Chapter 4 - Section A - Mathcad Solutions

4.1 (a) T0 := 473.15 K

For SO2:

T := 1373.15 K
3

B = 0.801 10

A = 5.699

ICPH 473.15 , 1373.15 , 5.699 , 0.801 10

3

ICPH := 5.654 10 K

n := 10 mol
5

D = 1.015 10

C = 0.0
5

, 0.0 , 1.015 10

H := R ICPH

) = 5.654 103

Q := n H
Q = 470.074 kJ

(b) T0 := 523.15 K
For propane:

T := 1473.15 K

n := 12 mol
3

ICPH 523.15 , 1473.15 , 1.213 , 28.785 10

4

ICPH := 1.947 10 K

B = 28.785 10

A = 1.213

Ans.

C = 8.824 10
6

, 8.824 10

H := R ICPH

, 0.0 = 1.947 10

Q := n H
3
Q = 1.942 10 kJ Ans.

4.2 (a) T0 := 473.15 K

For ethylene:
:= 2 (guess)

n := 10 mol

(b) T0 := 533.15 K
For 1-butene:

14.394 10
B :=
K

A := 1.424

C :=

4.392 10
2

Given

Q = n R A T0 ( 1) +
:= Find ( )

Q := 800 kJ

B
2 2
C 3 3

T0 1 + T0 1
2
3

= 2.905

T := T0

n := 15 mol
A := 1.967

T = 1374.5K
Q := 2500 kJ
3

31.630 10
B :=
K
61

Ans.

C :=

9.873 10
2

 := 3

(guess)

Given

Q = n R A T0 ( 1) +
:= Find ( )

B
C 3 3

2 2
T0 1 + T0 1
2
3

= 2.652

(c) T0 := 500 degF

T := T0

T = 1413.8K

Ans.
6

n := 40 lbmol

Q := 10 BTU

Values converted to SI units

4

T0 := 533.15K
For ethylene:
:= 2 (guess)

A := 1.424

B :=

Q = 1.055 10 kJ
3

14.394 10
K

4.392 10

C :=

Given

Q = n R A T0 ( 1) +
:= Find ( )

n = 1.814 10 mol

B
2 2
C 3 3

T0 1 + T0 1
2
3

= 2.256

T := T0

T = 1202.8K
Ans.
T = 1705.4degF

4.3 Assume air at the given conditions an ideal gas. Basis of calculation is 1 second.
P := 1 atm

T0 := 122 degF

V := 250 ft

T := 932 K
3

V = 7.079 m

Convert given values to SI units

T := ( T 32degF) + 273.15K

T0 := ( T0 32degF) + 273.15K

T = 1187.37 K

T0 = 323.15 K

n :=

P V
R T0

For air:

n = 266.985 mol
A = 3.355

B = 0.575 10
3

ICPH 323.15 , 773.15 , 3.355 , 0.575 10

62

C := 0.0
5

, 0.0 , 0.016 10

D = 0.016 10

) = 1648.702

ICPH := 1648.702 K

H := R ICPH

Q := n H
3
Q = 3.469 10 BTU Ans.

4.4 molwt := 100.1

n :=

gm
mol

T0 := 323.15 K

10000 kg
molwt

For CaCO3:

T := 1153.15 K

n = 9.99 10 mol
3

A := 12.572

ICPH 323.15 , 1153.15 , 12.572 , 2.637 10

ICPH := 11355.4 K

B = 2.637 10

D = 3.120 10
5

, 0.0 , 3.120 10

H := R ICPH

) = 11355.4

Q := n H
6
Q = 9.4314 10 kJ Ans.

4.7 Let step 12 represent the initial reversible adiabatic expansion, and step 23
the final constant-volume heating.
T1 := 298.15 K

T3 := 298.15 K

P1 := 121.3 kPa

P2 := 101.3 kPa

P3 := 104.0 kPa

T2 := T3

CP := 30

joule
mol K

P2
P3

T2 = 290.41 K

(guess)
R

Given

4.9

P2
T 2 = T 1
P1

CP

72.150
86.177

gm
M := 78.114
Tc :=
mol
92.141

84.161

CP := Find (C P)

469.7
507.6

562.2 K Pc :=
591.8

553.6
63

CP = 56.95

joule
mol K

33.70
30.25

48.98 bar Tn :=
41.06

40.73

Ans.

309.2
341.9

353.2 K
383.8

353.9

(273.15 + 25)K
Tr1 :=
Tc

H is the value at
25 degC.

Hexp is the given

value at the normal
boiling point.

366.3
366.1

J
H := 433.3
412.3 gm

392.5

357.2
0.635
336.7
0.587

Hexp := 393.9
Tr1 = 0.53
363.2 gm
0.504

358.2
0.539

(a) By Eq. (4.13)

Hn Hexp

PCE :=
100%
Hexp

357.1
334.9

J
Hn = 396.5
361.7 gm

357.4

(b)

By Eq. (4.12):

This is the % error

Pc

R Tn 1.092 ln bar 1.013


Hn :=

0.930 Tr2
M

0.4
0.03

PCE = 0.59 %
0.05

1.24

64

Tc

0.658
0.674

Tr2 = 0.628
0.649

0.639

0.38

1 Tr2
Hn := H

1 Tr1

0.01
0.53

PCE = 0.65 %
0.42

0.21

Hn Hexp

PCE :=
100%
Hexp

358.6
336.6

J
Hn = 391.6
363 gm

353.8

Tr2 :=

Tn

4.10 The ln P vs. 1/T relation over a short range is very nearly linear. Our
procedure is therefore to take 5 points, including the point at the temperature
of interest and two points on either side, and to do a linear least-squares fit,
from which the required derivative in Eq. (4.11) can be found. Temperatures
are in rankines, pressures in psia, volumes in cu ft/lbm, and enthalpies in
Btu/lbm. The molar mass M of tetrafluoroethane is 102.04. The factor
5.4039 converts energy units from (psia)(cu ft) to Btu.
(a) T := 459.67 + 5

V := 1.934 0.012

18.787
21.162

P := 23.767
26.617

29.726

Data:

5
0

t := 5
10

15

xi :=

1
t i + 459.67

i := 1 .. 5

yi := ln (Pi)

slope := slope ( x , y) slope = 4952

dPdT :=

( P) 3
T

H :=

slopedPdT = 0.545

T V dPdT
H = 90.078
5.4039

Ans.

The remaining parts of the problem are worked in exactly the same
way. All answers are as follows, with the Table 9.1 value in ( ):
(a) H = 90.078

(90.111)

(b) H = 85.817

(85.834)

(c) H = 81.034

(81.136)

(d) H = 76.007

(75.902)

(e) H = 69.863

(69.969)

65

4.11

119.377
gm
M := 32.042
Tc :=
mol
153.822

H is the value at
0 degC.

536.4
512.6 K Pc :=
556.4

Hexp is the given

value at the normal
boiling point.

54.72
80.97 bar Tn :=
45.60

273.15K
Tr1 :=
Tc

246.9
270.9
0.509

J
J
H := 1189.5
Hexp := 1099.5
Tr1 = 0.533
gm
gm
217.8
194.2
0.491

(a) By Eq. (4.13)

(b) By Eq. (4.12):

0.77
PCE = 4.03 %
0.52

c
R Tn 1.092 ln bar 1.013


Hn :=

0.930 Tr2
M

0.34
PCE = 8.72 %
0.96

66

Tn
Tc

0.623
Tr2 = 0.659
0.629

This is the % error

Hn Hexp

PCE :=
100%
Hexp

247.7
J
Hn = 1195.3
192.3 gm

Tr2 :=

0.38

1 Tr2
Hn := H

1 Tr1

Hn Hexp

PCE :=
100%
Hexp

245
J
Hn = 1055.2
193.2 gm

334.3
337.9 K
349.8

4.12 (a) := 0.210

Tc := 562.2K

Pc := 48.98bar

Tn := 353.2K

P := 1bar

Tr = 0.628

Pr :=

Zc := 0.271

cm
Vc := 259
mol
Tn

Tr :=

Tc

P
Pc

Pr = 0.02

Generalized Correlations to estimate volumes

Vapor Volume
0.422

B0 := 0.083

Tr

0.172

B1 := 0.139

Tr
Z := 1 + B0

V :=

1.6

Pr
Tr

4.2

+ B 1

Pr
Tr

Z R Tn

B0 = 0.805

Eq. (3.61)

B1 = 1.073

Eq. (3.62)

Z = 0.967
3
4 cm

V = 2.838 10

mol

Liquid Volume

( 1Tr) 0.2857

Vsat := V c Zc

cm
Vsat = 96.807
mol

Eq. (3.63)

Combining the Clapyeron equation (4.11) H = T V d Psat

dT
A

with Antoine's Equation

gives

Psat = e

B
TC

H = T V

67

B
( T C)

A B

( TC)
e

3
4 cm

V := V V sat

V = 2.829 10

A := 13.8594

B := 2773.78

mol
C := 53.00

A Tn
C

B
K kPa

e
H := Tn V
2
K
Tn

H = 31.197

kJ
Ans.
mol

Answers for parts (b)-(e)

(b) H = 36.262

kJ
mol

(c) H = 32.278

kJ
mol

(d) H = 28.948

kJ
mol

(e) H = 33.838

kJ
mol

4.13 Let P represent the vapor pressure.

T := 348.15 K

P := 100 kPa

P = 48.157543 5622.7 K 4.70504 ln T

T
kPa
K

Given

ln

P := Find ( P)

dPdT := P

P = 87.396 kPa

(guess)

5622.7 K 4.70504
2
T
T

joule
H := 31600
mol
68

dPdT = 0.029

bar
K
3

cm
Vliq := 96.49
mol

Clapeyron equation:

dPdT =

H
T ( V V liq)

V = vapor molar volume. V := V liq +

Eq. (3.38):

H
T dPdT
3

P V 1

R T

B := V

4.14 (a) Methanol: Tc := 512.6K

Pc := 80.97bar
BL := 51.28 10

BL

CL

T +

BV

P := 3bar

T +

CL := 131.13 10

BV := 12.216 10

CPV ( T) := AV +

Ans.

T R
3

AV := 2.211

cm
mol

Tn := 337.9K
3

AL := 13.431
CPL ( T) := AL +

B = 1369.5

CV
2

CV := 3.450 10

T R

Tsat := 368.0K

T1 := 300K

T2 := 500K

Estimate Hv using Riedel equation (4.12) and Watson correction (4.13)

Trn :=

Tn

Trn = 0.659

Tc

Trsat :=

Pc

1.013
bar
R T

Tsat
Tc

Trsat = 0.718

1.092 ln
Hn :=

0.930 Trn

1 Trsat
Hv := Hn

1 Trn

Hn = 38.301

kJ
mol

Hv = 35.645

kJ
mol

0.38

69

sat
2
H :=
C PL ( T) dT + Hv +
CPV ( T) dT
T
T
1

sat

kmol
hr

n := 100

H = 49.38

Q := n H

Q = 1.372 10 kW

kJ
mol
Ans.

(b) Benzene:

Hv = 28.273

kJ
mol

H = 55.296

kJ
mol

Q = 1.536 10 kW

(c) Toluene

Hv = 30.625

kJ
mol

H = 65.586

kJ
mol

Q = 1.822 10 kW

4.15 Benzene

Tc := 562.2K

Pc := 48.98bar

T1sat := 451.7K

Tn := 353.2K

T2sat := 358.7K

Cp := 162

J
mol K

Estimate Hv using Riedel equation (4.12) and Watson correction (4.13)

Trn :=

Tn

Trn = 0.628

Tc

Tr2sat :=

Pc
1.013
bar
R T

T2sat
Tc

Tr2sat = 0.638

1.092 ln
Hn :=

0.930 Trn

1 Tr2sat
Hv := Hn

1 Trn

Hn = 30.588

0.38

Hv = 30.28

kJ
mol

kJ
mol

Assume the throttling process is adiabatic and isenthalpic.

Guess vapor fraction (x): x := 0.5
Given

Cp (T1sat T2sat) = x Hv

4.16 (a) For acetylene:

Tc := 308.3 K
T := 298.15 K
70

x := Find ( x)

Pc := 61.39 bar

x = 0.498

Ans.

Tn := 189.4 K

Trn :=

Tn

Trn = 0.614

Tc

Tr :=

Pc
1.013
bar

Hn := R Tn 1.092

T
Tc

Tr = 0.967

ln

0.930 Trn

1 Tr
Hv := Hn

1 Trn
Hf := 227480

J
mol

Hv = 6.638

kJ
mol

H298 := H f Hv

H298 = 220.8

kJ
mol
kJ
mol

(c) For ethylbenzene:

H298 = 12.3

(d) For n-hexane:

H298 = 198.6

(e) For styrene:

H298 = 103.9

kJ
mol

kJ
mol

dQ = dU dW = CV dT + P dV

1st law:

P V = R T

Ideal gas:

and

P V = const

from which

then

(A)

P dV + V dP = R dT

V dP = R dT P dV

Whence
Since

kJ
mol

0.38

(b) For 1,3-butadiene: H298 = 88.5

4.17

Hn = 16.91

P V

(B)
1

dV = V dP

V dP = P dV
P dV =

Combines with (B) to yield:

71

R dT
1

kJ
mol

Ans.

dQ = CV dT +

Combines with (A) to give:

dQ = CP dT R dT +

or

or

R dT
1

dQ = CP dT +

which reduces to

R dT

CP

+
R dT
R 1

dQ =

R dT

(C)

Since CP is linear in T, the mean heat capacity is the value of

C P at the arithmetic mean temperature. Thus
Tam := 675

CPm := R 3.85 + 0.57 10

Tam

T2 := 950 K

Integrate (C):

CPm

+
R ( T 2 T 1)
1
R

Q :=

T1 := 400 K
Q = 6477.5

:= 1.55
J
mol

Ans.

P1 := 1 bar

4.18

T2
P2 := P1
T1

P2 = 11.45 bar

For the combustion of methanol:

CH3OH(g) + (3/2)O2(g) = CO2(g) + 2H2O(g)
H298 := 393509 + 2 ( 241818) ( 200660)
H298 = 676485
For 6 MeOH:

H298 = 4 , 058 , 910 J

For the combustion of 1-hexene:

C6H12(g) + 9O2(g) = 6CO2(g) + 6H2O(g)
72

Ans.

Ans.

H298 := 6 ( 393509) + 6 ( 241818) ( 41950)

H298 = 3770012

H298 = 3 , 770 , 012 J

Ans.

Comparison is on the basis of equal numbers of C atoms.

4.19

C2H4 + 3O2 = 2CO2 + 2H2O(g)

H298 := [ 2 ( 241818) + 2 ( 393509) 52510]

J
mol

Parts (a) - (d) can be worked exactly as Example 4.7. However, with
Mathcad capable of doing the iteration, it is simpler to proceed differently.
Index the product species with the numbers:
1 = oxygen
2 = carbon dioxide
3 = water (g)
4 = nitrogen
(a) For the product species, no excess air:

0
3.639
0.506
0.227

2
5.457
1.045

1.157
10
A :=
B :=

105K2
n :=
D :=
2
3.470
1.450 K
0.121

11.286
3.280
0.593
0.040
i := 1 .. 4

A :=

ni Ai B := niBi
i

A = 54.872

B = 0.012

1
K

D :=

ni Di
i

5 2

D = 1.621 10 K

For the products,

CP
HP = R
dT
R
T

T0 := 298.15K

The integral is given by Eq. (4.7). Moreover, by an energy balance,

H298 + H P = 0
73

 := 2

(guess)

Given

H 298 = R A T0 ( 1) +

:= Find ( )

= 8.497

B
D 1
2 2
T0 1 +

2
T0

T := T0

T = 2533.5K

Ans.

Parts (b), (c), and (d) are worked the same way, the only change being in the
numbers of moles of products.
(b)

nO = 0.75

nn = 14.107

T = 2198.6 K

Ans.

(c)

nO = 1.5

nn = 16.929

T = 1950.9 K

Ans.

(d)

nO = 3.0

nn = 22.571

T = 1609.2 K

Ans.

(e) 50% xs air preheated to 500 degC. For this process,

Hair + H298 + H P = 0
Hair = MCPH ( 298.15 773.15)
For one mole of air:

MCPH 773.15 , 298.15 , 3.355 , 0.575 10

, 0.0 , 0.016 10

) = 3.65606

For 4.5/0.21 = 21.429 moles of air:

Hair = n R MCPH T
Hair := 21.429 8.314 3.65606 (298.15 773.15)
Hair = 309399

J
mol

J
mol
H298 + H air + H P = 0

The energy balance here gives:

74

 1.5

n :=
2

16.929

3.639

5.457

A :=
3.470

3.280
A :=

ni Ai

0.506

3
1.045
10
B :=
1.450 K

0.593
B :=

A = 78.84

niBi

0.227

1.157
105 K2
D :=
0.121

0.040
D :=

B = 0.016

ni Di
i

1
K

5 2

D = 1.735 10 K

:= 2 (guess)
Given

:= Find ( )
4.20

= 7.656

T := T0 K

T = 2282.5KK

n-C5H12 + 8O2 = 5CO2 + 6H2O(l)

By Eq. (4.15) with data from Table C.4:
H298 := 5 ( 393509) + 6 ( 285830) ( 146760)
H298 = 3 , 535 , 765 J

4.21

2 2
H 298 Hair = R A T0 ( 1) + T0 1 ...
2
D 1

Ans.

The following answers are found by application of Eq. (4.15) with

data from Table C.4.
(a) -92,220 J

(n) 180,500 J

(b) -905,468 J

(o) 178,321 J

(c) -71,660 J

(p) -132,439 J

(d) -61,980 J

(q) -44,370 J

(e) -367,582 J

(r) -68,910 J
75

Ans.

4.22

(f) -2,732,016 J

(s) -492,640 J

(g) -105,140 J

(t) 109,780 J

(h) -38,292 J

(u) 235,030 J

(i) 164,647 J

(v) -132,038 J

(j) -48,969 J

(w) -1,807,968 J

(k) -149,728 J

(x) 42,720 J

(l) -1,036,036 J

(y) 117,440 J

(m) 207,436 J

(z) 175,305 J

The solution to each of these problems is exactly like that shown in

Example 4.6. In each case the value of Ho298 is calculated in
Problem 4.21. Results are given in the following table. In the first
column the letter in ( ) indicates the part of problem 4.21 appropriate to
the Ho298 value.

T/K
(a)
(b)
(f)
(i)
(j)
(l)
(m)
(n)
(o)
(r)
(t)
(u)
(v)
(w)
(x)
(y)

873.15
773.15
923.15
973.15
583.15
683.15
850.00
1350.00
1073.15
723.15
733.15
750.00
900.00
673.15
648.15
1083.15

A
-5.871
1.861
6.048
9.811
-9.523
-0.441
4.575
-0.145
-1.011
-1.424
4.016
7.297
2.418
2.586
0.060
4.175

103 B
4.181
-3.394
-9.779
-9.248
11.355
0.004
-2.323
0.159
-1.149
1.601
-4.422
-9.285
-3.647
-4.189
0.173
-4.766

106 C
0.000
0.000
0.000
2.106
-3.450
0.000
0.000
0.000
0.000
0.156
0.991
2.520
0.991
0.000
0.000
1.814

76

10-5 D
-0.661
2.661
7.972
-1.067
1.029
-0.643
-0.776
0.215
0.916
-0.083
0.083
0.166
0.235
1.586
-0.191
0.083

IDCPH/J
-17,575
4,729
15,635
25,229
-10,949
-2,416
13,467
345
-9,743
-2,127
7,424
12,172
3,534
4,184
125
12,188

HoT/J
-109,795
-900,739
-2,716,381
189,876
-59,918
-1,038,452
220,903
180,845
168,578
-71,037
117,204
247,202
-128,504
-1,803,784
42,845
129,628

4.23

This is a simple application of a combination of Eqs. (4.18) & (4.19) with

evaluated parameters. In each case the value of Ho298 is calculated in Pb.
4.21. The values of A, B, C and D are given for all cases except for
Parts (e), (g), (h), (k), and (z) in the preceding table. Those missing are as
follows:

A
103 B 106 C 10-5 D
-7.425 20.778
0.000
3.737
-3.629
8.816 -4.904
0.114
-9.987 20.061 -9.296
1.178
1.704 -3.997
1.573
0.234
-3.858 -1.042
0.180
0.919

Part No.
(e)
(g)
(h)
(k)
(z)

6 ft

4.24 q := 150 10

day

5
T := ( 60 32) K + 273.15K
9

T = 288.71 K

P := 1atm

The higher heating value is the negative of the heat of combustion with water
as liquid product.
Calculate methane standard heat of combustion with water as liquid product:
CH4 + 2O2 --> CO2 +2H2O
Standard Heats of Formation:
HfCH4 := 74520

J
mol

HfCO2 := 393509

J
mol

HfO2 := 0

J
mol

HfH2Oliq := 285830

J
mol

Hc := H fCO2 + 2 HfH2Oliq HfCH4 2 HfO2

5 J

HigherHeatingValue := H c

Hc = 8.906 10

mol

Assuming methane is an ideal gas at standard conditions:

n := q

P
R T

n HigherHeatingValue
4.25

8 mol

n = 1.793 10

day

5dollar
5 dollar
= 7.985 10
GJ
day

Ans.

Calculate methane standard heat of combustion with water as liquid product:

77

4.25

Calculate methane standard heat of combustion with water as liquid product:

Standard Heats of Formation: CH4 + 2O2 --> CO2 +2H2O
J
mol
J
HfCO2 := 393509
mol
HfCH4 := 74520

HfO2 := 0

J
mol

HfH2Oliq := 285830

J
mol

HcCH4 := HfCO2 + 2 H fH2Oliq HfCH4 2 H fO2

HcCH4 = 890649

J
mol

Calculate ethane standard heat of combustion with water as liquid product:

Standard Heats of Formation: C 2H6 + 7/2O2 --> 2CO2 +3H2O
HfC2H6 := 83820

J
mol

HcC2H6 := 2HfCO2 + 3 H fH2Oliq HfC2H6

HcC2H6 = 1560688

7
HfO2
2

J
mol

Calculate propane standard heat of combustion with water as liquid product:

Standard Heats of Formation: C 3H8 + 5O2 --> 3CO2 +4H2O
HfC3H8 := 104680

J
mol

HcC3H8 := 3HfCO2 + 4 H fH2Oliq HfC3H8 5 H fO2

HcC3H8 = 2219.167

kJ
mol

Calculate the standard heat of combustion for the mixtures

kJ
0.95

H
+
0.02

H
+
0.02

H
=

921.714
cCH4
cC2H6
cC3H8
a)
mol
kJ
b) 0.90 H cCH4 + 0.05 H cC2H6 + 0.03 H cC3H8 = 946.194 mol
kJ
0.85

H
+
0.07

H
+
0.03

H
=

932.875
cCH4
cC2H6
cC3H8
c)
mol
Gas b) has the highest standard heat of combustion.
78

Ans.

4.26

2H2 + O2 = 2H2O(l)

Hf1 := 2 (285830) J

C + O2 = CO2(g)

Hf2 := 393509 J

N2(g)+2H2O(l)+CO2(g)=(NH2)2CO(s)+3/2O2 H := 631660 J
.
N2(g)+2H2(g)+C(s)+1/2O2(g)=(NH2)2CO(s)
H298 := H f1 + Hf2 + H
4.28

H298 = 333509 J

Ans.

On the basis of 1 mole of C10H18

(molar mass = 162.27)
6

Q := 43960 162.27 J

Q = 7.133 10 J

This value is for the constant-volume reaction:

C10H18(l) + 14.5O2(g) = 10CO2(g) + 9H2O(l)
Assuming ideal gases and with symbols representing total properties,
Q = U = H (PV) = H R T ngas
T := 298.15 K

ngas := ( 10 14.5) mol

H := Q + R T ngas

H = 7.145 10 J

This value is for the constant-V reaction, whereas the STANDARD

reaction is at const. P.However, for ideal gases H = f(T), and for liquids H
is a very weak function of P. We therefore take the above value as the
standard value, and for the specified reaction:

C10H18(l) + 14.5O2(g) = 10CO2(g) + 9H2O(l)

9H2O(l) = 9H2O(g)
Hvap := 9 44012 J
___________________________________________________
C10H18(l) + 14.5O2(g) = 10CO2(g) + 9H2O(g)
H298 := H + H vap

H298 = 6748436 J
79

Ans.

4.29

FURNACE: Basis is 1 mole of methane burned with 30% excess air.

CH4 + 2O2 = CO2 + 2H2O(g)

Entering:

Moles methane

n1 := 1

Moles oxygen

n2 := 2 1.3

Moles nitrogen

n3 := 2.6

n2 = 2.6

79
21

n3 = 9.781

n := n1 + n2 + n3

Total moles of dry gases entering

n = 13.381

At 30 degC the vapor pressure of water is

4.241 kPa. Moles of water vapor entering:
n4 :=
Leaving:

4.241
13.381
101.325 4.241

CO2 -- 1 mol
H2O -- 2.585 mol
O2 -- 2.6 - 2 = 0.6 mol
N2 -- 9.781 mol

n4 = 0.585
(1)
(2)
(3)
(4)

By an energy balance on the furnace:

Q = H = H 298 + HP
For evaluation of HP we number species as above.

2.585

n :=
0.6

9.781

5.457

3.470

A :=
3.639

3.280

i := 1 .. 4

R := 8.314
A :=

ni Ai

1.045

1.450
10 3
B :=
0.506

0.593

B :=

A = 48.692

niBi
i

B = 0.010897
80

1.157

0.121
105
D :=
0.227

0.040

D :=

ni Di
i

D = 5.892 10

The TOTAL value for MCPH of the product stream:

MCPH 303.15 , 1773.15 , 48.692 , 10.897 10

, 0.0 , 0.5892 10

) = 59.89511

MCPH := 59.89511
HP := R MCPH (1773.15 303.15)
From Example 4.7:

H298 := 802625

Q := H P + H 298

Q = 70 , 612 J

Ans.

HEAT EXCHANGER: Flue gases cool from 1500 degC to

50 degC. The partial pressure of the water in the flue gases leaving the
furnace (in kPa) is
pp :=

n2
n1 + n2 + n3 + n4

101.325

pp = 18.754

The vapor pressure of water at 50 degC (exit of heat exchanger) is 12.34

kPa, and water must condense to lower its partial pressure to this value.
n := n1 + n3 + n4

Moles of dry flue gases:

n = 11.381

Moles of water vapor leaving the heat exchanger:

n2 :=

12.34
n
101.325 12.34

n2 = 1.578
n := 2.585 1.578

Moles water condensing:

Latent heat of water at 50 degC in J/mol:

H50 := 2382.9 18.015
Sensible heat of cooling the flue gases to 50 degC with all the water as
vapor (we assumed condensation at 50 degC):

MCPH 323.15 , 1773.15 , 48.692 , 10.897 10

MCPH := 60.01086

Q := R MCPH ( 323.15 1773.15) n H 50

81

, 0.0 , 0.5892 10

) = 60.01086

Q = 766 , 677 J

Ans.

4.30

4NH3(g) + 5O2(g) = 4NO(g) + 6H2O(g)

BASIS: 4 moles ammonia entering reactor
Moles O2 entering = (5)(1.3) = 6.5
Moles N2 entering = (6.5)(79/21) = 24.45
Moles NH3 reacting = moles NO formed = (4)(0.8) = 3.2
Moles O2 reacting = (5)(0.8) = 4.0
Moles water formed = (6)(0.8) = 4.8
ENERGY BALANCE:
H = H R + H 298 + HP = 0
REACTANTS: 1=NH3; 2=O2; 3=N2

4
n := 6.5
24.45

3.578
A := 3.639
3.280

i := 1 .. 3

A :=

3.020
3
B := 0.506 10
0.593

ni Ai

B :=

niBi

0.186

5
D := 0.227 10
0.040

D :=

A = 118.161

B = 0.02987

D = 1.242 10

TOTAL mean heat capacity of reactant stream:

MCPH 348.15 , 298.15 , 118.161 , 0.02987 , 0.0 , 1.242 10

MCPH := 126.61632

ni Di

) = 126.61632

HR := R MCPH ( 298.15 348.15)

The result of Pb. 4.21(b) is used to get

H298 := 0.8 ( 905468)
PRODUCTS:1=NH3; 2=O2; 3=NO; 4=H2O; 5=N2

0.8
2.5

n := 3.2
4.8

24.45

3.578
3.639

A := 3.387
3.470

3.280

3.020
0.506

3
B := 0.629 10
1.450

0.593
82

0.186
0.227

5
D := 0.014 10
0.121

0.040

i := 1 .. 5

A :=

ni Ai

B :=

A = 119.65

niBi

D :=

ni Di
i

B = 0.027

D = 8.873 10

By the energy balance and Eq. (4.7), we can write:

T0 := 298.15

(guess)

2 2

H 298 HR = R A T0 ( 1) + T0 1 ...
2
D 1

T0

Given

:= Find ( )
4.31

:= 2

= 3.283

T := T0 K

T = 978.9K

Ans.

C2H4(g) + H2O(g) = C2H5OH(l)

BASIS: 1 mole ethanol produced
Energy balance: H = Q = H + H
R
298
4

H298 := 277690 ( 52510 241818)

H298 = 8.838 10

Reactant stream consists of 1 mole each of C2H4 and H2O.

1
i := 1 .. 2 n :=
1
1.424
14.394 3
4.392 6
0.0 5
D :=
B :=
10 C :=
10
10
3.470
1.450
0.0
0.121

A :=
A :=

ni Ai B := niBi
i

C :=

A = 4.894

niCi

D :=

B = 0.01584

C = 4.392 10

MCPH 298.15 , 593.15 , 4.894 , 0.01584 , 4.392 10

83

ni Di
4

D = 1.21 10
5

, 0.121 10

) = 11.1192

MCPH := 11.1192
4

HR := R MCPH ( 298.15 593.15) HR = 2.727 10

Q := H R + H 298 J

Q = 115653 J Ans.

4.32 One way to proceed is as in Example 4.8 with the alternative pair of reactions:
CH4 + H2O = CO + 3H2

H298a := 205813

CH4 + 2H2O = CO2 + 4H2

H298b := 164647

BASIS: 1 mole of product gases containing 0.0275 mol CO2; 0.1725 mol
CO; & H2O 0.6275 mol H2
Entering gas, by carbon & oxygen balances:
0.0275 + 0.1725 = 0.2000 mol CH4
0.1725 + 0.1725 + 2(0.0275) = 0.4000 mol H2O
4

H298 := 0.1725 H 298a + 0.0275 H298b

H298 = 4.003 10

The energy balance is written

Q = H R + H 298 + HP

0.2

0.4

n :=

i := 1 .. 2

REACTANTS: 1=CH4; 2=H2O

1.702
9.081 3
2.164 6
0.0 5
C :=
D :=
B :=
10
10
10
3.470
1.450
0.0
0.121

A :=
A :=

ni Ai B := niBi
i

A = 1.728

C :=

D :=

C = 4.328 10

ICPH 773.15 , 298.15 , 1.728 , 2.396 10

HR := R ICPH

PRODUCTS: 1=CO2; 2=CO; 3=H2O; 4=H2

84

, 4.33 10

ni Di
i

B = 2.396 10

ICPH := 1377.435

niCi

D = 4.84 10

) = 1377.435

, 4.84 10

HR = 1.145 10

 0.0275
5.457

0.1725
3.376
A :=

n :=
0.1725
3.470

0.6275
3.249

1.045

0.557
10 3
B :=
1.450

0.422

1.157

0.031
105
D :=
0.121

0.083

i := 1 .. 4

B :=

D :=

A :=

ni Ai
i

B = 6.397 10

ICPH 298.15 , 1123.15 , 3.370 , 6.397 10

ni Di

A = 3.37

ICPH := 3164.293

niBi

D = 3.579 10

HP := R ICPH

Q := H R + H 298 + HP J

) = 3164.293

, 0.0 , 3.579 10

HP = 2.631 10
Q = 54886 J

Ans.

H298a := 802625

4.33 CH4 + 2O2 = CO2 + 2H2O(g)

H298b := 1428652

C2H6 + 3.5O2 = 2CO2 + 3H2O(g)

BASIS: 1 mole fuel (0.75 mol CH4; 0.25 mol C2H6) burned completely with
80% xs. air.
O2 in = 1.8[(0.75)(2) + (0.25)(3.5)] = 4.275 mol
N2 in = 4.275(79/21) = 16.082 mol
Product gases: CO2 = 0.75 + 2(0.25) = 1.25 mol
H2O = 2(0.75) + 3(0.25) = 2.25 mol
O2 = (0.8/1.8)(4.275) = 1.9 mol
N2 = 16.082 mol
H298 := 0.75 H 298a + 0.25 H298b
Energy balance:

Q = H = H 298 + HP

Q := 8 10

HP = Q H298

PRODUCTS: 1=CO2; 2=H2O; 3=O2; 4=N2

1.25

2.25

n :=
1.9

16.082

5.457

3.470

A :=
3.639

3.280

1.045

1.450 3

B :=
10
0.506

0.593
85

1.157

0.121 5

D :=
10
0.227

0.040

i := 1 .. 4

A :=

ni Ai

B :=

A = 74.292

niBi

D :=

ni Di
i

B = 0.015

D = 9.62 10

By the energy balance and Eq. (4.7), we can write:

T0 := 303.15
Given

(guess)

2 2

Q H298 = R A T0 ( 1) + T0 1 ...
2
D 1

T0

= 1.788
4.34

:= 2

T := T0 K

T = 542.2K

:= Find ( )

Ans.

BASIS: 1 mole of entering gases containing 0.15 mol SO2; 0.20 mol
O2; 0.65 mol N2
SO2 + 0.5O2 = SO3

Conversion = 86%

SO2 reacted = SO3 formed = (0.15)(0.86) = 0.129 mol

O2 reacted = (0.5)(0.129) = 0.0645 mol
Energy balance: H 773 = H R + H 298 + HP
Since HR and HP cancel for the gas that passes through the converter
unreacted, we need consider only those species that react or are formed.
Moreover, the reactants and products experience the same temperature
change, and can therefore be considered together. We simply take the
number of moles of reactants as being negative. The energy balance is
then written: H773 = H298 + H net
H298 := [ 395720 ( 296830) ] 0.129
1: SO2; 2: O2; 3: SO3

0.129
n := 0.0645
0.129

5.699
A := 3.639
8.060

0.801
3
B := 0.506 10
1.056

86

1.015
5
D := 0.227 10
2.028

i := 1 .. 3

A :=

ni Ai

niBi

B :=

A = 0.06985

ni Di
i

B = 2.58 10

MCPH 298.15 , 773.15 , 0.06985 , 2.58 10

MCPH := 0.019666

D :=

D = 1.16 10
4

, 0.0 , 1.16 10

) = 0.019666

Hnet := R MCPH ( 773.15 298.15)

H773 := H 298 + Hnet J

H773 = 12679 J

Ans.

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

BASIS: 1 mole of feed consisting of 0.5 mol CO and 0.5 mol H2O.
Moles CO reacted = moles H2O reacted = moles CO2 formed = moles H2
formed = (0.6)(0.5) = 0.3
Product stream:

moles CO = moles H2O = 0.2

moles CO2 = moles H2 = 0.3

Energy balance:

Q = H = H R + H298 + H P
4

H298 := 0.3 [ 393509 ( 110525 214818) ]

H298 = 2.045 10

Reactants: 1: CO 2: H2O

0.5

0.5

3.376

3.470

B :=

ni Ai

B :=

n :=

A :=

i := 1 .. 2

A :=

A = 3.423

0.557 3
10
1.450

D :=

0.031 5
10
0.121

niBi

D :=

B = 1.004 10
3

MCPH 298.15 , 398.15 , 3.423 , 1.0035 10

ni Di

D = 4.5 10

, 0.0 , 0.045 10

) = 3.8103

MCPH := 3.8103
HR := R MCPH ( 298.15 398.15)
Products:

1: CO 2: H2O 3: CO2 4: H2

87

HR = 3.168 10

 0.2

0.2
n :=
0.3

0.3

3.376

3.470

A :=
5.457

3.249

i := 1 .. 4

A :=

0.557

1.450
10 3
B :=
1.045

0.422

ni Ai

B :=

niBi

0.031

0.121
105
D :=
1.157

0.083
D :=

A = 3.981

B = 8.415 10

MCPH 298.15 , 698.15 , 3.981 , 0.8415 10

ni Di
4

D = 3.042 10
5

, 0.0 , 0.3042 10

) = 4.25405

MCPH := 4.25405
HP := R MCPH (698.15 298.15)

Q := H R + H 298 + HP J

HP = 1.415 10
Q = 9470 J

Ans.

4.36 BASIS: 100 lbmol DRY flue gases containing 3.00 lbmol CO2 and 11.80
lbmol CO x lbmol O2 and 100-(14.8-x)= 85.2-x lbmol N2. The oil therefore
contains 14.80 lbmol carbon;a carbon balance gives the mass of oil burned:
14.8

12.011
lbm = 209.133 lbm
0.85

The oil also contains H2O:

209.133 0.01
lbmol = 0.116 lbmol
18.015
Also H2O is formed by combustion of H2 in the oil in the amount
209.133 0.12
lbmol = 12.448 lbmol
2.016
Find amount of air entering by N2 & O2 balances.
N2 entering in oil:
209.133 0.02
lbmol = 0.149 lbmol
28.013
lbmol N2 entering in the air=(85.2-x)-0.149 =85.051-x
88

lbmol O2 in flue gas entering with dry air =

3.00 + 11.8/2 + x + 12.448/2
=
15.124 + x lbmol
(CO2) (CO) (O2) (H2O from combustion)
Total dry air = N2 in air + O2 in air = 85.051 - x + 15.124 + x = 100.175 lbmol
Since air is 21 mol % O2,
0.21 =

15.124 + x
100.175

x := (0.21 100.175 15.124) lbmol

x = 5.913 lbmol

O2 in air = 15.124 + x = 21.037 lbmols

N2 in air = 85.051 - x = 79.138 lbmoles
N2 in flue gas = 79.138 + 0.149 = 79.287 lbmols
[CHECK: Total dry flue gas
= 3.00 + 11.80 + 5.913 + 79.287
= 100.00 lbmol]
Humidity of entering air, sat. at 77 degF in lbmol H2O/lbmol dry air,
P(sat)=0.4594(psia)
0.4594
= 0.03227
14.696 0.4594
lbmol H2O entering in air:
0.03227 100.175 lbmol = 3.233 lbmol
If y = lbmol H2O evaporated in the drier, then
lbmol H2O in flue gas = 0.116+12.448+3.233+y
= 15.797 + y
Entering the process are oil, moist air, and the wet material to be dried, all at
77 degF. The "products" at 400 degF consist of:
3.00 lbmol CO2
11.80 lbmol CO
5.913 lbmol O2
79.287 lbmol N2
(15.797 + y) lbmol H2O(g)
Energy balance:

Q = H = H 298 + HP

where Q = 30% of net heating value of the oil:

89

Q := 0.3 19000

BTU
209.13 lbm
lbm

Q = 1.192 10 BTU

Reaction upon which net heating value is based:

OIL + (21.024)O2 = (14.8)CO2 + (12.448 + 0.116)H2O(g) + (0.149)N2
6

H298a := 19000 209.13 BTU

H298a = 3.973 10 BTU

To get the "reaction" in the drier, we add to this the following:

(11.8)CO2 = (11.8)CO + (5.9)O2
H298b := 11.8 ( 110525 + 393509) 0.42993 BTU
(y)H2O(l) = (y)H2O(g)

Guess: y := 50

H298c ( y) := 44012 0.42993 y BTU

[The factor 0.42993 converts from joules on the basis of moles to Btu on the
basis of lbmol.]
Addition of these three reactions gives the "reaction" in the drier, except
for some O2, N2, and H2O that pass through unchanged. Addition of the
corresponding delta H values gives the standard heat of reaction at 298 K:
H298 ( y) := H298a + H 298b + H298c (y)
For the product stream we need MCPH:
1: CO2 2: CO 3:O2 4: N2 5: H2O
T0 := 298.15
3

11.8

n ( y) := 5.913
79.278

15.797 + y
i := 1 .. 5

R := 1.986

5.457
3.376

A := 3.639
3.280

3.470

A ( y) :=

n(y)i Ai

T :=

1.045
0.557

3
B := 0.506 10
0.593

1.450
B ( y) :=

:=

T
T0

= 1.602

400 + 459.67
1.8

n(y)iBi
i

CP ( y) := R A ( y) +

90

T = 477.594

1.157
0.031

5
D := 0.227 10
0.040

0.121
D ( y) :=

n(y)i Di
i

B ( y)
D ( y)
T0 ( + 1) +
2
2
T0

CP ( y) ( 400 77) BTU = Q H298 ( y)

Given

y = 49.782
Whence

y := Find ( y)

(lbmol H2O evaporated)

y 18.015
= 4.288
209.13

(lb H2O evap. per lb oil burned)

Ans.

4.37 BASIS: One mole of product gas containing 0.242 mol HCN, and
(1-0.242)/2 = 0.379 mol each of N2 and C2H2. The energy balance is
Q = H = H 298 + HP
H298 := ( 2 135100 227480)

0.242
J
2

H298 = 5.169 10 J

Products:

0.242
n := 0.379
0.379

4.736
A := 3.280
6.132

i := 1 .. 3

A :=

ni Ai

1.359
3
B := 0.593 10
1.952

niBi

B :=

R := 8.314

A = 4.7133

0.725
5
D := 0.040 10
1.299

D :=

B = 1.2934 10

MCPH 298.15 , 873.15 , 4.7133 , 1.2934 10

ni Di
4

D = 6.526 10
4

, 0.0 , 6.526 10

) = 5.22010

MCPH := 5.22010
4

HP := R MCPH (873.15 298.15) J

HP = 2.495 10 J

Q := H 298 + HP

Q = 30124 J

Ans.

4.38 BASIS: 1 mole gas entering reactor, containing 0.6 mol HCl, 0.36 mol O2,
and 0.04 mol N2.
HCl reacted = (0.6)(0.75) = 0.45 mol
4HCl(g) + O2(g) = 2H2O(g) + 2Cl2(g)
For this reaction,
91

H298 := 2 ( 241818) 4 ( 92307)

H823

Evaluate
T0 := 298.15

H298 = 1.144 10

by Eq. (4.21) with

T := 823.15

R := 8.314

1: H2O 2: Cl2 3: HCl 4=O2

2

2
n :=
4

1

3.470

4.442

A :=
3.156

3.639

i := 1 .. 4

A :=

ni Ai

1.45

0.089
10 3
B :=
0.623

0.506
B :=

A = 0.439

0.121

0.344
105
D :=
0.151

0.227

ni Bi

D :=

B = 8 10

MDCPH 298.15 , 823.15 , 0.439 , 8.0 10

ni Di

D = 8.23 10
4

, 0.0 , 8.23 10

) = 0.72949

MDCPH := 0.72949
H823 := H 298 + MDCPH R ( T T0)

H823 = 117592

Heat transferred per mol of entering gas mixture:

Q :=

H823 J
4

0.45

Q = 13229 J

4.39 CO2 + C = 2CO

2C + O2 = 2CO

Ans.

H298a := 172459

(a)

H298b := 221050

(b)

Eq. (4.21) applies to each reaction:

For (a):

2
n := 1
1

i := 1 .. 3

3.376
A := 1.771
5.457

A :=

ni Ai

0.557
3
B := 0.771 10
1.045

B :=

ni Bi
i

92

0.031
5
D := 0.867 10
1.157

D :=

ni Di
i

A = 0.476

B = 7.02 10

MDCPH 298.15 , 1148.15 , 0.476 , 7.02 10

D = 1.962 10
5

, 0.0 , 1.962 10

) = 0.410505

MDCPHa := 0.410505
5

H1148a := H 298a + R MDCPHa (1148.15 298.15) H1148a = 1.696 10

For (b):

2
n := 1
2

3.376
A := 3.639
1.771

i := 1 .. 3

A :=

ni Ai

0.557
3
B := 0.506 10
0.771

B :=

A = 0.429

ni Bi

0.031
5
D := 0.227 10
0.867

D :=

B = 9.34 10

MDCPH 298.15 , 1148.15 , 0.429 , 0.934 10

ni Di
5

D = 1.899 10
5

, 0.0 , 1.899 10

) = 0.549680

MDCPHb := 0.549680
H1148b := H 298b + R MDCPHb ( 1148.15 298.15)
5

H1148b = 2.249 10

The combined heats of reaction must be zero:

nCO H1148a + nO H1148b = 0
2

nCO
Define:

r=

r :=

nO

H1148b
H 1148a

For 100 mol flue gas and x mol air, moles are:
Flue gas

Air

Feed mix

CO2

12.8

12.8

CO

3.7

3.7
93

r = 1.327

O2

5.4

0.21x

5.4 + 0.21x

N2

78.1

0.79x

78.1 + 0.79x

Whence in the feed mix:

r=

12.5
5.4
r
x :=
mol
0.21

12.8
5.4 + 0.21 x

x = 19.155 mol
100
= 5.221
19.155

Flue gas to air ratio =

Ans.

Product composition:
nCO := 3.7 + 2 ( 12.8 + 5.4 + 0.21 19.155)

nCO = 48.145

nN := 78.1 + 0.79 19.155

nN = 93.232

Mole % CO =

nCO
nCO + nN

100 = 34.054
Ans.

Mole % N2 =

100 34.054 = 65.946

H298a := 802625

4.40 CH4 + 2O2 = CO2 + 2H2O(g)

H298b := 519641

CH4 + (3/2)O2 = CO + 2H2O(g)

BASIS: 1 mole of fuel gas consisting of 0.94 mol CH4 and 0.06 mol N2
Air entering contains:
1.35 2 0.94 = 2.538
2.538

79
= 9.548
21

mol O2
mol N2

Moles CO2 formed by reaction =

0.94 0.7 = 0.658

Moles CO formed by reaction =

0.94 0.3 = 0.282

J
) mol

H298 := 0.658 H 298a + 0.282 H298b

94

5 J

H298 = 6.747 10

mol

Moles H2O formed by reaction =

0.94 2.0 = 1.88

Moles O2 consumed by reaction =

2 0.658 +

3
0.282 = 1.739
2

Product gases contain the following numbers of moles:

(1)
(2)
(3)
(4)
(5)

CO2: 0.658
CO: 0.282
H2O: 1.880
O2: 2.538 - 1.739 = 0.799
N2: 9.548 + 0.060 = 9.608

0.658
0.282

n := 1.880
0.799

9.608

5.457
3.376

A := 3.470
3.639

3.280

i := 1 .. 5

A :=

ni Ai

1.045
0.557

3
B := 1.450 10
0.506

0.593
B :=

J
R := 8.314
A = 45.4881
mol K

1.157
0.031

5
D := 0.121 10
0.227

0.040

niBi

D :=

B = 9.6725 10

MCPH 298.15 , 483.15 , 45.4881 , 9.6725 10

ni Di

D = 3.396 10
4

, 0.0 , 3.396 10

) = 49.03091

MCPH := 49.03091
4 J

HP := R MCPH (483.15 298.15) K

Hrx := H 298 + HP

Energy balance:

HH2O mdotH2O + Hrx ndotfuel = 0

HH2O mdotH2O

kJ
kg

ndotfuel = 16.635

H rx
95

mol

kJ
mol
kg
mdotH2O := 34.0
sec

Hrx = 599.252

HH2O := ( 398.0 104.8)

From Table C.1:

ndotfuel :=

HP = 7.541 10

mol
sec

Volumetric flow rate of fuel, assuming ideal gas:

V :=

ndotfuel R 298.15 K

m
V = 0.407
sec

101325 Pa

Ans.

H298 := 109780

4.41 C4H8(g) = C4H6(g) + H2(g)

J
mol

BASIS: 1 mole C4H8 entering, of which 33% reacts.

The unreacted C4H8 and the diluent H2O pass throught the reactor
unchanged, and need not be included in the energy balance. Thus
T0 := 298.15 K

1
n := 1
1

T := 798.15 K

H798

Evaluate

by Eq. (4.21):

1: C4H6 2: H2 3: C4H8

0.0
2.734
26.786
8.882

5
3
6
A := 3.249 B := 0.422 10
C := 0.0 10
D := 0.083 10
1.967
31.630
9.873
0.0

i := 1 .. 3
A :=

ni AiB := ni Bi
i

C :=

A = 4.016

ni Ci

ni Di

D :=

B = 4.422 10

C = 9.91 10

MDCPH 298.15 , 798.15 , 4.016 , 4.422 10

, 9.91 10

D = 8.3 10
5

, 0.083 10

) = 1.94537

MDCPH := 1.94537
H798 := H 298 + MDCPH R ( T T0)
Q := 0.33 mol H 798

Q = 38896 J

96

5 J

H798 = 1.179 10
Ans.

mol