Solution 3.

1,,
ΔP (100−3)
ΔPν= =
Energy = ρ 850 x 105
= 11,412 J kg-1

Power =
( kgJ )( kgs )
( 1000
= 11,412 3600
)
= 3170 W

Solution 3.2

200oC
Hevap Hvap

Hliq

0oC

[ ]
100
t2
ΔH liq =
∫ (4 .2−2 x 10−3 t )dt=1000 4 . 2 t−2 x 10−3 2
0

= 420 – 10
= 410 kJ kg-1
ΔH evap = 40,683 J mol-1 (From Appendix D)
40683
= 18 = 2260 kJ kg-1
From Appendix O, the specific heat of the vapour is given by:
Cp = 32.243 + 19.238 x 10-4T +10.555 x 10-6 T 2 – 3.596 x 10-9 T 3
Where Cp is in J mol-1 K-1 and T is in K. Now 100oC = 273.15K and 200oC =373.15K.
373. 15
∫
ΔH vap = 273. 15
(32 . 243+19 .238 x 10−4 T +10 . 555 x 10−6 T 2−3 . 596 x 10−9 T 3 )dT
 [ ]
2 3 4
373.15 −4 T −6 T −9 T
273.15 ( 32.243T +19.238 x 10 +10.555 x 10 −3.596 x 10 )
= 2 3 4
= 12,330.8 – 8945.7
= 3385.1 kJ kmol-1
3385 .1
= 18
= 188.1 kJ kg-1
Therefore, specific enthalpy:
ΔH liq = 410

ΔH evap = 2260

ΔH vap = 118.1
2778 kJ kg-1
From Steam Tables: 2876 kJ kg-1. Error = 98 kJ kg-1 (3.5 %).

Solution 3.3
Calculation of the enthalpy of reactions:
1. CO + ½O2  CO2
HF (kJ mol-1) -110.62 0 -393.77
HR = -393.77 – (-110.62) = -283.15 kJ mol-1 CO
2. H2 + ½O2  H2O
0 0 -242.00
HR = -242.00 – 0 = -242.00 kJ mol-1 H2
3. CH4 + 2O2  CO2 + 2H2O
-74.86 0 -393.77 -242.00
HR = [-393.77 + 2(-242.00)] – (-74.86) = -802.91 kJ mol-1 CH4
4. C2H6 + 3½O2  2CO2 + 3H2O
-84.74 0 -393.77 -242.00
HR = [2(-393.77) + 3(-242.00)] – (-84.74) = -1428.8 kJ mol-1 C2H6
5. C2H4 + 6O2  2CO2 + 2H2O
52.33 0 -393.77 -242.00
HR = [2(-393.77) + 2(-242.00)] – 52.33 = -1323.87 kJ mol-1 C2H4
6. C6H6 + 7½O2  6CO2 + 3H2O
82.98 0 -393.77 -242.00
HR = [6(-393.77) + 3(-242.00)] – 82.98 = -3171.6 kJ mol-1 C6H6

Composition (mol %):

CO2: 4, CO: 15, H2: 50, CH4: 12, C2H6: 2, C2H4: 4, C6H6: 2, N2: 11.

Basis: 100 mol

Component Quantity -(HR) H (kJ)
CO2 4 --
CO 15 283.15 4247.25
H2 50 242.00 12100.00
CH4 12 802.91 9634.92
C2H6 2 1428.8 2857.60
C2H4 4 1323.87 5295.48
C6H6 2 3171.60 6343.20
N2 11 --
100 40478.45 (kJ/100 mol)

Therefore, H = (40478.45)(10) = 404784.5 kJ kmol-1

404 , 784 .5
Gross CV (kJ m-3) = 22 . 4 = 18,071 kJ m-3 (= 485 BTU ft-3)
To calculate the Net CV, subtract the heat of vapourisation of the H2O burned.
Solution 3.4

20bar
Heat Transfer
Fluid
NB, 20oC
2500 kg h-1 H2, 30oC
366 kg h-1

Molecular weight of nitrobenzene = 123 and H2 = 2

2500
Molar flow of nitrobenzene = (123 )(3600 ) = 5.646 x 10–3 kmol s-1
366
Molar flow of H2 = (2)(3600 ) = 50.833 x 10-3 kmol s-1

Partial pressure of nitrobenzene = [(5

5 .646 x10 -3
.646×10 −3
+50 .83×10−3
] )
20
= 2.0 bar
B
ln P= A−
Using the Antoine Equation: T +C
The Antoine constants are obtained from Appendix D. (2 bar = 1500 mm Hg)
4032 .6
16 . 1484−
ln (1500) = T −71 .81
−4032. 6
7.313 – 16.1484 = T −71. 81
−4032 .6
T – 71.81 = −8 . 8352 = + 456.4
T = 528 K = 255oC
The boiling point of nitrobenzene at 1 atm = 210.6oC (Appendix D)

255oC
evap
. 210.6oC

H2 30oC
NB 20oC
The specific heat capacity of the nitrobenzene liquid can be estimated using Chueh and
Swanson’s method.

CH C N O

(18.42 x 5) 12.14 18.84 (35.17 x 2) Total = 193 kJ kmol-1 C-1

The specific heat capacity of the nitrobenzene gas:

a b x 102 c x 104 d x 106
HC -6.1010 8.0165 -0.5162 0.01250
(x 5) -30.505 40.083 -2.581 0.0625
C -5.8125 6.3468 -0.4776 0.01113
NO2 4.5638 11.0536 -0.7834 0.01989
-31.7537 57.4829 -3.8420 0.0935

Nitrobenzene:
Hliq = (5.646 x 10-3)(193)(210.6 – 20) = 208 kW
528
∫ (−31 .7537+57 . 4829×10−2T −3 . 842×10−4 T 2+0. 0935×10−6 T 3 ) dT
Hgas = 0.005646484
 = 43 kW

Hevap
(= 44 , 031 kJkmol )(5 . 636×10
−3 kmol
s )= 248.15 kW
H2:
528
∫ (27 .143+92. 783×10−3 T −1 .38×10−5 T 2+76 . 45×10−10 T 3 ) dT
Hgas = 0.05083303
= 730 kW
Therefore: Total H = 208 + 43 + 248 + 730 = 1229 kW
Note: It is not worth correcting the heat capacities for pressure.
Solution 3.5

mol %
NB 0.45
AN 10.73
H2O 21.68
Cycl. 0.11
Inerts 3.66
2500 kg h-1 H2 63.67
NB
H2
Inerts

Nitrogen Balance:
2500
Molar flow of nitrobenzene = (123 )(3600 ) = 5.646 x 10-3 kmol s-1
Therefore, katoms N = 5.646 x 10-3 s-1
Let the total mass out be x, then:

5.646 x 10-3 =
x
[ 0 . 45+10 . 73+0 . 11
100 ]
x = 0.050 kmol s-1
H2 reacted

Aniline produced
( ) 10 . 73
= (0.05) 100 = 0.00536 0.0161

( )
0 .11
Cyclo-hexylamine produced = (0.05) 100 = 0.000055 0.0003
0.0164 kmol s-1

Unreacted H2 = (0.05) 100

(
63 . 67
) 0.0318
So, total H2 In = 0.0482 kmol s-1
Now, Hreaction = 552,000 kJ kmol-1 (Appendix G8)
From Hf (Appendix D) NB -67.49 kJ mol-1
 AN 86.92
H2O -242.00
Hreaction =  products –  reactants
= [86.92 + 2(-242.00)] – (-67.49)
= -329.59 kJ mol-1
= 329,590 kJ kmol-1

Reactions: C6H5NO2 + 3H2  C6H5NH2 + 2H2O

C6H5NH2 + 3H2  C6H11NH2

The second reaction can be ignored since it represents a small fraction of the total.
The problem can be solved using the ENRGYBAL program. Heat capacities can be
found in Appendix D and calculated values for nitrobenzene obtained from Solution 3.4.

Solution 3.6
A straight-forward energy balance problem. Best to use the energy balance programs:
ENERGY 1, page 92 or ENRGYBAL, Appendix I, to avoid tedious calculations. Data on
specific heats and heats of reaction can be found in Appendix D.

What follows is an outline solution to this problem.

200oC

1.5bar
50oC
95 % H2 CW
25 o
C 10,000 T yr-1 HCl
5 % N2 H2 + Cl2  2HCl
Mass balance (1 % excess) gives feed.
Cl2 Tsat

Solution: 1. Tsat for Cl2 from Antoine Equation (Appendix D),

 2. Hreaction from the HCl heat of formation,
3. Cp’s from Appendix D,
4. Reactor balance to 200oC (4 % free Cl2),
5. Datum temperature 25oC,
6. Ignore pressure effects on Cp’s.
Reactor:
IN - 1. H2 + N2 = zero (at datum temperature),
2. Cl2 at Tsat (note as gas, Hreaction for gases),
3. Hreaction at 25oC (96 % Cl2 reacted).
OUT - 1. HCl + Cl2 + H2 (excess) + N2 at 200oC,
2. Cooling in jacket.

Cooler:
IN - 1. Reactor outlet H,
2. 4 % Cl2 reacted (Hreaction).
OUT - 1. Sensible heat of HCl, H2 (excess) and N2,
2. Heat to cooling water.

Check on Tsat:
1978 . 32
ln (1 . 5×750 )=15 . 9610−
T sat −27 .01
1978 .32
=15 . 9610−7 . 026
T sat −27 . 01
1978. 32
T sat = +27 . 01
8 . 935 = 248.4 K
Tsat = -24.6oC (Within the temperature limits)

The Cl2 may need preheating.

Solution 3.7
As P2 < Pcritical, the simplified equation can be used.
 5 bar

N2 100m3 h-1
γ = 1.4 for air.
0.5 bar, 20oC

( ){( ) }
n−1
n P2 n
−w=P1 v 1 −1
n−1 P1

1 γ −1
n= m=
where: 1−m and γE p .
Compression ratio = 10 – from Figure 3.7, Ep = 86 %.

( )
m
P2
T 2=T 1
P1

1. 4−1 1
m= n= =1 . 49
(1 . 4 )(0 . 86) = 0.33, 1−0 .33 .

( )
0 .33
10
T 2=(20+273 )
1 = 626 K = 353oC
In practice the compressor cylinder would be fitted with a cooling jacket.
v 1 = 100 m3 h-1 = 0.0278 m3 s-1

){ }
1 . 49−1
5
−w=(10 )(0. 0278 ) (
1 . 49
1. 49−1
( 10 ) 1. 49
−1

= 9.6 kW (Say 10 kW)

Solution 3.8

10,000 kg h-1 HCl

H2 or
HCl H2 + Cl2  2HCl
Burner operating pressure, 600 kN m -2 required. Take burner as operating at 1 atm. = 10 2
kN m-2 g or 600 kN m-2 g.
H2 is compressed from 120 kN m-2 to 600 kN m-2.
600
=5
Pressure ratio = 120

Intermediate pressure = √
P1 P2 =√(120)(600 )=268 kN m-2
Note: For H2 the inlet temperature will not be the same as the intercooler outlet so the
cool stage should be calculated separately.
A material balance gives the H 2 flow. The 1 % excess H 2 is ignored in the HCl
compressor calculation.
Material balance:
10 , 000
HCl produced = (36 . 5)(3600 ) = 0.0761 kmol s-1

H2 required =
( )
0 . 0761
2
1. 01
= 0.0384 kmol s-1

Cl2 required =
( 2 )
0 . 0761
= 0.0381 kmol s-1
Excess H2 = 0.0384 – 0.0381 = 0.0003 kmol s-1

The simplified equations (3.36a and 3.38a) can be used since conditions are far removed
from critical.

Take γ=1 . 4 since both H2 and HCl are diatomic gases.

(1. 4−1 )
m= =0 . 408
(1 . 4 )(0 .7 ) (3.36a)
1
n= =1. 689
1−0 . 408 (3.38a)

( ){( ) }
n−1
n P2 n
−w=P1 v 1 −1
n−1 P1
(3.31)
H2:

1st Stage:
v 1= ( )(
2
22. 4 120×103 )( )
1. 013×105 298
273
= 0.0823 m3 kg-1

( ){( ) }
1.689−1
3 1.689 268
−w 1=(120×10 )(0.0823) 1.689 −1
1.689−1 120 = 9,391 J kg-1

2nd Stage:
v ′=
1 ( )(
2
22. 4 268×103 )( )
1. 013×105 323
273
= 0.0399 m3 kg-1

( ){( ) }
1.689−1
3 1.689 600
−w 2=(268×10 )(0.0399) 1.689 −1
1.689−1 268 = 10,204 J kg-1

Power = (9,391 + 10,204)(0.0384)(2) = 1505 W = 1.505 kW

HCl:
Take both stages as performing equal work with the same inlet temperature.
Pi =√ P1 P 2=√(101 . 3)(600 )=246 . 5 kN m-2 (3.39)

v 1= ( )(
36 .5
22. 4
1. 013×105 323
)( )
1. 013×105 273 = 1.927 m3 kg-1

( ){( ) }
1.689−1
5 1.689 600
−w 1=(1.013×10 )(1.927) 1 .689 −1
1.689−1 101.3 = 510,173 J kg-1
Power = (510,173)(0.0761)(36.5) = 1,417,082 W = 1417 kW

It is necessary to divide by the efficiency to get the actual power but it is clear that the
best choice is to compress the H2 and operate the burner under pressure.

Check:
Temperature of saturated Cl2 at 600 kN m-2.
ln ( 600×10 3
133 .32 )
=15 . 9610−
1978. 32
T −27 . 01
1978 .32
=15 . 9610−8. 412
T −27 .01
T = 262 + 27.01 = 289 K = 16oC

Solutions 3.9 and 3.10 .

Refer to example 3.17 and the worked solution to problem 3.12

Solution 3.11
Ts Tt Cp
Streams: (oC) (oC) (kW oC-1)
900 kW
Preheater C 1 20 50 30
50oC 20oC
1350 kW
Condenser 1 H 2 70 60 135
70oC 60oC
1100 kW
Condenser 2 H 3 65 55 110
65oC 55oC
1400 kW
Reboiler 1 C 4 85 87 700
87oC 85oC
900 kW
Reboiler 2 C 5 75 77 450
77oC 75oC
30 kW
Cooler H 6 55 25 1
55oC 25oC

For Tmin = 10oC

T int =T out +5 (cold)
T int =T out −5 (hot)
Stream Type Tact Tint
1 C 20 50 25 55
2 H 70 60 65 55
3 H 65 55 60 50
4 C 85 87 90 92
5 C 75 77 80 82
6 H 55 25 50 20

Ranked Streams
(oC) kW Cascade Add
92 0 2300
90 C 4 +1400 -1400 900
82 0 -1400 900
80 C 5 +900 -2300 0
65 0 -2300 0
60 H -550 -1750 550
2
55 H -1225 -525 1775
3
50 C -400 -125 2175
1
25 725 -850 1450
6
H
20 5 -855 1445

ΔH =(∑ ( C p )C −∑ ( C p ) H ) ΔT

Hot Utilities = 2300 kW

Cold Utilities = 1445 kW

Pinch = 60 – 82oC