, yE , x E ) (1 - xE )

P
R1 ( E, yE , xE , yI1 , x )

OP
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
R1 ( E, yE , x E , yI1, x )

yI 2 O23 ( E, yE , x E )
(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
N39.58 Q
3

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

E := 3500

P = 39.58 kmol/h
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
N

E3 ( E, yE , xE ) (1 - xE ) - E3 ( E, yE , xE )
FE = 115.693

FE 28.0538 = 3.246.103 kg/h

(1 - x E ) P
R1 ( E, yE , xE , yI1 , x )

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

OP
Q

Stoichiometry and Digital Computation 383

Recycle ratio:

R2 ( E, yE , x E , yI1 , x, P)
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.

ratio :=

EXERCISE 9.6
Double recycle system of ammonia synthesis loop

384 Solutions ManualStoichiometry

Stoichiometry and Digital Computation 385

386 Solutions ManualStoichiometry

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.