Solution Manual for 7th Edition Intro to Chemical Thermodynamics | Fuels | Coal

# Chapter 1 - Section A - Mathcad Solutions

1.4 The equation that relates deg F to deg C is: t(F) = 1.8 t(C) + 32. Solve this equation by setting t(F) = t(C). Guess solution:

t

0

Given

t = 1.8t

32

Find t ()

40

Ans.

1.5 By definition:

P=

F A

F = mass g

Note: Pressures are in gauge pressure.

P

3000bar

D

4mm

A

4

D

2

A

12.566 mm

2

F

PA

g

9.807

m s
2

mass

F g

mass

384.4 kg

Ans.

1.6 By definition:
P 3000atm

P=
D

F A
0.17in

F = mass g
A

4

D

2

A

0.023 in

2

F

PA

g

32.174

ft sec
2

mass

F g

mass

1000.7 lbm

Ans.

1.7 Pabs =

gh

Patm

13.535

gm cm
3

g

9.832

m s
2

h

56.38cm

Patm

101.78kPa

Pabs

gh

Patm

Pabs

176.808 kPa Ans.

1.8

13.535

gm cm
3

g

32.243

ft s
2

h

25.62in

Patm

29.86in_Hg

Pabs

gh

Patm

Pabs

27.22 psia

Ans.

1

1.10 Assume the following:

13.5

gm cm
3

g

9.8

m s
2

P

400bar

h

P g

h

302.3 m

Ans.

1.11

The force on a spring is described by: F = Ks x where Ks is the spring constant. First calculate K based on the earth measurement then gMars based on spring measurement on Mars. On Earth:

F = mass g = K x

mass

0.40kg

g

9.81

m s
2

x

1.08cm

F

mass g

F

3.924 N

Ks

F x
4 10

Ks
3

363.333

N m

On Mars:

x

0.40cm
FMars mass

FMars

Kx

FMars

mK

gMars

gMars

0.01

mK kg

Ans.

1.12 Given:

d P= dz

g

and:

=

MP RT

Substituting:

d P= dz

MP g RT

PDenver

Separating variables and integrating:
Psea

1 dP = P

zDenver

Mg dz RT

0

After integrating:

ln

PDenver Psea

=

Mg zDenver RT
Mg zDenver RT

Taking the exponential of both sides and rearranging: Psea 1atm

PDenver = Psea e gm mol

M

29

g

9.8

m s
2

2

R

82.06

cm atm mol K

3

T

( 10

273.15) K

zDenver

1 mi

Mg zDenver RT
Mg

0.194

PDenver

Psea e

RT

zDenver

PDenver

0.823 atm

Ans.

PDenver 1.13 The same proportionality applies as in Pb. 1.11.

0.834 bar

Ans.

gearth

32.186

ft s
2

gmoon

5.32

ft s
2

lmoon

18.76

learth

lmoon

gearth gmoon

learth

113.498

M
wmoon

learth lbm
M gmoon

M

113.498 lbm
18.767 lbf

Ans.

wmoon

Ans.

1.14

costbulb

hr 5.00dollars 10 day 1000hr

costelec

hr 0.1dollars 70W 10 day kW hr

costbulb

18.262

dollars yr

costelec

25.567

dollars yr

costtotal

costbulb

costelec

costtotal

43.829

dollars yr Ans.

1.15

D

1.25ft

mass

250lbm

g

32.169

ft s
2

3

Patm

30.12in_Hg

A

4

D

2

A

1.227 ft

2

(a) F

Patm A

mass g

F

2.8642

10 lbf

3

Ans.

(b) Pabs

F A

Pabs

16.208 psia

Ans.

(c)

l

1.7ft

Work

F l

Work

4.8691

3 10 ft lbf Ans.

PE

mass g l

PE

424.9 ft lbf

Ans.

1.16

D

0.47m

mass

150kg

g

9.813

m s
2

Patm

101.57kPa

A

4

D

2

A

0.173 m

2

(a) F
(b) Pabs

Patm A
F A

mass g

F
Pabs

1.909

10 N

4

Ans.

110.054 kPa

Ans.

(c)

l

0.83m

Work

F l

Work

15.848 kJ Ans.

EP

mass g l

EP

1.222 kJ

Ans.

1.18

mass

1250kg

u

40

m s

EK

1 2 mass u 2

EK

1000 kJ

Ans.

Work

EK

Work

1000 kJ

Ans.

1.19

Wdot =

mass g h 0.91 0.92 time

Wdot

200W

g

9.8

m s
2

h

50m

4

mdot

Wdot g h 0.91 0.92
25.00 ton

mdot

0.488

kg s

Ans.

1.22 a) cost_coal

MJ 29 kg
2.00 gal

cost_coal

0.95 GJ

1

cost_gasoline

37

GJ m
3

cost_gasoline

14.28 GJ

1

cost_electricity

0.1000 kW hr

cost_electricity

27.778 GJ

1

b) The electrical energy can directly be converted to other forms of energy whereas the coal and gasoline would typically need to be converted to heat and then into some other form of energy before being useful. The obvious advantage of coal is that it is cheap if it is used as a heat source. Otherwise it is messy to handle and bulky for tranport and storage. Gasoline is an important transportation fuel. It is more convenient to transport and store than coal. It can be used to generate electricity by burning it but the efficiency is limited. However, fuel cells are currently being developed which will allow for the conversion of gasoline to electricity by chemical means, a more efficient process. Electricity has the most uses though it is expensive. It is easy to transport but expensive to store. As a transportation fuel it is clean but batteries to store it on-board have limited capacity and are heavy.

5

1.24 Use the Matcad genfit function to fit the data to Antoine's equation. The genfit function requires the first derivatives of the function with respect to the parameters being fitted.
A

Function being fit:

f ( A B C) T

e

B T C

First derivative of the function with respect to parameter A

d f ( A B C) T dA

exp A

B T C

First derivative of the function with respect to parameter B

d f ( A B C) T dB

1 T C

exp A

B T C

First derivative of the function with respect to parameter C

d f ( A B C) T dC
18.5 9.5 0.2 11.8 t 23.1 32.7 44.4 52.1 63.3 75.5

B ( T C)
2

exp A

B T C

3.18 5.48 9.45 16.9 Psat 28.2 41.9 66.6 89.5 129 187

6

T

t

273.15

lnPsat

ln ( ) Psat

Array of functions used by Mathcad. In this case, a0 = A, a1 = B and a2 = C.

exp a0
exp a0

a1 T
a1 T a2

a2

Guess values of parameters

15 guess 3000 50

F ( a) T

1 exp a0 T a2 a1 T a2
2

a1 T a2 a1 T a2

exp a0

Apply the genfit function

A B C
Compare fit with data.
200

A
genfit ( Psat guess F) T

13.421 2.29 10
3

B C

Ans.

69.053

150
Psat f ( A B C) T

100

50

0 240

260

280

300
T

320

340

360

To find the normal boiling point, find the value of T for which Psat = 1 atm.

7

Psat

1atm

Tnb A

B Psat ln kPa

C K

Tnb

329.154 K

Tnb
1.25 a) t1
C2

273.15K

56.004 degC
dollars gal
dollars gal

Ans.

1970
C1 ( 1 i)

t2
t2 t1

2000

C1
C2

0.35

i

5%

1.513

The increase in price of gasoline over this period kept pace with the rate of inflation. b) t1 1970
Given
C2 C1

t2
= (1

2000
i)
t2 t1

C1
i

16000

dollars yr
i

C2
5.511 %

80000

dollars yr

Find ( i)

The salary of a Ph. D. engineer over this period increased at a rate of 5.5%, slightly higher than the rate of inflation. c) This is an open-ended problem. The strategy depends on age of the child, and on such unpredictable items as possible financial aid, monies earned by the child, and length of time spent in earning a degree.

8

Chapter 2 - Section A - Mathcad Solutions
2.1 (a)

Mwt

35 kg

g

9.8

m s
2

z

5m

Work

Mwt g z

Work

1.715 kJ Ans.

(b)

Utotal

Work

Utotal

1.715 kJ

Ans.

(c) By Eqs. (2.14) and (2.21):

dU

d ( )= CP dT PV

Since P is constant, this can be written:

MH2O CP dT = MH2O dU

MH2O P dV

Take Cp and V constant and integrate: MH2O CP t2 t1 = Utotal kJ MH2O 30 kg CP 4.18 t1 20 degC kg degC
t2 t1 Utotal MH2O CP

t2

20.014 degC Ans.

(d) For the restoration process, the change in internal energy is equal but of opposite sign to that of the initial process. Thus

Q

Utotal

Q

1.715 kJ

Ans.

(e)

In all cases the total internal energy change of the universe is zero.

2.2 Similar to Pb. 2.1 with mass of water = 30 kg. Answers are: (a) W = 1.715 kJ (b) Internal energy change of the water = 1.429 kJ (c) Final temp. = 20.014 deg C (d) Q = -1.715 kJ
9

2.4

The electric power supplied to the motor must equal the work done by the motor plus the heat generated by the motor.

i 9.7amp

E

110V

Wdotmech

1.25hp

Wdotelect

i E

Wdotelect

1.067

10 W

3

Qdot

Wdotelect

Wdotmech

Qdot

134.875 W

Ans.

2.5

Eq. (2.3):

U = Q

t

W

Step 1 to 2:

Ut12

200J

W12

6000J

Q12

Ut12

W12

Q12

5.8

10 J

3

Ans.

Step 3 to 4:

Q34

800J

W34

300J

Ut34

Q34

W34
t

Ut34

500 J
t

Ans.

Step 1 to 2 to 3 to 4 to 1: Since U is a state function, U for a series of steps that leads back to the initial state must be zero. Therefore, the sum of the

U values for all of the steps must sum to zero.

t

Ut41

4700J

Ut23

Ut12

Ut34

Ut41

Ut23 Step 2 to 3:

4000 J

Ans.

Ut23

4

10 J

3

Q23

3800J

W23

Ut23

Q23

W23

200 J

Ans.

For a series of steps, the total work done is the sum of the work done for each step.

W12341

1400J
10

W41

W12341

W12

W23

W34

W41

4.5

10 J

3

Ans.

Step 4 to 1:

Ut41

4700J

W41

4.5

10 J

3

Q41

Ut41

W41

Q41

200 J

Ans.

Note:

Q12341 = W12341

2.11 The enthalpy change of the water = work done.

M

20 kg

CP

4.18

kJ kg degC

t

10 degC

Wdot

0.25 kW

M CP t Wdot

0.929 hr

Ans.

2.12 Q

7.5 kJ

U

12 kJ

W

U

Q

W
U 12 kJ

19.5 kJ
12 kJ

Ans.
Ans.

Q

U

Q

2.13Subscripts: c, casting; w, water; t, tank. Then

mc Uc

mw Uw

mt Ut = 0

Let C represent specific heat,

C = CP = CV

Then by Eq. (2.18)

mc Cc tc

mw Cw tw

mt Ct tt = 0

mc

2 kg

mw

40 kg

mt

5 kg

Cc

0.50

kJ kg degC

Ct

0.5

kJ kg degC

Cw

4.18

kJ kg degC

tc

500 degC

t1

25 degC

t2

30 degC

(guess)

Given

mc Cc t2

tc = mw Cw

mt Ct

t2

t1

t2

Find t2
11

t2

27.78 degC

Ans.

2.15

mass

1 kg

CV

4.18

kJ kg K

(a)

T

1K

Ut

mass CV T

Ut

4.18 kJ

Ans.

(b)

g

9.8

m s
2

EP

Ut

z

EP mass g

z

426.531 m Ans.

(c)

EK

Ut

u

EK 1 mass 2

u

91.433

m s

Ans.

2.17

z

50m

1000

kg m
3

u

5

m s
2

D
mdot

2m
uA

A
mdot

4

D

2

A
4 kg

3.142 m

1.571 10

s
3

Wdot

mdot g z Wdot

7.697

10 kW

Ans.

2.18 (a)

U1

kJ 762.0 kg

P1

1002.7 kPa

V1

cm 1.128 gm

3

H1

U1

P1 V 1

H1

763.131

kJ kg

Ans.

(b)

U2

kJ 2784.4 kg

P2

1500 kPa

V2

cm 169.7 gm

3

H2

U2

P2 V 2

U

U2

U1

H

H2

H1

U

2022.4

kJ kg

Ans.

H

2275.8

kJ kg

Ans.

12

2.22

D1

2.5cm

u1

2

m s

D2

5cm

(a)

For an incompressible fluid, =constant. By a mass balance, mdot = constant = u 1A1 = u2A2

u2
(b)

u1
1 2

D1 D2
u2
2

2

u2

0.5

m s

Ans.

EK

1 2

u1

2

EK

1.875

J kg

Ans.

2.23 Energy balance:

mdot3 H3

mdot1 H1

mdot2 H2 = Qdot

Mass balance:

mdot3

mdot1

mdot2 = 0

Therefore:

mdot1 H3
mdot Cp T3

H1
T1

mdot2 H3

H2 = Qdot
T2 = Qdot

or

mdot2 CP T3

T3 CP mdot1

mdot2 = Qdot

mdot1 CP T1

mdot2 CP T2

mdot1

1.0

kg s

T1

25degC

mdot2

0.8

kg s

T2

75degC

Qdot

30

kJ s

CP

4.18

kJ kg K

T3

Qdot

mdot1 CP T1 mdot1

mdot2 CP T2

mdot2 CP

T3

43.235 degC

Ans.

2.25By Eq. (2.32a):

H

By continuity, incompressibility

u2 = u1

u = 0 2 A1

2

H = CP T

A2

CP

4.18

kJ kg degC

13

2 u = u1

2

A1 A2

2

1

2 u = u1

2

D1 D2

4

1

SI units:

u1
2

14

m s

D1

2.5 cm

D2

3.8 cm

T
D2

u1

2 CP
7.5cm

1

D1 D2

4

T

0.019 degC

Ans.

T

u1

2

2 CP

1

D1 D2

4

T

0.023 degC

Ans.

Maximum T change occurrs for infinite D2:

D2

cm

T

u1

2

2 CP

1

D1 D2

4

T

0.023 degC

Ans.

2.26 T1

300K

T2

520K

u1
50

10
kmol hr

m s

u2

3.5

m s

molwt

29

kg kmol

Wsdot

98.8kW

ndot

CP

7 R 2

H

CP T2

T1

H

6.402

10

3 kJ

kmol

By Eq. (2.30):

Qdot

H

u2 2

2

u1 2

2

molwt ndot
2

Wsdot Qdot

9.904 kW

Ans.

2.27By Eq. (2.32b):

H=

u

2 gc

also

V2 V1

=
2

T 2 P1 T 1 P2
2

By continunity, constant area

u2 = u1

V2 V1
14

u2 = u1

T 2 P1 T 1 P2

u = u2

u1

2

29 u1 30 u2 m s m 500 s H1 3112.28 u1 3 m s u2 200 m s H1 2 334.67 rankine R 3. (2.9 rankine Ans.75 cm 3 gm .36 m s Ans.5 kJ kg By Eq.15 degF) 2.32a): Given H2 H1 = u1 2 u2 2 2 u2 Find u2 u2 578. 2.7 kJ kg (guess) By Eq.9 2 kJ kg H2 2726.32a): Q H2 H1 u2 u1 2 Q 2411.5 kJ kg H2 2945.61 cm gm 15 V2 667.6 kJ kg Ans. (2.2 u = u1 2 T 2 P1 T 1 P2 2 1 H = CP T = ft s 7 R T2 2 T1 T1 P1 100 psi P2 20 psi u1 20 579.407 ft lbf mol rankine molwt 28 gm mol T2 578 rankine (guess) Given T2 7 2 R T2 T1 = T2 u1 2 2 T 2 P1 T 1 P2 2 1 molwt Find T2 578. 3 D1 5 cm V1 388. ( 119.

(2. Take into account the heat capacity of the vessel.31 (a) t1 70 degF t2 350 degF n 3 mol CV 5 BTU mol degF By Eq. (b) t1 200 degC t2 40 degC n 4 mol CP 29.19): Q n CV t2 t1 Q 13.8 J mol degC By Eq. Take account of the heat capacity of the vessel: mv 200 lbm cv 0.23): Q 18.12 BTU lbm degF Q mv cv n CV t2 t1 Q 10920 BTU Ans.493 cm Ans.5 kJ kg degC Q mv cv n CV t2 t1 Q 11014 kJ Ans.Continuity: D2 D1 u1 V2 u2 V1 D2 1. (b) t1 400 degF t2 150 degF n 4 mol 16 . (2.728 kJ Ans. 2.19): Q n CV t2 t1 Q 4200 BTU Ans.30 (a) t1 30 degC t2 250 degC n 3 mol CV 20.1 joule mol degC Q n CP t2 t1 By Eq. then mv 100 kg cv 0. (2.62 kJ Ans. 2.

263 lb hr u2 mdot 4 V2 u2 2 9. (2.34 H1 307 BTU lbm H2 330 BTU lbm u1 20 ft s molwt 44 gm mol V1 9.52 hp 2.99 BTU lb 39.32a): Ws Wdot Ws mdot H2 H1 Wdot u2 2 u1 2 Ws Ans.058 ft 3 lbm 2 V2 78. 2. (2.28 ft 3 lbm D1 4 in D2 1 in mdot 4 D1 u1 V1 2 mdot 679.6 BTU lbm u1 10 ft s V1 3.32a): Q H2 H1 u2 2 u1 2 17 2 Ws molwt Q 98.33 H1 1322.23): Q n CP t2 t1 Q 7000 BTU Ans. (2.82 BTU lbm . 173.CP 7 BTU mol degF By Eq.686 D2 ft sec Ws 5360 BTU lbmol Eq.6 BTU lbm H2 1148.14 ft 3 lbm 4 lb D1 3 in D2 10 in mdot 4 D 1 u1 V1 mdot 3.997 D2 ft sec 2 Eq.463 10 sec u2 mdot 4 V2 u2 2 22.25 ft 3 lbm V2 0.

315 K 18 .14 mol K P V1 cm 24942 mol V2 W= n V1 P dV = n P V 1 V2 = n P V1 3 V1 Whence W n P 2 V1 W 172. namely R.4 3 T1 kJ mol CP 29 joule mol K H CP T2 T1 Ans. Q n H Q 602. Given: T2 = T1 V2 V1 = T1 3 Whence T2 H 17.9 gm mol 3 n 34. U Q n W U 12. 2.61 kJ Ans.Qdot mdot Q Qdot 67128 BTU hr Ans.15 K P1 1000 kPa P2 100 kPa (a) Cool at const V1 to P2 (b) Heat at const P2 to T2 CP 7 R 2 CV 5 R 2 Ta2 T1 P2 P1 Ta2 29. R 8. 2.10: 2 steps. A value is required for PV/T.314 J mol K T1 293.15 K T2 333.37 Work exactly like Ex. 2.41 kJ mol Ans. (a) & (b).36 T1 300 K P 1 bar n 1 kg 28.602 mol V1 3 bar cm T1 83.08 kJ Ans.

831 kJ Ub 6.437 8.0001 Note: D = /D in this solution D cm u 1 m 5 s 5 22133 Re D u Re 55333 110667 276667 19 . H H 1. 10 3 J mol mol kJ mol Ans.677 mol Ub U Hb Ua Ha kg m 2 5 2 5 3 P2 V 2 Ub Hb V1 U 0.Tb T2 Ta2 Tb 303.164 2.315 Ans.841 5.028 m 3 mol P1 7.835 K Ta Ta2 T1 Ta 263.484 10 3 J mol 3 J 10 mol V2 R T2 P2 10 V1 V 1 P2 10 3 3 m mol Ha V2 3 J 0.0 10 1 4 kg ms D 0.39 996 9.835 K Hb Ua V1 Ha C P Tb CV Ta R T1 P1 Ua Hb Ua 2.

0.42 mdot 4.88 2.009 10 kW 3 Wdot kW Cost 799924 dollars Ans.5 kg s H1 761.00452 0.565 s 9.00517 0. Wdot Cost mdot H2 15200 H1 0. Neglect changes in KE and PE. 3.206 Ans.00635 fF 0.254 m 0.9 kJ kg Assume that the compressor is adiabatic (Qdot = 0).632 P L 2 fF D u 2 P L kPa 11.27 D 7 Re 0. 20 .9 2 fF 0.3305 ln 0.778 Ans.0039 0.313 mdot u 4 D 2 mdot 1.1 kJ kg H2 536.956 kg 1.573 Wdot 1. 0.

Chapter 3 - Section A - Mathcad Solutions
3.1
=

1 d

dT

=

1

d dP
T

P

At constant T, the 2nd equation can be written:

d

=

dP
ln ( ) 1.01

ln

2 1

=

P

44.1810

6

bar

1

2 = 1.01

1

P

P

225.2 bar
3

P2 = 226.2 bar

Ans.

3.4 b

2700 bar

c

cm 0.125 gm
V2

P1

1 bar

P2

500 bar

Since

Work =
V1
P2

P dV

a bit of algebra leads to

Work

c
P1

P P b

dP

Work

0.516

J gm

Ans.

Work

c P2

P1

b ln

P2 P1

b b

Work

0.516

J gm

Ans.

3.5

= a

bP

a

3.9 10

6

atm

1

b

0.1 10

9

atm

2

P1

1 atm

P2

3000 atm

V

1 ft

3

(assume const.)

Combine Eqs. (1.3) and (3.3) for const. T:
P2

Work

V
P1

( a

b P)P dP
21

Work

16.65 atm ft

3

Ans.

3.6

1.2 10

3

degC
3

1

CP

0.84

kJ kg degC

M

5 kg

V1

1

m

1590 kg

P

1 bar

t1

0 degC

t2

20 degC

With beta independent of T and with P=constant,

dV = V
Vtotal

dT
M V

V2
Vtotal

V1 exp
7.638

t2
10
5

t1
m
3

V

V2

V1

Ans.

Work

P Vtotal

(Const. P)

Work

7.638 joule

Ans.

Q

M CP t2

t1

Q

84 kJ

Ans.

Htotal

Q

Htotal

84 kJ

Ans.

Utotal

Q

Work

Utotal

83.99 kJ
7 R 2

Ans.
5 2

3.8

P1

8 bar

P2

1 bar

T1

600 K

CP

CV

R

(a) Constant V:

W= 0

and

U = Q = CV T

T2

T1

P2 P1

T

T2

T1

T

525 K

U

CV T

Q and

U

10.91

kJ mol

Ans.

H

CP T

H

15.28

kJ mol

Ans.

(b) Constant T:

U=

H= 0
Work

and
10.37

Q= W
kJ mol

Work

R T1 ln

P2 P1

Q

and

Ans.

Q= 0
22

and

U = W = CV T

1

CP CV
U

T2

T1

P2 P1
T2 331.227 K

T

T2

T1

CV T

H

CP T

W

and

U

5.586

kJ mol

Ans.

H

7.821

kJ mol

Ans.

3.9 P4

2bar

CP

7 R 2

CV

5 R 2

P1

10bar

T1

600K

V1

R T1 P1
R CP

V1

4.988

10

3 3 m

mol

T4

T1

P4 P1

T4

378.831 K
3 J

U41

CV T1

T4

U41

4.597

10

H41

CP T1

T4

H41

6.436

10

mol 3 J

mol

Q41

J 0 mol

Q41

J 0 mol

W41

U41

W41

4.597

10
3

3 J

mol

P2

3bar

T2

600K

V2

R T2 P2

V2

m 0.017 mol

Step 12: Isothermal

U12

0

J mol

U12

0

J mol

H12

0

J mol

H12

0

J mol

23

Q12
W12

R T1 ln
Q12

P2 P1

Q12

6.006

10

3 J

mol
3 J

W12

6.006

10

mol

P3

2bar

V3

V2

T3

P3 V 3 R

T3

400 K
3 J

Step 23: Isochoric

U23

CV T3

T2

H23

CP T3

T2

Q23

CV T3

T2

W23

0

J mol

mol 3 J H23 5.82 10 mol 3 J Q23 4.157 10 mol J W23 0 mol

U23

4.157

10

P4

2 bar

T4

378.831 K

V4
CV T4

R T4 P4
T3

V4
U34

m 0.016 mol
439.997 J mol J

3

Step 34: Isobaric

U34

H34

CP T4

T3

H34

615.996

mol

Q34

CP T4

T3

Q34

615.996

W34

R T4

T3

W34

175.999

J mol J

mol

3.10 For all parts of this problem: T2 = T1

and

Also Q = Work and all that remains is U= H= 0 to calculate Work. Symbol V is used for total volume in this problem.

P1

1 bar

P2

12 bar
24

V1

12 m

3

V2

1m

3

(a)

Work = n R T ln

P2
Work

P1
Work

P1 V1 ln

P2 P1 Ans.

2982 kJ

(b) Step 1: adiabatic compression to P2
1

5 3

Vi

V1

P1 P2

(intermediate V)

Vi

2.702 m

3

W1

P2 V i

P1 V 1 1

W1

3063 kJ

Step 2: cool at const P2 to V2

W2

P2 V 2

Vi

W2

2042 kJ

Work

W1

W2

Work

5106 kJ

Ans.

(c) Step 1: adiabatic compression to V2
Pi P1 V1 V2 (intermediate P)

Pi

62.898 bar

W1

Pi V 2

P1 V 1 1

W1

7635 kJ

Step 2: No work.

Work

W1

Work

7635 kJ

Ans.

(d) Step 1: heat at const V1 to P2

W1 = 0

Step 2: cool at const P2 to V2

W2

P2 V 2

V1

Work

W2

Work

13200 kJ

Ans.

(e) Step 1: cool at const P1 to V2

W1

P1 V 2

V1
25

W1

1100 kJ

Step 2: heat at const V2 to P2

W2 = 0

Work

W1

Work

1100 kJ

Ans.

3.17(a)

No work is done; no heat is transferred.

U =

t

T= 0

T2 = T1 = 100 degC

Not reversible

(b)

The gas is returned to its initial state by isothermal compression.

Work = n R T ln
3

V1 V2
V2 4 3

but

n R T = P2 V 2

V1

4m

m

3

P2

6 bar

Work

P2 V2 ln

V1 V2
P2 500 kPa

Work

878.9 kJ Ans.

3.18 (a) P1

100 kPa

T1

303.15 K

CP

7 2

R

CV

5 R 2

CP CV
1

Adiabatic compression from point 1 to point 2:

Q12
U12

0

kJ mol
CV T2 T1

U12 = W12 = CV T12
H12 CP T2 T1

T2
W12

T1

P2 P1
U12

U12

3.679

kJ mol

H12

5.15

kJ mol

W12

3.679

kJ mol

Ans.

Cool at P2 from point 2 to point 3:

T3

T1

H23

CP T3

T2

Q23

H23

U23

CV T3

T2

W23

U23

Q23

26

H23

5.15

kJ mol

U23

3.679

kJ mol

Ans.

Q23

5.15

kJ mol

W23

1.471

kJ mol

Ans.

Isothermal expansion from point 3 to point 1:

U31 =
Q31

H31 = 0
W31

P3

P2

W31

R T3 ln

P1 P3

W31

4.056

kJ mol

Q31

4.056

kJ mol

Ans.

FOR THE CYCLE:

U=

H= 0

Q

Q12

Q23

Q31

Work
Work

W12
1.094

W23
kJ mol

W31

Q

1.094

kJ mol

(b) If each step that is 80% efficient accomplishes the same change of state, all property values are unchanged, and the delta H and delta U values are the same as in part (a). However, the Q and W values change. Step 12:

W12

W12 0.8

W12

4.598

kJ mol

Q12

U12

W12

Q12

0.92

kJ mol

Step 23:

W23

W23 0.8

W23

1.839

kJ mol

Q23

U23

W23

Q23

5.518

kJ mol

Step 31:

W31

W31 0.8

W31

3.245

kJ mol

Q31

W31

Q31
27

3.245

kJ mol

FOR THE CYCLE:

Q

Q12

Q23

Q31

Work

W12

W23

W31

Q

3.192

kJ mol

Work

3.192

kJ mol

3.19Here, V represents total volume.

P1

1000 kPa

V1

1m

3

V2

5 V1

T1

600 K

CP

21

joule mol K

CV

CP

R

CP CV

(a) Isothermal:
T2 T1

Work = n R T1 ln
T2 600 K

V1 V2
200 kPa

P2

P1

V1 V2

P2
Work

Ans.

Work

P1 V1 ln

V1 V2
V1 V2

1609 kJ

Ans.

P2

P1

T2

T1

P2 V 2 P1 V 1

T2

208.96 K

P2

69.65 kPa

Ans.

Work

P2 V 2

P1 V 1 1

Work

994.4 kJ Ans,

Work =

U = Pext V

Pext

100 kPa

Work

Pext V2

V1

Work

400 kJ Ans.

n

P1 V 1 R T1

U = n CV T

T2

Work n CV

T1

T2

442.71 K

Ans.

P2

P1

V 1 T2 V 2 T1
28

P2

147.57 kPa

Ans.

3.20

T1

423.15 K

P1

8bar

P3

3 bar

CP

7 2

R

CV

5 2

R

T2

T1

T3

323.15 K

Step 12:

H12

0

kJ mol

U12

0

kJ mol

If

r=

V1 V2

=

V1 V3

Then

r

T 1 P3 T 3 P1

W12

R T1 ln r ()

W12

2.502

kJ mol
W23 0

Q12
kJ mol

W12

Q12

2.502

kJ mol

Step 23:

U23

CV T3

T2

Q23

U23

H23

CP T3

T2

Q23

2.079

kJ mol

U23

2.079

kJ mol

H23

2.91

kJ mol

Process:

Work

W12

W23

Work

2.502

kJ mol

Ans.

Q

Q12

Q23

Q

0.424

kJ mol

Ans.

H

H12

H23

H

2.91

kJ mol

Ans.

U

U12

U23

U

2.079

kJ mol

Ans.

29

3.21 By Eq. (2.32a), unit-mass basis:

molwt

28

gm mol

H

1 2

u = 0

2

But

H = CP T

Whence

T=

u2

2

u1

2

2 CP

CP

R 7 2 molwt

u1

2.5

m s

u2
2 2

50

m s

t1

150 degC

t2

t1

u2

u1

2 CP

t2

148.8 degC

Ans.

3.22

CP
P1

7 R 2
1 bar

CV
P3

5 R 2
10 bar

T1

303.15 K

T3

403.15 K

U

CV T3

T1

H

CP T3

T1

U

2.079

kJ mol

Ans.

H

2.91

kJ mol

Ans.

Each part consists of two steps, 12 & 23. (a) T2

T3

P2

P1

T2 T1
Work W23

W23

R T2 ln

P3 P2

Work

6.762

kJ mol

Ans.

Q

U

Work

Q

4.684

kJ mol

Ans.

30

(b) P2

P1

T2

T3

U12

CV T2

T1

H12

CP T2

T1

Q12

H12

W12

U12

Q12

W12
W23

0.831

kJ mol

W23

R T2 ln

P3 P2
W23

7.718

kJ mol

Work

W12

Work

6.886

kJ mol

Ans.

Q

U

Work

Q

4.808

kJ mol

Ans.

(c)

T2
H23 U23

T1
CP T3 CV T3

P2
T2 T2

P3

W12
Q23

R T1 ln
H23

P2 P1

W23

U23

Q23

Work

W12

W23

Work

4.972

kJ mol

Ans.

Q

U

Work

Q

2.894

kJ mol

Ans.

For the second set of heat-capacity values, answers are (kJ/mol):

U = 1.247

U = 2.079

(a)

Work = 6.762

Q = 5.515

(b)

Work = 6.886

Q = 5.639

(c)

Work = 4.972

Q = 3.725

31

3.23

T1

303.15 K

T2

T1

T3

393.15 K

P1

1 bar

P3

12 bar

CP

7 R 2

CV

5 R 2

For the process:

U

CV T3

T1

H

CP T3

T1

U

1.871

kJ mol

H

2.619

kJ mol

Ans.

Step 12:

P2
kJ mol

P3

T1 T3
W12

W12

R T1 ln

P2 P1

W12

5.608

Q12

Q12

5.608

kJ mol

Step 23:
For the process:

W23
Work

0

kJ mol
W23

Q23

U

W12

Q

Q12

Q23

Work

5.608

kJ mol

Q

3.737

kJ mol

Ans.

3.24

W12 = 0

Work = W23 = P2 V3

V 2 = R T3

T2

But

T3 = T1

So...

Work = R T2
Therefore

T1

Also

W = R T1 ln

P P1
350 K

ln

T2 T1 P = P1 T1

T2

T1

800 K

P1

4 bar

P

P1 exp

T2 T1

T1

P

2.279 bar

Ans.

32

3.25

VA

256 cm

3

Define:

P P1

= r

r

0.0639

Assume ideal gas; let V represent total volume:

P1 V B = P 2 V A

VB

From this one finds:

P P1

=

VA VA VB

VB

VA ( 1) r r

VB

3750.3 cm

3

Ans.

3.26

T1

300 K

P1

1 atm

CP

7 R 2

CV

CP

R

CP CV

The process occurring in section B is a reversible, adiabatic compression. Let

P ( )= P2 final
nA = nB

TA ( )= TA final

TB ( )= TB final

Since the total volume is constant,

nA R TA 2 nA R T1 = P2 P1

TB

or

TA TB 2 T1 = P2 P1
1

(1)

(a)

P2
TA

1.25 atm
P2 P1

TB
TB

T1

P2 P1
UA UB

(2)

2 T1

Q = nA

Define

q=

Q nA

q

CV TA

TB

2 T1

(3)

TB

319.75 K

TA

430.25 K

q

3.118

kJ mol

Ans.

33

(b)

Combine Eqs. (1) & (2) to eliminate the ratio of pressures:

TA

425 K

(guess)
1

TB

300 K

Given

TB = T1

TA

TB

2 T1

TB

Find TB

TB

319.02 K
1.24 atm

Ans.
Ans.

P2
q

P1

TA

TB

2 T1
TB 2 T1

(1)

P2

CV TA

q

2.993

kJ mol

Ans.

(c)

TB

325 K
1

By Eq. (2),

P2

P1

TB T1
P2 P1

P2

1.323 atm

Ans.

TA

2 T1

TB

(1)

TA

469 K

Ans.

q

CV TA

TB

2 T1

q

4.032

kJ mol

Ans.

(d)

Eliminate

TA

TB

from Eqs. (1) & (3):

q

3

kJ mol

P2
1

q P1 2 T1 C V

P1

P2

1.241 atm

Ans.

TB

T1

P2 P1
P2 P1

(2)

TB

319.06 K

Ans.

TA

2 T1

TB

(1)
34

TA

425.28 K

Ans.

15 K mol mol P1 1 bar P2 55 bar B' B RT B' 7. for initial V.3) by the virial equation: V2 Work RT V1 1 B V C V 2 1 dV V Work 12.492 10 5 1 bar 2 (a) Solve virial eqn. Guess: V2 RT P2 Given P2 V 2 RT = 1 B V2 C 2 V2 V2 Find V2 V2 cm 241. (1. .596 kJ mol Ans.62 kJ mol Ans. (b) Eliminate dV from Eq.30 B 242.817 10 3 1 bar C' C 2 B 2 R T 2 C' 3.3) by the virial equation in P: P2 dV = R T P 1 2 C' dP W RT P1 1 P C' P dP W 35 12.3.5 cm 3 C 25200 cm 6 T 2 373.33 mol 3 Eliminate P from Eq. (1. Guess: V1 RT P1 Given P1 V 1 = 1 RT B V1 C V1 2 V1 Find V1 V1 cm 30780 mol 3 Solve virial eqn. for final V.

238 0.54) T r Pr Pr Tr Eq.1 ( ) Tr Tr Table 3.929 Ans.139 0.32 Tc 282.056 Pc 50.Note: The answers to (a) & (b) differ because the relations between the two sets of parameters are exact only for infinite series.083 B0 0.53) 36 .422 Tr 1.42748 Table 3.172 Tr 4.08664 0. (3. 1924 mol 3 (c) For Redlich/Kwong EOS: 1 0.3 K T 298.087 (a) (guess) B 140 cm 3 mol C 7200 cm 6 2 V mol RT P V 2066 cm 3 mol Given PV = 1 RT B V C V 2 V Find ( ) V V 0. 3.6 cm 1919 mol 3 Z PV RT Z 0. (b) B0 0.5 0 0.262 10 3 Z 1 B0 B1 Pr Tr Z 0.15 K Tr T Tc Tr 1.1 q Tr Tr Tr Eq.2 B1 2.304 B1 0.932 V ZRT P V cm Ans.4 bar P 12 bar Pr P Pc Pr 0. (3.

574 0.928 V Z RT P V 1916. (3.54226 0.45724 1 2 Table 3.54) 37 T r Pr Eq. (3.54) Guess: Tr Z T r Pr 0.480 1.53) .176 2 1 Tr 2 Table 3.52) Z= 1 T r Pr q Tr T r Pr Z Z T r Pr T r Pr Z T r Pr Z Find Z) ( Z 0.1 Tr q Tr 1 Tr 0.1 Eq.1 q Tr Eq. (3.52) Z= 1 T r Pr q Tr T r Pr Z Z T r Pr T r Pr Z T r Pr Z Find Z) ( Z 0.928 V Z RT P V 1918 cm 3 mol Ans. (3. (3.37464 Tr Tr 1.07779 0.Calculate Z Guess: Z 0. (3.9 Given Eq.26992 2 1 Tr Pr Tr 2 Table 3.1 Tr 1 0.9 Pr Tr Eq. (d) For SRK EOS: 1 0 0.53) Calculate Z Given Eq.42748 Table 3. (e) For Peng/Robinson EOS: 1 2 1 2 0.5 cm 3 mol Ans.08664 1 2 0.

92 V ZRT P V 1900.2 B1 3. 3.302 B1 0. (3.422 Tr 1.33 Tc 305.517 10 3 Z 1 B0 B1 Pr Tr Z 0. (b) B0 0.912 V ZRT P V cm Ans.7 mol PV = 1 RT 3 C C V 2 9650 cm 6 2 V mol RT P V cm 1791 mol 3 Given B V V Find ( V) V cm 1625 mol 3 Z PV RT Z 0.42748 Table 3.6 B0 0. 1634 mol 3 (c) For Redlich/Kwong EOS: 1 0 0.139 0.3 K T 323.9 Given Eq.058 Pc 48.Calculate Z Guess: Z 0.172 Tr 4.15 K Tr T Tc Tr 1.08664 38 0.52) Z= 1 T r Pr q Tr T r Pr Z Z T r Pr T r Pr Z T r Pr Z Find ( Z) Z 0.6 cm 3 mol Ans.72 bar P 15 bar Pr P Pc Pr 0.907 Ans.1 .083 0.308 0.100 (a) (guess) B cm 156.

(3.176 2 1 Tr 2 Table 3. (e) For Peng/Robinson EOS: 1 2 1 2 39 0.42748 Table 3.1 Eq.1 Tr q Tr 1 Tr 0.8 cm 3 mol Ans. (3.906 V Z RT P V cm 1622.9 Given Eq.53) Calculate Z Guess: Z 0.907 V Z RT P V 1624.52) Z= 1 T r Pr q Tr T r Pr Z Z T r Pr T r Pr Z T r Pr Z Find Z) ( Z 0. (3.07779 0.52) Z= 1 T r Pr q Tr T r Pr Z Z T r Pr T r Pr Z T r Pr Z Find Z) ( Z 0. (d) For SRK EOS: 1 0 0.53) Calculate Z Guess: Z 0.480 1.45724 Table 3.54) Tr T r Pr Pr Tr Eq. (3.9 Given Eq.7 mol 3 Ans.54) T r Pr Pr Tr Eq.( ) Tr Tr 0.1 q Tr Tr Tr Eq.1 .5 Table 3.08664 1 2 0. (3.574 0. (3.

7 K T 348.422 Tr 1.5 mol 3 Ans.26992 2 1 Tr Pr Tr 2 Table 3.37464 Tr Tr 1.1 2 Tr 1 0.1 q Tr Eq.54) T r Pr Eq.9 Given Eq.54226 0.399 0.896 V ZRT P V cm 1605.092 37.15 K Tr Pr T Tc P Pc Tr Pr 1. 3. (3.083 0.286 (guess) (a) 3 B 194 cm mol C 15300 cm 6 2 V mol RT P V 1930 cm 3 mol Given PV = 1 RT B V C V 2 V Find ( V) V cm 1722 mol 3 Z PV RT Z 0. (3. (3.6 bar P 15 bar 0.893 Ans.6 B0 0.52) Z= 1 T r Pr q Tr T r Pr Z Z T r Pr T r Pr Z T r Pr Z Find ( Z) Z 0. (b) B0 0.34 Tc Pc 318.53) Calculate Z Guess: Z 0.283 40 .

9 Calculate Z Given Eq.899 V Z RT P V 1734 cm mol Ans. (3. (c) For Redlich/Kwong EOS: 1 0 0.172 Tr 4. (3. (3.02 3 Z 1 B0 B1 Pr Tr Z 0.52) Z= 1 T r Pr q Tr T r Pr Z Z T r Pr T r Pr Z T r Pr Z Find Z) ( Z 0.574 0.08664 0.2 B1 0.1 ( ) Tr Tr 0.53) Guess: Z 0. (3.888 V Z RT P V cm 1714.54) Tr T r Pr Pr Tr Eq.54) T r Pr Pr Tr Eq.08664 1 2 0.176 2 1 Tr 2 Eq. (3.5 Table 3.139 0.1 mol 3 Ans.480 1.42748 Table 3. (d) For SRK EOS: 1 0 0.1 q Tr Tr Tr Eq.B1 0.42748 Table 3.1 Table 3.1 Tr q Tr 1 Tr 0.53) 41 .

37464 Tr Tr 1.15 K P 3 1800 kPa (a) B cm 152.52) Z= 1 T r Pr q Tr T r Pr Z Z T r Pr T r Pr Z T r Pr Z Find ( Z) Z 0.5 mol C 5800 cm 6 2 V mol RT (guess) P Given PV = 1 RT B V C V 2 V Find ( V) Z PV RT V 2250 42 cm 3 mol Z 0.45724 1 2 Table 3.882 V ZRT P V cm 1701.9 Z= 1 T r Pr q Tr T r Pr Z Z T r Pr T r Pr Z T r Pr Z Find ( Z) Z 0. (3.54226 0. .9 cm 3 mol Ans.Calculate Z Guess: Eq.52) Given Z 0.1 Tr 1 0.26992 2 1 Tr Pr Tr 2 Table 3.07779 0.54) Guess: T r Pr Z 0. (3.895 V ZRT P V 1726.35 T 523.53) Calculate Z Given Eq.1 q Tr Eq. 3.931 Ans.9 Eq. (3. (3. (e) For Peng/Robinson EOS: 1 2 1 2 0.5 mol 3 Ans.

(3.808 Pr 0.51 B1 0.37 B cm 53.281 Z 1 B0 3 B1 Pr Tr V Z RT P Z 0.939 V cm 2268 mol Ans.(b) Tc 647.083 0.99 gm cm 2252 mol 3 or V 6 2 Ans.1 K Pc 220.015 mol V cm molwt 124.6 Tr 0.38) Z2i 1 2 1 4 B Pi RT Eq.345 Tr T Tc Pr P Pc B0 0. 3.172 Tr 4.15 K Given PV RT = 1 B V 10 C V 2 D V 3 fP V) ( Find V) ( i 0 10 Pi 10 20 i bar Vi RT Pi (guess) Zi fPi Vi Pi RT Eq.12) Z1i 1 B Pi RT Eq.4 mol 3 C 2620 cm D 5000 cm 9 3 n mol mol mol T 273.39) 43 .139 0. (3. 3 (c) Table F.082 B0 0.2 B1 0. (3.422 Tr 1.55 bar 0.2: molwt gm 18.

179i 0.735 0.39) are not physically meaningful for pressures above 100 bar.861 Z1i 1 0.819 0.5 0 50 100 Pi bar 1 150 200 44 . 1 0.784 0.906 0.5+0.765 0.953 0.895 0.355i 0.859 0.5+0.906 0.5+0.953 0.733 0.749 0.671 0.812 0.53 Z2i 1 0.743 Note that values of Z from Eq.5+0.624 0.9 Zi Z1 i Z2 i 0.281i 0. (3.757 0.83 0.469i Pi 100 120 140 160 180 200 bar 0.6 0.74 0.5+0.7 0.1·10 -10 20 40 60 80 Zi 1 0.951 0.718 0.577 0.622 0.8 0.416i 0.

1 ( ) Tr Tr 0.71 bar Tr T Tc Tr 0.56) Guess: Z 0.847 Pr P Pc Pr 0.057 V Z RT P V 108. 45 . (3.08664 0. (3.323 For Redlich/Kwong EOS: 1 0 0.54) T r Pr Pr Tr Calculate Z for liquid by Eq. (3.3. Calculate Z for vapor by Eq.152 T 313.52) Guess: Z 0.53) q Tr Tr Tr Eq.01 Given Z= T r Pr Z T r Pr Z T r Pr 1 q Tr T r Pr T r Pr Z Z Find Z) Z ( 0.15 K P 13.9 Given Z= 1 T r Pr q Tr T r Pr Z Z Z T r Pr T r Pr Z Find Z) ( Z 0.2 mol 3 Ans.5 Table 3.48 bar 0.1 Eq.1 cm 3 mol Ans.789 V Z RT P V cm 1499.38 (a) Propane: Tc 369.8 K Pc 42. (3.42748 Table 3.

468 B1 0.2 B1 0.Rackett equation for saturated liquid: cm 3 Tr T Tc Tr 0.422 Tr 1.847 Vc 200.17 cm 3 mol Ans.172 Tr 4.538 10 3 3 cm mol Ans.0 mol Zc 0.207 V RT P R B0 B1 Tc Pc V 1.083 B0 0.139 0. 46 . For saturated vapor.2857 V 94.6 B0 0.276 V V c Zc 1 Tr 0. use Pitzer correlation: 0.

Vap.4 700.5 (c) 122.2 856.1 (l) 201.5 55.0 1405.3 645.cm.8 1074.8 1252.4 67.2 1318.6 835.7 64.9 (f) 158.8 1319.9 835.3 955.8 74.4 707.4 805.2 (k) 179. Rackett Pitzer (a) 108.1 (i) 153.9 1038.8 (b) 114.9 70.3 (g) 170.7 137.1 57.8 1276.4 (h) 187.4 70.4 133.1 102.3 148.2 (j) 164.7 990.2 1216.6 56. Volume units are cu.5 1006.0 59.7 1046.2 1537.0 1516.8 109.3 64.4 146.0 1577.8 1174.4 130.4 795.2 94./mole.6 53.0 125.3 60.3 717.1 971.3 58.9 814.9 140.7 920.0 896.8 1330.6 160.1 66.6 669.0 1296.7 1154.1 1499.7 (d) 133.0 1057. R/K.4 (m) (n) (o) (p) (q) (r) (s) (t) 61.3 1057. R/K.1 54.5 47 .5 853. Liq.5 661.1 768.6 1228. All results are summarized as follows.5 98.Parts (b) through (t) are worked exactly the same way.6 (e) 148.

8 K Pc 42. (3.71 bar Tr T Tc Tr 0.78 V Z RT P V 1480.54) T r Pr Z Pr Tr 0.7 mol Ans.7 cm mol Ans.847 Pr P Pc Pr 0.480 1.1 for SRK: 1 0 0. (3.152 T ( 40 273. 48 .323 From Table 3.176 2 1 Tr 2 Eq.15)K T 313.56) Guess: Given Z= T r Pr Z T r Pr Z T r Pr 1 q Tr T r Pr T r Pr 3 Z Z Find Z) ( Z 0.574 0.15 K P 13. (3.53) Calculate Z for liquid by Eq.08664 0.42748 1 2 Tr q Tr 1 Tr Tr 0. (3.39 (a) Propane Tc 369.52) Guess: Z 0. Calculate Z for vapor by Eq.9 Given Z= 1 T r Pr q Tr T r Pr Z Z T r Pr T r Pr Z T r Pr 3 Z Find Z) ( Z 0.48 bar 0.055 V Z RT P V cm 104.01 Eq.3.

2 63.8 1276.9 947. Vap.4 130.4 707.0 59.5 61.7 (g) 161.7 990.0 1405.1 54.0 1057.7 137.9 66. Liq.5 49 .8 1305.3 1487. Rackett Pitzer (a) 104.3 1035.3 148.3 (m) (n) (o) (p) (q) (r) (s) (t) 61.2 856.1 (i) 146.4 63.9 (k) 170.1 1189.9 1003.4 133.0 125./mole.0 1296.9 140.2 (d) 128.0 896.Parts (b) through (t) are worked exactly the same way.7 (l) 191.7 657.3 955.4 146.8 (h) 177.5 853.5 55.7 1154.8 109.1 57.6 56.9 703.3 60.1 (f) 150.5 1157.8 1074.4 700.5 66.6 1228.1 102.3 817.cm.5 (e) 142.4 1296.4 795.8 1026.8 1319.2 810. All results are summarized as follows.7 1480.6 160.3 69.9 70.3 58.2 1537.5 1248.6 53.8 904.4 805.5 98.6 (c) 118.0 1577.8 (b) 110.9 1038.1 628. Volume units are cu.8 747.7 (j) 156.2 815.7 94.0 652. SRK. SRK.

323 From Table 3.48 bar 0. 50 .45724 q Tr Tr Tr Eq.8 K Pc 42.07779 0.6 Given Z= 1 T r Pr q Tr T r Pr Z Z T r Pr T r Pr Z T r Pr Z Find Z) ( Z 0.53) Calculate Z for liquid by Eq.40 (a) Propane Tc 369.766 V Z RT P V 1454. Calculate Z for vapor by Eq.15)K T 313. (3.5 cm 3 mol Ans.1 for PR: 1 2 Tr 1 2 1 0. (3.37464 1 2 1.3.54226 0.152 T ( 40 273.56) Guess: Given Z= T r Pr Z T r Pr Z T r Pr 1 q Tr T r Pr T r Pr 3 Z Z Find Z) ( Z 0.049 V Z RT P V cm 92.15 K P 13.54) T r Pr Z Pr Tr 0.01 Eq.847 Pr P Pc Pr 0.2 mol Ans.26992 2 1 Tr 2 0. (3.71 bar Tr T Tc Tr 0.52) Guess: Z 0. (3.

2 (m) (n) (o) (p) (q) (r) (s) (t) 54.6 56.9 (g) 143.4 707.8 879.3 60.2 (l) 170.7 1154.0 1405. Liq.3 148.0 987.9 62.6 1228.7 990.8 641.4 61.0 125.3 794.6 (k) 151.8 1271.0 (h) 157.4 700.3 782.5 1156.3 955.6 53.4 130.2 856.6 1280.4 54.8 1074. Vap.4 795.3 1233.8 1276. PR.0 1577.0 715.1 (i) 129./mole.5 853.2 (f) 132.5 51 (c) 104.5 636.0 59.0 1057.0 56.9 140.cm.1 98.0 896. All results are summarized as follows.4 (d) 113.0 1296.7 137.3 58.Parts (b) through (t) are worked exactly the same way.0 58.7 (e) 125.8 597.5 94.1 57.1 102.3 915.9 1038.8 1319.8 (b) 97.6 160.1 56.4 146.2 1454. Volume units are cu.7 800.4 133.1 1453.3 58.6 1131.2 678.9 1002.8 109. PR.5 55.4 (j) 138.4 805.1 54.2 1537.2 1009. Rackett Pitzer (a) 92.2 .

3.3 & E.087 T 328.3 K Pc 50.033 Z Z0 Z1 Z 0.145 0. .38).15 K P 35 bar Tr T Tc Pr P Pc Tr 1. molwt 28.493 n P Vtotal ZRT n 2171 mol mass n molwt mass 60.898 kg Ans. (3.1 & E. (b) T 323.942 10 3 3 cm mol With this B.25 m 3 Tr T Tc Tr 1.4: Z0 Z Z0 Z1 Z 0.126 Pr 2.15 K P 115 bar Vtotal 0.40 bar 0.046 10 mol Ans.41 (a) For ethylene.3.2: Z0 0.611 V2 52 R T1 Z2 P2 V2 3.482 Pr Z1 P Pc 0.42 Assume validity of Eq.694 From Tables E.838 Z1 0. P1 1bar T1 300K V1 cm 23000 mol 3 Z1 P1 V 1 R T1 Z1 0.421 m 3 Ans.841 n 18 kg molwt Vtotal ZnRT P Vtotal 0.282 From Tables E.162 Pr 0.922 B R T1 Z1 P1 1 B 1. recalculate at P2 P2 5bar 3 3 cm Z2 1 B P2 R T1 Z2 0.054 gm Tc mol 282.

139 0.172 Tr 4.146 B1 0.104 V RT P B0 B1 R Tc Pc V cm 989 mol 3 Ans.8 Vtank Vliq molwt mliq 127.43 T 753.152 P 16 bar 369.6 B0 0. B0 0.35 m 3 mliq 0.15 K Tc 513.139 0.083 0.466 P 6000 kPa Pc 61.172 Tr 4.2 B1 0.48 bar Pr P Pc Pr 0.48 bar Vc cm 200 mol Zc 0.769 cm mol Vtank 0.2 B1 0.9 K Tr T Tc Tr 1.865 Pr P Pc Pr 0.594 kg Ans.422 Tr 1.3.083 0.2857 0.097 gm mol Tr T Tc 1 Tr Tr 0.177 53 .44 T 320 K 0.449 B1 0.8 K 42.276 molwt 44. 3 For an ideal gas: V RT P Tc 3 V cm 1044 mol Pc 3.377 3 Vliq V c Zc Vliq 96.422 Tr 1.645 B0 0.6 B0 0.976 0.

3 K Tr T Tc Tr 1.45 T 298.2 B1 0.123 gm mol B0 0. 3.318 10 3 3 cm mol mvap 0.469 10 mol mvap Vvap V molwt mvap 98.624 3 3 cm V RT P B0 B1 R Tc Pc V 9.2 Vtank Vvap molwt mvap 2.6 B0 0.701 P 2.96 bar 3 Pr Pc Pr 0.1 K Tr T Tc P Tr 0.341 kg Ans.72 bar Pr 3 P Pc Pr 2.091 P 14000 kPa Pc 48.661 B1 0.15 K Tc 425.172 Tr 4.15 K Tc 305.213 kg Ans.064 0.46 (a) T 333. 3.422 Tr 1.07 gm mol From tables E.874 0.43 bar Pc 37.Vvap RT P B0 B1 R Tc Pc Vvap 1.139 0.4: Z0 0.463 54 Z1 0.083 0.15 m molwt 30.200 Vvap 16 m molwt 58.037 .100 Vtotal 0.3 & E.

054 gm mol V Vtotal 40 kg molwt Pr = Z or where RT Pc V 4.283 T and Tr Tc Z 0.40 bar P V = P r Pc V = Z R T 0.056 55 .889 Z at Pr P Pc Pr 4.57) in conjunction with Tables E.47 Vtotal 0.Z Z0 Z1 Z 0.693 Whence T 391.3 K Pc 50.5 degC Ans.3 & E.15 m 3 T 298.7 K or 118.675 Z at Tr T Tc Tr 1. The intersection of these two relations can be found by one means or another to occur at about: Tr 1.548 mol kg Whence Tr = 0.87 cm 3 mol methane Vtotal V molwt methane 49.4 are two relations in the same variables which must be satisfied at the given reduced pressure. 3.105 This equation giving Tr as a function of Z and Eq. (3. (b) V Vtotal 40 kg P 20000 kPa P V = Z R T = Z R Tr Tc or Tr = Z where PV R Tc 29.675 Whence Pr = 4.459 V Z RT P V 90.15 K Tc 282.087 molwt 28.64 kg Ans.

083 0.615 Assume Eq.2 B1 0. The intersection of these two relations can be found by one means or another to occur at about: Pr 1.100 0. (3. 3.57) in conjunction with Tables E. 3.977 P1 Vtotal 2200 kPa 0.338 P Pc Pr P 79.49 T1 298.38) applies at the final state.4 m 3 V Vtotal mwater V 26.113 B1 0.This equation giving Pr as a function of Z and Eq.4 are two relations in the same variables which must be satisfied at the given reduced temperature.8105 Z1 0.35 m 3 Pc 48.667 cm 3 gm Interpolate in Table F.73 bar Ans.6 B0 0.172 Tr2 4.0479 Z Z0 Z1 Z 0.116 P2 V1 B0 R T2 B1 R Tc Pc 56 P2 42.2 at 400 degC to find: P = 9920 kPa Ans.422 Tr2 1. .15 K Tc 305.582 and Z 0.3 K Tr1 Pr1 T1 Tc P1 Pc Tr1 Pr1 0.1 & E.2: Z0 .72 bar 0.3 & E.15 K Tr2 T2 Tc Tr2 1. B0 0.68 bar Ans.452 From Tables E.806 V1 Z R T1 P1 V1 cm 908 mol 3 T2 493.139 0. (3.48 mwater 15 kg Vtotal 0.

6 B0 0.51 Basis: 1 mole of LIQUID nitrogen Tn 77.172 Tr 4.139 0.15 K Tc 3 304. 3.3.863 bar Ans.172 Tr 4.2 K Tr T Tc Tr 0.50 T 303.842 B1 0.2 B1 1.997 Vtotal 0.224 molwt 44.0 bar Pr P Pc Pr 3 0.3 K Tc 126.957 57 .613 P 1 atm Pc 34.014 gm mol Vliq 34.2 B1 0.422 Tr 1.01 gm mol B0 0.5 m Pc 73.083 0.341 B1 0.2 10 mol P P 10.036 3 3 cm V Vtotal 10 kg molwt RT V B0 B1 R Tc Pc V 2.03 0.422 Tr 1.2 K Tr Tn Tc Tr 0.83 bar 0.139 0.6 B0 0.209 Z 1 B0 B1 Pr Tr Z 0.038 molwt 28.083 0.7 cm B0 0.

42) b R Tc Pc Eq.15 K Tr T Tc Tr 2.824 cm 3 gm T1 300 K P1 4 bar T2 415 K P2 75 bar Tr1 T1 Tc Pr1 P1 Pc Tr2 T2 Tc Pr2 P2 Pc Tr1 0.056 58 .5 Tr 0.44) P Ans. 0.48 bar V1 1.901 m 2 mol b cm 26. (3.718 10 3 mol Final conditions: ntotal 1 mol nvapor V 2 Vliq ntotal V 69.2 bar Use Redlich/Kwong at so high a P. (3.005 cm 3 mol T 298.363 Pig RT V Pig 359. 3.08664 0. (3.nvapor P Vliq Z R Tn nvapor 5.42748 2 2 ( ) Tr Tr .737 mol 450.11 Tr2 1.651 a Tr R Tc Pc Eq.017 Pr2 2.43) a 3 3 bar cm 0.1 K Pc 36.1 bar 3 P RT V b a V ( b) V Eq.52 For isobutane: Tc 408.735 Pr1 0.

and Fig.7 cm 3 mol 0.03 Tr2 r2 0.3356 Z1 r2 0. (3.75).561 From Fig.16 probably should not be used.15 K T2 Tc P2 Pr2 120 bar P2 Pc Tr1 Tr1 T1 Tc 0.75): V2 V1 V2 cm 2. (3. 3.7 K Pc 33.88 Pr2 3.069 gm mol .From Fig.9 K T 453.253 Vc 167 cm 3 mol molwt 59 46.45 The final T > Tc. One can easily show that r= P Vc Z RT with Z from Eq.519 gm 3 Ans.774 Eq. 3.27 By Eq.63 gm cm 3 T1 291.48 bar P 200 bar Pr P Pc Pr 3.322 r1 r2 P2 V c Z R T2 1.54 For ethanol: Tc 513.181 Z0 r2 0.57) and Tables E.4.62 Pr1 r1 0.7 bar 1 0.15 K P1 Pr1 1 bar P1 Pc T2 Tr2 413.53 For n-pentane: Tc 469.69 r2 2. 2 1 r1 2 0. (3.0756 Z Z0 Z1 Z 0. 3.882 Pc 61. Thus Vc 262. (3.17): r1 2.532 gm cm 3 Ans.3 and E. (3.15 K Tr T Tc Tr 0.16): 2.

6 V c Zc 1 Tr Vliquid cm 27.From Fig.11 mol 3 B0 0.242 0.55 For ammonia: Tc 405.15 K Tr T Tc Tr 0.2 B1 0. 3.076 Vc Zc 0.083 B0 0.5 mol 3 P 857 kPa Pr P Pc 0.28 r Vc molwt = r c= r Vc 0. 3.534 Vvapor RT P B0 B1 R Tc Pc Vvapor cm 2616 mol 3 3 V Vvapor Vliquid V cm 2589 mol Ans.629 gm cm 3 Ans.8 bar cm 72.422 Tr 1.253 Pr 0. 60 .627 B1 0.172 Tr 4.2857 Eq.7 K T 293. (3.139 0.72): Vliquid 0.16: r 2.723 Pc 112.

67 rankine P 1 atm V 1400 ft 3 n PV RT T Tc n 3.Alternatively.071 Z Z0 Z1 Z 3 0. use Tables E.911 Vvapor ZRT P Vvapor 2591 cm mol 3 V Vvapor Vliquid V 2564 cm mol Ans.498 0.7302 lbmol rankine 3 T 519. Assume at these conditions that methane is an ideal gas: R ft atm 0.636 ft 61 .3 & E.1 & E. of gasoline is equivalent to 1400 cu ft.012 From Tables E. 3.99 bar P 3000 psi Pr P Pc Pr 4. of methane at 60 degF and 1 atm. Z 0.8 rankine T 519.515 Pc 45.822 Vtank Vtank 5.2 to get the vapor volume: Z0 0.929 Z1 0.6 1.234 Z 3 Z0 Z1 Ans.5810 gal.819 ZnRT P Z1 0.689 lbmol For methane at 3000 psi and 60 degF: Tc 190.67 rankine Tr Tr 1.4: Z0 0.

7757 For Redlich/Kwong EOS: 1 0.903 mol Use the generalized Pitzer correlation B0 Z 1 0.56) Tc 1 43.54) T r Pr Pr Tr Eq.294 Tr T Tc Tr 0.58) and (3.6 B0 0.2 B1 0.016T K Tc 30.08664 0.821 3 Initial guess of volume: V RT P V cm 646.1 q Tr Tr Tr Eq.254 B0 B1 Pr Tr Z 0.083 0.3.59 T 25K P 3.5 0 0.495 B1 0.213bar Calculate the effective critical parameters for hydrogen by equations (3.922 bar 0 Pr P Pc Pr 0.823 Ans.435 K Pc 1 20.42748 Table 3.1 Tr Tr Table 3.5 44. (3.422 Tr 1.172 Tr 4.016T bar Pc 10.53) 62 . (3.139 0.8K 2.2K 2. Experimental: Z = 0.6 21.

022 B0 Z0 0.024 mol P 300psi 3 (a) At actual condition: Pitzer correlations: T T ( 50 32) 5 9 273.998 V1 Z RT P V1 m 0.99bar T 288.109 1 B0 Z0 0.139 0.15 K 283.15 K P 1atm Tr T Tc Tr 1. (3.012 Tc 190.106 63 .791 Ans.083 0.134 0.45 B0 0.Calculate Z Guess: Z 0.9 Given Eq.2 Pr B1 0. Experimental: Z = 0.15 K Tr T Tc 1.6K Pc 45.172 Tr 4.00158 Z Z0 Z1 Z 0.422 Tr B0 0.139 0.6 Tr 1.172 Tr 4.141 B1 0.2 B1 0.486 Pr P Pc Pr 0.515 Pr B1 P Pc 0.422 Tr Pr Tr 1.706 K At standard condition: Pitzer correlations: T ( 60 32) 5 9 273.998 Z1 B1 Pr Tr Z1 0.083 0.52) Z= 1 T r Pr q Tr T r Pr Z Z Z T r Pr T r Pr Z Find Z) ( Z 0.7757 3.61For methane: 0.6 B0 0.

Z0 1 B0 Pr Tr Z0 0.958 V2 ZRT P V2 0.259 m 2 u u 8.624in q2 A A 4 D 2 A 0.957 Z1 B1 Pr Tr Z1 0. (c) D 22.738 m s Ans. 64 .485 10 hr Ans.915 10 6 ft day Ans. (b) n1 q1 V1 n1 7.0322 3 Z Z0 Z1 3 Z 0.00109 3 m mol q1 150 10 6 ft day q2 q1 V2 V1 3 kmol q2 6.

271 0.19 0.275 0.196 0. . m slope ZC ( 0.087 0.266 0.28 0.218 0.274 0.26 0.28 b 0.191 0.31 0.194 0.261 65 Use the first 29 components in Table B.282 0.271 0.23 0.235 0.29 ZC m 0.2 0.205 0.140 0.1 0.1 0.301 0.302 0.181 0.152 0.187 0.27 0.267 0.273 0.272 0.878) r 0.3.4 The equation of the line is: Zc = 0.012 0.303 0.276 0.27 0.21 0.1 sorted so that values are in ascending order.771 0.21 0.322 0.291 0.269 0.262 0.265 0.212 0.3 0.277 0.326 ZC 0.25 0 0.26 0.291) 2 r corr ZC ( 0.091 Ans.256 0.273 0.279 0.297 0.272 0.62 0.264 0.263 0.281 0. This is required for the Mathcad slope and intercept functions.266 0.091) b intercept ZC ( 0.275 0.2 0.286 0.263 0.252 0.289 0.273 0.

4 T1 298.3. mol Ans.065 kJ mol kJ Ans. Q12 0 kJ mol Q12 W12 0 kJ mol kJ mol Ans. W23 R T3 T2 W23 1.618 H12 Cp T2 T1 H12 5.447 mol kJ Ans. W12 U12 3.065 Q23 H23 Q23 5. Ans. mol .065 mol kJ Ans.618 Step 2->3 Isobaric cooling U23 Cv T3 T2 U23 3.618 kJ mol kJ Ans.65 Cp 7 R 2 Cv 5 2 R Cp Cv 1. Ans. mol Ans. H23 Cp T3 T2 H23 5.15K P1 1bar P2 5bar T3 T1 P3 5bar Step 1->2 Adiabatic compression 1 T2 U12 T1 P2 P1 Cv T2 T1 T2 472. Step 3->1 Isothermal expansion U31 Cv T1 T3 U31 0 H31 Cp T1 T3 66 H31 0 kJ mol kJ Ans.216 K U12 3.

For the cycle Qcycle Q12 Q23 Q31 Qcycle 1. mol Wcycle W12 W23 W31 Wcycle 1. Step 2->3 Isobaric cooling W23 W23 W23 1.076 kJ Ans.14 67 . mol Now assume that each step is irreversible with efficiency: 80% Step 1->2 Adiabatic compression W12 W12 W12 4.99 W31 kJ mol kJ 3.076 kJ Ans. Q23 U23 W23 Q23 5. For the cycle Qcycle Q12 Q23 Q31 Qcycle Wcycle W12 W23 W31 Wcycle kJ Ans.522 kJ mol Ans. Q12 U12 W12 Q12 0.14 mol Ans.192 Q31 U31 W31 Q31 3.427 kJ mol Ans. mol kJ 3.904 kJ mol Ans. Step 3->1 Isothermal expansion W31 W31 W31 3. Ans.809 kJ mol Ans. mol Ans.Q31 W31 R T3 ln Q31 P1 P3 Q31 3. 3.99 mol Ans.192 kJ mol kJ Ans.

7 1757.1 V 1316.45 875.2 1051. Use the Mathcad intercept function to find the y-intercept and hence.2 1169.2 at pressures above 1atm.15) K gm mol M 18. the value of B Yi A Zi i 1 Xi i B intercept ( Y) X 6 5 cm 10 2 B cm 128.42 mol 3 Ans.01 1 VM i 0 7 If a linear equation is fit to the points then the value of B is the y-intercept.0 1505.3. 68 .567 5 mol 3 mol X 0 10 5 mol 3 8 10 cm cm Below is a plot of the data along with the linear fit and the extrapolation to the y-intercept.6 955. 125 150 175 P 200 225 250 275 300 Z PVM RT kPa 2109.67 a) PV data are taken from Table F. slope ( Y) X mol cm 3 A 1.29 cm 3 gm T ( 300 273.

7 953.2 1638.2 at pressures above 1atm.8 1273.52 cm gm 3 T ( 350 273. .2 1040.1 1145. 125 150 175 P 200 225 250 275 300 Z PVM RT kPa 2295.899 cm 3 mol Ans.3 V 1432.15)K gm mol M 18.115 120 (Z-1)/p 125 130 0 2 10 (Z-1)/p Linear fit 5 4 10 p 5 6 10 5 8 10 5 b) Repeat part a) for T = 350 C PV data are taken from Table F.01 1 VM i 0 7 If a linear equation is fit to the points then the value of B is the y-intercept.6 1912. Use the Mathcad intercept function to find the y-intercept and hence. the value of B Yi Zi i 69 1 Xi i B intercept ( X Y) B 105.

15)K M 18.01 gm mol .A slope ( X Y) A 5 mol 3 1. 90 95 (Z-1)/p 100 105 110 0 2 10 (Z-1)/p Linear fit 5 4 10 p 5 6 10 5 8 10 5 c) Repeat part a) for T = 400 C PV data are taken from Table F.1 V 1549.9 1771. 125 150 175 P 200 225 250 275 300 kPa 2481.5 1125.2 1376.4 70 cm gm 3 T ( 400 273.2 at pressures above 1atm.2 2066.5 1031.784 5 mol 3 6 5 cm 10 2 mol X 0 mol cm 3 10 8 10 cm cm Below is a plot of the data along with the linear fit and the extrapolation to the y-intercept.6 1238.

044 5 mol 3 mol X 0 mol cm 3 10 5 mol 3 8 10 cm cm Below is a plot of the data along with the linear fit and the extrapolation to the y-intercept.Z PV M RT 1 VM i 0 7 If a linear equation is fit to the points then the value of B is the y-intercept. the value of B Yi Zi i 1 Xi i B intercept ( X Y) 6 5 cm 10 2 B 89.902 cm 3 mol Ans. A slope ( X Y) A 2. 70 75 (Z-1)/p 80 85 90 0 2 10 (Z-1)/p Linear fit 5 4 10 p 5 6 10 5 8 10 5 71 . Use the Mathcad intercept function to find the y-intercept and hence.

8 1 1.65) and (3.05 0.9967 0.4 The second virial coefficient (Bhat) is the value when X -> 0 Bhat Intercept B0 0.9300 0.60 0.01 0.339 Ans. By Eqns.6355 Tr 1 X Y (Z 1) Z Tr Pr Create a linear fit of Y vs X Slope Intercept Rsquare slope ( X Y) intercept ( X Y) corr ( X Y) 0.3.2 1.10 Pr 0.8509 0.80 Pr Z Tr 0. (3.40 0.9659 Z 0.9965 Y Slope X Intercept 0.32 0.6 X 0.332 0.033 0.422 Tr 72 Bhat 1.20 0.332 0.9832 0. B0 .70 Create a plot of (Z 1) Z Tr Pr vs Pr Z Tr Data from Appendix E at Tr = 1 0.34 0 0.66) These values differ by 2%.2 0.28 Slope Intercept Rsquare 0.6 0.4 0.3 0. Ans.7574 0.083 0.

n 5mol Vt 0.025 V Z RT P V cm Ans. (3.98 bar P 300 bar Pr Pc Pr 6. (3.53) Given Eq.42748 Table 3. (3.08664 1 0. there will be 5 moles of C 2H2 and 5 moles of Ca(OH)2.009 Pc 48.71 Use the SRK equation to calculate Z Tc 150.9 K T ( 30 T 273.0 1 0 0.72 After the reaction is complete.125 0.480 1.52) Z= 1 T r Pr q Tr T r Pr Z Z T r Pr T r Pr Z T r Pr Z Find Z) ( Z 1.9 Pr Tr Eq. 86.0 mol 3 Vt 555 cm 3 V Vt n 73 V 111 cm 3 mol .5% of the ideal gas value.3.54) Guess: T r Pr Z 0.176 2 1 Tr 2 Table 3.574 0.1 Eq.4 1800 cm 3 cm 5 mol 33. First calculate the volume available for the gas.1 2 Tr q Tr Calculate Z 1 Tr Tr 0. 3.15)Kr T Tc P Tr 2.1 mol 3 This volume is within 2.

389 .276 Vc 200. Tc 308.2 Eq.42748 Table 3.480 1.15) K Tr T Tc Tr 1.175 mol P RT V b a V (V b) T ( 10 273. 3. (3.Use SRK equation to calculate pressure.39 bar 0.172 Tr 4.45) b R Tc Pc Eq.937 gm mol 5 Zc 0.8 bar Ans.73 mass 35000kg 0.995 m 2 mol b cm 36. (3-65) B1 0.574 0.422 Tr 1. (3-66) B0 0.1 Eq.0 1 0 0.08664 1 2 0. (3.54) a Tr Pc R Tc 2 2 Eq.0 cm mol n mass M 10 mol a) Estimate the volume of gas using the truncated virial equation Tr T Tc Tr 0.139 0.1 Tr q Tr 1 Tr Tr 0.176 2 1 Tr 2 Table 3.46) 3 a 3 3 bar cm 3.15)K P 197.291 Pc 61.8K Pc 3 42.564 74 B1 0.3 K T ( 125 273.083 0.48bar M n 44.097 7.766 P 1atm Pr P Pc B0 0. (3.152 Tc 369.6 Eq.

If the tank D were spherical.5 psi). the diameter would be: 3 Vtank D 5.379 6 10 m m This would require a very large tank. refrigeration would be required to liquify the gaseous propane stream.24 10 mol Vtank Vliq = n Vtank Vtank Find Vtank 75.Z 1 B0 B1 Pr Tr Z 0. If the D tank were spherical the diameter would be: 0.294atm 1 Tr Vliq Pr B1 Pr Tr Z 85.981 7 3 3 Vt ZnRT P Vt 3 2. 75 .72) Vliq P V c Zc 6.133 m 6 3 This would require a small tank.878 3 3 cm Vvap Guess: Given Vvap 90% Vliq n 10% Vtank Vvap 3.294 atm (92.444 0. Also.2857 Vt D 32.235 m Although the tank is smaller. it would need to accomodate a pressure of 6.15 cm 3 mol P Pc Pr Z 1 B0 ZRT P Vtank 90% 0.565 m b) Calculate the molar volume of the liquid with the Rackett equation(3.

801 10 3 C 0.15 K T 1473.873 10 K 2 6 .834 kJ mol Q n H Q 1.Chapter 4 .785 10 C 8.942 10 kJ Ans.392 10 K 2 6 2 (guess) Given Q= nR A T0 1 B 2 T0 2 T 2 1 C 3 T0 3 3 1 Find 2.1 (a) T0 473.213 B 28.15 K n 10 mol For SO2: A 5.424 B 14.905 T0 T 1374.15 K n 15 mol Q 3 2500 kJ For 1-butene: A 1.073 kJ Ans.007 kJ mol Q n H Q (b) T0 470.15 K n 10 mol Q 3 800 kJ For ethylene: A 1.824 10 6 D 0 H R ICPH T0 T A B C 0.15 K T 1373.394 10 K C 4.2 (a) T0 473. (b) T0 533. 523.Mathcad Solutions 4.15 K n 3 12 mol For propane:A 1.0 D 1.630 10 K 76 C 9. 3 4.Section A .967 B 31.699 B 0.5 K Ans.015 10 5 H R ICPH T0 T A B C D H 47.0 H 161.

3 Assume air at the given conditions an ideal gas.3 (guess) Given Q= nR Find A T0 1 B 2 T0 2 2.15 K T0 323.8 K Ans.392 10 K 2 6 2 (guess) Given Q= nR Find A T0 1 B 2 T0 2 T 1 C 3 T0 3 3 1 2.15 K n PV R T0 n 266. T = 1705.15K T0 T0 32degF 273.424 B 14.8 K Ans.15K n 1.814 10 mol 4 Q 3 1. Basis of calculation is 1 second. 6 (c) T0 500 degF n 40 lbmol Q 10 BTU Values converted to SI units T0 533.016 10 5 H R ICPH T0 T A B C D 77 . P 1 atm T0 122 degF V 250 ft 3 T 3 932 degF Convert given values to SI units V 7.15K T 773.985 mol For air: A 3.4degF 4.079 m T ( T 32degF) 273.055 10 kJ 6 For ethylene: A 1.0 D 0.394 10 K 2 C 4.652 2 1 T0 C 3 T0 3 3 1 T T 1413.256 T0 T 1202.575 10 3 C 0.355 B 0.

469 3 10 BTU Ans.0 kPa P1 T2 121. (4.092 ln Hncalc R Tn Pc bar Trn 1.9a) Acetone: Tc 508. 4.H 13.572 B 2.4 molwt 3.15 K 101.648 Use Eq.0 D 3. mol K 4.4K Hn 29.1 gm mol T0 323.10 kJ mol Trn Tn Tc Trn 0.15 K n 10000 kg molwt n 9.637 10 3 C 0. 78 .707 kJ mol Q n H Q 4.7 Let step 12 represent the initial reversible adiabatic expansion.441 10 4 J mol Q n H Q 9.930 Hncalc 30. and step 23 the final constant-volume heating.41 K Given T2 = T1 P2 P1 CP Find CP CP 56.95 J Ans.120 10 5 H R ICPH T0 T A B C D H 9. T1 P2 298.4315 10 kJ 6 Ans.15 K 4 T 1153.2K Pc 47.12) to calculate H at Tn ( Hncalc) 1.3 kPa T3 P2 P3 CP 30 J mol K (guess) R CP T2 290.99 10 mol For CaCO3: A 12.15 K 104.3 kPa T3 P3 298. 100.013 0.01bar Tn 329.108 kJ mol Ans.

5 29.2% 1.1 39.9 46.6 41.8 51.7% 1.9% -0.2 are given below.0 38 .8 33.3 37.6 29. Except for acetic acid.3% 1.2% 0.5 32.6% -0.0 36.2% 3.3 30.8 % -0.6 35.0% 0.2 35.0 29.0 36. Acetone Acetic Acid Acetonitrile Benz ene iso-Butane n-Butane 1-Butanol Carbon tetrachloride Chlorobenz ene Chloroform Cyclohexane Cyclopentane n-Decane Dichloromethane Diethyl ether Ethanol Ethylbenz ene Ethylene glycol n-Heptane n-Hexane M ethanol M ethyl acetate M ethyl ethyl k etone Nitromethane n-Nonane iso-Octane n-Octane n-Pentane Phenol 1-Propanol 2-Propanol Toluene W ater o-Xylene m-Xylene p-Xylene Hn (k mol) J/ 30.8 % 1.7% 0.8 25.9% 2.6 40.464 % Values for other components in Table B.1 33.7 27.3% 6.1 22. %error Hncalc Hn Hn %error 3.1% 0.8 26.1% -0.4 42.0 30.8 % 0.9 36.7% 1.8 % 3.To compare with the value listed in Table B.0% -0.9% -0.3 % error 3.6 32.6% -1.4% 9.3% 0.3% -3. methanol and nitromethane. acetonitrile.5% 8 .5% -0.3% -0.6% 79 .5% 0.2.2 40.5 36.7 29.7% 0.3% 1.1% 2.7% 0.5 41.3% 4.1 40.1 27. calculate the % error.2 30.6 21.7 34. agreement is within 5% of the reported value.3% 1.4% 69.

Our procedure is therefore to take 5 points.052 0.13) are within 2% of the handbook values.15 K bar 25. including the point at the temperature of interest and two points on either side.0 80.847 mol 32.847 mol %error 0.13) %error H2calc H2 0.11) can be found.15) K Tc H2 H25 M 26.0 Tn 68.04.5 M 86.242 1 1 Tr2 Tr1 0.628 0. (4.429 H2 31.549 H1 Hn Tr1 kJ 33.816 32.4039 converts energy units from (psia)(cu ft) to Btu.3 273.814 1.631 Tr2 ( 25 273.571 mol 26.7 80.79 Hn 28.10 The ln P vs.177 gm 78.448 H2calc 31. 1/T relation over a short range is very nearly linear.4 K 33. (4.70 Pc 30.25 48.150 J 36.114 mol 82.673 0.1 433. from which the required derivative in Eq. 4.6 562.242 The values calculated with Eq.7 H25 366. 33. The molar mass M of tetrafluoroethane is 102. The factor 5.72 mol 29.38 H2calc H1 Eq. Temperatures are in rankines. (4. and enthalpies in Btu/lbm.2 560.97 72.50 366.072 H2 26. pressures in psia.429 H2 31. 80 .7 Tc 507.658 0.98 43.533 kJ Ans.549 kJ 33.781 % 32.3 gm 392. and to do a linear least-squares fit.85 kJ 30. volumes in cu ft/lbm.145 Tr1 Tn Tc 0.b) 469.

72 80.67 yi ln Pi slope slope ( x y) slope 4952 dPdT ( P) 3 T 2 slopedPdT 0.60 334.162 Data: P 23.012 i 1 5 18. Tr1 273.4039 H 90.4 Tc 512.042 153.034 ( 81.3 337.822 gm mol 536.111) ( 85.078 Ans.545 H T V dPdT 5.617 29.9 K 349.787 21.767 26.863 ( 69.377 M 32. with the Table 9.8 Tn Tc H is the value at 0 degC. The remaining parts of the problem are worked in exactly the same way. 81 54.11 119.078 H = 85.1 value in ( ): (a) H = 90.007 ( 75.902) (e) H = 69. All answers are as follows.(a) T 459.6 K Pc 556.934 5 0 0.969) 4.97 bar Tn 45.726 t 5 10 15 xi ti 1 459.136) (d) H = 76.4 Hexp is the given value at the normal boiling point.817 ( 90.15K Tc Tr2 .834) (b) (c) H = 81.67 5 V 1.

13) Hn H PCE Hn Hexp Hexp 100% This is the % error 245 Hn J 1055.307 Vc Tr Tc 3 508.623 Tr2 0.270.38 0.96 % 4.5 194. (4.2 J gm 0.1 kJ mol cm 209 mol Tn Tc Tn Tr 0.022 82 .092 ln Pc bar Tr2 1.8 J gm 246.4K 0.9 Hexp 1099.233 29.533 0.52 (b) By Eq.12 Acetone 0.03 % 0.3 J gm 0.3 192.2K 329.7 Hn 1195.12): Hn R Tn M 1.491 1 1 Tr2 Tr1 0. (4.01bar 1atm P Pc Zc Hn Pr 0.648 Pc P Pr 47.77 PCE 4.9 H 1189.629 (a) By Eq.34 PCE 8.930 PCE Hn Hexp Hexp 100% 247.5 217.2 gm 193.509 Tr1 0.72 0.013 0.659 0.2 0.

917 mol d Psat dT 3 Combining the Clapyeron equation (4. (3.422 Tr B1 0.965 (Pg.924 Eq.66) Z 1 B0 Pr Tr B1 Z 0.609 10 mol Liquid Volume 1 Tr 7 Vsat V c Zc Eq.Generalized Correlations to estimate volumes Vapor Volume B0 0.3145 83 .2 B1 Pr Tr 0.65) 0.6 B0 0.22 10 mol C 228. (3.11) B T C A with Antoine's Equation Psat = e gives H= T V ( T 3 4 cm B C) 2 A B ( C) T e V A V Vsat V B 2.139 1. (3. 102) 3 4 cm V Z R Tn P 2 V 2.72) Vsat H= T V cm 70.083 0.602 2756.762 Eq.060 14.172 Tr 4.

4% 3.2 31.5 30.2% 0.0 36 .2% 1.8 % 0.6 35.6 28 .7 53.9 % The table below shows the values for other components in Table B.6 % 0.6 % 0.9 % 2.9 35. mol %error Hcalc Hn Hn %error 1.5% 0.9 37.2 30.3% 0.3 29 .2.4 43.7 34.panol Pro Hn ( J/ k mol) 29 .3% 0.1% .4 31. Acetone Acetic Acid Acetonitrile Benz ene isoButane nButane 1Butanol Carbon tetrachloride Chlorobenz ene Chloroform Cyclohexane Cyclopentane nDecane Dichloromethane Diethyl ether Ethanol Ethylbenz ene Ethylene glycol nHeptane nHexane M ethanol M ethyl acetate M ethyl ethyl k etone Nitromethane nNonane isoOctane nOctane nPentane Phenol 1.3 30.9 45.662 kJ Ans.9 % 0.7% 3.9 29 .9 % 58 .2% 0.1% 0.2% 0.3 29 .15K 2 C e C K kPa K Hcalc 29.9 84 % error 1. Values agree within 5% except for acetic acid.6 % 0.2 22.8 34.8 21.15K Hcalc Tn V Tn K B 273.7 37.6 1.2% .6 25.4% 2.9 27.1% 0.3% 2.0% 0.9 41.% 0.1 26 .8 39 .7% 0.4 39 .5 29 .5% 4.1% 0.4% 0.A B Tn 273.6 31.6 % 0.7% 0.

14 (a) Methanol: Tc 512.7 K T 2 4.431 BL 51.157543 kPa P 5622.5 mol 3 Eq.97bar Tn 3 337.49 mol Clapeyron equation: dPdT = H T V Vliq V = vapor molar volume.7% 0.2% 1.9K AL 13. V Vliq H T dPdT cm 1369.5 33.70504 T dPdT P 87. 4.5 36.396 kPa H joule 31600 mol Vliq cm 96.029 bar K 3 P Find ( ) dPdT P 4.13 Let P represent the vapor pressure.13 10 6 CPL ( ) T AL BL K BV 85 T CL K 2 T 2 R AV 2.5% 2.6K Pc 80. (3.2 35.4% 0.15 K P 100 kPa (guess) 5622.8% 4.450 10 6 .7 K T Given ln P = 48.7 36.3 41.70504 ln T K 0.28 10 CL 131.0% 1.211 12.9 1.p 2-Propanol Toluene W ater o-Xylene m-Xylene p-Xylene 40.216 10 3 CV 3.39) B PV V RT 1 B Ans. T 348.

273 kJ mol H = 55.98bar Tn 353.822 10 kW 3 4.645 H T1 CPL ( ) T T d Hv T sat CPV ( ) T T d H 49.7K Cp 162 J mol K 86 .0K T1 300K T2 500K Estimate Hv using Riedel equation (4.659 Trsat Tsat Tc Trsat 0.301 kJ mol kJ mol Hv Hn Tsat 1 1 Trsat Trn 0.718 1.586 kJ mol Q = 1.625 kJ mol H = 65.CPV ( ) T AV BV K T CV K 2 T 2 R P 3bar Tsat 368.536 10 kW 3 (c) Toluene Hv = 30.38 kJ mol Ans.930 R Tn Hn 38.372 10 kW 3 (b) Benzene: Hv = 28. n 100 kmol hr Q n H Q 1.092 ln Hn Pc bar Trn 1.7K T2sat 358.13) Trn Tn Tc Trn 0.2K T1sat 451.013 0.296 kJ mol Q = 1.12) and Watson correction (4.38 Hv T2 35.15 Benzene Tc 562.2K Pc 48.

8 kJ mol Ans.638 1.930 R Tn Hn 30.967 ln Hn R Tn 1.13) Trn Tn Tc Trn 0. Guess vapor fraction (x): x 0.15 K Trn Tn Tc Trn 0.013 Trn Hn 16.Estimate Hv using Riedel equation (4.12) and Watson correction (4.39 bar Tn 189.628 Tr2sat T2sat Tc Tr2sat 0.588 kJ mol Hv Hn 1 1 Tr2sat Trn 0.38 1.38 Hv 30.498 Ans.614 Tr T Tc Tr 0.16 (a) For acetylene: Tc 308.092 ln Hn Pc bar Trn 1.930 0.638 Hf 227480 H298 Hf Hv H298 220. 4.3 K Pc 61.5 Given Cp T1sat T2sat = x Hv x Find ( x) x 0.092 1 1 Tr Trn J mol Pc bar 0.4 K T 298. 87 .013 0.28 kJ mol Assume the throttling process is adiabatic and isenthalpic.91 kJ mol kJ mol Hv Hn Hv 6.

(b) For 1.3 kJ mol (d) For n-hexane: H298 = 198.6 kJ mol (e) For styrene: H298 = 103.9 kJ mol 4.3-butadiene: H298 = 88. the mean heat capacity is the value of CP at the arithmetic mean temperature. Thus Tam 675 88 .17 1st law: dQ = dU dW = CV dT P dV (A) Ideal gas: PV= RT and P dV V dP = R dT Whence Since V dP = R dT P V = const then P dV P V 1 (B) dV = V dP from which V dP = P dV Combines with (B) to yield: P dV = R dT 1 Combines with (A) to give: dQ = CV dT R dT 1 or dQ = CP dT R dT R dT 1 which reduces to dQ = CP dT R dT 1 (C) R dT or dQ = CP R 1 Since CP is linear in T.5 kJ mol (c) For ethylbenzene: H298 = 12.

45 bar Ans. 89 .18 For the combustion of methanol: CH3OH(g) + (3/2)O2(g) = CO2(g) + 2H2O(g) H298 H298 393509 676485 2 ( 241818) ( 200660) For 6 MeOH: H298 = 4 058 910 J Ans. Comparison is on the basis of equal numbers of C atoms. it is simpler to proceed differently.57 10 3 Tam 950 K T1 400 K 1.CPm R 3.55 Integrate (C): T2 R T2 Q CPm R 1 T1 Q 6477.(d) can be worked exactly as Example 4. For the combustion of 1-hexene: C6H12(g) + 9O2(g) = 6CO2(g) + 6H2O(g) H298 H298 6 ( 393509) 6 ( 241818) ( 41950) 3770012 H298 = 3 770 012 J Ans. P1 1 bar P2 P1 T2 T1 1 P2 11.19 C2H4 + 3O2 = 2CO2 + 2H2O(g) H298 [ ( 241818) 2 ( 393509) 52510] 2 J mol Parts (a) . with Mathcad capable of doing the iteration. 4.85 0. However.7. 4.5 J mol Ans.

(d) nO = 3. and (d) are worked the same way. (c) nO = 1.280 0.593 10 K 3 0.9 K T = 1609.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 2 n 2 11.286 i 1 4 A 3. (c). (b) nO = 0.929 2 T = 1950. the only change being in the numbers of moles of products.15K The integral is given by Eq.872 B 0.497 1 B 2 T0 2 T 2 1 D T0 1 Find T T0 2533.470 3.621 10 K 5 2 For the products.157 D 0.0 2 nn = 22.506 1. H298 HP = 0 2 (guess) Given H298 = R A T0 8.639 5.571 2 90 .5 2 nn = 16.457 B 3. Parts (b).7).5 K Ans.121 0. HP = R T0 CP R dT T0 298. (4.75 2 nn = 14. Ans.107 2 T = 2198.6 K Ans.227 1.045 1. by an energy balance.040 10 K 5 2 A i ni Ai B i ni Bi D i ni D i A 54.450 0.2 K Ans. Moreover.012 T 1 K D 1.

639 A 5.656 91 1 T T0 K T 2282.470 3.65606 21.227 10 K 3 D 1.15) J mol The energy balance here gives: 1.429 moles of air: Hair = n R MCPH T Hair Hair 3 0.15 3.575 10 For 4.65606 ( 298.045 1.15 298.5 K K Ans.121 0.457 3.314 3.735 10 K 5 2 A B D 2 (guess) Given H298 Hair = R A T0 1 B 2 T0 2 2 1 D T0 Find 7.593 773.15) Hair = MCPH ( 298.506 B 1.84 B i ni Bi 1 0.355 0.(e) 50% xs air preheated to 500 degC.0 0.5/0.040 10 K 5 2 A i ni Ai 78.450 0. For this process. .15 309399 J mol H298 0.016 K D i ni D i 1.5 n 2 2 16.429 8.280 0.929 Hair HP = 0 3.15 For one mole of air: MCPH 773.21 = 21.016 10 5 = 3.157 0. Hair H298 HP = 0 773.

910 J (s) -492.4.728 J (l) -1. (a) -92.140 J (h) -38.780 J (u) 235.292 J (i) 164.660 J (d) -61.305 J 92 .807.321 J (p) -132. The following answers are found by application of Eq. (4.4: H298 5 ( 393509) 6 ( 285830) ( 146760) H298 = 3 535 765 J 4.370 J (r) -68.220 J (b) -905.20 n-C5H12 + 8O2 = 5CO2 + 6H2O(l) By Eq.720 J (y) 117.582 J (f) -2.980 J (e) -367.016 J (g) -105.15) with data from Table C.036.4.15) with data from Table C.439 J (q) -44.440 J (z) 175.969 J (k) -149.436 J (n) 180.030 J (v) -132.038 J (w) -1.640 J (t) 109.968 J (x) 42.500 J (o) 178.21 Ans.732.647 J (j) -48.036 J (m) 207. (4.468 J (c) -71.

601 -4.573 0.060 4.016 7.19) with evaluated parameters.323 0.083 0.00 673.178 (k) 1.15 923.811 -9. C and D are given for all cases except for Parts (e).871 1.149 1.248 11.21.23 This is a simple application of a combination of Eqs. Results are given in the following table.15 773.029 -0. In each case the value of Ho298 is calculated in Problem 4.159 -1.15 733.416 13.145 -1.184 125 12.424 12.520 0.114 (h) -9.661 2. (k).987 20.441 4.523 -0.766 106 C 0.661 7.083 0.991 2.204 247.188 J HoT/ -109.4.578 -71.716. Ho298 T/ K A (a) (b ) (f ) (i ) (j ) (l ) (m) (n ) (o ) (r ) (t ) (u ) (v ) (w) (x ) (y ) 873.803.15 583.949 -2.21.904 0.234 (z) -3.422 -9.15 683.394 -9.229 -10.296 1.778 0.175 103 B 4.635 25.000 0.6.21 appropriate to the value.381 189.042 0.048 9. (h).972 -1.000 0.166 0.127 7.876 -59. (4.586 0.355 0.297 2.919 93 .15 1083.575 4.00 1073. (g).15 723.181 -3.202 -128.858 -1.191 0.903 180.15 -5.916 -0. In the first column the letter in ( ) indicates the part of problem 4.215 0.000 2. B.845 168.776 0.000 0.083 IDCPH/ J -17.816 -4.22 The solution to each of these problems is exactly like that shown in Example 4.15 973.000 0.729 15.061 -9.504 -1.106 -3.000 0. In each case the value of Ho298 is calculated in Pb. and (z) in the preceding table.991 0.861 6.452 220.000 1.575 -0.534 4.15 750.795 -900.418 2.739 -2.00 900. The values of A.172 3. A 103 B 106 C 10-5 D (e) -7.704 -3.235 1.425 20.000 3.814 10-5 D -0.18) & (4.467 345 -9.918 -1.189 0.743 -2.845 129.037 117.997 1.156 0.647 -4.779 -9.15 648.629 8.173 -4.586 -0.15 850.628 4.424 4.000 0.004 -2.067 1.180 0.011 -1. 4.038.00 1350.643 -0.784 42.737 (g) -3. Those missing are as follows: Part No.285 -3.000 0.450 0.

71 K P 1atm The higher heating value is the negative of the heat of combustion with water as liquid product.793 10 5dollar GJ 8 mol day 5 dollar n HigherHeatingValue 4. Calculate methane standard heat of combustion with water as liquid product Standard Heats of Formation: CH4 + 2O2 --> CO2 +2H2O HfCH4 HfCO2 HcCH4 HcCH4 74520 J mol J mol HfO2 0 J mol 285830 J mol 393509 HfCO2 890649 HfH2Oliq HfCH4 2 HfH2Oliq J mol 94 2 HfO2 .985 10 day Ans.4.25 7. Calculate methane standard heat of combustion with water as liquid product: CH4 + 2O2 --> CO2 +2H2O Standard Heats of Formation: HfCH4 74520 J mol HfO2 0 J mol HfCO2 393509 J mol HfH2Oliq 285830 J mol Hc HfCO2 2 HfH2Oliq HfCH4 2 HfO2 HigherHeatingValue Hc Hc 8.906 10 5 J mol Assuming methane is an ideal gas at standard conditions: n q P RT n 1.15K T 288.24 q 150 10 6 ft 3 day T ( 60 5 32) K 9 273.

90 HcCH4 c) 0.05 HcC2H6 0.95 HcCH4 0.Calculate ethane standard heat of combustion with water as liquid product: Standard Heats of Formation:C2H6 + 7/2O2 --> 2CO2 +3H2O HfC2H6 83820 J mol HcC2H6 2 HfCO2 3 HfH2Oliq HfC2H6 7 2 HfO2 HcC2H6 1560688 J mol Calculate propane standard heat of combustion with water as liquid product Standard Heats of Formation:C3H8 + 5O2 --> 3CO2 +4H2O HfC3H8 104680 J mol HcC3H8 3 HfCO2 4 HfH2Oliq HfC3H8 5 HfO2 HcC3H8 2219. 4.194 kJ mol kJ mol 932.714 kJ mol b) 0. .02 HcC2H6 0.26 2H2 + O2 = 2H2O(l) Ans.03 HcC3H8 946.03 HcC3H8 0. 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 .85 HcCH4 0.875 Gas b) has the highest standard heat of combustion.07 HcC2H6 0.167 kJ mol Calculate the standard heat of combustion for the mixtures a) 0.02 HcC3H8 921. N2(g)+2H2(g)+C(s)+1/2O2(g)=(NH2)2CO(s) H298 Hf1 Hf2 H 95 H298 333509 J Ans.

CH4 + 2O2 = CO2 + 2H2O(g) Entering: Moles methane Moles oxygen Moles nitrogen n1 n2 n3 96 1 2 1. FURNACE: Basis is 1 mole of methane burned with 30% excess air. We therefore take the above value as the standard value.3 2. whereas the STANDARD reaction is at const.145 10 J This value is for the constant-V reaction. and for liquids H is a very weak function of P.27) Q 43960 162.133 10 J 6 This value is for the constant-volume reaction: C10H18(l) + 14. P.However.5O2(g) = 10CO2(g) + 9H2O(g) H298 4.15 K Q R T ngas 7.5O2(g) = 10CO2(g) + 9H2O(l) H 9H2O(l) = 9H2O(g) Hvap 9 44012 J ___________________________________________________ C10H18(l) + 14.781 . for ideal gases H = f(T).5O2(g) = 10CO2(g) + 9H2O(l) Assuming ideal gases and with symbols representing total properties.5)mol 6 298. and for the specified reaction: C10H18(l) + 14.28 On the basis of 1 mole of C10H18 (molar mass = 162. Q= T H U= H ( )= PV H ngas H R T ngas ( 10 14.29 H Hvap H298 6748436 J Ans.6 79 21 n2 n3 2.6 9.4.27 J Q 7.

Moles of water vapor entering: n4 4.9.6 9.2 = 0.121 0.892 10 4 The TOTAL value for MCPH of the product stream: HP R M CPH ( 303.593 10 3 1 n 2.1 mol H2O -.2.040 10 5 A 3.314 J mol K A i ni Ai B i ni Bi 3 D i ni Di A 48.241 13.896983 10 C 0 D 5.7: H298 802625 J mol Q HP H298 Q = 70 612 J 97 Ans.692 B 10.280 8.381 101.639 3.6 .15K A B C D) ( 1773.15)K HP 732. .506 0.241 n4 (1) (2) (3) (4) 0.045 B 1.227 0.325 4.381 At 30 degC the vapor pressure of water is 4.2.585 mol O2 -.781 mol By an energy balance on the furnace: Q= H= H298 HP For evaluation of HP we number species as above.241 kPa.450 0.15 303.470 3.585 Leaving: CO2 -.Total moles of dry gases entering n n1 n2 n3 n 13.013 kJ mol From Example 4.585 0.457 1.157 D 0.781 i 1 4 R 1. 5.15K 1773.6 mol N2 -.

2 Moles O2 reacting = (5)(0.918.15) K n H50 Ans.0 Moles water formed = (6)(0.15 K 1773.8) = 3.381 Moles of water vapor leaving the heat exchanger: n2 12.5 Moles N2 entering = (6.34 kPa.325 pp 18.754 The vapor pressure of water at 50 degC (exit of heat exchanger) is 12.015 J mol Sensible heat of cooling the flue gases to 50 degC with all the water as vapor (we assumed condensation at 50 degC): Q R MCPH ( 323.8) = 4.15 1773.34 n2 n 1.578 Moles water condensing: Latent heat of water at 50 degC in J/mol: H50 2382.578 2.30 4NH3(g) + 5O2(g) = 4NO(g) + 6H2O(g) BASIS: 4 moles ammonia entering reactor Moles O2 entering = (5)(1.8) = 4.8 98 . Q = 766 677 J 4.34 n 101. Moles of dry flue gases: n n1 n3 n4 n 11.HEAT EXCHANGER: Flue gases cool from 1500 degC to 50 degC.325 12.15 K A B C D)( 323.585 1. and water must condense to lower its partial pressure to this value.45 Moles NH3 reacting = moles NO formed = (4)(0. The partial pressure of the water in the flue gases leaving the furnace (in kPa) is pp n2 n1 n2 n3 n4 101.3) = 6.5)(79/21) = 24.

506 10 0.65 B 1 0.450 0.15K 99 .45 i 1 5 A 3.593 3 0.121 0.387 3.873 10 K 4 2 By the energy balance and Eq.639 3.506 0. 4.0 D 1.02987 C 0.040 10 K 5 2 A i ni Ai B i ni Bi D i ni Di A 119.161 B 0.639 3.5 24.7).470 3.280 B 3.629 1. 3=NO.027 K D 8.014 0.15K A B C D) ( 298.ENERGY BALANCE: H= HR H298 HP = 0 REACTANTS: 1=NH3.040 5 A i ni Ai B i ni Bi D i ni Di A 118.45 i 1 3 A 3.227 D 0.593 10 K 3 0.21(b) is used to get J H298 0. 5=N2 1 0.020 0.578 3.15K 298.020 0. 2=O2.8 2. we can write: (guess) 2 T0 298.8 24.578 3.15K) HR 52.5 n 3.186 D 0.280 B 3. 2=O2.8 ( 905468) mol PRODUCTS: =NH3.2 4. 4=H2O.242 10 5 TOTAL mean heat capacity of reactant stream: HR R MCPH ( 348.186 0.15K 348.227 10 0.635 kJ mol The result of Pb. 3=N2 4 n 6. (4.

470 1 1 B 14. 100 .424 3.394 1.0 10 6 D 0.392 0.838 10 4 J mol Reactant stream consists of 1 mole each of C2H4 and H2O.283 T T0 T 978.Given H298 H R = R A T0 1 B 2 T0 2 2 1 D T0 Find 1 3.727 10 4 J mol Q HR H298 1mol Q 115653 J Ans.9 K Ans.15K 593.0 0. 4.31 C2H4(g) + H2O(g) = C2H5OH(l) BASIS: 1 mole ethanol produced Energy balance: n 1mol H= Q= HR H298 H298 [ 277690 ( 52510 241818) ] J mol H298 8.21 10 4 HR R M CP ( H 298.15K 593.392 10 6 D 1.450 10 3 A C 4. i 1 2 n 1.894 B 0.01584 C 4.15K) HR 2.121 10 5 A i ni Ai B i ni Bi C i ni Ci D i ni Di A 4.15K A B C D)( 298.

6275 A 5.1725 0.450 i 1 2 2.0275 H298b mol The energy balance is written H298 4.157 D 0.470 9. 4=H2 0.422 10 3 1.1725 + 0. 2=H2O 1.702 3.0275 + 0.32 One way to proceed is as in Example 4.031 0.728 B 2.84 10 3 HR RI CPH ( 773.6275 mol H2 Entering gas.083 10 5 101 .0 0.1725 + 2(0.2 0. 0. & H2O 0.045 0.1725 = 0.450 0.557 1.0275 n 0.8 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. 2=CO.457 3.1725 mol CO.121 0.15K 298.15K A B C D) HR 1.328 10 7 D 4.376 3.081 1.0275 mol CO2. 3=H2O.1725 0. by carbon & oxygen balances: 0.145 10 4 J mol PRODUCTS: 1=CO2.4000 mol H2O J H298 0.164 0.396 10 3 C 4.003 10 4 J mol Q= HR H298 HP REACTANTS: 1=CH4.1725 H298a 0.249 B 1.4.121 10 5 A i ni Ai B i ni Bi C i ni Ci D i ni Di A 1.0275) = 0.2000 mol CH4 0.470 3.0 n 0.4 10 6 A B 10 3 C D 0.

i 1 4 A i ni Ai B i ni Bi 4 D i ni Di A 3.082 i 1 4 A 5.157 1.33 CH4 + 2O2 = CO2 + 2H2O(g) C2H6 + 3.25) = 2.25 H298b J mol Q 8 10 5 J mol Energy balance: Q = H = H298 HP PRODUCTS: 1=CO2.75 mol CH4.25 mol O2 = (0.470 3.25 mol H2O = 2(0.506 0.75 + 2(0.397 10 C 0. 2=H2O.8[(0. 3=O2.15K 1123.75)(2) + (0.5)] = 4.292 B 0.25 1.082 mol H298 0. 4=N2 HP = Q H298 1.5O2 = 2CO2 + 3H2O(g) H298a 802625 H298b 1428652 BASIS: 1 mole fuel (0.593 10 K 3 D 0.62 10 K .9 16.37 B 6.25 n 2.15K A B C D) 4 J 2. 4.280 B 1.275(79/21) = 16.75 H298a 0. O2 in = 1.227 0.639 3.0 D 9.8)(4.25) = 1. air.040 10 K 5 2 A i ni Ai B i ni Bi D i ni Di 4 2 A 74. 0.75) + 3(0.457 3.275 mol N2 in = 4.63 10 mol Q HR H298 HP mol Q 54881 J Ans.0 D 3.082 mol Product gases: CO2 = 0.015 102 1 K C 0.275) = 1.579 10 3 HP HP RI CPH ( 298.9 mol N2 = 16.450 0.25)(3.25 mol C2H6) burned completely with 80% xs.8/1.121 0.045 1.

We simply take the number of moles of reactants as being negative.15K 2 (guess) Q H298 = R A T0 1 B 2 T0 2 2 1 Find D T0 1.By the energy balance and Eq.86) = 0. we need consider only those species that react or are formed.0645 mol Energy balance: H773 = HR H298 HP Since HR and HP cancel for the gas that passes through the converter unreacted.34 BASIS: 1 mole of entering gases containing 0.2 K 4. and can therefore be considered together.506 10 1. the reactants and products experience the same temperature change. 3: SO3 0.056 3 1.129 A 5.15)(0.65 mol N2 SO2 + 0. 0. 2: O2.639 8.58 10 103 ni Di D 1.060 B 0.699 3. The energy balance is then written: H773 = H298 Hnet H298 [ 395720 ( 296830) ]0. Moreover.129) = 0.0645 0.028 D i 5 i 1 3 A i ni Ai B i ni Bi 2. we can write: T0 Given 303.129 mol O2 reacted = (0.129 J mol 1: SO2.5)(0.7).06985 B 7 C 0 .801 0.15 mol SO2. (4.129 n 0.227 10 2.16 10 4 A 0.5O2 = SO3 Conversion = 86% SO2 reacted = SO3 formed = (0. T 542.20 mol O2. 0.788 T T0 1 Ans.015 D 0.

450 H298 2.083 10 5 .6)(0.5 1 2 A 3.15K 298.168 10 3 J mol Products: 1: CO 2: H2O 3: CO2 4: H2 3. Moles CO reacted = moles H2O reacted = moles CO2 formed = moles H2 formed = (0.5 0.15K 773.249 104 0.470 5.15K A B C D)( 298.157 0.Hnet R M CPH ( 298.045 0.423 B 1.457 3.3 0.2 0.121 10 5 A i ni Ai B i ni Bi D i ni Di A 3.3 Q= H= HR H298 HP H298 0.5) = 0.15K 398.422 10 3 0.031 0.2 n 0.35 CO(g) + H2O(g) = CO2(g) + H2(g) BASIS: 1 mole of feed consisting of 0.15K 398.5 10 3 HR R M CPH ( 298.3 Product stream: Energy balance: moles CO = moles H2O = 0.557 B 1.004 10 3 C 0 D 4.617 J mol H773 H298 Hnet H773 12679 J mol Ans.2 moles CO2 = moles H2 = 0.15K) Hnet 77. 4.031 D 0.5 mol CO and 0.121 1.3 [ 393509 ( 110525 J 214818) ] mol 0.376 A 3.450 1.376 3.5 mol H2O.557 1.045 10 4 J mol Reactants: 1: CO 2: H2O n i 0.15K A B C D)( 773.15K) HR 3.470 B 10 3 D 0.3 0.

80 lbmol CO x lbmol O2 and 100-(14.448 lbmol Find amount of air entering by N2 & O2 balances.8/2 + x + 12.051-x lbmol O2 in flue gas entering with dry air = 3.80 lbmol carbon.133 0.133 0.15K 698.15K) mol HP mol Q 9470 J Ans.415 10 HR 4 J 298.016 12.00 + 11.01 lbmol 0.448/2 = 15.415 10 4 D i ni Di 3. H298 4.015 Also H2O is formed by combustion of H2 in the oil in the amount 209.85 209.36 BASIS: 100 lbmol DRY flue gases containing 3.12 lbmol 2.a carbon balance gives the mass of oil burned: 14.133 lbm The oil also contains H2O: 209.8-x)= 85.i 1 4 A i ni Ai 3.116 lbmol 18.149 lbmol lbmol N2 entering in the air=(85.124 + x lbmol (CO2) (CO) (O2) (H2O from combustion) Total dry air = N2 in air + O2 in air = 85.133 0.00 lbmol CO2 and 11.15K A B C D) ( 698.042 10 4 A B C 0 D HP HP Q R MCPH ( 298.981 B i ni Bi 8. N2 entering in oil: 209.149 =85.051 .175 lbmol 105 .013 0.124 + x = 100.2-x)-0.02 lbmol 28.011 lbm 0. The oil therefore contains 14.8 12.x + 15.2-x lbmol N2.15K 1.

moist air.913 + 79.149 = 79.4594 0.192 10 BTU Reaction upon which net heating value is based: 106 . sat.448+3.Since air is 21 mol % O2.80 lbmol CO 5. 15. then lbmol H2O in flue gas = 0.3 19000 Q 1.287 lbmol N2 (15.03227 lbmol H2O entering in air: 0.175 lbmol 3.00 lbmol CO2 11.21 100.116+12.913 lbmol O2 in air = 15.233 lbmol If y = lbmol H2O evaporated in the drier.138 + 0.797 + y) lbmol H2O(g) Energy balance: Q= H= H298 HP where Q = 30% of net heating value of the oil: BTU 209.00 + 11. and the wet material to be dried.80 + 5.4594 14.21 = x ( 0.x = 79.03227 100.138 lbmoles N2 in flue gas = 79.4594(psia) 0.051 . at 77 degF in lbmol H2O/lbmol dry air. P(sat)=0.175 0. The "products" at 400 degF consist of: 3.124 x 100.287 lbmols [CHECK: Total dry flue gas = 3.124 + x = 21.696 0.287 = 100.13 lbm lbm 6 Q 0.233+y = 15. all at 77 degF.037 lbmols N2 in air = 85.797 + y Entering the process are oil.913 lbmol O2 79.175 15.124)lbmol x 5.00 lbmol] Humidity of entering air.

040 0. N2.470 1.280 3.045 0.8 T 477.031 3 5 0.594 5.602 CP ( y) r A ( y) B ( y) T0 2 1 107 .13 BTU H298a 3.973 10 BTU 6 To get the "reaction" in the drier.448 + 0.42993 BTU Guess: y 50 (y)H2O(l) = (y)H2O(g) H298c ( y) 44012 0. we add to this the following: (11.593 1.024)O2 = (14.121 i 1 5 A ( y) i n y) i Ai B ( y) ( i n y) i Bi D ( y) ( i n y) i Di ( D ( y) T0 2 T T0 1.8)CO2 + (12.457 3.42993 converts from joules on the basis of moles to Btu on the basis of lbmol.67 1. except for some O2.9)O2 H298b 11. Addition of the corresponding delta H values gives the standard heat of reaction at 298 K: H298 ( y) H298a H298b H298c ( y) For the product stream we need MCPH: 1: CO2 2: CO 3:O2 4: N2 5: H2O T0 298. and H2O that pass through unchanged.639 3.8 n y) ( 5.450 D 0.797 y A r 1.157 0.] Addition of these three reactions gives the "reaction" in the drier.15 3 11.986 T 1.OIL + (21.8 ( 110525 393509) 0.278 15.8)CO2 = (11.227 10 0.42993 y BTU [The factor 0.376 3.913 79.557 B 400 459.149)N2 H298a 19000 209.8)CO + (5.116)H2O(g) + (0.506 10 0.

359 0. containing 0.36 mol O2.2934 10 3 C 0 D 6.379 mol each of N2 and C2H2.242 mol HCN.15K A B C D)( 873.952 3 0.7133 B 1.6)(0.495 10 J 4 HP 2.242 n 0.782 (lbmol H2O evaporated) y 18.242 J 2 H298 5. and 0.75) = 0. and (1-0.13 4.242)/2 = 0.526 10 4 HP R M CPH ( 298.Given CP ()( y 400 77)BTU = Q H298 () y y Find y () y Whence 49.379 i 1 3 A i 4.379 0.299 10 5 B i ni Bi D i ni Di A 4.280 6. 0. 4.15K 873.45 mol 4HCl(g) + O2(g) = 2H2O(g) + 2Cl2(g) 108 . HCl reacted = (0.04 mol N2.6 mol HCl.15K)mol HP 2.736 A 3. The energy balance is Q= H= H298 HP H298 ( 135100 2 227480) 0.015 209. per lb oil burned) Ans.288 (lb H2O evap.495 10 J 4 Q H298 HP Q 30124 J Ans.38 BASIS: 1 mole gas entering reactor.37 BASIS: One mole of product gas containing 0.593 10 1. 4.725 D 0.169 10 J 3 Products: 0.040 1.15K 298.132 ni Ai B 1.

457 109 0.39 CO2 + C = 2CO 2C + O2 = 2CO Eq.344 0.470 4. 4. H298 [ ( 241818) 2 4 ( 92307) ] J mol H298 1.439 MCPH T0 T B A 8 10 B 5 C 0 D C D R T T0 H823 117592 J mol Heat transferred per mol of entering gas mixture: Q H823 4 0.557 B 0.089 0.031 D 0.21) with T0 298.21) applies to each reaction: H298a 172459 H298b J (a) mol J (b) 221050 mol For (a): 2 n 1 1 A 3.442 3.506 10 3 0.639 B 1.15K 1: H2O 2: Cl2 3: HCl 4=O2 2 n 2 4 1 i 1 4 A 3.144 10 5 J mol Evaluate H823 by Eq.45 0.045 3 0. (4.771 10 1.For this reaction.23 10 4 A H823 H298 0.376 1.227 10 5 A i ni Ai B i ni Bi D i ni Di 8.867 10 1.45 mol Q 13229 J Ans.121 D 0.151 0. (4.156 3.157 5 .623 0.771 5.15K T 823.

15K 298.15K H A B C D ( 1148.506 10 0.899 10 5 A H1148b 0.327 2 110 .696 10 5 J mol For (b): 2 n 1 2 i 1 3 A 3.771 3 0.02 10 C 0 D 1.34 10 D H298b R M CP 298.15K 1148.771 B 0.15K) H1148a 1.227 10 0.429 9.376 3.15K 1148.i 1 3 A i ni Ai B i ni Bi 4 D i ni Di A H1148a 0.476 B 7.557 0.15K) H1148b 2.639 1.867 5 A i ni Ai B B i 4 ni Bi C 0 D i ni Di 1.15K 298.031 D 0.962 10 5 H298a R M CP 298.15K H 5 J A B C D ( 1148.249 10 mol The combined heats of reaction must be zero: nCO 2 H1148a nO 2 H1148b = 0 2 nCO Define: r= nO r H1148b H1148a r 1.

21 x x 12.1 + 0.06 mol N2 Air entering contains: 1.221 Ans.054 65.40 CH4 + 2O2 = CO2 + 2H2O(g) CH4 + (3/2)O2 = CO + 2H2O(g) H298a 802625 J mol H298b 519641 J mol BASIS: 1 mole of fuel gas consisting of 0.21 19.79x 12.946 4.94 2.5 5. moles are: Flue gas Air Feed mix CO2 CO O2 N2 12.232 nN 2 78. Product composition: nCO 3.8 3.4 78.For 100 mol flue gas and x mol air.054 Ans.4 r mol 0.548 mol N2 111 .21x 78.8 5.538 79 21 9.155 nCO nCO nN 2 Mole % CO = 100 34.21 x 19.7 2 ( 12. Mole % N2 = 100 34.155 mol Flue gas to air ratio = 100 19.79x Whence in the feed mix: r= 12.155) nCO nN 2 48.21x 0.145 93.4 0.1 0.1 0 0 0.8 5.538 mol O2 2.35 2 0.4 + 0.155 5.4 0.7 5.7 5.79 19.8 3.94 mol CH4 and 0.

450 10 0.6725 10 C 0 D R M CPH ( 298.880 O2: 2.94 2.3 0.1.282 n 1.396 10 298.880 0.252 kJ mol kg 34.031 D 0.557 1.94 0.121 0.15K) 4 A HP HP 9.548 + 0.15K A B C D)( 483.227 0.658 3 0.7 0.0 sec Energy balance: HH2O mdotH2O Hrx ndotfuel = 0 mdotH2O 112 .282 H2O: 1.88 Moles O2 consumed by reaction = 2 0.060 = 9.658 CO: 0.538 .282 2 1.470 3.739 Product gases contain the following numbers of moles: (1) (2) (3) (4) (5) CO2: 0.045 0.282 H298 0.658 0.639 3.Moles CO2 formed by reaction = 0.157 0.94 0.658 H298a 0.799 N2: 9.0 1.593 3 1.457 3.15K 483.040 10 5 ni Ai 45.799 9.282 H298b H298 6.541 10 4 J mol Hrx H298 HP Hrx 599.747 10 5 J mol Moles H2O formed by reaction = 0.608 0.4881 B B i ni Bi 3 D i ni Di 3.376 A 3.15K 7.658 Moles CO formed by reaction = 0.608 i 1 5 A i 5.280 B 1.739 = 0.506 0.

0 104.179 10 mol Q 0.873 10 6 0.1: HH2O ( 398. 4.635 mol sec Volumetric flow rate of fuel.15K 5 J A B C D R T T0 H798 1. (4.15 K T 798.734 A 3.3 10 H798 H298 MCPH 298.882 C 0.15 K 101325 Pa V m 0.0 5 A i ni Ai B i ni Bi 3 C i ni Ci 7 D i ni Di 3 A 4.8) kJ kg ndotfuel HH2O mdotH2O Hrx ndotfuel 16. The unreacted C4H8 and the diluent H2O pass throught the reactor unchanged.33 mol H798 Q 38896 J 113 Ans.From Table C.41 C4H8(g) = C4H6(g) + H2(g) H298 109780 J mol BASIS: 1 mole C4H8 entering.0 9. assuming ideal gas: V ndotfuel R 298.083 10 0.630 10 3 8.249 1. and need not be included in the energy balance. Thus 1 n 1 1 2.967 i 1 3 B T0 298.15 K by Eq.21): Evaluate H798 1: C4H6 2: H2 3: C4H8 26.422 10 C 9.91 10 D 8. .016 B 4.422 31.0 D 0.786 0.407 sec 3 Ans.15K 798. of which 33% reacts.

575 10 0 0.314 10 kJ mol K 3 ICPH T0 T 3.355 0.7707 s Ans.995 K ndot Q R ICPH T0 T 3. 4.261 K 3 T 305.355 0.659 K ndot Q R ICPH T0 T 3.943 s T T0 Vdot ft 33.575 10 3 0 0.67) rankine R 1.15) K 3 13K 8.355 0.016 10 5 ndot 31.575 10 0 0.051 3 mol s Vdot ndot R T0 P Vdot m 0.4.016 10 5 45.88 10 3 BTU mol K a) T0 ( 70 459.43Assume Ideal Gas and P = 1 atm P 1atm a) T0 ( 94 459.298 sec Q 12 kJ s Ans.67) rankine 3 T ( 68 459.372 K ICPH T0 T 3.61 10 atm ft mol rankine 3 Vdot ft 50 sec 3 ndot P Vdot R T0 114 ndot 56.575 10 3 0 3 0.016 10 5 38.016 10 5 ndot 39.097 mol s .42Assume Ideal Gas and P = 1 atm P 1atm R 7.67) rankine T T0 20rankine Q 12 BTU sec T0 294.355 0.611 3 mol s Vdot ndot R T0 P Vdot m 0. b) T0 R ( 24 273.

016 10 5 ndot 59.575 10 R Q 35.20 115 .5 sec 3 mol K ndot 3 Vdot P Vdot R T0 0 0.314 10 3 kJ mol K 3 R ICPH T0 T 3.3216 kJ Ans.355 0.355 0.355 0.88 10 3 BTU 50. sec Q b) T0 ( 35 273.205 10 m 1.575 10 R 7.016 10 5 ICPH T0 T 3.575 10 0 0.7 K mol K 3 Q R ICPH T0 T 3.594 K 3 T 0 293.355 0.119 K 8.15)K 3 5 atm m T ( 25 273.016 10 5 ndot 22.043 10 dollars gal 6 J mol 80% Cost 2.T0 307.325 mol s ICPH T0 T 3.44 First calculate the standard heat of combustion of propane C3H8 + 5O2 = 3CO2(g) + 4H2O (g) H298 H298 3 393509 J mol 4 241818 J mol 104680 J mol 2.4121 BTU Ans.15)K R 8.15 K 0.016 10 5 ndot 17.575 10 0 0. s Q 4.

h) Hydrogen chloride 14.8K ( 25 273. 779 e) Carbon monox ide 14. 0 73 k) Nitrogen 14. 147 116 . 120 b) Ammonia 20.299 10 5 mol The calculations are repeated and the answers are in the following table: J/mol a) Acetylene 26.132 1.528 4.Estimate the density of propane using the Rackett equation Tc T 369.373 mol 3 Heating_cost Vsat Cost H298 Heating_cost Heating_cost 0.952 10 2.0 mol 0. 964 d) Carbon diox ide 21. 276 l) Nitrogen diox ide 20.612 10 4 J 0 1. 33. g) Hydrogen 13866 .18 j Nitric ox ) ide 14.806 3 0. 846 m) Nitrous ox ide 22. 052 o) Propylene 46. 457 f) Ethane 3 420 8. 040 i) M ethane 233 .15) K 1 Tr Zc 0.032 dollars MJ dollars 10 BTU 6 Ans. 200 c) nbutane 71.276 Tr T Tc Vc Tr cm 200.15) K 3 a) Acetylene R ICPH T0 T 6.15) K Q Q T ( 500 273.2857 Vsat V c Zc Vsat cm 89.45 T0 ( 25 273. 019 n) Ox ygen 15.

2 degC The calculations are repeated and the answers are in the following table: T( K) 835.2 1298.952 10 Find ( T) T 835.1 986.3 1230.4 932.132 1.0 534.46 T0 Q ( 25 30000 273.15) K 0.299 10 5 273.7 959.15)K a) Acetylene T Given Q = R ICPH T0 T 6.2 957.47 T0 ( 25 273.1 1025.225 10 Find ( y) y 0.4.15)K J mol T ( 500 273.9 417.3 690.2 1209.164 10 3 6 0 R 6 = Q y) ICPH T0 T 1.3 1003.637 Ans.0 877.0 690.2 1259.081 10 (1 y 3 2.9 604.2 a) Acetylene b) Ammonia c) n-butane d) Carbon dioxide e) Carbon monoxide f) Ethane g) Hydrogen h) Hydrogen chloride i) Methane j) Nitric oxide k) Nitrogen l) Nitrogen dioxide m) Nitrous oxide n) Oxygen o) Propylene 4.3 T( C) 562.6 686.15K 562.9 261.4 964.702 9.3 654.5 Q 11500 J mol a) Guess mole fraction of methane: Given y ICPH T0 T 1. 117 5.8 363.9 1248.561 10 0 R .131 19.8 974.4 1277.1 936.3 659.15)K T ( 250 y 273.9 636.369 K T 3 0 1.4 927.

512 Ans.249 10 Ans.301 10 3 6 0 R 6 = Q y)ICPH T0 T Find y () ( 150 3.124 55.716 10 3 6 0 R 6 = Q y)ICPH T0 T 1.15) K T ( 400 y 273.476 10 0 R 4. In the first case the minimum temperature difference.064 10 3 13.b) T0 ( 100 273.15)K 0.48 Temperature profiles for the air and water are shown in the figures below.290 47.928 10 0 R y 0.245 273. 18.15)K 0.380 10 Find y () y 0. In the second case.5 Q 17500 J mol Guess mole fraction of toluene Given y ICPH T0 T 0. or "pinch" point occurs at an intermediate location in the exchanger.052 10 ( 1 y 3 15.5 Q 54000 J mol Guess mole fraction of benzene Given y ICPH T0 T ( 1 y c) T0 0.876 63.206 39. I e m e a e Pi h nt r di t nc Se ton I ci TH1 Pi h a End nc t TH1 Se ton I ci I Se ton I ci THi T THi Se ton I ci I TC1 TCi TH2 TC1 TCi TC2 TH2 T TC2 118 .15) K 273. the pinch occurs at one end of the exchanger. There is no way to know a priori which case applies. T ( 250 y 20. There are two possible situations.

016 10 Assume as a basis ndot = 1 mol/s.255 0. If the pinch is at the end. ndotH kmol s Assume pinch at end: TH2 TC2 T Guess: mdotC 1 kg s THi 110degC Given mdotC HC1 mdotC HCi HCi = ndotH R ICPH THi TH1 A B C D Energy balances on Section I and HC2 = ndotH R ICPH TH2 THi A B C D II kg s mdotC THi mdotC ndotH Find mdotC THi THi 170.261 degC mdotC 11. T H1 Section I balance: mdotC HC1 HCi = ndotH THi CP dT T Hi Section II balance: mdotC HCi HC2 = ndotH TH2 CP dT If the pinch is intermediate.0 kJ kg HCi 419. apply an energy balance around each section of the exchanger. a) TH1 1000degC TC1 100degC TCi 100degC TC2 25degC T 10degC HC1 2676.355 B 0.1 3 kJ kg HC2 104. then THi = TCi + T.1:A 3.To solve the problem.8 kJ kg 5 For air from Table C.575 10 1 C 0 D 0.261 degC TH2 119 TC2 10 degC . THi TCi 70.011 kg mol Ans. then TH2 = TC2 + T.

the assumption of an intermediate pinch is correct.695 degC mdotC 5. THi .TC2.TCi is greater than the temperature difference at the end point.0 kJ kg HCi 419. THi TCi 10 degC TH2 TC2 23.1 kJ kg HC2 104.4 kJ mol H0f2 120 0 kJ mol M1 180 gm mol . THi .8 kJ kg Assume as a basis ndot = 1 mol/s. 4.03 10 mol Ans. TH2 . 4 = H2O H0f1 1274.TC2.03 kg s mdotC ndotH 5.TCi is less than the temperature difference at the end point. the assumption of a pinch at the end is correct.50a) C6H12O6(s) + 6 O2(g)= 6 CO2(g) + 6 H2O(l) 1 = C6H12O6 . 3 = CO2 . ndotH 1 kmol s Assume pinch is intermediate: THi TCi T Guess: mdotC 1 kg s TH2 110degC Given mdotC HC1 HCi = ndotH R ICPH THi TH1 A B C D Energy balances on Section I and HC2 = ndotH R ICPH TH2 THi A B C D II Find mdotC TH2 TH2 3 kg mdotC HCi mdotC TH2 48.Since the intermediate temperature difference. TH2 . 2 = O2 .695 degC Since the intermediate temperature difference. b) TH1 500degC TC1 100degC TCi 100degC TC2 25degC T 10degC HC1 2676.

520 kJ mol H0f2 83.634 kJ mol Ans. 2 = C2H6.05 H0f3 H0c 825.85 CH4(g) + 0.85 (CH4(g) + 2 O2(g) = CO2(g) + 2 H2O(g)) 0.830 kJ mol M3 44 gm mol H0r 6 H0f3 6 H0f4 H0f1 6 H0f2 H0r 2801.10(C2H6 (g) + 3.509 kJ mol H0f5 241.820 kJ mol H0f3 0 kJ mol H0f4 393. the exit gas will contain the following numbers of moles: n3 0. b) For complete combustion of 1 mole of fuel and 50% excess air.025 mol Excess O2 . 4.509 kJ mol H0f4 285.51 Assume as a basis.05 H0f4 2 H0f5 0.05 O2(g) = 1.05 CO2(g) + 2 H2O(g) 1 = CH4.549 kg Ans.5 O2(g) = 2 CO2(g) + 3 H2O(g)) -----------------------------------------------------------------0.05mol 121 n3 1. 0.85 H0f1 0. Use molecular mass to get ratio of mass CO2 produced per mass of glucose.096 kJ mol Ans.10 H0f2 1.818 kJ mol a) H0c 1.H0f3 393.10 C2H6(g) + 2. 4 = CO2.216 10 kg 8 Ans. 5 = H2O 6 = N2 H0f1 74. 6 275 10 mass_glucose 6 M3 M1 2. 1 mole of fuel. b) energy_per_kg 150 kJ kg mass_person 57kg mass_glucose mass_person energy_per_kg H0r M1 mass_glucose 0.5 2. c) 6 moles of CO2 are produced for every mole of glucose consumed. 3 = O2.

15) K A n3 3.450 mol n6 0.05mol 79 1.040 10 5 Q H0c ICPH T1 T2 A B C D R Q 529.805 n5 1.15) K T2 ( 600 273.470 n6 3.n4 1.121 mol n6 0.5 2.05mol 21 n6 11.639 n4 6.227) n4 ( 0.618 mol Total N2 Air and fuel enter at 25 C and combustion products leave at 600 C.906) n5 0.280 3 mol B n3 0.889 kJ mol Ans.506 n4 0. 122 .05mol n5 2mol n6 0.593 10 C n3 0 n4 0 n5 0 mol n6 0 10 6 D n3 ( 0. T1 ( 25 273.311 n5 3.

Section A . (5.15 K 148.3 (a) Let symbols Q and Work represent rates in kJ/s TH 750 K TC 300 K Work 95000 kW By Eq. Work By Eq.282 Ans.714 10 kW Ans.78 kJ s QH 250 kJ s Work QH 1 TC TH or Work Work QH 148.6 Work 5 1.15 K TH 623.15 K TH 798. QC QC 101.8) = Work QH = 1 TC TH TC 323. But = Whence QH QC (b) QH QH QC Work QC 6.35 Work QH Work QH QC 5 2. 5. .22 kJ s Ans.1). Ans.Mathcad Solutions 5.583 10 kW Ans.78 kW which is the power. 1.4 (a) TC 303.2 Let the symbols Q and Work represent rates in kJ/s. 5. 0.333 4 10 kW Ans.55 123 Carnot 0.Chapter 5 . (5. (5. Then by Eq.8): Work QH 1 TC TH QH 0.15 K Carnot 1 TC TH 0.764 5 10 kW Ans.

5. TH TC 1 Carnot TH 833.15 K TC QC 113.336 10 kW Ans.184 (a) T1 273. (5.15 K T2 373.4 kJ kg K kJ kg SH2O Sres CP ln Q T2 T2 T1 SH2O 1.0133 bar T 298. .55 Carnot 0.202 10 kW 6 QC 1 Work 5.66 K Ans. QH QC Work QH 8.8).305 Sres 124 1.(b) 0. for which Work QC = QH QC QC = QH QC 1= TH TC 1 TH 303.8 Take the heat capacity of water to be constant at the valueCP 4.121 kJ kg K Ans.15 K molwt 17 gm mol mLNG PV molwt RT mLNG 6254 kg s Maximum power is generated by a Carnot engine.15 K Q CP T2 kJ kg K T1 Q 418.538 10 kW 6 Ans.35 Carnot 0.7 K 6 QC Work 512 kJ mLNG kg TH TC 3.7 Let the symbols represent rates where appropriate. Calculate mass rate of LNG evaporation: V 9000 m s 3 P 1.636 By Eq. 5.

208 kJ kgK Stotal Sres SH2O Stotal 0. but divided into two halves.184 kJ kgK Ans. P2 P1 S = n CP ln T2 T1 T2 T1 R ln P2 P1 But = Whence S n CV ln T2 T1 S 20. The entropy change of the surroundings is zero.443 mol CV 5 2 R Q 15000 J (a) Const. each one exchanging an infinitesimal quantity of heat with the water and raising its temperature by a differential increment.794 J K Ans.-V heating. (5. 125 . Sres Q 2 1 323.Stotal SH2O Sres Stotal 0. 3 5. and the total heat transfer is the same.794 J K Ans. U= Q W = Q = n CV T2 T1 T2 T1 Q n CV T2 1 10 K 3 By Eq.15 K Sres 1. (b) The entropy change of the water is the same as in (a). (c) The reversible heating of the water requires an infinite number of heat reservoirs covering the range of temperatures from 273.15 K 1 373. (b) The entropy change of the gas is the same as in (a).06m n P1 V R T1 n 1. Whence Stotal = 10.9 P1 1 bar T1 500 K V 0. The stirring process is irreversible.15 to 373.097 kJ kgK Ans.15 K.18).

Now SA SA CP ln 8.726 463. (c) In this case the final temperature of steam B is 80 degC. (5.15 SB 6.82 10 3 J mol 126 . i.726 463. The exit temperature of the second stream is therefore 200 degC.214 J mol K Ans. dW dQ = 1 T T dW = dQ T dQ T Since dQ/T = dS.8). there is a 10-degC driving force for heat transfer throughout the exchanger. T1 600 K T2 400 K T 300 K Q CP T2 T1 Q 5.10 (a) The temperature drop of the second stream (B) in either case is the same as the temperature rise of the first stream CP (A).15 593.15 343.15 J mol K SB CP ln 473.15 SB 8. (b) For both cases: Stotal SA SB Stotal 2.15 473.e. 5.5. In both cases we therefore have: 7 R 2 SA SA CP ln 8.15 343. dW = dQ T dS Integration gives the required result.577 J mol K Ans.. Stotal SA SB Stotal 0.16 By Eq.. 120 degC.15 J mol K SB CP ln 353.e.149 J mol K Ans. i.512 J mol K Ans.

r r 2.365 10 3 J mol Ans.2bar T2 450K P2 6bar Cp 7 R 2 H C p T2 T1 R ln 3 J H P2 P1 4. (5.582 J mol K Ans.7) to get: TC2 QC2 Equate the two work quantities and solve for the required ratio of the heat quantities: TC2 TH1 TC1 Ans.82 10 mol S = 1.S CP ln Q T2 T1 T S S 11. 5.18 (a) T1 300K P1 1.8) & (5.5 TH1 TH2 TC2 5. (b) H = 5. use Eq.799 J mol K Work Work 2280 J mol Ans.17 TH1 600 K TC1 300 K TH2 300 K TH1 TC2 TC1 250 K For the Carnot engine. Sreservoir Q T Sreservoir 11. S Sreservoir 0 J mol K Process is reversible. (5. W TH2 TC2 = Combine Eqs. S Cp ln T2 T1 S 1. Q Q Work Q 3540 J mol Ans.8 J mol K Ans.484 J mol K 127 .8): W QH1 = TH1 The Carnot refrigerator is a reverse Carnot engine.

(A) p. For adiabatic steps 1 to 2 and 3 to 4: T1 V 1 1 = T2 V 2 1 T3 V 3 1 = T4 V 4 1 For constant-volume step 4 to 1: For isobaric step 2 to 3: V1 = V4 P2 T2 = P3 T3 Solving these 4 equations for T4 yields: T4 = T1 7 R 2 T2 T3 Cp Cv 5 R 2 Cp Cv 1. The following equations are used to derive and expression for T4. B=4.19This cycle is the same as is shown in Fig. The efficiency is given by Eq.741 10 mol 3 J S = 2.607 J mol K 5.618 J mol K (e) H = 6. (A) on p. 128 .953 J mol K (d) H = 3.15) K T3 ( 1700 273.15) K T2 T4 ( 1000 273. C=1. 305. 305.(c) H = 3.651 10 mol S = 3.4 T1 ( 200 273.759 K Eq. 8.15) K T4 T1 T2 T3 1 873. The equivalent states are A=3. Temperature T4 is not given and must be calaculated.591 Ans. and D=2. 306 1 T4 T3 T1 T2 0.10 on p.118 10 3 J mol 3 J S = 4.

15 K CP CV 1.35 R T1 1 P2 1 Work 3. Work is done on the system.6 10 3 J P1 U = C V T2 T1 Whence mol But Q = 0. W12 = P V2 V1 = R T2 T1 Step 2-3: Isothermal compression.21 CV CP R P1 2 bar P2 7 bar T1 298. we get for the actual W: 1 Work 1.4 With the reversible work given by Eq. Heat flows into the system.34). Heat flows out of the system. Heat flows out of the system. Work is done on the system.914 J mol K Ans. and W = T2 T1 Work CV T2 471. P dT T dP = 0 T dP = dT P (A) PV= RT P dV V dP = R dT P dV = R dT V dP = R dT RT dP P 129 . Since the PT product is constant. W23 = R T2 ln P3 P2 = R T2 ln P3 P1 Step 3-1: Expansion process that produces work.25 P 4 T 800 Step 1-2: Volume decreases at constant P. (3. 5.5.374 K S CP ln T2 T1 R ln P2 P1 S 2.

R dT = 2 R dT P3 = P 1 T1 T3 = P1 T1 T2 V1 W31 = V3 P dV = 2 R T 1 U31 W31 = CV T1 2R T1 T3 = 2 R T1 T3 2 R T1 R T1 T2 Q31 = T3 T2 Q31 = CV T3 = C P W23 Q31 = Wnet Qin = W12 W31 CP 7 R 2 T1 P1 700 K T2 P3 W12 2.In combination with (A) this becomes P dV = R dT Moreover.5 bar P1 10 W12 R T2 T1 mol 3 J W23 W31 Q31 R T2 ln P3 P1 T2 T1 T2 W23 W31 Q31 2.82 10 mol R W23 Q31 1.309 10 4 J mol W31 0.017 10 mol 3 J 2 R T1 CP W12 5.068 Ans.91 350 K T1 T2 3 J 1. 130 .

15 K P1 2.213 28. we have Sres Stotal Q Tres S Sres Sres Stotal 13.15K 1373.02 Ans.15 K By Eq. we get for the entropy change of 10 moles n 10 mol S n R ICPS 473.1 J K Ans.15K 1473.699 0. (5.0 S 2018.163 10 3 J mol Q Work Q here is with respect to the system. (3.824 10 6 0. 6.27 (a) By Eq. (5. and Eq. (5.96 J mol K J mol K Ans. With the reversible work given by Eq.7 J K Ans.18).944 Ans.26 T 403. (b) By Eq.0 1.3 R T ln P2 P1 (Isothermal compresion) Work 4. 131 .785 10 3 8.14) with P = const.5 bar P2 6.15K 1.14) with P = const.640 10 3 0.15).27).15K 5. So for the heat reservoir. S R ln P2 P1 S 7. and Eq. (5.15).5 bar Tres J mol K 298. we get for the entropy change of 12 moles n 12 mol S n R ICPS 523.5. 5. (5.015 10 5 S 536. we get for the actual W: Work 1.

5.15K 1374. The entropy change for 15 moles is then found as follows: n S S 15 mol n R ICPS 533.15 K 248. 5.3 (guess) 132 . The entropy change for 10 moles is then found as follows n S S 10 mol n R ICPS 473.392 10 6 0.28 (a) The final temperature for this process was found in Pb.5 J K Ans. the enthalpy changes of the two streams must cancel. and let x = moles of chilled air.394 10 900.424 14. Then 1 .9 K. Take a basis of 1 mole of air entering.2a to be 1374.392 10 6 0.0 K Ans. 4.5 K.86 J K Ans.8K 1.2b to be 1413.29 The relative amounts of the two streams are determined by an energy balance.5K 1.967 31.15K 1413.8 K.x = the moles of warm air. Since Q = W = 0.0 (c) The final temperature for this process was found in Pb.14 kg moles is then found as follows n S S 18140 mol n R ICPS 533.873 10 6 0.0 (b) The final temperature for this process was found in Pb.15K 1202. 3 9. T0 T1 T2 298.394 10 1. 3 4. 4. The entropy change for 18.9K 1.424 14.2c to be 1202.630 10 2657.2436 10 6 J 3 4.15 K 348. 4.15 K T0 ( 1 Temperature of entering air Temperature of chilled air Temperature of warm air x)CP T2 T0 = 0 x C P T1 x 0.

there is no violation of the second law.5.733 10 mol S CP ln T2 T1 R ln P2 P1 S 2. 5.Given x 1 x = T2 T1 T0 T0 x Find x () x 0. the total entropy change is as follows. On the basis of 1 mole of entering air.301 J mol K Stotal S Sres Stotal 3.30 T1 523. The only remaining question is whether the process violates the second law. mol K 133 .15 K P1 3 bar P2 1 bar Tres CV Sres 303.97 J mol K Ans.15 K T2 353. CP 7 2 R P0 5 bar P T2 T0 1 bar P P0 Stotal x CP ln T1 T0 ( 1 x)CP ln R ln Stotal 12.5 Thus x = 0.15 K Work 1800 J mol CP Q Q 7 2 R CP R Q Q= Sres U Work 5. and the process produces equal amounts of chilled and warmed air.718 J mol K C V T2 T1 3 J Work Tres 1. Since this is positive.42 J PROCESS IS POSSIBLE.

7 amp T 300 K Wdotmech 1. 5. (5.45 W K Ans.27 T1 ( 273.938 kW Wdotideal t 951.15 K T ( 273.5 kJ kg K T 40 K mdot 20 kg sec t 0.15 25) K T1 298.15 K T2 ( 273.504 Eq.875 W SdotG Qdot T SdotG 0.15 30) K T 303. (5.26): By Eq.28): mdot H T S Wdotideal Wdot 256.33 For the process of cooling the brine: CP 3.15 15) K T2 258.15 K H CP T H 140 kJ kg kJ kg K S CP ln T2 T1 Wdotideal Wdot S 0.34 E 110 volt i 9.067 10 W 3 At steady state: Qdot Wdotelect Wdotmech = d t U = 0 dt Qdot T SdotG = d t S = 0 dt Qdot Wdotelect Wdotmech Qdot 134.6 kW Ans.5. 134 .25 hp Wdotelect iE Wdotelect 1.

. 5.2bar Cp 7 R 2 Cv Cp R Cp Cv 7 5 (a) Assuming an isenthalpic process: T2 T2 T1 T2 298.628 J mol K Ans. (5. S (b) = R T1 Cp 1 R T dT ln P2 P1 P2 P1 Eq.15 K Ans.38 mdot 10 kmol hr T1 ( 25 273.35 25 ohm i 2 10 amp T 300 K Wdotelect i Wdotelect 2.14) S T2 7 R ln T1 2 R ln S 17.2bar Cp 7 R 2 T 300K Basis: 1 mol n 1mol H n C p T2 T1 Ws 135 H Ws 3753.333 watt K Ans.15) K Wlost T S Wlost 5.5 10 watt 3 SdotG 8.15) K P1 10bar P2 1.5.8 J Ans. 5. 3 J (d) T ( 20 273.168 10 mol Ans.5 10 W 3 At steady state: Qdot Wdotelect = d t U = 0 dt Qdot Wdotelect Qdot T SdotG = d t S = 0 dt SdotG Qdot T Qdot 2.966 W K Ans.39(a) T1 500K P1 6bar T2 371K P2 1. (c) SdotG mdot S SdotG 48.

9J 4193.45kJ 273. Eq. (5.698 1.45 136 .15 K W actual QH actual 0.3J 493J 1130J 1409.468 kJ sec K Ans.8J 3.3 J 4.9J 3063. TH TC Wdotlost 5.4J 4119.344 kW ( 250 ( 25 0. Ans.4J 1098.7J Ws Wlost SG Wlost 1409.15 K 298.698 J K Ans.767 Ans.023 kJ mol K T 300K mdot 20 S SdotG R ln P2 P1 mol sec mdot S T SdotG W 0.546 K 5.39) Ws (a) (b) (c) J K 3753.698 SG 4. Eq.8J 3.15)K 523.41 P1 2500kPa P2 S SdotG 150kPa 0.15)K 273. (5.663 J K J (e) 3055.7J J K J K J K (d) 3853.8J 2460. Ans. (5.5J 4952.2J 1063.30) H T S Wideal 5163 J Wlost SG Wideal Wlost T Wideal 5163J 2953.643 3.42 QH 1kJ Wdotlost TH TC 140.27) Eq.S n Cp ln T2 T1 Wideal R ln P2 P1 S 4.

492 10 W 9 QdotC QdotH QdotC 1.297 MW (b) 0. 137 . 5. 5.43 Since actual> max. 293.15)K TC TC ( 20 273.max 1 TC TH max 0.43 QH 150 kJ Q1 50 kJ Q2 100 kJ TH 550 K T1 350 K T2 250 K T 300 K (a) SG QH TH Q1 T1 Q2 T2 SG 0.15 K 0.522 K Ans.502 Ans. (b) Wlost T SG Wlost 81.742 3 (actual value) River temperature rise: Vdot m 165 s 1 gm cm 3 Cp 1 cal gm K T QdotC Vdot Cp T 2.039 kJ Ans.6 max QdotH Wdot Wdot QdotH 10 MW 3 2.44 Wdot 750 MW TH ( 315 273.15 K 1 TC TH max QdotH Wdot max QdotC QdotC QdotH Wdot (minimum value) 745.15)K TH (a) max 588. the process is impossible.27 kJ K Ans.

575 10 1 7 3 0 0.46 T1 P1 ( 20 5bar 273. (5.23) SG 6 7 R ICPS T1 T2 3.776 hp 138 .575 10 T 3 0 0.016 10 5 R ln P2 P1 SG 0.016 10 5 R ICPS T1 T3 3.013 0.67)rankine Assume air is an Ideal Gas ndot P Vdot R T1 ndot 258.355 0.016 10 5 R H 8.575 10 10 4 kJ 3 0 0.355 0.575 10 kJ mol K Since SG 0 0.797 mol H is essentially zero so the first law is satisfied.67)rankine ( 20 459.575 10 0 0.575 10 1 7 3 0 3 0.555 lbmol hr Calculate ideal work using Eqn.15)K T2 P2 ( 27 1atm 273.016 10 Wideal 1.47 a) Vdot P ft 100000 hr 1atm 3 T1 T ( 70 ( 70 459.26) Wideal ndot R ICPH T1 T2 3.15)K First check the First Law using Eqn. this process is possible.016 10 5 ICPH T1 T3 3.67)rankine T2 459.355 0. 5. (2.016 10 3 5 5 R ICPS T1 T2 3.15) K T3 ( 22 273. Calculate the rate of entropy generation using Eqn. H 6 7 R ICPH T1 T2 3.355 0. (5.355 0.33) neglect changes in kinetic and potential energy.355 0.5.

: T2 ndotgas T1 Cp ( ) T T d T2 mdotsteam Hv = 0 Cp ( ) T T d mdotndot T1 Hv mdotndot 15.016 10 3 5 5 R ICPS T1 T2 3. SdotG = SdotGsteam SdotGgas 139 .355 0.016 10 Wideal 5.575 10 0 0.043 lb lbmol Calculate the rate of entropy generation in the boiler. (5.67) rankine T2 ( 300 459.000306 T rankine R Hv Tsteam 970 BTU lbm M 29 gm mol 459.575 10 T 3 0 0.48 T1 1.355 0.15) K T2 (8 273.064 mol s Wideal ndot R ICPH T1 T2 3. This is the sum of the entropy generation of the steam and the gas.67) rankine ( 212 459.952 kW 459.67) rankine ( 2000 Cp ( ) T T ( 70 3.b) Vdot P 3000 1atm m 3 hr T1 T ( 25 ( 25 273.83 0.67) rankine a) First apply an energy balance on the boiler to get the ratio of steam flow rate to gas flow rate.26) ndot P Vdot ndot 34.15) K Assume air is an Ideal Gas R T1 Calculate ideal work using Eqn.15) K 273.

071 Calculate lbs of steam generated per lbmol of gas cooled.Calculate entropy generation per lbmol of gas: SdotG ndotgas Ssteam = mdotsteam ndotgas Hv Tsteam T2 Ssteam Sgas BTU lb rankine 3 kg Ssteam 1.34) Wlost SdotG T Hv Tsteam Wlost 6227 BTU Ans. lbmol 1.085 T2 10 3 BTU lbmol Ans.043 lb lbmol Use ratio to calculate ideal work of steam per lbmol of gas Wideal mn 3. T2 C p ( T ) dT mn T1 Hv mn 15.444 BTU lb rankine BTU lb b) Hsteam Hv Ssteam Ssteam Wideal Hsteam T Ssteam Wideal 205. 140 .756 BTU lbmol rankine Calculate lost work by Eq.969 10 BTU mol lb rankine SdotG mdotndot Ssteam 11. c) Hgas T1 Cp ( T) dT Hgas T Sgas Wideal 9.444 Sgas T1 C p ( T) T dT Sgas Sgas SdotG 9. (5.312 10 3 BTU Wideal lbmol Ans.

9 ( 100 kJ kg M 29 gm mol 273. SdotG = SdotGsteam SdotGgas Calculate entropy generation per lbmol of gas: SdotG ndotgas Ssteam = mdotsteam ndotgas Hv Tsteam T2 Ssteam Sgas 3 Ssteam 6.708 J mol K Ans.835 J mol K SdotG mdotndot Ssteam 49. Calculate lost work by Eq.: T2 ndotgas T1 Cp ( ) T T d T2 mdotsteam Hv = 0 Cp ( ) T T d mdotndot T1 Hv mdotndot 15.15) K T2 ( 150 273.048 10 J kg K Sgas T1 Cp ( ) T dT T Sgas Sgas SdotG 41. This is the sum of the entropy generation of the steam and the gas.000551 T R K Hv Tsteam 2256.15) K Cp ( ) T T ( 25 3.5.15) K a) First apply an energy balance on the boiler to get the ratio of steam flow rate to gas flow rate.135 gm mol Calculate the rate of entropy generation in the boiler.34) Wlost SdotG T Wlost 14.15) K 273.83 0. (5.49 T1 ( 1100 273.8 kJ mol 141 .

135 gm mol Use ratio to calculate ideal work of steam per lbmol of gas Wideal mn 6. 142 .392 10 6 Wideal Ans.392 10 6 0 Sethylene Wlost 33.563 kJ mol Qethylene 3 4.09 kJ mol K R ICPH T1 T2 1. therefore.b) Hsteam Hv Ssteam Hv Tsteam Ssteam 6.618 Calculate lbs of steam generated per lbmol of gas cooled.15)K Sethylene Sethylene Qethylene Qethylene Wlost T R ICPS T1 T2 1. c) Hgas T1 Cp ( T) dT Hgas T Sgas Wideal 21.394 10 0.048 10 kJ kg 3 J kg K Wideal Hsteam T Ssteam Wideal 453.686 kJ mol T 4. This would constitute a reversible process.803 kJ mol Now place a heat engine between the ethylene and the surroundings. 5.424 14. the total entropy generated must be zero.424 14.15)K T2 ( 35 273. calculate the heat released to the surroundings for Stotal = 0. T2 Cp ( T) dT mn T1 Hv mn 15.866 T2 kJ mol Ans.394 10 60.50 T1 a) ( 830 273.15)K 3 ( 25 0 273.

803 kJ mol The lost work is exactly equal to the work that could be produced by the heat engine 143 . QH Qethylene WHE QH QC WHE 33.76 kJ mol Now apply an energy balance around the heat engine to find the work produced. Note that the heat gained by the heat engine is the heat lost by the ethylene.Sethylene QC T = 0 Solving for QC gives: QC T Sethylene QC 26.

assume properties independent of pressure. & 3 2 7 131.78 P1 4000 kPa J gm K 3 P2 2000 kPa molwt gm 58.63) for volume of a saturated liquid may be used for the volume of a compressed liquid if the effect of pressure on liquid volume is neglected.7 mol Eq.Section A . (6.095 10 K 1 S V P2 P1 H 1 T V P2 P1 S 2.7 At constant temperature Eqs.26) can be written: dS = V dP and dH = 1 T V dP For an estimate.Mathcad Solutions 6.551 10 kg 2.8) is integrated to yield: 144 . (3.1 K Zc 0.88 Tr 0.7 J kg Ans.138 132.123 mol Vc cm 262. H 551.8 Isobutane: 408. T 270 K P1 3 3 m 381 kPa P2 1200 kPa 3 V 1.882 0.683 V V c Zc 1 Tr cm mol 3 Assume that changes in T and V are negligible during throtling. 6.282 CP 2.661 J kg K Tc Ans. 359 T 360 K 361 Tr T Tc 0. (6.885 (The elements are denoted by subscripts 1. Then Eq.25) and (6.Chapter 6 .604 V 132. 2.

5).574 kg 3 Vave kg By Eqs.29). We use the additional values of T and V to estimate the volume expansivity: V V3 V1 V 1. U 5.93 kJ kg Ans.H= T S V P but H= 0 Then at 360 K. (3. Work kg 4. 6.84 145 kJ Ans.768 K Ans.733 J mol K Ans.28) & (6.9 T 298.03636 kJ kg K Ans.098835 10 3 K 1 Assuming properties independent of pressure. H Vave 1 T P2 P1 U H P2 V 2 P1 V 1 H 134. S V 1 P2 T1 P1 S 0. (6. (6.079 cm 3 mol T T3 T1 T 2K 1 V1 V T 4.15 K 250 10 6 P1 K 1 1 bar 45 10 6 P2 1500 bar bar 1 V1 cm 1003 kg 3 By Eq.6 kJ kg Ans. .29) may be integrated to give S = CP T T V P P P2 P1 P 2 10 kPa 3 Whence T T1 CP S V1 P molwt T 0. V1 2 V2 V2 Vave V1 exp 970. S Vave P2 P1 Q T S Work U Q S 0. Q 10.287 cm P2 3 P1 V2 cm 937. Eq.91 kJ kg Ans.

(3.48 46. for Parts (a) through (n): 61.8 365.9 562.6.16 300 175 575 500 325 175 575 T 650 300 400 150 575 375 475 K T1 P1 P2 205.63 34.187 .40 89.10 For a constant-volume change.140 Tr T Tc Pr P Pc 146 .90 42.400 .000 .1 304. by Eq.42 10 bar P2 6.210 .4 K Pc 553. T2 T1 5 P2 1 P1 = 0 T1 298.99 45.98 48.96 73.2 132. Pc.65 .9 556.038 . and 40 75 30 50 60 60 35 P 50 35 70 50 15 25 75 bar Tc 308.60 . P.3 373. Tc.6.73 50.15 K 5 1 T2 P1 323.2 10 T2 K 4.2 425.094 .00 24.75 bar Ans.048 .5).39 48.200 .152 .210 .83 34.087 .7 369.6 40.224 .15 K 1 bar 36.3 150.5 126.14 --.2 568.193 bar Vectors containing T.6 282.98 37.

316·103 -5.767 -4.772 0.65b) HRi SRi R Ti Z i qi i qi 1 i 1.08664 0.623·103 J mol -5.362·103 -4.698 -7.52) 1 14 Ii ln Z Z i qi i qi i Eq.605 0.461 -8.68) equations equals -0.659·103 -1.764·103 -2.257 -4.6.122·103 -3.12 -4.53) q Tr z 1 q z z z 1.706 0.39·103 -2.771 0.75 HRi -2.709 0.663 0.542 -5.744 0.3·103 -1.346 -5.766 0.024 -5.5 SRi R ln Z Z i qi 0.068·103 -3.319·103 -4.14 Redlich/Kwong equation: Pr Tr 0.5 Eq.026 -6. (6. (6.503·103 -2.5 qi Ii Eq.488·103 -3. (3. (3.939 -5.648 -5.685 0.729 0.54) Guess: Given Z i z= 1 q Find z () Eq.67) The derivative in these 0.523 J mol K Ans. 147 .775 0. (3.978 -4.302·103 -2.695 0.5 qi Ii Eq.75 0.381·103 -1.115 -3.42748 Eq. (6.

5 2 0.947 -4.816·103 -5.02 -6.751·103 -4.098 -7. (3.480 1.53) q Eq.527·103 -4.42748 Pr Tr c 0.806·103 -1.412 -8.974 -6.741 0.67) SRi R ln Z i qi i ci Tri i qi Ii Eq.769 0.774 0.821·103 -2.15 Soave/Redlich/Kwong equation: 0.768 0.65b) HRi R Ti Z i qi 1 ci 1 qi Ii 0.244·103 -2.585·103 -1.5 Eq.103 J mol K Ans.406·103 -4.787 HRi -2.099·103 -3.68) Z i qi 0.323·103 -3.581 -5.807·103 -1.246 -6.595·103 -2.618 -4.451 -5.6.715 0.691 0.5 i Eq.673 0. (6. (6.606 0.176 2 1 c 1 Tr Eq.774 0.776 0.08664 0.795 -7. (6.52) Z q Find z () The derivative in the following equations equals: ci i 1 14 Ii ln Z Z Tri i i qi i qi 0.776·103 SRi J mol -6. 148 .741 0.482 -6.749 0.722 0.54) Tr Guess: Given z z= 1 1 q z z z Eq.5 Tri i 0.574 0.849 -4.408 -5. (3. (3.857·103 -2.

37464 1.39·103 -3.725 0.572 0.917·103 -2.099 -7.357·103 -2.07779 0.691 0. (3.947·103 J mol -6.665·103 -1.573·103 -4.71 0.6.64 0.716 0.53) q Eq.95·103 -6.846 -4.69 0.754 0.993 -6.748 0.014·103 -1.756 0. (6.54) Tr 1 Given z= 1 q z z z Eq.68) SRi -2.65b) HRi R Ti Z Tri i 0.468·103 -4.752 0. (3.655·103 -2.667 0.804 -7.539 -5.422 -5.861·103 -4.753 R ln Z HRi i qi i ci Tri i qi Ii Eq.5 0.484 -6.016 -6.732 0.5 Find ( z) The derivative in the following equations equals: ci i 1 14 Ii 1 2 i qi Tri i ln 2 1 Z Z ci i qi i qi i i Eq.45724 2 c Pr Tr 0.631 -4.126 J mol K Ans. (3.16 Peng/Robinson equation: 1 2 1 2 0.872 -4.5 1 qi Ii 0. 149 .26992 2 1 Guess: c 1 z Tr Eq.146·103 -3. (6.985·103 -2.67) SRi Z i qi 0.54226 0.41 -8.896·103 -1.52) Z q 0.5 Eq.256 -6.452 -5. (6.

962 1.744 Z0 .319 .001 .Lee/Kesler Correlation --.686 .034 .875 1.742 .102 .651 .590 .604 .200 .550 .699 .165 .118 .709 .12: h0 equals ( ) HR RTc ( ) SR R 0 0 h1 equals ( ) HR RTc ( ) SR R 1 1 h equals HR RTc SR R s0 equals s1 equals s equals .770 .019 .635 .154 h0 .003 .032 .471 .211 Z Z0 Z1 Eq.008 .746 Z1 .767 .444 .466 .144 .598 .770 .85) HR ( Tc R) h 150 .631 .723 .024 .774 .751 .950 1.705 .701 1.591 .705 1.007 .437 .184 .776 .093 .57) h h0 h1 (6.155 .1--E.216 h1 1.675 . (3.265 .By linear interpolation in Tables E.725 .405 .993 1.

667 -5. (6.612·103 -2.918 -0.138 -1.699 0.656 0.727 -7.793 -1. 151 .961 .293 -0.207 -4..587 .492 .92·103 -2.786·103 s s0 s1 SR ( s R) Eq.091 -7.768 hi -1.975 -0.750 .407·103 -5.711 1.727 0.554·103 -4.509 .345 -6.752 0.818 -0.639 -0.438·103 -3.843 -0.769 0.829 -1.771 0.891 -1.135 -1.429 .759 -6.77 0.405 -9.916·103 -2.441 .701 0.549 .612 -0.11 -0.274 -1.809 -0.443 .709 -0.917 .314 -7.723 -0.110 .121·103 -5.590 .892·103 -1.144·103 -3.013 -6.497 .952·103 -1.753 0.700 .674 .517 .669 0.054 J mol K Ans.794 -6.511 .481 -0.629 -6.871·103 -1.728 -2.555 .86) Zi 0.229 -5.005 -4.406 -1.246 si SRi J mol -7.491 .763 -0.743 0.931 -1.563 .829 .276 s1 .72 0.933 -0.688 .875·103 -4.561 -0.589 .287 HRi -0.631 .971·103 -2.747 -0.577 -0.107 -1.59 0.710 s0 .

271 Vc 259 cm 3 mol Tr T Tc Tr 0.2 B1 3 4 cm 1.14 J mol K Ans. .422 Tr 1.2 K Pc 48.15 K The pressure is the vapor pressure given by the Antoine equation: T 323.6.72).72) for the latent heat and divide by T to get the entropy change of vaporization: S dPdt Vvap Vliq S 100.34 J mol K Ans.375 t dPdt 1. Vliq V c Zc Vliq 93. we need the volume change of vaporization.007 By Eqs.66).61).139 0.575 Pr P Pc Pr 0.941 B1 0.98 bar Zc 0.306 10 mol cm 3 By Eq.63) and the vapor volume by the generalized virial correlation.63) B0 0.6 B0 0. (3. (3. (3. (b) Here for the entropy change of vaporization: S RT dPdt P 152 S 102. (3.172 Tr 4. For this we estimate the liquid volume by Eq.210 Tc 562.17 t 50 273.166 kPa P ( ) 36.151 mol Solve Eq. & (3.51 t 220.15 K t T P () t d dt exp 13.79 P 36. For benzene: 0. For the Clapeyron equation.65).69). Eq. (6.166 50 P () 1.8858 2788.375 kPa K (a) The entropy change of vaporization is equal to the latent heat divided by the temperature.621 Vvap RT P 1 B0 B1 Pr Tr 1 Tr 2/7 Vvap 7. (3. (6.083 0.

The entropy change for the two steps is: T2 273. because it does not occur at the equilibrium temperature of 0 degC. and may for calculational purposes be considered to occur in two steps: (1) Heating of the water from -6 degC to the final equilibrium temperature of 0 degC.076 Ans.4 BTU lbm S1 1.67)rankine P1 20 psi P2 50 psi T1 382. 6.034709 10 J Ans.20 The process may be assumed to occur adiabatically and at constant pressure.6. (4.226 J gm K t 6K Hfusion 333.266 BTU Ans.3 BTU lbm H2 1533. Enthalpy changes for these two steps sum to zero: CP t x Hfusion = 0 CP 4.017 K T2 810. gm K The freezing process itself is irreversible.15 6) K 3 S CP ln T2 T1 S 1. Table F.7320 BTU S2 lbm rankine 1.4 joule gm x CP t Hfusion x 0. lbm rankine For steam as an ideal gas.21 Data. It is therefore isenthalpic.928 K 153 .4: H1 1156.1 BTU lbm S 0.9977 BTU lbm rankine H H2 H1 S S2 S1 H 377.67)rankine T2 ( 1000 459.9) and (5.15 K T1 x Hfusion T2 ( 273. [t in degF] T1 ( 227.96 459. (2) Freezing of a fraction x of the water at the equilibrium T. apply Eqs.18).

154 .121 10 T2 T1 R MCPS T1 T2 3.5 kJ 192.2076 J gm K J gm K Vvap cm 23.450 10 molwt 372.191 kg mliq Hliq mliq Sliq mvap mvap 3.15 10 3 cm 2 Vvap 6 5.7471 mliq mliq Htotal Stotal 0. 6.0 0. 0.molwt 18 lb lbmol 3 5 H H R MCPH T1 T2 3.0 0.15 10 3 cm 2 Vliq 54.384 gm 3 Hliq 3 1317.470 1. Table F.22 Data.1 J gm J gm Sliq 3.145 kJ K Ans. Ans.2 at 8000 kPa: Vliq cm 1.259 Ans.525 gm 6 Hvap 2759.9 Svap 0.536 BTU lbm Ans.470 1.121 10 5 ln T2 T1 ln P2 P1 molwt S 0.450 10 S BTU lbm rankine 3 0.188 kg Htotal Stotal mvap Hvap mvap Svap 80173.

605 J gm Sliq 2.76 BTU lbm Hvap 1192. Table F.5 (Guess) Given x Vvap ( 1 x)Vliq = 70 30 x Find x () x 0.364 lb mvap 3 lbm mliq mvap 0.24 Data.013 H ( 1 x)Hliq x Hvap S S ( 1 x)Sliq J gm K x Svap Ans.3 BTU lbm mliq mvap = 3 lbm mvap Vvap = 50 mliq Vliq mliq 50 mliq Vliq = 3 lbm Vvap mliq 1 3 lbm 50 Vliq Vvap mliq 2.636 lb Htotal mliq Hliq mvap Hvap Htotal 1519. H 789.29 cm gm Hvap 2776.1382 J gm K Vvap 194.01799 lbm 3 Vvap ft 3.1 BTU Ans.342 lbm 3 Hliq 321.495 J gm 2.2 at 1000 kPa: Vliq 1.198 6.23 Data.6.3 at 350 degF: Vliq ft 0.127 cm 3 gm Hliq 3 762.2 J gm Svap 6.5828 J gm K Let x = fraction of mass that is vapor (quality) x 0. 155 . Table F.

3 J gm Sliq 2.552 H 1991 J gm S 4. 156 . 6.0 J gm Svap 6. 30 degC: Vliq cm 1. 150 degC: Vtotal 0.543 10 3 kg mliq mtotal mvap Vtot.1.025 gm 3 Data.25 V 1 cm 0.004 gm Vlv cm 32930 gm 3 mtotal Vtotal Vvap mvap Vtotal mtotal Vliq Vlv mtotal 0.4 gm 3 Table F.209 cm gm Hliq 3 990.1 at 230 degC: 3 Vliq 1.23 cm 3 Ans.6102 J gm K Vvap 71.1.2107 J gm K V= ( 1 x)Vliq x Vvap x V Vvap Vliq Vliq H ( 1 x)Hliq x Hvap S ( 1 x)Sliq x Svap x 0.382 kg mvap 4.45 cm gm Hvap 2802.72 gm Vtot.liq mliq Vliq mliq 377.15 m 3 Vvap 3 cm 392.6.26 Vtotal = mtotal Vliq mvap Vlv Table F.599 J gm K Ans.liq 379. Table F.

6. by interpolation: H1 2923.268 J gm K Ans.2 at 2100 kPa and 260 degC. For steam as an ideal gas.8316 J gm K S S2 S1 S 1.7 BTU lbm S1 1.29 BTU lbm rankine .302 J gm K Ans.87 degF and S2 1.80 degC and S2 7.5703 BTU lbm rankine H2 1257. the final temperature is 438.1 J gm J gm Const.27 Table F.-H throttling: H2 = Hliq x Hvap Hliq x H2 Hvap Hliq Hliq x 0.7 Interpolate @101.8606 BTU lbm rankine S 157 S2 S1 S 0.5 gm Final state is at this enthalpy and a pressure of 125 kPa.953 Ans. 1100 kPa: Hliq 781.7 BTU lbm Final state is at this enthalpy and a pressure of 20(psia).28 Data. Table F.325 kPa & 105 degC: H2 2686.5 J gm J S1 6. By interpolation at these conditions. the final temperature is 224. By interpolation at these conditions.4 at 300(psia) and 500 degF: H1 1257.29 Data. there would be no temperature change and the entropy change would be given by: P1 2100 kPa P2 125 kPa S P2 R ln P1 molwt S 1. 6. 6.2.5640 J gm K molwt 18.124 J gm Hvap 2779.015 gm mol H2 2923. Table F.

Table F.34 kPa xwater Psat P xwater 0. 158 . for which Sliq 1.For steam as an ideal gas.9 J gm S2 = S1 = Sliq x Svap Sliq x S1 Svap Sliq Sliq J gm x 0.4614 J gm K The final state is at this entropy and a pressure of 50 kPa.166 kPa P 101. 6.98 H2 Hliq x Hvap Hliq H2 2599.031 Ans.122 Ans. This is a state of wet steam.1: At 25 degC: Psat 3. molwt 6.6 Ans.299 BTU lbm rankine Ans. At 50 degC: Psat 12.31 Vapor pressures of water from Table F.30 Data.5947 J gm K Hliq 340.33 kPa xwater Psat P xwater 0.564 J gm Hvap 2646. there would be no temperature change and the entropy change would be given by: P1 300 psi P2 20 psi molwt 18 lb lbmol R ln S P2 P1 S 0.0912 J gm K Svap 7.2 at 500 kPa and 300 degC S1 7.

66 gm 3 U1 2592.75 for wet steam 159 . 25% condenses making the quality 0.4 J gm mass Vtotal V1 Of this total mass.1 at 100 degC: Uliq 419.8 J gm Ans. Table F.7 J gm U1 Uliq x Uvap Uliq U1 419.044 cm 3 3 gm Vvap 1673.014 0.33 Vtotal 0.75 V2 = V1 = Vliq x Vvap Vliq Whence x= V1 Vvap Vliq Vliq (A) Find P for which (A) yields the value x = 0.6.83 degC V2 Vtotal mass V2 cm 1.158 10 (initial quality) This state is first reached as saturated liquid at 349.739 gm 3 For this state. we have for the final state: x 0. Table F. and U2 Q 1641.32 Process occurs at constant total volume: Vtotal ( 0.25 m Data. vapor at 1500 kPa: V1 cm 131.021 m Vliq mvap 0. 6.1 kPa.0 J gm Uvap 3 2506.5 J gm Vliq 1.0 cm 3 gm mliq 0.868 J gm U2 U1 3 Q 1221.75 Since the total volume and mass don't change. sat. P = 16.2.021)m 3 Data.014 m Vvap 4 mass mliq mvap x mvap mass x 4.500.

160 .326 cu cm/gm. we find t = 213.326 gm J gm x 0. By interpolation in Table F.5 kPa and Uliq 782. 6.0 gm 0. The final state is therefore the state for which the specific volume of saturated vapor is 98.4 J gm Q mtotal U2 U1 Q 41860.5 gm mliq mvap cm 3 mliq x V1 U1 x Vvap x Uvap Vliq Uliq V1 U1 98.9 J gm U2 Uliq x Uvap Uliq U2 2134.959 gm 1.2.547 cm 3 gm This value occurs at a pressure a bit above 1100 kPa. Evaluate x at 1100 and 1150 kPa by (A).058 540. Interpolate on x to find P = 1114.5 kJ Ans.325 kPa: Vliq cm 1.044 gm 3 Vvap cm 1673.Since the liquid volume is much smaller than the vapor volume.9 kJ Ans.0 degC and U2 2598.3 J gm Q mass U2 U1 Q 869. the initial and final specific volumes are the same.101.02 m Vliq mvap mtotal 3 3 Uliq mvap J 418.1.421 Since the total volume and the total mass do not change during the process.34 Table F.98 m Vvap Vliq Uliq 3 Uvap mtotal J 2506.41 J gm Uvap 2584. we make a preliminary calculation to estimate: Vvap V1 x Vvap 175.

6.367 10 gm W mass U2 U1 W 262.2234 J gm K Uliq 444.15 kJ Ans.6439 J gm K Ans.9 J gm S1 6.6.8148 J gm K mass 1 kg (a) Isothermal expansion to 150 kPa and 200 degC U2 Q 2656. T 473.2 at 800 kPa and 200 degC: U1 2629.4336 J gm K Svap 7. Table F.929 3 J U2 Uliq x Uvap Uliq U2 2. The final state is wet steam: Sliq 1.89 kJ (b) Constant-entropy expansion to 150 kPa.527 kJ Ans. By interpolation. 161 .36 Data.224 J gm Uvap 2513.15 K mass T S2 392. Table F.2 at 800 kPa and 350 degC: V1 354.4 kPa and U2 2638.4 m 3 The final state at 200 degC has the same specific volume as the initial state.29 kJ Also: Work mass U2 U1 Q Work 365.35 Data.7 J gm Q Vtotal V1 U2 U1 Q 271.9 J gm Vtotal 0.3 J gm S1 S2 Q 7.4 J gm x S1 Svap Sliq Sliq x 0.34 cm 3 gm U1 2878. we find P = 596. and this occurs for superheated steam at a pressure between 575 and 600 kPa.

8943 J gm K Uliq 604.9 U1 Uliq x1 Uvap Uliq U1 2.7764 J gm K Svap 6.439 10 gm S1 Sliq x1 Svap Sliq S1 5.5924 J gm K Svap 6. 400 kPa: Sliq 1.37 Data.861 2 3 m 10 2 s K Table F.2 J gm Hliq 908. by interpolation: H2 3633.4 J gm Q mass H2 H1 Q 949.7 J gm Vliq cm 1. 2700 kPa: Uliq 977. 6.2244 J gm K 3 J x1 0.52 kJ Ans. Table F.2.6.22 cm 3 gm 162 .2 at 2000 kPa: x 0.38 First step: Q12 = 0 W12 = U2 U1 Second step: For process: W23 = 0 Q = U3 U2 Q23 = U3 W = U2 U2 U1 Table F.684 10 3 J gm mass 1 kg For superheated vapor at 2000 kPa and 575 degC.8 J gm Sliq 2.084 gm Vvap 462.237 J gm 3 Uvap 2552.94 Hvap 2797.2.589 J gm H1 Hliq x Hvap Hliq H1 2.968 J gm Uvap 2601.

2003 J gm K 163 .317 J gm Ans.6 J gm S1 7.0548 J gm K U2 2578.0854 J gm K Table F.6221 J gm K mass 4 kg T ( 175 273.2. 3000 kPa and 450 degC: H1 3344.8 J gm J gm S1 7. 6.5 J gm S2 7.40 (a)Table F. W 667. Interpolate to find that this V occurs at T = 509.15)K Q mass T S2 S1 W mass U2 U1 Q Q 775.23 degC and U3 2560.sat. interpolate 235 kPa and 140 degC: H2 2744.8 S2 6. 6.7 J gm Whence Q U3 U2 Work U2 U1 Q 401.39 Table F. S2 = S1 = Sliq x2 Svap Sliq x2 S1 Svap Sliq Sliq 3 J x2 0. vapor.798 U2 Uliq x2 Uvap Uliq U2 2.159 10 gm 3 V2 Vliq x2 Vvap Vliq V2 369. Work 280.1.66 kJ Ans. vapor with this specific volume.66 kJ Ans.034 J gm Ans.2.2. 400 kPa & 175 degC: Table F.135 cm gm V3 = V2 and the final state is sat.Since step 1 is isentropic. 175 degC U1 2605.

0605 0.1 K J gm Pc 220.15)K T2 ( 140 273. S S2 S1 S 0. (6.63846 Pr2 0.55 bar Sig 0.01066 The generalized virial-coefficient correlation is suitable here H H HRB Tr1 Pr1 R Tc HRB Tr2 Pr2 molwt J Ans.96) for an ideal gas: Hig gm mol 3 5 R ICPH T1 T2 3. (b) T1 ( 450 273.H H2 H1 H 600.115 J gm K Ans.15 K T2 413.0 0.95 gm Hig S Sig R SRB Tr2 Pr2 SRB Tr1 Pr1 molwt S 0.450 10 0.078 J gm K Ans.0 0.1 J gm Ans.11752 Pr1 0.95) & (6.345 J gm K Ans.121 10 5 ln P2 P1 620.121 10 molwt 18 molwt R ICPS T1 T2 3. Tr1 T1 Tc Pr1 P1 Pc Tr2 T2 Tc Pr2 P2 Pc Tr1 1. 164 . 593.15 K P1 3000 kPa P2 235 kPa Eqs.470 1.15)K T1 723.13602 Tr2 0.450 10 Sig Hig (c) Tc molwt 3 0.6 647.470 1.

67) rankine H1 1202.1675 Ans.9 BTU lbm T1 877.6 J gm S1 7. and U2 2963. the internal energy change = 0.6 BTU lbm S2 1.1 J gm S2 7. interpolation gives t = 401. Q12 322. T 473.5 J gm Q23 = 0 S3 = S 2 S3 7.2 superheated steam at 550 kPa and 200 degC: V1 385. 6.5782 J gm K Q12 U2 U1 Step 2--3: Isentropic expansion to initial T.74 degC.5782 J gm K Step 3--1: Constant-T compression to initial P.4. Wcycle = Qcycle = Q12 Q31 = Wcycle Q12 1 Q31 Q12 0.41 Data.02 rankine S1 1.027 BTU lbm 165 . sat.15 K Q31 T S1 S3 Q31 268. 300(psi): T1 ( 417.35 459.vapor.0108 J gm K Step 1--2: Const.-V heating to 800 kPa.42 Table F.7591 BTU lbm rankine S3 S2 Q12 H2 H1 Q31 T 1 S1 S3 Q31 218.5105 BTU lbm rankine Superheated steam at 300(psi) & 900 degF H2 1473.19 cm 3 gm U1 2640. At the initial specific volume and this P.465 J gm For the cycle. Table F.6.

2 at the final conditions of saturated vapor at 50 kPa: S2 7.0 kJ kg S1 S2 Find the temperature of superheated vapor at 2000 kPa with this entropy. Table F. Wcycle = Qcycle = Q12 Q31 = Wcycle Q12 Whence 1 Q31 Q12 0.0520 J gm K S2 Sliq x Svap Sliq S2 6. 6. superheated steam at 4000 kPa and 400 degC: S1 6.For the cycle. P2 = 572.95 S2 = Sliq x Svap Sliq So we must find the presure for which this equation is satisfied. 6.16 kPa Ans.6071 J gm K Svap 7.7733 By interpolation P2 = 250.7733 J gm K For both parts of the problem: S2 S1 (a)So we are looking for the pressure at which saturated vapor has the given entropy. This occurs at a pressure just above 250 kPa.2.5947 kJ kg K H2 2646. This occurs at a pressure just below 575 kPa.83 kPa Ans.7798 J gm K Slightly > 6.43 Data. By interpolation. the internal energy change = 0. At 250 kPa: Sliq 1. By interpolation 166 . (b)For the wet vapor the entropy is given by x 0. It occurs between 550 and 600 degC.44 (a) Table F.1946 Ans.

4 kJ kg S1 7.1511 kJ kg K Hliq 191.t1 559.294 10 3 kJ H2 H1 kg H' H1 0. the final entropy would be S2 S1 Table F.16 212.2 for superheated vapor at the initial conditions.2 for sat. 1300 kPa and 400 degC. the final entropy would be S2 S1 Table F. liquid and vapor at 10 kPa: Sliq 0. 6.46 Table F.2 for sat.8 kJ kg x2 S2 Svap Sliq Sliq x2 0.8 kJ kg If the turbine were to operate isentropically.3404 kJ kg K H2 2683. 1350 kPa and 375 degC. and for the final condition of 40 kPa and 100 degC: H1 3259. liquid and vapor at 40 kPa: 167 . vapor at 10 kPa: H1 3205.2 for superheated vapor at the initial conditions. and for the final condition of sat. 6.0 kJ kg Superheat: t ( 559. (b) mdot 5 kg sec Wdot mdot H2 H1 4760 kW Ans.832 kJ kg Hvap 2584.7 kJ kg S1 7.879 H' Hliq x2 Hvap Hliq H' 2.37)K t 346.16 (degC) H1 3598.8 kJ kg If the turbine were to operate isentropically.681 Ans.6493 kJ kg K Svap 8.79 K Wdot Ans.45 Table F.2410 kJ kg K H2 2584.

377 168 .2 B1 0.6 B0 0. but the entropy DOES depend on P: HR H Hig cm 3 Sig R molwt 72.4 J gm ln P P0 SR S Sig Sig VR 10. 1 kPa and 225 degC) Hig 2928. 6.78 Ans.522 10 3 kJ kg H' H1 0.083 0.6709 kJ kg K Hliq 317.55 bar Tr T Tc Tr 0.7 J gm Sig 10.558 B1 0.0681 J gm K P0 VR 1 kPa T R molwt P T ( 225 273.15)K T 498.2 at 1600 kPa and 225 degC: P 1600 kPa V cm 132.2 (ideal-gas values.96 gm HR SR 0.422 Tr 1.47 Table F.85 gm 3 H 2856.95 H' Hliq x2 Hvap Hliq H2 H1 H' 2. gm K Reduced conditions: 0.Sliq 1.1 K Pc 220.0261 kJ kg K Svap 7.9 kJ kg x2 S2 Svap Sliq Sliq x2 0.16 kJ kg Hvap 2636.345 Tc 647.11 J Ans.139 0.072546 The generalized virial-coefficient correlation is suitable here B0 0.5503 J gm K Table F.15 K V The enthalpy of an ideal gas is independent of pressure.3 J gm S 6.172 Tr 4.76982 Pr P Pc Pr 0.

163 gm Hlv 2.5828 Slv Sv Sl Vlv cm 193.By Eqs.2) molwt 3 18.4 J gm SR 0.2 at 1 kPa: 169 .015 gm mol 3 Vl cm 1.06 J gm Gv Hv T Sv G v 206.445 J gm K (c) VR Vv T R molwt P VR cm 14. (3.2 J gm J gm K Hv Hl 2.61) + (3.88 degC and 1 kPa is an ideal gas.03 K (Table F.15) K T 453.605 J gm Hv Sv 2776.1382 J gm K 3 6. (6. assume that steam at 179.077 J gm K Ans.935 VR RT ( Z 1) P molwt HR R Tc molwt HRB Tr Pr 3 SR R molwt SRB Tr Pr VR 9.88 273.40) Z 1 B0 B1 Pr Tr Z 0.445 J gm K (a) Gl Hl T Sl G l 206. 6.48 P 1000 kPa T ( 179.62) & (3. By interpolation in Table F.01 J gm (b) Slv 4. For enthalpy and entropy.127 gm Vv cm 194.785 gm Ans.014 10 3 J gm Slv 4.29 gm Vlv Hlv Vv Vl Hl Sl 762.445 J gm K r Hlv T r 3 4.33 cm gm HR 53.63) along with Eq.

345 Tc 647.984 kPa K Slv Vlv dPdT Slv 4.172 Tr 4.1 K Pc 220. 1/T linear and fit three data pts @ 975.79 t 179.15 P T 2 ln ppi kPa Slope slope ( y) Slope x 4717 Slope K dPdT 22.083 0.Hig 2841. & 1050 kPa.63) along with Eq.61) + (3.188 J gm K Ans.55 bar Tr T Tc Tr 0. (6.40) Z 1 B0 B1 Pr Tr Z 0.62) & (3. SR 0. the entropy DOES depend on P: HR SR Hv Sv Hig Sig Sig Sig HR P R ln P0 molwt 64.2 B1 0. Reduced conditions: 0. 975 Data: 178.6 B0 0.1 J gm Sig 9.88 182.02 (degC) pp 1000 kPa 1050 i 1 3 xi dPdT ti 1 yi 273.9 J gm Sig 3. (3.63 By Eqs.664 B1 0. 1000.44 J gm K Ans.8834 J gm K P0 1 kPa The enthalpy of an ideal gas is independent of pressure.1126 J gm K Ans.0453 The generalized virial-coefficient correlation is suitable here B0 0.422 Tr 1. (d) Assume ln P vs.139 0.7001 Pr P Pc Pr 0.943 VR RT ( 1) Z P molwt 170 .

014 lbm 3 Vlv Vv Vl Hl 330.1492 171 BTU lbm rankine P0 1 psi .6 BTU lbm Sig 2.93 cm 3 gm HR 43.4 at 1 psi: Hig 1222. By interpolation in Table F.91 BTU lbm (b) Slv 1.HR R Tc molwt HRB Tr Pr SR R SRB Tr Pr molwt VR 11.5141 BTU lbm rankine 3 Sv 1.996 lbm Hlv 863.4) molwt 3 18.65 BTU lbm Hv 1194.055 BTU lbm rankine r Hlv T r 1.0181 lbm Vv ft 3.1 rankine P 150 psi (Table F. assume that steam at 358.015 gm mol Vl ft 0.45 BTU lbm (a) Gl Hl T Sl Gv Hv T Sv Gl 89. 6.67) rankine T 818.1 BTU lbm Hlv Slv Hv Hl Sl 0.49 T ( 358.069 J gm K Ans.5695 BTU lbm rankine Sv Sl Vlv ft 2. For enthalpy and entropy.43 459.43 degF and 1 psi is an ideal gas.18 J gm SR 0.94 BTU lbm Gv 89.055 BTU lbm rankine (c) VR Vv T R molwt P VR 0.235 ft 3 lbm Ans.

62 172 .345 Tc 647. (d) Assume ln P vs.7024 Pr P Pc Pr 0.The enthalpy of an ideal gas is independent of pressure.1 K Pc 220.083 0. 1/T linear and fit threedata points (@ 145.422 Tr 1.66 B1 0.6 B0 0.172 Tr 4.501 10 3 dPdT P T 2 Slope rankine dPdT 1.43 361. & 155 psia) 145 Data: 355.55 bar Tr T Tc Tr 0. the entropy DOES depend on P: HR Hv Hig HR Sig 28.67 yi ln ppi psi Slope Slope slope ( y) x 8.056 BTU Ans.77 t 358.0274 BTU lbm rankine Ans. Sig P R ln P0 molwt Sv Sig Sig 0.0469 The generalized virial-coefficient correlation is suitable here B0 0.2 B1 0.905 psi rankine Slv Vlv dPdT Slv 1.552 BTU lbm rankine SR SR 0.02 (degF) pp 150 psi 155 i 1 3 xi ti 1 459. lbm rankine Reduced conditions: 0.5 BTU lbm Ans.139 0. 150.

48 bar 0.785 10 173 8.61) + (3.1636 Z 3 Z0 Z1 Z 0.674 10 3 J mol HR1 1.2 mol Ans.824 10 0.496 R Tc HR1 0.717 R SR0 12.0168 BTU lbm rankine Ans.942 VR RT P molwt (Z 1) HR R Tc molwt HRB Tr Pr 3 SR R SRB Tr Pr molwt VR 0.463 R SR1 0. HR0 2.178 1 bar Tr T Tc Tr 1.15 K P 135 bar P0 Pr 3.40) Z 1 B0 B1 Pr Tr Z 0.6141 Z1 0.152 T ( 195 273. Z0 0. by interpolation.62) & (3. 6.961 J mol K HR HR0 HR1 3 J SR SR0 SR1 HR 7.639 V ZRT P V cm 184.0 HR .213 28.By Eqs.15K T 1.802 10 3 J mol SR0 1.50 For propane: Tc 369. (3.1894 ft lbm HR 19.069 J mol K 6 H R ICPH 308.266 Pr P Pc Use the Lee/Kesler correlation.024 BTU lbm SR 0.586 R Tc HR0 7. (6.163 J mol K SR1 5.15) K T 468.948 10 mol SR 3 13.63) along with Eq.8 K Pc 42.

0 ln P P0 SR H 6734.48 bar 0.9 Ans. 6.38551 Given () T 1 T Tc 1.92793 Pr P Pc Pr 0.5 Guess: 3 T 6 200 K P = Pc exp T A () B T () T C () T () T D () T 1 T Find T) ( 230.35311 Assume propane an ideal gas at the initial conditions. 6.213 28. it must exist at its saturation temperature at 1 bar.276 Pc 42.15 K P0 101.287 Ans. S R SRB Tr Pr ln P P0 S 25.9 Ans.33 kPa P 1500 kPa Tr T Tc Tr 0. This temperature is found from the vapor pressure equation: 3 P 1 bar A 6.S R ICPS 308.785 10 J mol 3 8.8 K mol If the final state is a two-phase mixture. Use generalized virial correlation at final conditions.824 10 J mol K 6 0.13868 D 1.52 For propane: 0.33236 C 2.0 Zc 0. S 15.15)K T 343.15K T 1.152 T ( 70 273.48 bar Tc 369.703 K 174 . H R Tc HRB Tr Pr H 1431.152 cm Vc 200.51 For propane: Tc 369.3 J mol J mol K Ans.72219 B 1.8 K Pc 42.

(2) Carry out the temperature and pressure changes to the final T & P in the ideal-gas state. It is found by the Clapeyron equation. The sum of the enthalpy changes for these steps is set equal to zero. We proceed exactly as in Pb.624 B0 0.546 cm 3 mol 10 4 J Hlv T Vvap 1.The latent heat of vaporization at the final conditions will be needed for an energy balance.109 Vvap RT P 1 B0 3 4 cm B1 Pr Tr Vliq V c Zc 1 Tr Vvap 1. (3) Transform the ideal gas into a real gas at the final T & P.024 Tr Tr 0.847 10 mol Vliq dPdT Vliq Hlv 75.172 Tr 4. P ( T) Pc exp 230. (4) Partially condense the gas at the final T & P.083 0. 6.703 K A ( T) B ( T) 1.422 Tr 1.879 mol ENERGY BALANCE: For the throttling process there is no enthalpy change.815 B1 0. and let r0 = H R 0 R Tc and 175 r1 = H R 1 R Tc .5 C ( T) kPa K ( T) 3 D ( T) 6 1 d P ( T) dT Pr P Pc B0 T 4.139 B1 2 7 1.7 & E.17. The calculational path from the initial state to the final is made up of the following steps: (1) Transform the initial gas into an ideal gas at the initial T & P.6 0.2 4.428124 kPa K P 1 bar Pr 0.8. use the generalized correlation of Tables E.428 dPdT T Tc 0. For Step (1). and the resulting equation is solved for the fraction of the stream that is liquid.

33 kPa Tr T Tc Tr 0.001 Pr P1 Pc Pr 4. find: r0 3.708 By interpolation.7 K T 380 K P 1919.95). (6.4 mol 3 Tn 268.85) H1 R Tc r0 r1 H1 1. for which H2 R ICPH T1 T 1.87).213 28.77 bar Zc 0.2 K Pc 42.048 10 4 J mol For Step (3) the enthalpy change is given by Eq.703 K Tc Tr 0.T1 370 K P1 200 bar Tr T1 Tc Tr 1.568 By Eq. (6.729 J mol For Step (4).6239 Pr 1 bar Pc Pr 0.0235 H3 H3 R Tc HRB Tr Pr 232.773 r1 3.824 10 6 0.4 kPa T0 273.327 10 4 J mol For Step (2) the enthalpy change is given by Eq.894 Pr P Pc Pr 0.15 K P0 101.785 10 3 8.3-butadiene: 0.267 Vc cm 220.53 For 1. 6.136 Ans.449 176 . for which Tr 230.190 Tc 425. H1 H2 H3 x Hlv = 0 x H1 H2 Hlv H3 x 0.0 H2 1. (6. H4 = x Hlv For the process.

882 10 0. Z 0. 177 .888 R 7. Svap 1. There may be some choice in how this is done. For saturated vapor.12) 2 Vliq V c Zc 1 Tr 7 Vliq cm 109.718 1182. EXTRAPOLATIONS must be made from the vapor side. the values for a saturated vapor lie on the very edge of the vapor region. but the following values are as good as any: Z0 Vvap HR0 HR0 0.9 J mol 8.7442 ZRT P 0.892 R Tc 3.035 SR1 SR1 SR SR 0. Rather. by Eqs.Use Lee/Kesler correlation.1366 Vvap HR1 HR1 Z Z0 cm 3 Z1 Ans.383 SR0 5.540 R 4.734 26. HOWEVER.624 J mol K Ans. These must NOT be used for interpolation.882 10 6 6 R ICPH T0 T 2.63) & (4.0 ln P P0 SR Ans.49 HR0 3.689 R Tc 2.2 mol 0.0 HR Svap R ICPS T0 T 2. (3.153 10 3 J 3 J mol mol SR0 SR0 HR HR Hvap 0. and some adjacent numbers are for the liquid phase.786 10 3 0.89 mol 3 Ans.436 10 Z1 0.786 10 Hvap 6315.892 3 J mol K HR1 10 3 J J mol K SR1 mol J mol K 8.734 26.

38 H 14003 J mol Hliq Hvap H Hliq 7687.7692 Z1 0. Rather.831 R Tc HR0 2. and some adjacent numbers are for the liquid phase.145 10 3 J mol 178 HR1 2. (4. HR0 0.607 R Tc HR1 0.274 1435 kPa Vc T0 cm 255 mol 3 Tn P0 272.7 K 101.1 mol Ans.1.15 K Tr 0. but the following values are as good as any: Z0 0.96 bar Zc P 0. the values for a saturated vapor lie on the very edge of the vapor region.54 For n-butane: 0.200 Tc 425.4 J mol Ans.937 10 3 J mol .13) H Hn 1 1 Tr Tn Tc 0.475 J mol K Ans.930 J mol By Eq. There may be some choice in how this is done.1372 Z Z0 Z1 3 Z 0.87 Pr P Pc Pr 0. These must NOT be used for interpolation. Sliq Svap H T Sliq 38.742 V ZRT P V cm 1590. 6. HOWEVER.1 K Pc 37.33 kPa T Tr 370 K T Tc 273.092 ln Hn R Tn Pc bar Tn Tc 1.013 Hn 22449 0.378 Use Lee/Kesler correlation. EXTRAPOLATIONS must be made from the vapor side.

0 HR Svap R ICPS T0 T 1.SR0 SR0 HR HR Hvap 0.421 mol K HR1 10 3 J J mol K SR1 mol J mol K 6 R ICPH T0 T 1.0 ln P P0 SR Hvap 7427.402 10 0.942 SR0 5. (4.402 10 6 0.485 R 4. 179 .092 ln Hn R Tn Pc bar Tn Tc 1.13) H Hn 1 1 Tr Tn Tc 0.930 J mol By Eq.86 mol 3 Ans. Svap 4.915 10 J mol 11.197 J mol K Ans.141 Ans. 1.8 J mol J mol K Ans.2 J mol Hliq Sliq Hvap Svap H H T Hliq Sliq 7867. (3.733 SR1 J SR1 SR SR 3 0.72) & (4.915 10 3 11.032 HR0 2.935 36.12) 1 Tr 2/7 Vliq V c Zc Vliq cm 123.4 Ans. by Eqs.835 R 6. 37.38 H 15295.013 Hn 22514 0.935 36. For saturated vapor.

and for this process of steam addition to a tank the equation developed in Problem 6-74 is applicable: m1 Hprime m2 = Hprime Hf2 Vf2 H1 Vtank P2 P1 Hfg2 Vfg2 Hfg2 Vfg2 We can replace Vtank by m2V2. 000 tm e i 4. and rearrange to get m2 m1 Hprime Hf2 Vf2 Hfg2 Vfg2 V 2 P2 P1 Hfg2 Vfg2 m2 m1 = Hprime H1 Eq.55 Under the stated conditions the worst possible cycling of demand can be represented as follows: 10. (A) However M1 v1 = m2 V2 = Vtank and therefore = V1 V2 180 .3 kg We consider this storage leg. kg/ 000 hr netst age or ofst eam netdepl i eton ofst eam This situation is also represented by the equation: 4000 where 10000 1 = 6000 = time of storage liquid 2 Solution gives hr 3 The steam stored during this leg is: mprime mprime 6000 kg hr 4000 kg hr 1333. kg/ 000 hr Dem and ( hr kg/ ) 2/ hr 3 1/ hr 3 1 hr 6.6.

95V2 = 1 therefore x2 Vf2 19 = 1 0. (C) Now we need property values: Initial state in accumulator is wet steam at 700 kPa.Making this substitution and rearranging we get Hprime Hf2 Vf2 Hfg2 Vfg2 V2 P2 P1 Hfg2 Vfg2 = Hprime V1 H1 In this equation we can determine from the given information everything except Hprime and Vprime. These quantities are expressed by H1 = Hf1 x1 Hfg1 and V1 = Vf1 x1 Vfg1 Therefore our equation becomes (with Hprime = Hg2) Hg2 Hf2 V2 Vf2 Hfg2 Vfg2 P2 P1 Hfg2 Vfg2 = Hg2 Hf1 Vf1 x1 Hfg1 Eq.061 kJ Hg1 kg 2762.05 Vf2 19Vg2 Vf2 = 20 19 Vf2 1 Vg2 Eq. First we need V2: From the given information we can write: 0.05V2 = x2 Vg2 or x2 = Vf2 19Vg2 Vf2 x2 Vf2 x2 Vg2 Then V2 = Vg2 0. We find from the steam tables Hf1 697. (B) x1 Vfg1 In this equation only x1 is unknown and we can solve for it as follows.939 kJ kg P1 700kPa 181 .0 kJ kg Hfg1 Hg1 Hf1 Hfg1 2064.

22419 cm 3 Eq. From the steam tables P2 1000kPa Hf2 762.108 cm 3 gm Vg1 272.68 cm 3 gm Vfg1 Vg1 Vf1 Vfg1 271. (C) for V2 V2 Vg2 0.18595 10 3 3m kg Next solve Eq.595 kJ kg 3 Vf2 1.279 10 4 Thus V1 Vf1 x1 Vfg1 V1 1.1 Hg2 Hf2 V2 Vf2 Hfg2 Vfg2 P2 P1 Hfg2 Vfg2 = Hg2 Hf1 Vf1 x1 Hfg1 x1 Vfg1 x1 Find x1 x1 4.163 cm gm Solve Eq.605 kJ kg 3 Hg2 2776.2 kJ kg Hfg2 3 Hg2 Hf2 Hfg2 2013.873 182 m1 m2 Find m1 m2 10 kg 10 kg 4 .05 Vf2 19Vg2 Vf2 V2 1. (B) for x1 Given Guess: x1 0.29 cm gm Vfg2 Vg2 Vf2 Vfg2 193. (A) gives V1 m2 = V2 m1 gm and mprime = m2 m1 = 2667kg Solve for m1 and m2 using a Mathcad Solve Block: mprime Guess: m1 m2 m1 2 Given m1 m2 m1 3.572 cm 3 gm Final state in accumulator is wet steam at 1000 kPa.127 cm gm Vg2 194.Vf1 1.752 = 4 V1 V2 m2 m2 m1 = 2667lb 3.

837 m2 Vf2 0.5 m 0. For the initial conditions: 183 . Note that just to store 1333. may be split into two steps: (1) Transform into an ideal gas at the initial conditions.95 10 kg 3 4 V 45.15 K The throttling process.9 m 3 Ans. Tc P 6.776 = Hprime Hprime 3 kJ Hf1 Hf2 Hprime Given m2 m1 Hprime 10 kg = Hprime Hprime Hf1 Hf2 m1 m2 m1 = 2667lb m2 Find m1 m2 m2 V 3. By first equation of problem 3-15 m2 m1 Hprime = U1 U2 Hprime Hg2 = Hprime Hprime Uf1 Uf2 2. (2) Change T and P in the ideal-gas state to the final conditions.3 kg of saturated vapor at 1000 kPa would require a volume of: 1333.Finally. occurring at constant enthalpy.56 Propylene: T 365. evaluating property changes from a generalized correlation. evaluating property changes by equations for an ideal gas. find the tank volume Vtank m2 V2 Vtank 45.3kg Vg2 259 m 3 One can work this problem very simply and almost correctly by ignoring the vapor present.140 Ans.65 bar 1 bar 400. Property changes for the two steps sum to the property change for the process.6 K 38 bar Pc P0 46.

See Eq.7).0 ln P0 P S SR Sig S 28.815 Step (1): Use the Lee/Kesler correlation. 184 .915 10 0. Sig Sig R ICPS T Tf 1.863 R Tc H1 0.534 R Tc HR H0 H1 H0 2. A 1.623 10 3 J mol HR 2.Tr T Tc Tr 1.915 10 K 2 6 Solve energy balance for final T.637 B 22.048 J mol K Ans.496 R SR S0 S1 S0 4.275 J mol K Step (2): For the heat capacity of propylene.774 J mol K 6.908 2 1 Tf 3 C 3 T 3 3 1 T Tf 6 363.095 Pr P Pc Pr 0.565 R S1 0.637 22.706 10 K 3 C 6. interpolate. H0 0.697 J mol K S1 4. 1 (guess) Given HR = R Find AT 1 B 2 T 2 0.124 J mol K SR 5.27 K Ans.85 10 3 J mol S0 0.706 10 22. (4.623 10 3 J mol H1 1.

824 10 6 0.213 28.8 K Pc 42.967 T Tf 408.0 ln P0 P S SR Sig S 24.785 10 22.48 bar P0 1 bar P 22 bar T 423 K The throttling process. occurring at constant enthalpy. .144 Pr P Pc 3 J Pr 0.415 J mol K 8.91 K Ans.7).57 Propane: 0. (2) Change T and P in the ideal-gas state to the final conditions. evaluating property changes by equations for an ideal gas.366 10 mol SR R SRB Tr Pr SR 2. evaluating property changes from a generalized correlation. may be split into two steps: (1) Transform into an ideal gas at the initial conditions. See Eq.785 10 K 3 C 8. (4.699 185 J mol K Ans.152 Tc 369.824 10 K 2 Solve energy balance for final T.6.213 B 28. A 1. Sig Sig R ICPS T Tf 1. For the initial conditions: Tr T Tc Tr 1. 1 (guess) Given HR = R Find AT 1 B 2 T 2 2 1 Tf 3 C 3 T 3 3 1 0.518 Step (1): Use the generalized virial correlation HR R Tc HRB Tr Pr HR 1. Property changes for the two steps sum to the property change for the process.284 J mol K 6 Step (2): For the heat capacity of propane.

48 bar 0.056 Tr2 1.63 bar T1 400 K P1 5 bar T2 600 K P2 25 bar Tr1 T1 Tc Pr1 P1 Pc Tr2 T2 Tc Pr2 P2 Pc Tr1 1. 6. H R Tc HRB Tr Pr H 801.490 10 0.232 10 R Tc HRB Tr2 Pr2 HRB Tr1 Pr1 3 5 S R ICPS T1 T2 3.490 10 R SRB Tr2 Pr2 3 0.91) & (6.152 T ( 100 273. 186 .828 J mol K Ans.606 Pr2 0. Eqs.5 K Pc 89.232 10 5 ln P2 P1 SRB Tr1 Pr1 H 7407.071 Pr1 0. (6.3 J mol S 1.009 Pr P Pc Pr 0.279 Use generalized virial-coefficient correlation for both sets of conditions.9 J mol J mol K Ans.639 Ans.0 0.235 Assume ideal gas at initial conditions.92) are written H R ICPH T1 T2 3.931 1.931 1.094 Tc 373.58 For propane: Tc 369. Use virial correlation at final conditions.6.15)K T 373. S R SRB Tr Pr ln P P0 S 20.15 K P0 1 bar P 10 bar Tr T Tc Tr 1.59 H2S: 0.8 K Pc 42.0 0.

33 kPa P 1600 kPa T 318. (2) Change T and P of ideal gas to final T & P.951 2 1 Tf D T T 3 1 Tf 302.60 Carbon dioxide: 0.457 1.046 Pr P Pc Pr 0. Property changes by equations for an ideal gas. generalized correlation for property changes. See Eq. constant enthalpy.36 J mol K Ans. may be split into two steps: (1) Transform to ideal gas at initial conditions.0 1.313 J mol K Step (2): For the heat capacity of carbon dioxide.83 bar P0 101.047 S SR Sig S 22.157 10 K 5 2 Solve energy balance for final T.6.457 B 1.045 10 J mol K 0.15 K Throttling process. Given 1 (guess) HR = R A T Find 1 B 2 T 2 0. For the initial T & P: Tr T Tc Tr 1.7). A 5. (4. 187 .224 Tc 304.71 K 5 Ans.217 Step (1): Use the generalized virial correlation HR R Tc HRB Tr Pr HR 587.045 10 K 3 D 1. Sum property changes for the process.999 J mol SR R SRB Tr Pr SR 1.157 10 ln P0 P Sig 21. Assume ideal gas at final T & P.2 K Pc 73. Sig R ICPS T Tf 5.

424 14. Hig R ICPH T0 Tf 1.19 K 6 Ans. combine Eqs.087 Tc 282.589 C T0 2 1 2 1 ln P P0 Tf T0 3 Tf 308.75397 At final conditions as calculated in (a) Tr T Tc Tr 1.392 10 2 6 K (a) For the entropy change of an ideal gas.6.15 K P0 3800 kPa P 120 kPa S 0 J mol K For the heat capacity of ethylene: A 1.394 10 K 3 C 4.15) with D = 0: 0.0 Hig Ws 1.02381 Use virial-coefficient correlation.185 10 4 J mol Ws 11852 J mol Hig Ans.424 B 14. (6.3 K Pc 50.92): 0.5 (guess) Given 188 .14) & (5. (5.394 10 4.61 T0 523.392 10 0.4 (guess) Given S = R A ln Find B T0 0. The entropy change is now given by Eq.40 bar Tr0 T0 Tc Tr0 1.85317 Pr0 P0 Pc Pr0 0. (b) Ethylene: 0.12699 Pr P Pc Pr 0.

15) with D = 0: (guess) Given 0.074 The work is given by Eq.131 19.424 14.4 19.745 T T0 3 T 367.14) & (5.0 .91): Hig R ICPH T0 T 1.561 10 2 6 S = R A ln Find B T0 C T0 2 1 2 1 ln P P0 0.131 B K (a) For the entropy change of an ideal gas. Hig R ICPH T0 T 1.225 10 K 3 C 5.225 10 189 5. Tr T Tc Tr 1. (6. combine Eqs.6 bar For the heat capacity of ethane: A 1.394 10 3 4. 6.62 T0 S 493. (5.15 K 0 J mol K P0 30 bar P 2.208 10 4 J mol Ws Hig R Tc HRB Tr Pr HRB Tr0 Pr0 Ws 11567 J mol Ans.561 10 0.11 K Ans.0 Hig 1.59 K 6 Ans.S = R A ln SRB B T0 T0 Tc C T0 2 1 2 1 ln P P0 Pr SRB Tr0 Pr0 Find T T0 T 303.392 10 6 0.

83): 0. (b) Ethane: 0.Hig 8.188 The work is given by Eq.73 K Ans.034 10 3 J mol Ws Hig R Tc HRB Tr Pr HRB Tr0 Pr0 Ws 8476 J mol Ans. The entropy change is now given by Eq. 190 .72 bar Tr0 T0 Tc Tr0 1.3 K Pc 48.61576 At final conditions as calculated in (a) Tr ( ) T T Tc Tr ( ) 1. (6.6153 Pr0 P0 Pc Pr0 0.0 Hig 9. Tc Tr 1. (6.131 19.225 10 3 5.5 (guess) Given S = R A ln SRB B T0 T0 Tc C T0 2 1 2 1 ln P P0 Pr SRB Tr0 Pr0 Tr Find T T T0 T 362.05337 Use virial-coefficient correlation.100 Tc 305.20404 T Pr P Pc Pr 0.561 10 6 0.91): Hig R ICPH T0 T 1.735 10 3 J mol Ws Hig Ws 8735 J mol Ans.

915 10 K 3 C 11.92) combined with Eq.18 T T0 T 381. (6. (6.05679 HRB Tr0 Pr0 = 0.551 10 3 J mol Ws Hig R Tc HRB Tr Pr HRB Tr0 Pr0 Ws 5680 J mol Ans.15) with D = 0: (guess) 0.91): Hig R ICPH T0 T 1.935 B 36.915 10 3 11.63 n-Butane: 0.05679 The entropy change is given by Eq.8 bar S 0 J mol K For the heat capacity of n-butane: A 1.402 10 6 0.15 K P0 1 bar P 7.76017 Pr0 P0 Pc P Pr0 0.89726 The work is given by Eq.43 K Ans.205 0.96 bar T0 323.935 36. (5.1 K Pc 37.0 Hig 6.02634 Pr Pc HRB0 Pr 0. 191 .200 Tc 425. Tr T Tc Tr 0.6.4 Given S = R A ln SRB T0 Tc B T0 Pr C T0 2 1 2 1 ln P P0 SRB Tr0 Pr0 Find 1.402 10 K 2 6 Tr0 T0 Tc Tr0 0.

6.64

The maximum work results when the 1 kg of steam is reduced in a completely reversible process to the conditions of the surroundings, where it is liquid at 300 K (26.85 degC). This is the ideal work. From Table F.2 for the initial state of superheated steam:

H1

3344.6

kJ kg

S1

7.0854

kJ kg K

From Table F.1, the state of sat. liquid at 300 K is essentially correct:

H2

112.5

kJ kg

S2

0.3928

kJ kg K

T

300 K

By Eq. (5.27),

Wideal

H2

H1

T

S2

S1

Wideal

1224.3

kJ kg

Ans.

6.65

Sat. liquid at 325 K (51.85 degC), Table F.1:

Hliq

kJ 217.0 kg

Sliq

kJ 0.7274 kg K

Vliq

cm 1.013 gm

3

Psat
P1

12.87 kPa
8000 kPa

For the compressed liquid at 325 K and 8000 kPa, apply Eqs. (6.28) and (6.29) with

T

325 K

460 10

6

K

1

H1

Hliq

Vliq 1

T

P1

Psat

H1

223.881

kJ kg

S1

Sliq

Vliq P1

Psat

S1

0.724

kJ kg K

For sat. vapor at 8000 kPa, from Table F.2:

H2

2759.9

kJ kg

S2

5.7471

kJ kg K

T

300 K

Q

H2

H1

Q

2536

kJ kg

Maximum work from steam, by Eq. (5.27):

Wideal

H1

H2

T

S1

S2
192

Wideal

1029

kJ kg

Work as a fraction of heat added:

Frac

Wideal
Q

Frac

0.4058

Ans.

The heat not converted to work ends up in the surroundings.

SdotG.surr

Q

Wideal T

10

kg sec

SdotG.surr

50.234

kW K

SdotG.system

S1

S2 10

kg sec

SdotG.system

50.234

kW K

Obviously the TOTAL rate of entropy generation is zero. This is because the ideal work is for a completely reversible process. 6.66 Treat the furnace as a heat reservoir, for which

Qdot

2536

SdotG

kg sec kg kW Qdot 50.234 K T
kJ

10

T

( 600

273.15)K

T
Ans.

873.15 K

SdotG

21.19

kW K

By Eq. (5.34)

T

300 K

Wdotlost

T SdotG

Wdotlost

6356.9 kW

Ans.

6.67

For sat. liquid water at 20 degC, Table F.1:

H1

83.86

kJ kg

S1

0.2963

kJ kg K

For sat. liquid water at 0 degC, Table F.1:

H0

0.04

kJ kg

S0

0.0000

kJ kg K

For ice at at 0 degC:

H2

H0

333.4

kJ kg

S2

S0

333.4 kJ 273.15 kg K

193

H2

333.44

kJ kg

S2

1.221

kJ kg K

T

293.15 K

mdot

0.5

kg sec
t

0.32

By Eqs. (5.26) and (5.28):

Wdotideal
Wdot

mdot H2

H1

T

S2

S1
Wdot

Wdotideal

13.686 kW

Wdotideal
t

42.77 kW

Ans.

6.68

This is a variation on Example 5.6., pp. 175-177, where all property values are given. We approach it here from the point of view that if the process is completely reversible then the ideal work is zero. We use the notation of Example 5.6:

H1
S2

2676.0

kJ kg

S1
Q'

7.3554

kJ kg K
kJ kg

H2
T

0.0

kJ kg

0.0

kJ kg K

2000

273.15 K

The system consists of two parts: the apparatus and the heat reservoir at elevated temperature, and in the equation for ideal work, terms must be included for each part.

Wideal =

Happaratus.reservoir

T

Sapparatus.reservoir

Happaratus.reservoir = H2

H1

Q'

Sapparatus.reservoir = S2

S1

Q' T'

Wideal = 0.0

kJ kg

T'

450 K

Given

(Guess) kJ 0 = H2 H1 kg
Find ( ) T'

Q'

T

S2
T'

S1

Q' T'
409.79 K Ans.

T'

(136.64 degC)

194

6.69 From Table F.4 at 200(psi):

H1

1222.6

BTU lbm

S1

1.5737

BTU lbm rankine

(at 420 degF) (Sat. liq. and vapor)

Hliq

BTU 355.51 lbm

Hvap

1198.3

BTU lbm

Sliq

0.5438

BTU lbm rankine

Svap

1.5454

BTU lbm rankine

x

0.96

H2

Hliq

x Hvap
3 BTU

Hliq

S2

Sliq

x Svap

Sliq

H2

1.165 10

lbm

S2

1.505

BTU lbm rankine

Neglecting kinetic- and potential-energy changes, on the basis of 1 pound mass of steam after mixing, Eq. (2.30) yields for the exit stream:

H

0.5 H1
H Hvap

0.5 H2

H

1193.6

BTU lbm
Ans.

(wet steam)

x

Hliq Hliq

x

0.994

S

Sliq

x Svap

Sliq

S

1.54

BTU lbm rankine

By Eq. (5.22) on the basis of 1 pound mass of exit steam,

SG

S

0.5 S1

0.5 S2

SG

2.895

10

4

BTU lbm rankine

Ans.

6.70

From Table F.3 at 430 degF (sat. liq. and vapor):

Vliq

ft 0.01909 lbm

3

Vvap

ft 1.3496 lbm

3

Vtank

80 ft

3

Uliq

406.70

BTU lbm

Uvap

1118.0

BTU lbm

mliq

4180 lbm

VOLliq

mliq Vliq
195

VOLliq

79.796 ft

3

VOLvap
mvap
U1

Vtank
VOLvap Vvap

VOLliq

VOLvap
mvap

0.204 ft

3

0.151 lbm
406.726 BTU lbm

mliq Uliq mliq

mvap Uvap mvap

U1

By Eq. (2.29) multiplied through by dt, we can write, d mt Ut H dm = 0 (Subscript t denotes the contents of the tank. H and m refer to the exit stream.)
m

Integration gives:

m2 U2

m1 U1
0

H dm = 0

From Table F.3 we see that the enthalpy of saturated vapor changes from 1203.9 to 1203.1(Btu/lb) as the temperature drops from 430 to 420 degF. This change is so small that use of an average value for H of 1203.5(Btu/lb) is fully justified. Then m2 U2
m1

m1 U1
mvap

Have m = 0

Have

1203.5
m1

BTU lbm
mass

mliq

m2 ( mass)

Property values below are for sat. liq. and vap. at 420 degF
ft 0.01894 lbm
395.81 BTU lbm
Vtank m2 ( mass)
Uliq
3

Vliq

Vvap

ft 1.4997 lbm
1117.4 BTU lbm

3

Uliq

Uvap

V2 ( mass)
U2 ( mass)
mass

x mass) (
Uliq

V2 ( mass) Vliq Vvap Vliq

x mass) Uvap (

50 lbm (Guess)
196

Given

mass =

m1 U1 U2 ( mass) Have U2 ( mass)

mass

Find ( mass)

mass

55.36 lbm

Ans.

6.71 The steam remaining in the tank is assumed to have expanded isentropically. Data from Table F.2 at 4500 kPa and 400 degC:

S1

6.7093

J gm K

V1

64.721

cm

3

gm

Vtank

50 m

3

S2 = S1 = 6.7093

J gm K

By interpolation in Table F.2 at this entropy and 3500 kPa:

V2

cm 78.726 gm

3

t2 = 362.46 C

Ans.

m1

Vtank V1

m2

Vtank V2

m

m1

m2

m

137.43 kg Ans.

6.72

This problem is similar to Example 6.8, where it is shown that

Q=

mt Ht

H mt

Here, the symbols with subscript t refer to the contents of the tank, whereas H refers to the entering stream. We illustrate here development of a simple expression for the first term on the right. The1500 kg of liquid initially in the tank is unchanged during the process. Similarly, the vapor initially in the tank that does NOT condense is unchanged. The only two enthalpy changes within the tank result from: 1. Addition of 1000 kg of liquid water. This contributes an enthalpy change of

Hliq mt 2. Condensation of y kg of sat. vapor to sat. liq. This contributes an enthalpy change of

y Hliq Thus

Hvap = y Hlv

mt Ht = Hliq mt

y Hlv
197

Similarly,
Whence
mt 1000 kg

mt Vt = Vliq mt
Q = Hliq mt y Hlv

y Vlv = 0
H mt

Required data from Table F.1 are:
H 209.3 kJ kg
Vliq 1.251 cm
3

At 50 degC:

At 250 degC:

Hliq

kJ 1085.8 kg
kJ 1714.7 kg

gm
3

Hlv
y
Q

Vlv

cm 48.79 gm

Vliq mt Vlv
mt Hliq H

y

25.641 kg
Q 832534 kJ
Ans.
kJ kg

y Hlv

6.73

Given:
C 0.43 kJ kg K

Vtank
T1

0.5 m
295 K

3

Hin
mtank

120.8
30 kg

Data for saturated nitrogen vapor:

80 85 90 T 95 100 105 110
K

1.396 2.287 3.600 P 5.398 bar 7.775 10.83 14.67
V

0.1640 0.1017 0.06628 0.04487 0.03126 0.02223 0.01598 m kg
3

198

78.9 82.3 85.0 H 86.8 87.7 87.4 85.6
By Eq. (2.29) multiplied through by dt, d nt Ut H dm = dQ
kJ kg

At the point when liquid nitrogen starts to accumulate in the tank, it is filled with saturated vapor nitrogen at the final temperature and having properties

mvap Tvap Vvap Hvap Uvap

Subscript t denotes the contents of the tank; H and m refer to the inlet stream. Since the tank is initially evacuated, integration gives mvap Uvap
Also,

Hin mvap = Q = mtank C Tvap
mvap = Vtank Vvap

T1

(A)
(B)

Calculate internal-energy values for saturated vapor nitrogen at the given values of T: 56.006

U

( H

P V)

59.041 61.139 U 62.579 63.395 63.325 62.157
kJ kg

Fit tabulated data with cubic spline: Us lspline ( U) T
interp ( T U t) Us
(guess)

Vs

lspline ( V) T
interp ( T V t) Vs

Uvap () t
Tvap

Vvap () t

100 K

Combining Eqs. (A) & (B) gives:

199

Given
Uvap Tvap
Tvap
mvap

Hin =

mtank C T1

Tvap Vvap Tvap Vtank

Find Tvap
Vtank Vvap Tvap

Tvap
mvap

97.924 K

13.821 kg

Ans.

6.74

The result of Part (a) of Pb. 3.15 applies, with m replacing n: m2 U2
Whence
Also U2 = Uliq.2
V2 = Vliq.2

H

m1 U1

H = Q= 0
m2 H
x2 Ulv.2
x2 Vlv.2
V2 = Vtank m2

U2 = m1 H

U1

Eliminating x2 from these equations gives

Vtank m2 H Uliq.2 m2

Vliq.2

Vlv.2

Ulv.2 = m1 H

U1

which is later solved for m2 Vtank 50 m
3

m1

16000 kg

V1
V1

Vtank m1
3.125 10
3 3m

kg

Data from Table F.1
Vliq.1 cm 1.003 gm
3

@ 25 degC:
Vlv.1 cm 43400 gm
3

Uliq.1

104.8

kJ kg

Ulv.1

2305.1

kJ kg

200

x1
x1

V1

Vliq.1 Vlv.1

U1
5

Uliq.1
104.913

x1 Ulv.1
kJ kg

4.889

10

U1

Data from Table F.2 @ 800 kPa:
Vliq.2 1.115 cm
3

Uliq.2
3

720.043

gm
1.115) cm
Ulv.2
Ulv.2
H

kJ kg
kJ kg

Vlv.2
Vlv.2

( 240.26
m 0.239 kg
3

gm

( 2575.3

720.043)
3 kJ

1.855
kJ kg

10

kg

Data from Table F.2 @ 1500 kPa:

2789.9

m1 H m2
H

U1

Vtank

Ulv.2 Vlv.2
Ulv.2 Vlv.2

m2

2.086

10 kg

4

Uliq.2

Vliq.2

msteam

m2

m1

msteam

4.855

10 kg

3

Ans.

6.75

The result of Part (a) of Pb. 3.15 applies, with
Whence U2 = H

n1 = Q = 0

From Table F.2 at 400 kPa and 240 degC

H = 2943.9

kJ kg

Interpolation in Table F.2 will produce values of t and V for a given P where U = 2943.9 kJ/kg.
201

1 100 P2 200 300 400

384.09 384.82 t2 385.57 386.31 387.08

303316 3032.17 V2 1515.61 1010.08 757.34
3

cm

3

gm

i

1 5

Vtank

1.75 m

massi

Vtank V2
i

5.77 mass

10

3

T rises very slowly as P increases
3 2
massi

0.577 1.155 1.733 2.311
kg

1 0

0

200
P2
i

400

6.76

Vtank
Vliq
Hliq
x1

2m

3
3

Data from Table F.2 @ 3000 kPa:
Vvap
Hvap
V1

cm 1.216 gm
1008.4
0.1

cm 66.626 gm
2802.3
Vliq

3

kJ kg

kJ kg
Vliq
m1 Vtank V1

x1 Vvap
3 3m

V1

7.757 10

kg

m1

257.832 kg

The process is the same as that of Example 6.8, except that the stream flows out rather than in. The energy balance is the same, except for a sign: Q= mt Ht H mtank
202

where subscript t denotes conditions in the tank, and H is the enthalpy of the stream flowing out of the tank. The only changes affecting the enthalpy of the contents of the tank are: 1. Evaporation of y kg of sat. liq.:

y Hvap 2. Exit of

Hliq

0.6 m1 kg

of liquid from the tank:

0.6 m1 Hliq Thus

mt Ht = y Hvap

Hliq

0.6 m1 Hliq

Similarly, since the volume of the tank is constant, we can write,

mt Vt = y Vvap Whence

Vliq

0.6 m1 Vliq = 0

y=

0.6 m1 Vliq Vvap Vliq

Q=

0.6 m1 Vliq Hvap Vvap Vliq

Hliq

0.6 m1 Hliq
0.6 m1 =

H mtank

But

H = Hliq

and

mtank

and therefore the last two terms of the energy equation cancel:
Q 0.6 m1 Vliq Hvap Vvap Vliq

Hliq

Q

5159 kJ

Ans.

6.77

Data from Table F.1 for sat. liq.:
H1 100.6 kJ kg
(24 degC)
H3 355.9 kJ kg
(85 degC)

Data from Table F.2 for sat. vapor @ 400 kPa:
H2 2737.6 kJ kg

By Eq. (2.30), neglecting kinetic and potential energies and setting the heat and work terms equal to zero: H3 mdot3 H1 mdot1 H2 mdot2 = 0
203

Also

mdot1 = mdot3

mdot2

mdot3

5

kg sec

Whence

mdot2

mdot3 H1 H1 H2

H3

mdot1

mdot3

mdot2

mdot2

0.484

kg sec

Ans.

mdot1

4.516

kg sec

Ans.

6.78 Data from Table F.2 for sat. vapor @ 2900 kPa:

H3

2802.2

kJ kg

S3

6.1969

kJ kg K

mdot3

15

kg sec

Table F.2, superheated vap., 3000 kPa, 375 degC:

H2

3175.6

kJ kg

S2

6.8385

kJ kg K

Table F.1, sat. liq. @ 50 degC:

Vliq

cm 1.012 gm

3

Hliq

209.3

kJ kg

Sliq

0.7035

kJ kg K

Psat

12.34 kPa

T

323.15 K

Find changes in H and S caused by pressure increase from 12.34 to 3100 kPa. First estimate the volume expansivity from sat. liq, data at 45 and 55 degC:

V

( 1.015

1.010)
3 3 cm

cm

3

gm

T

10 K

P

3100 kPa
4 1

V

5 10

1 Vliq

V T

gm

4.941

10

K

Apply Eqs. (6.28) & (6.29) at constant T:

H1

Hliq

Vliq 1

T

P

Psat

H1

211.926

S1

Sliq

Vliq P

Psat
204

S1

0.702

kJ kg kJ

kg K

By Eq. (2.30), neglecting kinetic and potential energies and setting the heat and work terms equal to zero:

H3 mdot3 Also

H1 mdot1

H2 mdot2 = 0

mdot2 = mdot3

mdot1

Whence

mdot1

mdot3 H3 H2 H1 H2

mdot1

1.89

kg sec

Ans.

mdot2

mdot3

mdot1

mdot2

13.11

kg sec

For adiabatic conditions, Eq. (5.22) becomes

SdotG

S3 mdot3

S1 mdot1

S2 mdot2

SdotG

1.973

kJ sec K

Ans.

The mixing of two streams at different temperatures is irreversible. 6.79 Table F.2, superheated vap. @ 700 kPa, 200 degC:

H3

2844.2

kJ kg

S3

6.8859

kJ kg K

Table F.2, superheated vap. @ 700 kPa, 280 degC:

H1

3017.7

kJ kg

S1

7.2250

kJ kg K

mdot1

50

kg sec

Table F.1, sat. liq. @ 40 degC:

Hliq

167.5

kJ kg

Sliq

0.5721

kJ kg K

By Eq. (2.30), neglecting kinetic and potential energies and setting the heat and work terms equal to zero:

H2

Hliq

H3 mdot3

H1 mdot1

H2 mdot2 = 0

Also

mdot3 = mdot2

mdot1

mdot2

mdot1 H1 H3 H2

H3

mdot2

3.241

kg sec

Ans.

For adiabatic conditions, Eq. (5.22) becomes
205

5 mol air at T and P. 2nd law: P 5 bar (guess) = 0 J K Given n1 CP ln T P R ln T1 P1 T P n2 CP ln R ln T2 P2 P 4.248 BTU lbm rankine Ms = steam rate in lbm/sec Mn = nitrogen rate in lbm/sec Mn 40 lbm sec 206 .508 kJ sec K Ans. The mixing of two streams at different temperatures is irreversible.5 mol CP 7 R 2 CP 29.5 mol air at 2 bar and 400 K (2) = 3.099 J mol K 1st law: T 600 K (guess) T1 n2 CP T T2 = 0 J Given n1 CP T T Find ( ) T T 542.81 molwt 28. 6.857 K Ans.80 Basis: 1 mol air at 12 bar and 900 K (1) + 2. T1 900 K T2 400 K P1 12 bar P2 2 bar n1 1 mol n2 2. 6.S2 Sliq mdot3 mdot2 mdot1 SdotG S3 mdot3 S1 mdot1 S2 mdot2 SdotG 3.014 lb lbmol CP R 7 2 molwt CP 0.319 bar P Find ( ) P Ans.

water @ 212 degF entering (2) = exit steam at 1 atm and 300 degF (3) = nitrogen in at 750 degF (4) = nitrogen out at 325 degF BTU lbm BTU lbm T3 T4 0.6 1.67 rankine 784.30) applies with negligible kinetic and potential energies and with the work term equal to zero and with the heat transfer rate given by Ms Given Ms 3 lbm sec Ms H2 (guess) Q = 60 Mn CP T4 Ms BTU Ms lbm Ms H1 T3 = 60 lbm sec BTU lbm Find Ms 3. Eq.67 rankine SdotG SdotG Ms S2 2.933 Ans. (5.67 rankine H1 H2 180. liq.17 S1 S2 (Table F.(1) = sat. (2.8158 (Table F.3) 1192.22) here becomes SdotG = Ms S2 S1 Mn S4 S3 Q T S4 T S3 = CP ln T4 T3 Q 60 BTU Ms lbm Q 235. 207 .064 S1 Mn CP ln T4 T3 Q T BTU sec rankine Ans.967 BTU sec 529.4) Eq.3121 BTU lbm rankine BTU lbm rankine 1209.

33 kPa and 150 degC (3) = nitrogen in @ 400 degC T3 673.22) here becomes SdotG = Ms S2 S1 Mn S4 S3 T Q T 298.961 kg sec Ans.3069 kJ kg K (Table F.30).15 K Q T S4 S3 = CP ln Ms S2 4. neglecting kinetic and potential energies and setting the work term to zero and with the heat transfer rate given by Ms 1 kg sec (guess) Q = 80 kJ Ms kg Given Ms H2 H1 Mn CP T4 T3 = 80 kJ Ms kg Ms Find Ms Ms 1.039 J gm K Ms = steam rate in kg/sec Mn= nitrogen rate in kg/sec Mn 20 kg sec (1) = sat. Q 80 kJ kg Ms SdotG SdotG T4 T3 kJ sec K 208 .6075 kJ kg K (Table F. liq.194 T4 T3 S1 Mn CP ln Ans.2 kJ kg S2 7.15 K (4) = nitrogen out at 170 degC T4 443. (2.2) By Eq.2) H2 2776.014 gm mol CP R 2 molwt 7 CP 1.33 kPa entering (2) = exit steam at 101.15 K H1 419.6. water @ 101. (5. Eq.82 molwt 28.064 kJ kg S1 1.

propane = 2 T 1 363.082 Z Z0 Z1 Z 0.1100 y1 1 y2 2 0.286 Zc2 0.07 10 sec A Vdot u A 6.012 0.6 K Tc2 369. We choose the latter.6.276 Tc1 190.5 y2 1 y1 0.788 gm 3 mdot 3 4 cm 1. 209 .99 bar Pc2 42.901 cm D 4A D 2.81 For the molar mass of the mixture.8010 Z1 0.8 K Pc1 45.152 Zc1 0.48 bar The elevated pressure here requires use of either an equation of state or the Lee/Kesler correlation with pseudocritical parameters.86 Methane = 1.097 mol 30.07 gm mol V ZRT P molwt V cm 14.3 and E. Tpc y1 Tc1 y2 Tc2 Ppc y1 Pc1 y2 Pc2 Tpc 280.043 y2 44.15 K P 2 5500 kPa y1 0. we have: gm molwt molwt y1 16.4 kg sec u 30 m sec 2 Vdot V mdot Vdot 2.964 cm Ans.296 Ppr P Ppc Ppr 1.243 By interpolation in Tables E.235 bar Tpr T Tpc Tpr 1.4: Z0 0.2 K Ppc 44.

297 0.176 1.971 425.77 73.2 154.315 0.045 1.815 0.By virial equation: 500 150 T 500 K P 450 400 T Tc 20 20 10 bar Tc 35 15 P Pc 425.7 430.6 469. P.97 1.8 374.0 617.252 .312 0.327 Tr Pr 210 .2 Tc 190.8 374.190 . Tc.957 0.022 .948 20 200 60 20 20 P 90 20 10 35 15 Pc 42.77 50.43 33.709 0.2 0.70 bar 78.83 79.7 K Pc 430.87 Vectors containing T.069 Pr 0.369 Parts (a).759 0.444 0.6.7 617.99 50.005 1.43 33.84 40.06 45.555 1.397 0.468 2.60 Tr T Tc Pr P Pc Tr 1.00 21.2 304.10 36. (h).2 552.84 40.2 42.6 154.6 469.245 . and Pc for the calculation of Tr and Pr: 500 400 450 600 620 T 250 150 500 450 400 1.70 78.065 1. and (j) --.6 . (g). (i).

6 0.65) B1 0.675 Tr 2.2 B0 0. (3.90) 0.73 DB0 0.51 Combine Eqs.045 1.568 DB1 0.603 0.718 4.66) DB0 0.722 Tr 5. and (6.009 10 10 10 3 3 3 0.176 0.1.576 0.052 0.443 0.397 Pr 0.2 Eq.468 0.253 0.88) 211 .065 1. (6.574 0. (3.6 Eq. (6.89) DB1 0.369 0.309 0.217 9.311 0.61) + (3.62).139 Eq.444 0.297 0.40) and the definitions of Tr and Pr to get: VR R Tc B0 Pc B1 HR R Tc Pr B0 Tr DB0 ( B1 Tr DB1) Eq.321 0.522 0.87) SR R Pr DB0 DB1 Eq. (3.056 6.069 0. (3.63).37 B0 0.845 0.172 Tr 4.306 B1 0. (6.073 Eq.422 Tr 1.97 Tr 1. (6.

256 mol Parts (b).473 0.050 .224 .74 2.492 .049 0.596 0.377 10 559.910 0.2 190.278 .12: DEFINE: h0 equals ( ) HR RTc ( ) SR R 0 0 ( ) HR h1 equals RTc s1 equals ( ) SR R 2. (c).647 94.169 304.824 400 450 T 600 K 620 250 P s1 Z1 s equals 0.289 200 60 20 20 90 bar 0.012 212 .501 HR 1.745 2. and (f) --.675 0.405 5.907 146. (e).454 cm 3 1.138 0.303 .By Lee/Kesler correlation: By linear interpolation in Tables E.088 .0 Tc 617.274 2.783 .663 .251 10 3 1.226 10 1.6 .671 1.121 h1 2.2 552.036 0.008 4.233 5.137 4.707 1.486 1 1 h equals HR RTc SR R s0 equals .469 J mol J mol K 3 3 3 SR 1.1--E.445 h0 3.593 VR 355.381 s0 2.970 0.1 232.746 10 1.557 0.7 K 617.200.952 2.124 Z0 . (d).208 .111 .

2 K Tc2 553. Tc2.71 0.358 10 48.2 Tc1 305.7 154.57) s1 (6.291 J mol 2.86) h h0 h1 Eq. Pc2.85) ( h Tc R) SR ( s R) 0.21 2.2 469.118 Z 0.396 67.7 282.9 568.772 0.88 J mol K 3 3 2.709 HR 5. (3. Pc1.2 304.235 0.336 6.284 3 cm mol 3 And.3 190.5 190.6 K 213 .2 304.6 126. 1.289 VR T (Z R P 549.6 126.909 10 587.207 4 4 10 41.143 5.Z s HR Z0 s0 Z1 Eq.316 10 4.3 373.301 10 3 10. and 2 for Parts (a) through (h) 650 300 600 T 350 400 200 450 250 K 60 100 100 P 75 150 75 80 100 bar 562. (6. 6. P.6 190.88 Vectors containing T.691 1) VR 1. Tc1. The Lee/Kesler tables indicate that the state in Part (c) is liquid.37 10 SR 34.6 132.

4 330.781 Ppr Ppc 0.212 1.338 1.70 50.012 .418 1.03 .136 0.210 .99 45.087 .855 54.875 2.5 2 Tpc ( Tc1 .90 Pc2 50.83 Pc1 48.165 1.72 89.845 42.9 218.373 1.99 24.43 .56 67.5 Tc2) Ppc P Ppc 44.5 1 2 .41 49.5 Pc2) .263 1.363 1.838 2.98 73.63 45.224 .400 .094 .21 0.026 1.022 .191 1.81 39.053 0.369 214 0.012 .132 0.094 0.73 34.99 34.038 .215 1.025 0.4 1.15 140.83 73.513 2.995 39.8 282.5 T Tpc ( Pc1 .00 33.048 .008 2.375 Tpr 1.00 bar 40.100 .45 Tpc 293.99 34.312 bar 49.365 K bar .48.252 .224 1 .05 158.038 .40 45.210 .55 436.5 Tpr Ppr 557.012 .

750 .348 .372 0.461 . (6.86) 215 .110 0.1749 .1929 .1219 .400 . (6. (3.430 .7744 .9168 .250 .7706 .944 .7436 .965 .361 Z1 .Lee/Kesler Correlation --.224 .12: .254 .346 1.116 .57) h h0 h1 Eq.049 .097 .510 1.729 s0 .658 .1933 .1501 .466 .704 .6543 .1853 .820 h1 .623 1.7527 Z0 .242 s1 .By linear interpolation in Tables E.890 .1990 .235 .340 1.095 0 h0 equals ( HR) RTpc ( SR) R h1 equals ( HR) RTpc ( SR) R 1 h equals HR RTpc SR R 0 1 s0 equals s1 equals s equals Z Z0 Z1 Eq.1--E.217 1.6434 .6631 .395 1.172 .1839 h0 1.85) s s0 s1 Eq.

36kPa T2 453.726psi 216 . 8.952 mol K Ans.51 3.55bar At Tr = 0.7 Tc T 452.97 K T1 451.96 Tc 374.025 6.7: T 0.151 5.95 Tc 647.2K Pc 40.769 0.762 J 8.785 0.344 Ans.7: T 0.7kPa Psat P2 T2 Psat Pc P1 ( T T1 T1) P1 Psat 998.794 0. This is very close to the value reported in Table B.689 SR 8.345).97 K Find Psat in the Saturated Steam Tables at T = 452.095 6.7 Tc T 471.922 3148.984 4993.822 F T1 10degF P1 26.986 bar Psatr Psatr 0.341 mol 2145.15K P2 1002.1 ( = 0.15K P1 957.668 0.213 5.492 rankine T T 459.619 kPa Psat 9.813 SR ( R) s 6919.736 6.045 1 log Psatr 0.183 J Z 0.60bar At Tr = 0.974 HR 3779. 6.657 0.68 0.583 2239.1K Pc 220.813 951.752 3805.HR ( hTpc R) 0.822 degF Find Psat in Table 9.1 at T = 11.67rankine T 11.617psi T2 15degF P2 29.

4721 ln ( Tr) 0.09648 Tr 15.28862 ln ( Tr) 0.64) B0 0.00334 B0 0.65) Z0 1 B0 Psatrn Trn Eqn.805 Z0 0.92714 6. (3. (3. (6.79) lnPr1 ( Tr) 15.207 lnPsatr ( Tr) lnPr0 ( Tr) lnPr1 ( Tr) 2 7 Eqn.2 Eqn.073 217 Z1 0.210 Tc 562.Psat P2 T2 P1 (T T1 T1) P1 Psat 27.81). (3. This is exactly the same as the value reported in Table B. (3.035 .75 psi Psat 1.422 Trn 1.43577 Tr Eqn.327 Ans.1.64) B1 1.6875 Tr 1.6 Eqn. (6.913 bar Psatr Psat Pc Psatr 0.98bar Zc 0.2K Trn Tn Tc Trn 0. 0.101 For benzene a) 0.80) ln Psatrn lnPr0 Trn lnPr1 Trn Eqn.271 Tn 353.021 lnPr0 ( Tr) 5.083 Zc 1 1 T rn Eqn.139 0. (6.73) Zsatliq 0.2K Pc 48.2518 13.169347 Tr 6 6 Eqn. 6.047 1 log Psatr 0.78) Zsatliq Psatrn Trn 0.66) Z1 B1 Psatrn Trn Equation following Eqn.628 Psatrn 1 atm Pc Psatrn 0. (6. (3.172 Trn 4.974 B1 0.

224 Tc Tt 304.103 For CO2: 0.2 of 30.169347 Tr Tr 6 Eqn.39 21.03 29.79) lnPr1 ( ) Tr 15.80) ln Ptr lnPr0 Ttr lnPr1 Ttr Eqn.97 Cy clohex ane 39.2K 216.72 Benz ene 21.lene Xy 6.2 (kJ/mol) 30.57) Zsatvap 0.30 isoButane 29. (3.55K Pc Pt 73.81). (6.82 Carbon tetrachlorid e 30.23 36.72 33.18 Toluene 37.83bar 5. EstimatedValue (kJ/mol) Table B.27 28.6875 Tr 13.41 nOctane 33. .4721 ln ( ) 0.92714 6.07 lnPr0 ( ) Tr 5.28862 ln ( ) 0.81 29.Zsatvap Z0 Z1 Eqn.802 kJ mol Ans.966 Zlv Zsatvap Zsatliq 2 Zlv 0.43577 Tr Tr Eqn.80 30.24 o.19 kJ/mol The results for the other species are given in the table below. (6. This compares well with the value in Table B. (6.75 nDecane 29.70 34.85 n.ane Hex 34.963 Hhatlv d dTrn lnPsatr Trn Trn Zlv Hhatlv 6.7 T 0.09648 Tr 1.7Tc T 212.59 Hlv R Tc Hhatlv Hlv 30.97 38.712 Ptr Pt Pc Ptr 6 0. 218 0.2518 15.94 K Ttr Tt Tc Ttr 0.224 Ans.170bar At the triple point: a) At Tr = 0.

This seems reasonable.6 is common for triatomic species.7 Given ln Psatr = lnPr0 Trn lnPr1 Trn Trn Find Trn Trn 0.3 K Ans.1 b) Psatr 1atm Pc Psatr 0.This is exactly the same value as given in Table B. 219 . a Trn of about 0.609 Tn Trn Tc Tn 185.014 Guess: Trn 0.

314 J mol K molwt 28. A2 mdot V2 u2 A2 7. (2.1595 kJ/(kg*K) yields: H2 kJ 2855.2 kg V2 cm 531.32a) reduces to H u2 2 2 = 0 But H = CP T Whence T u2 2 2 CP T 52. and potential-energy terms set equal to zero and with the initial velocity equal to zero.75 kg sec With the heat.1595 kJ kg K Interpolation in Table F. (2. work. (2. Initial property values are as in the preceding problem.2 at P = 525 kPa and S = 7.Chapter 7 . and potential-energy terms set equal to zero and with the initial velocity equal to zero.21 gm 3 mdot 0.45 K Ans.9 gm CP mol 7 R 2 molwt With the heat.2 m sec 2 Ans.27).4 From Table F. By Eq. Eq.5 The calculations of the preceding problem may be carried out for a series of exit pressures until a minimum cross-sectional area is found.9 kJ kg S1 7.2 at 800 kPa and 280 degC: H1 3014. The corresponding pressure is the minimum obtainable in the converging nozzle.05 cm Ans.Mathcad Solutions 7. Eq.Section A . work.1 u2 325 m sec R 8. 7. 220 . 7.32a) reduces to: H u2 2 2 = 0 Whence u2 2 H2 H1 u2 565.

127 2 u2 m 518.05 7. i s pmin Given pmin 1 5 cspline P A2 400 kPa pi Pi A( ) P (guess) 2 a2 i A2 i interp s p a2 P cm d A pmin = 0 kPa dpmin 431.7 u2 2 H2 H1 A2 7.H1 3014.028 cm 7.69 447.75 565.45 465.1 sec 494.2 H2 2880.059 7.2 541.78 kPa Ans. 221 .7 2892.021 cm Ans.21 507.9 kJ kg 531.2 Fit the P vs. A2 data with cubic spline and find the minimum P at the point where the first derivative of the spline is zero.12 V2 485.2 2868.8 471.9 kJ kg S1 7. pmin A pmin Find pmin 2 7.72 mdot V2 u2 cm 3 gm mdot 0.1595 kJ kg K S2 = S 1 Interpolations in Table F.2 at several pressures and at the given entropy yield the following values: 400 425 P 450 kPa 475 500 kg sec 2855.5 2903.022 A2 7.

09 7.5 kJ kg S1 7.03 7.0499 kJ kg K S2 S1 Interpolate in Table F.81 302.13 p 400 kPa 401 kPa 500 kPa 7.8 2932.07 2 A( ) p cm 2 7.69 cm gm 3 u2 2 H2 H1 A2 = mdot 222 .97 326.0499 kJ/(kg*K) to find the minimum cross-sectional area.82 317.2 at a series of downstream pressures and at S = 7.2 at 1400 kPa and 325 degC: H1 3096.11 A2 cm i 7.05 7.5 2940.Show spline fit graphically: 7.12 V2 309.9 V2 u2 kJ kg 294.8 2924. 800 775 P 750 kPa 725 700 H2 2956.9 From Table F.0 2948.01 400 420 440 Pi 460 480 500 p kPa kPa 7.

Since mdot is constant. Sliq 1.561 V2 u2 5.553 5. Its minimum value occurs very close to the value at vector index i = 3.03 Btu lbm Btu lbm rankine Hvap Svap 1167.4 at 35(psi). At the nozzle exit.8 Btu lbm Btu lbm Btu lbm rankine H 78. the initial value.10 u1 230 u2 2000 ft sec From Table F.6 Btu lbm S1 1.577 cm sec kg 2 At the throat.6872 223 .6310 u1 2 Btu lbm rankine u2 2 By Eq. By interpolation.32a). mdot A2 u2 3 V2 3 A2 mdot 6 cm 2 1. (2. H H2 2 1154.557 5. we see that the final state is wet steam: Hliq Sliq 228.2479 kJ kg K x x 0. 5.1 0.081 kg sec Ans.8 Btu lbm H2 H1 H From Table F.4 at 130(psi) and 420 degF: H1 1233.552 5. the quotient V2/u2 is a measure of the area.2 we see that steam at these conditions is wet.966 7. From Table F.4098 S1 Svap Sliq Sliq ft sec kJ kg K Svap 7.3809 1. P = 140 kPa and S = S1.

7.05 K Ans.25) to the constant-enthalpy throttling process.13 58.9 gm CP mol R 2 molwt 7 By Eq. H= u1 2 u2 2 2 = u2 2 2 But u2 2 H = CP T T Whence T 2 CP 167.5 10 K P 4 atm Cp 4.15 K Enthalpy difference for saturated liquid for a temperature change from 14 to 15 degC: H ( 67.15 15)K molwt 28.11 u2 580 m T2 sec ( 273. 7.19 J gm K Apply Eq. (2.x H2 Hvap Hliq Hliq x 0.67 BTU lbm rankine SdotG S2 S1 SdotG 0. (7.039 Btu lbm rankine Ans. Initial t = 15 + 167.001 gm 3 T 288.05 degC Ans.32a). 224 .75) 4 J gm t 2K Cp H t 1.12 Values from the steam tables for saturated-liquid water: At 15 degC: V cm 1.05 = 182.987 (quality) S2 Sliq x Svap Sliq S2 1. Assumes very small temperature change and property values independent of P.

152 5.0 10 K 5 2 10 K 3 225 .824 10 K 2 6 1.457 A 1.86923 cm3 atm T 0. (7.040 0.280 1.224 .40 34.424 3.038 .2bar 80 P1 60 60 20 bar 73.2 369.13--7.394 .045 B 14.785 1.83 Pc 50.0 C 4.36) with Q=0: Wlost T S Wlost T 0.T V 1 Cp T P 1 joule 9.15 350 T1 350 250 400 304.413 Wlost 0.213 0.0 8.093 K The entropy change for this process is given by Eq.392 0.087 .413 kJ kg Ans.2 Tc 282. 7.157 D 0.48 bar .593 28.3 126.0 0. (5.408 10 3 J gm K Apply Eq.26): S Cp ln T T T V P S 293.15 K J gm or 1.8 K K P2 1.00 42.

and then calculating it.24 1.93) is applied to this constant-enthalpy process.13 Redlich/Kwong equation: 0. 1.151 1.765 0. Its use requires expressions for HR and Cp at the initial conditions. Eq. (6.08664 Tr T1 Tc Tr 1.68) equations equals -0.52) q 1 4 Ii ln Z Z i qi i qi i Eq.42748 Pr Tr Guess: Eq.53) q Tr z 1 1. (3.4 (pg. If the final state at 1.65b) HRi SRi R T1i R ln Z Z i qi i qi 1 i 1. (3.4.5 qi Ii Eq. 280 Guesses T2 302 232 385 K 226 .As in Example 7. (6.981 1.5 Eq.5 qi Ii Eq. (A) of Example 7. (6.19 1. 265) applies. then Eq.5 The simplest procedure here is to iterate by guessing T2.67) The derivative in these 0. (6.2 bar is assumed an ideal gas.082 7. (3.471 0.084 Pr P1 Pc Pr 1.54) Given Z i z= 1 Find z () q z z z Eq.

08664 0.67) 227 .947 J 31.Z i qi 0.956 0. (6.953 mol K Ans. (3.941 7.026 232.253 kJ 0.176 1 c 1 Tr Eq. 22. (3.574 0.59 2.062 384.346 1.14 Soave/Redlich/Kwong equation: 2 K Ans.65b) HRi R T1i Z i qi 1 ci Tri i 0.42748 0.721 0.681 HR 2.521 mol 5. (3.33 J mol K 1.53) q Eq.54) Tr Guess: z 1 Given z= 1 q z z z i Eq.480 Pr Tr 1.396 T2 T1 Cp R A B T1 2 1 C 2 T1 3 2 1 D T1 2 T2 HR Cp T1 S Cp ln 31. (6.773 0.52) Z q Find ( z) i 1 4 Ii ln Z Z i qi i qi Eq.5 1 qi Ii Eq. S 29.971 T2 302.177 SR 4.545 T2 T1 R ln P2 P1 SR 279.862 2.5 2 c 0.163 0.

741 231.028 J 32. (6.526 mol 6.565 S Cp ln T2 T1 R ln P2 P1 SR S 30.5 The derivative in these equations equals: Now iterate for T2: ci Tri i 273 Guesses T2 300 232 384 K Z i qi 0.873 383.523 2.866 2.128 mol K 22. 228 . 31.126 SR 4.75 0.68) 0.679 T2 T1 Cp R A B T1 2 1 C 2 T1 3 2 1 D T1 2 272.789 mol K 1.554 K Ans.SRi R ln Z i qi i ci Tri i 0.769 J 1.356 kJ 0.936 HR 2.5 qi Ii Eq.975 0.79 0.757 T2 HR Cp T1 T2 299.18 Ans.

45724 2 c 0. (3.52) q 1 4 Find z () Ii 1 2 2 ln Z Z i qi i qi 0.5 Eq.67) SRi R ln Z i qi i ci Tri i qi Ii Eq.37464 1.68) The derivative in these equations equals: Now iterate for T2: 270 Guesses T2 297 229 383 K ci Tri i 0.07779 0.5 229 .15 Peng/Robinson equation: 1 2 1 2 0.54) Tr Guess: Given Z i z z= 1 1 q z z z Eq.5 Pr Tr Eq.7.26992 2 1 c 1 Tr 0. (6. (3.5 i i Eq.53) q Eq. (6. (3. (6.65b) HRi R T1i Z i qi 1 ci Tri i 1 qi Ii 0.54226 0.

152 SR 4.2: H2 2609.735 T2 HR Cp T1 T2 297.92 (quality) 230 .041 HR 2.18 Wdot H1 3500 kW 3462. (7.13).459 0.103 kg sec Ans.694 J 31.76 0.95 0.Z i qi 0. exhaust is wet steam: Sliq 0.85 3. 22. For isentropic expansion.2 S Cp ln T2 T1 R ln P2 P1 SR S 29. 31.784 J 1.3439 kJ kg K By Eq.865 mol K Ans.847 mol K 2.911 K Ans.366 229. mdot Wdot H2 H1 mdot 4.9 kJ kg Data from Table F.9094 kJ kg K S2 S1 x x 0.9 kJ kg S1 7.6 1.04 7.32 382.722 0.689 T2 T1 Cp R A B T1 2 1 C 2 T1 3 2 1 D T1 2 269.8321 S2 Svap Sliq Sliq kJ kg K Svap 7.581 kJ mol 6.

4536 kJ kg K kJ 2801.75 0.8143 kJ kg K 0. For intake conditions: 3274.77 0.819 Ans.5597 kJ kg K 3509.421 10 kg H2 H'2 H1 H1 0.5677 Btu lbm rankine 231 .9 kJ kg 3 kJ H'2 Hliq x Hvap Hliq H'2 2.9813 kg K S1 kJ 3161.19 The following vectors contain values for Parts (a) through (g).6000 Btu lbm rankine 1389.4941 kg K 1444.2 kg 6.5 kg H1 kJ 6.7 Btu lbm 1.Hliq 251.80 0.8 kJ kg 6.6 Btu lbm 1. 7.80 0.4 kg kJ 6.75 0.82 0.453 kJ kg Hvap 2609.75 kJ 3634.3 kJ kg 6.

3 Btu lbm 100 lbm sec 232 .1750 Btu lbm rankine 1.1268 kJ kg K 0.7695 kJ kg K 0.8625 Btu lbm rankine 80 kg sec 289.3 kJ kg 50 kg sec 94.9200 Btu lbm rankine 0.0912 kJ kg K Svap 7.1 Btu lbm 150 lbm sec 120.0 kJ kg mdot 65 kg sec 504.For discharge conditions: 0.302 2625.8 kJ kg 70 kg sec Hliq 340.701 kJ kg 2706.5947 kJ kg K S'2 = S1 1.9441 kJ kg K 7.2200 Btu lbm rankine kJ kg 1.453 kJ kg 2609.99 Btu lbm 1127.5301 kJ kg K 7.832 kJ kg 2584.564 kJ kg Hvap 2646.4 kJ kg 251.03 Btu lbm 1116.6493 kJ kg K 8.9094 kJ kg K 0.8321 kJ kg K 7.1511 kJ kg K Sliq 1.9 kJ kg 90 kg sec 191.

6873 7.7127 kJ kg K S2 S2 S2 S2 S2 S2 Ans.1808 7.9 kJ 2467.7842 7.9 2535.8 kg 2471.x'2 S1 Svap Sliq Sliq H'2 Hliq x'2 Hvap Hliq H H2 Hvap H'2 Hliq H1 H2 H1 H Wdot H mdot x2 Hliq S2 Sliq x2 Svap Sliq H2 H2 H2 H2 H2 H2 H2 1 2 3 4 5 6 7 S2 2423.7484 lbm rankine 68030 87653 81672 Wdot 44836 kW 12900 65333 35048 Wdot 91230 117544 109523 60126 17299 87613 46999 hp Ans.1022 6.4 1 2 3 4 5 7. 1031. 233 .4 2543.4 lbm 6 7 1.9 Btu 1057.7762 Btu 1.

15 K P0 8. They combine to give: R CP W's C P T1 P2 P1 1 W's 15231 J mol Ws W's H Ws 234 Ws 11728 J mol Ans. S 0 J mol K For the heat capacity of nitrogen: A 3. (7. (5. Thus the initial temperature is 489.7.15 K P1 10 bar P2 1.20 T 423.19) derived for isentropic compression apply equally well for isentropic expansion.15) with C = 0.280 B 0.593 10 K 3 D 0.14) & (5.21 T1 1223.77 Eqs.27 degC 7. combine Eqs.18) and (7.5 (guess) Given S = R A ln B T D T 2 1 1 ln 2 T P P0 Find T0 T0 762.040 10 K 5 2 For the entropy change of an ideal gas.42 K Ans.5 bar P 1 bar For isentropic expansion. . Substitute: 0.5 bar CP 32 J mol K 0.

853 10 K 1.21) also applies to expansion: T2 T1 H CP T2 856.15 K P0 5000 kPa P 500 kPa S 0 J mol K For the heat capacity of isobutane: A T0 Tc 1.5 (guess) Given S = R A ln SRB B T0 T0 Tc C T0 2 1 2 1 ln P P0 Pr SRB Tr0 Pr0 Find T T0 T 445.Eq.92) combined with Eq.945 10 K 2 6 Tr0 Tr0 Pr0 Pr0 1.48 bar 0.71 K Tr T Tc Tr 1.137 The entropy change is given by Eq.15) with D = 0: 0. 7.181 T0 523. (5.1 K Pc 36.092 235 .677 B 37.64 K Ans. (7.22 Isobutane: Tc 408. (6.282 3 C P0 Pc P 11.3706 Pr Pc Pr 0.

23 From Table F.95 236 .853 10 11.1 J mol The actual final temperature is now found from Eq.7 Given (guess) H = R A T0 1 Tc HRB Find B 2 T0 2 T0 Pr Tc 0.91) combined with Eq (4.6 kW H Ans.2 @ 1700 kPa & 225 degC: H1 2851.16): 0. (7.875 T 2 1 C 3 T0 3 3 1 HRB Tr0 Pr0 T0 T 457. 7.8 K Ans.8 Wdot ndot ndot H 700 mol sec Wdot H H' 4665.0 kJ kg S1 x2 6.078 kJ mol 3 11.0 Hig 8331. 6665.5138 kJ kg K Sliq 0.The enthalpy change is given by Eq.677 37. written: 0.4 R Tc HRB Tr Pr J mol HRB Tr0 Pr0 H' The actual enthalpy change from Eq.7). (6.91): Hig Hig H' R ICPH T0 T 1.6493 kJ kg K At 10 kPa: 0.945 10 6 0. (6.

5 Given S = R A ln B T0 D T0 2 1 2 T' T0 1 ln P P0 Find 0.2 kW 7. producing wet steam: x'2 S1 Svap Sliq Sliq H'2 Hliq x'2 Hvap Hliq x'2 0.848 kJ kg (a) Qdot mdot H Wdot Qdot 12.832 kJ kg Hvap 2584.14) & (5.693 237 T' 466.045 10 K 3 D 1.465 10 3 kJ kg H 385. For the heat capacity of carbon dioxide: S 0 J mol K 5 2 A 5.457 B 1. Wdot' mdot H'2 H1 Wdot' 394.92 kJ sec Ans.15 K P0 8 bar P 1 bar For isentropic expansion.8 kJ kg Svap 8.1511 kJ kg K mdot 0.5 kg sec Wdot 180 kW H2 Hliq x2 Hvap Hliq H H2 H1 H2 2.782 H'2 2.15) with C = 0: (guess) 0.157 10 K For the entropy change of an ideal gas. combine Eqs. (5.Hliq 191.46 K .24 T0 673.063 10 3 kJ kg Ans. (b) For isentropic expansion to 10 kPa.

772 2 1 D T0 T0 1 Find T T 519.H' R ICPH T0 T' 5.22) Applies to expanders as well as to compressors 238 .75 H Work H' 7.157 10 5 H' 0.75 degC 7. For the enthalpy change of an ideal gas.768 kJ mol Work H 3 0.5 2. Thus the final temperature is 246.9 K Ans.5 Ideal gases with constant heat capacities HS Cp T1 P2 P1 1 Eq.0 1.457 1. (7.045 10 9.0 5.5 R 4.0 3.2 2.2) and (4.2 Cp 3.5 4.0 1.7) with C = 0: Given H = R A T0 1 B 2 T0 2 0.25 Vectors containing data for Parts (a) through (e): 500 450 T1 525 475 550 H [ ( Cp T2 P1 6 5 10 7 4 T1) ] R Cp 371 376 T2 458 372 403 P2 1.5 1. (4.326 kJ mol Work 7. combine Eqs.326 kJ mol Ans.

37).08 ln 0.14): S R T2 Cp ln T1 R ln P2 P1 S 6.26 Cp 7 2 R ndot 175 mol sec T1 550K P1 6bar P2 1.08 ln Wdot kW ndot Cp T1 P2 P1 R Cp 1 Find ( Wdot) Wdot kW Wdot 594.065 . 0.0.435 J mol K By Eq. (5.213 K By Eq. one can show that: R Cp T2 T1 1 P2 P1 1 T2 433.75 Wdot 600kW Wdot = Wdot 0.748 0.803 H HS 0. For an expander operating with an ideal gas with constant Cp. . for adiabatic operation : SdotG ndot S SdotG 1. (5.576 Ans.2bar Guesses: Given 0.649 0.699 7.126 239 10 3 J K sec Ans.065 0.716 kW Ans.7 0.

" i.1 = ( HS) = (0.8.e. Fig.75 Hl .2.4) must produce "wet" steam.. because a smaller pressure drop would be required to produce the same work and H. p.7.3207.1293 The two equations for x are: xH Hv 801. then isentropicexpansion to the same pressure (Point 2'.27 Properties of superheated steam at 4500 kPa and 400 C from Table F.924 xS 0. and substitution into the equations for x produces two values.5276 Hv Sv 2706.7 .4) is "dry.0 7. Sliq.54 kPa If were 0. values for Svap. and we conclude that: t=120 degC.75 ( Hv Hl) xS 6. Fig.3207. and Hliq are found from the table for saturated steam. (7. 742.925 The trial values given produce: xH These are sufficiently close. P=198.16). Given a final temperature and the corresponding vapor pressure. the pressure would be higher. 7. 240 . written: [x is quality] H = Hvap . This is clearly a trial process. The required pressure is the one for which the two values of x agree.1 S1 6. 7.75)[ (x)(Hvap) + (1-x)(Hliq) . withentropy: S2 = S1 = 6. the following values of H and S for saturated liquid and saturated vapor are found in the steam table: Hl Sl 503. For a final trial temperature of 120 degC. Hvap.7 1.1] Each of these equations may be solved for x. saturated vapor.7093 Sl Sv Sl 0. H1 3207.7093 = (x)(Svap) + (1-x)(Sliq) A second relation follows from Eq.7093 If the exhaust steam (Point 2.

From this value.15 T0 773.1 for saturated liquid water at 15 degC give: cm 3 V 1001 kg Cp 4.29 P1 5 atm P2 1 atm T1 15 degC 0. (7.80 0.7) with C = 0. (7.5 453.15 673. the actual temperature is found by a second application of the preceding equation.75 mol sec 1 bar 1 bar P 1 bar 2 bar 15 psi J mol K S i 0 1 5 0.7.15 755. The following vectors contain values for Parts (a) through (e): 753.190 kJ kg degC H kJ kg T T Eqs.37 200 150 ndot 175 100 0.20).2) and (4.15 K 723. (4.223 V ( P2 P1) Eq.044 degC Ans.30 Assume nitrogen an ideal gas. (5.14) Ws 0.24) combine to give: Ws H (7. this time solving it for the temperature.59 241 6 bar 5 bar P0 7 bar 8 bar 95 psi 0.16) and (7.15) with C = 0.78 0. First find the temperature after isentropic expansion from a combination of Eqs.85 0.14) & (5. 7. Then find the work (enthalpy change) of isentropic expansion by a combination of Eqs.80 . The actual work (enthalpy change) is found from Eq. (7.55 Data in Table F.25) with =0 is solved for T: H V ( P2 Cp P1) 0.

040 10 K 5 2 S = R A ln B T0 D T0 2 2 1 2 1 ln P P0 Tau T0 P0 P Find 460.48 K 494.5 7289.4 6941.5 Given (guess) H = R A T0 Tau T0 H 1 Find B 2 T0 2 2 1 D T0 i 1 i Tau T0 Hi Ti T0 i i 242 .36 i Tau T0 P0 Pi i i Ti T0 i i T 453.67 431.54 455.280 0.0 0.For the heat capacity of nitrogen: A 0.4 5459.8 H' 9714.5 Given 3.14 H'i R ICPH T0 Ti 3.040 10 5 8879.2 5900.593 10 K 3 D 0.593 10 i 3 0.280 (guess) B 0.8 H H' J mol H 7577.7 9112.2 7279.1 J mol 7103.7 0.

520.0 kJ kg S2 7.04 K. 1421 819 Wdot ndot H Wdot 1326 kW Ans. Wdotlost T SdotG Wdotlost 17685 kW Ans.14 K 529.5194 kJ kg K The saturation temperature is 187. 590 1653 7.6858 kJ kg K mdot 59.2963 kJ kg K 243 .02 kg sec H2 2436.33) becomes: SdotG mdot S2 S1 SdotG 58.28 Ans.6 kJ kg S1 6. (5. Table F.26) Wdotideal t mdot H2 H1 T t S2 0.34 516.96 degC. For the water at 20 degC from Table F. Eq. 7.949 kW K Ans.86 kJ kg S1 0.31 Property values and data from Example 7.2: H2 2782.62 T 525.6: H1 3391.761 S1 Ans.32 For sat.6846 kJ kg K Wdot 56400 kW T 300 K By Eq.2 492.7 kJ kg S2 6. The exit temperature of the exhaust gas is therefore 197.96 degC. and the temperature CHANGE of the exhaust gas is -202.1. (5. Wdotideal 74084 kW Wdot Wdotideal The process is adiabatic. vapor steam at 1200 kPa. H1 83.

liquid and sat.The turbine exhaust will be wet vapor steam. the best property values are found from Table F.34 1. vapor at the turbine exhaust pressure of 25 kPa.9391 0.519 kJ kg K H'3 437.11 K molwt gm mol 3 Hgas Sgas R MCPH T1 T2 3.0 0.96)K For the exhaust gases: T1 T1 ndot 125 T2 T2 ( 273.811 H3 H3 S3 S3 kg H2 2.883 x'3 x'3 H2 kJ kg S'3 Sliq Slv H'3 H'3 Hliq 2.8932 Slv 6.12 10 0.34 1.0 T2 T2 T1 T1 3 0.1 by interpolation between 64 and 65 degC: kJ kJ Hliq 272.0 ln 244 .72 For isentropic expansion of steam in the turbine: S'3 S'3 H23 H23 x3 x3 S2 6.023 x3 Slv kJ kg K mol sec 197.0 0.996 H3 Hliq Hlv 0.0 Hlv 2346. For sat.15 673.174 x'3 Hlv 10 3 kJ 0.15 K 18 400)K ( 273.15 471.345 H23 10 3 kJ kg Sliq 7.12 10 R MCPS T1 T2 3.3 kg kg kJ kg K kJ kg K Sliq 0.

731 kW Fractionboiler Wdotlost.65 kW Ans.boiler 0.4534 kW K T Wdotlost.turbine 0.156 kW K Ans.791 kJ kmol K Energy balance on boiler: mdot ndot Hgas H2 H1 mdot 0.4316 Ans.turbine Fractionboiler 45. For the boiler: SdotG Boiler: ndot Sgas mdot S2 S1 SdotG 0. (5.4229 Ans.302 kW t S1 t Wdotideal Wdot Wdotideal 0. (d) Wdotlost.15 K Wdotideal ndot Hgas mdot H3 H1 T ndot Sgas mdot S3 314.4534 kW K Ans.boiler Wdotideal 0. (c) For both the boiler and the turbine.boiler 132. 245 .Hgas 6. For the turbine: SdotG mdot S3 S2 Turbine: SdotG 0.30971 kg sec (a) Wdot mdot H3 H2 Wdot 135.25): T 293.33) applies with Q = 0.687 10 3 kJ kmol Sgas 11. (5. (b) By Eq.1560 kW T K Wdotlost. Eq.914 kW Wdotlost.

Interpolation in Table F.Fractionturbine Note that: Wdotlost. mdot H Wdot 1173.6 Ans.2 at 700 kPa for the entropy of steam with this enthalpy gives S2 mdot 2.turbine Wdotideal t Fractionturbine Fractionturbine 1 0.4 kW Ans.4586 kJ kg K Ans.5 kg sec Wdot 7.78 H kJ kg H'2 H1 H 469.1455 Ans.3 kJ kg 0. vap.2847 Interpolation in Table F.2 kJ kg S1 7.2 for sat. S'2 = S1 = 7. at 125 kPa: H1 2685.34 From Table F.359 kJ kg H1 H H2 3154.2847 kJ kg K kJ kg K For isentropic expansion. 246 .2 at 700 kPa for the enthalpy of steam with this entropy gives H'2 H2 3051. Fractionboiler 7.

75 0. this time solving it for the temperature.7 psi 55 psi 375 kPa 1000 kPa P 500 kPa 1300 kPa 55 psi 135 psi 0.75 0.15 T0 303.80 0.35 Assume air an ideal gas.15) with C = 0. First find the temperature after isentropic compression from a combination of Eqs.5 453. (4. (7.70 i S 0 J mol K 1 6 For the heat capacity of air: A 0.14) & (5.71 100 100 ndot 150 50 0.2) and (4.5 453.70 0.5 Given 3.355 (guess) B 0.59 0.82 338.15 299.7) with C = 0. Then find the work (enthalpy change) of isentropic compression by a combination of Eqs.575 10 K 3 D 0. The actual work (enthalpy change) is found from Eq. The following vectors contain values for Parts (a) through (f): 298. (5.15 373.20).15 353.59 mol sec K 101. From this value.33 kPa 375 kPa P0 100 kPa 500 kPa 14. the actual temperature is found by a second application of the preceding equation.7.75 0.016 10 K 5 2 S = R A ln B T0 D T0 2 2 1 2 1 ln P P0 Tau T0 P0 P Find 247 i Tau T0 P0 Pi i i .

2 4109.4 J mol 1.19 T 486.2 H' J 3397.0 0.016 10 5 3925.575 10 i 3 0.74 435.431.1 H H' H 6416.06 464.4 2876.6 5233.6 4735.5 (guess) Given Tau T0 H = R A T0 H Find 1 B 2 T0 2 i 2 1 D T0 Hi 1 Tau T0 i Ti T0 i i Wdot ndot H 248 .87 434.6 5133.71 K H'i R ICPH T0 Ti 3.5 mol 3986.5 Ti T0 i i 476.355 0.2 3314.5 4530 5315.

186 10 K 5 2 Tr0 T0 Tc Tr0 Pr0 Pr0 0.68 511. (6.8 bar 0.58 T 518.15 K P0 200 kPa P 1000 kPa S 0 J mol K For the heat capacity of ammonia: A 3.15).020 10 K 0.437 T T0 T 422.578 B 3. C = 0: 1.042 .79 K 702 635 Wdot 1291 304 1617 1250 hp 523 474 Wdot 962 227 1205 932 kW Ans.01 476.7 K Pc 112.725 3 D P0 Pc P 0. 7.4 (guess) Given S = R A ln B T0 T0 Tc D T0 2 1 2 1 ln P P0 SRB Pr SRB Tr0 Pr0 Find 1.66 524.36 Ammonia: Tc 405.089 Use generalized second-virial correlation: The entropy change is given by Eq.0177 Pr Pc Pr 0.253 T0 294.92) combined with Eq. (5.3 479.818 K Tr 249 T Tc Tr 1.474.

Hig Hig H' H' R ICPH T0 T 3. 250 .020 10 4.82 H H' H 5673.347 J mol K Ans.7).4 Given (guess) H = R A T0 1 Tc HRB B 2 T0 2 T0 Pr Tc 1. (7.47 K 1. written: 1.826 Hig 4652 3 0.578 3.17): 0.0 0.521 2 1 D T0 1 HRB Tr0 Pr0 Find T Tr T0 T Tc T Tr 447.186 10 5 kJ mol R Tc HRB Tr Pr HRB Tr0 Pr0 J mol The actual enthalpy change from Eq. (6. S R A ln B T0 D 2 2 T0 SRB Tr0 Pr0 1 1 ln P P0 SRB Tr Pr S 2.91) combined with Eq (4.2 J mol The actual final temperature is now found from Eq.103 Ans.

069 T T0 T 324.8292 Pr0 P0 Pc P Pr0 Pr 0.6 K Pc 46. (6.140 T0 303.7.128 K Tr T Tc Tr 0.915 10 6 0.637 B 22.91). with HRB for this T: Hig R ICPH T0 T 1. (5.0 Hig 1.2465 0.887 The enthalpy change for the final T is given by Eq.37 Propylene: Tc 365.5 bar P 18 bar S 0 J mol K For the heat capacity of propylene: A 1.15) with D = 0: 1.915 10 K 2 6 Tr0 T0 Tc Tr0 0.637 22.409 10 3 J mol H' Hig R Tc HRB Tr Pr 251 HRB Tr0 Pr0 .706 10 K 3 C 6.15 K P0 11.1 (guess) Given S = R A ln SRB B T0 T0 Tc C T0 2 1 2 1 ln P P0 Pr SRB Tr0 Pr0 Find 1.65 bar 0. (6.386 Pr Use generalized second-virial correlation: Pc The entropy change is given by Eq.92) combined with Eq.706 10 3 6.

164 10 K 2 6 Tr0 T0 Tc Tr0 1.91) combined with Eq (4.079 Tc 190.012 45.1 J mol The actual enthalpy change from Eq.H' 964. written: 1.196 252 .6167 Pr0 P0 Pc P Pr0 0.38 Methane: B 2 T0 2 T0 Pr Tc T 2 1 C 3 T0 3 3 1 HRB Tr0 Pr0 1.2 kW Ans.2 J mol ndot 1000 mol sec Wdot ndot H Wdot 1205. (6.7).761 Pr Pc Pr 1.702 B 9.1 (guess) Given H = R A T0 1 Tc HRB Find 7.80 H H' H 1205.081 10 K 3 C 2.17): 0. (7. The actual final temperature is now found from Eq.6 K T0 Pc T 327.99 bar T0 308. 0.15 K P0 3500 kPa P 5500 kPa S 0 J mol K For the heat capacity of methane: A 1.15 K Ans.

298 10 Hig 1158.91) combined with Eq (4.78 mol sec H H' H 1485.1 (guess) 253 . (6.081 10 1.15) with D = 0: 1. (6.702 9.4 kW The actual final temperature is now found from Eq. written: 1. (5.8 3 J 3 2.7). (6.164 10 6 0.1 Given (guess) S = R A ln SRB B T0 T0 Tc C T0 2 1 2 1 ln P P0 Pr SRB Tr0 Pr0 Find 1.379 K 1. with HRB for this T: Hig Hig H' H' R ICPH T0 T 1.6 J mol Ans.114 T Tr T0 T Tc T Tr 343. ndot 1500 Wdot ndot H Wdot 2228.802 The enthalpy change for the final T is given by Eq.0 mol HRB Tr0 Pr0 R Tc HRB Tr Pr J mol The actual enthalpy change from Eq.91).17): 0.92) combined with Eq. (7.Use generalized second-virial correlation: The entropy change is given by Eq.

8 J mol Ans.702 9.164 10 6 0.9.18 K Ans. Wlost T S Wlost 938.4 J mol Ans.823 Ans.081 10 5288. 254 .201 Since the process is adiabatic: SG S SG 3.702 9.15 K T2 428.0 S R ICPS T1 T2 1.2012 J mol K Ans.164 10 0.2 J mol 2.65 K P1 140 kPa P2 560 kPa Work 5288.15 K 3 6 H H R ICPH T1 T2 1.081 10 J mol K 3 2.3 J T mol 293. 7.0 ln P2 P1 S 3.14 T0 T 351.39 From the data and results of Example 7. Wideal t Work t 0. Wideal H T S Wideal 4349.Given H = R A T0 1 Tc HRB Find B 2 T0 2 T0 Pr Tc T 2 1 C 3 T0 3 3 1 HRB Tr0 Pr0 1. T1 293.

design for 4 stages. In kW/stage: R Cp Wdotr ndot Cp T1 r 1 Wdotr 255 87.) ( T2 T1) T1 Eq. 1 N (b) Calculate r for 4 stages: N 4 r P2 P1 r 2. (7.5 m 3 sec Cp 3. (7. (7. and the same power delivered to each stage.5 R V R T1 P1 ndot Vdot V ndot 19. the same efficiency in each stage.15) K T2 473.22).T2) in each stage.944 kW Ans.15) K T1 308.4 K R1 N Cp Eq.743 (a) Although any number of stages greater than this would serve.T1) to the same final conditions (P2.65 Vdot 0.18) written for a single stage is: T'2 = T1 P2 P1 Put in logarithmic form and solve for N: N R Cp ln ln P2 P1 T'2 T1 N 3.15 K 0. .7. the applicable equations are: 1 N r= P2 P1 (where r is the pressure ratio in each stage and N is the number of stages.15 K P2 50atm T2 ( 200 273.42 P1 1atm T1 ( 35 273.659 Power requirement per stage follows from Eq.23) may be solved for T2prime: T'2 T'2 415.775 mol sec With compression from the same initial conditions (P1.

8) Hw 83.15 K).5 4.4 104.6 kg kg mdotw 7.22) . Heat duty = 87.94 kW/interchanger (d) Energy balance on each interchanger (subscript w denotes water): With data for saturated liquid water from the steam tables: kJ kJ Hw ( 188.5 6 5 6 bar 8 7 Cp 3.944 kW Ans.5 R 5.2 bar 1. and the first law yields: Qdotr Wdotr Qdotr 87. there is no enthalpy change for the compressor/interchanger system.(c) Because the gas (ideal) leaving the intercooler and the gas entering the compressor are at the same temperature (308.44 Qdotr Hw mdotw 1. (in each interchanger) 300 290 T1 295 K 300 305 464 547 T2 455 K 505 496 P2 P1 2.5 4.052 kg sec Ans.0 1.5 1.1 1.0 H [ ( Cp T2 T1) ] R Cp Ideal gases with constant heat capacities HS Cp T1 P2 P1 1 256 (7.5 2.

70 0.48 2000 kPa 5000 kPa P2 5000 kPa 20 atm 1500 psi 100 kPa 200 kPa P1 20 kPa 1 atm 15 psi 0.3 10 K 6 From the steam tables for sat.959 4. (7.185 4.24) cm gm 3 4.002 1.793 0.2 523.036 V 1. water at the initial temperature (heat capacity calculated from enthalpy values): 1.3.15 363.636 0.75 0.765 kJ mol 0.15 K 294.75 Ans.liq.20 CP 4.219 3.70 0. 7.675 HS H 0.017 1.15 T1 333.1 217.003 1.26 366.2 696.698 0.20 4.75 0.3 714.47 The following vectors contain values for Parts (a) through (e).75 mdot 20 kg 30 kg 15 kg 50 lb 80 lb 1 sec 257.038 By Eq.15 4.729 HS 4.745 5. Intake conditions first: 298.20 HS V P2 P1 H HS kJ kg K 257 .

7 degF t2 258 .338 363.104 H 6.227 1.19 90.81 60.807 T 0.541 7.756 14.29 kW Wdot 62.15 t2 t2 t2 t2 T2 K 1.065 1.986 t2 t2 T2 K 1 2 3 68.188 kJ kg By Eq.21 298.957 T2 T1 T T2 333.84 hp 83.612 K 0.973 HS 5.8 135.61 degC 273.56 Ans.487 367.15 285.628 kJ kg 2.8 459.5 514.25) T H V 1 T1 CP P2 P1 0.1.81 689. 25.929 10.41 202.753 2.12 Wdot H mdot Wdot 101.762 K 294.906 4.67 4 5 70.17 0.506 50. (7.82 213.

10: H 11.802 mol 3 Calculate pump power Ws V P2 P1 Ws 0.48 Results from Example 7.57 kJ kg W 11.7 kJ kg Ans.0090 kJ kg K T 300 K Wideal H T S Wideal t W Wideal 8.57 kJ kg S 0. Wlost T S Wlost 2.15) K P1 P3 1.271 Vc 259 cm 3 mol From Table B.87 kJ kg Ans.72 kJ mol 0.2K Zc 0. t 0.1 for benzene: Tc 562.767 Ans. Since the process is adiabatic. 259 .72).53 T1 T3 ( 25 ( 200 273. 7.15) K Trn Tn Tc Assume Vliq = Vsat: V V c Zc 1 T rn Eq. From Table B.72) V cm 96.0 2 7 273. SG S SG 9 10 3 kJ kg K Ans.7. (3.053 kJ mol Ans.2bar 5bar P2 5bar Cpv 105 J mol K Hlv 30.7 Estimate the specific molar volume of liquid benzene using the Rackett equation (3.15) K 273.2 for benzene: Tn ( 80.

15K Tsat 415. Q R ICPH T2 Tsat 0.13) Hlv2 26.74 Hlv2 Hlv 1 1 Tr2 Tr1 Eq.96 10 Hlv2 Cpv T3 Tsat 51.38 0.1 kJ mol Ans.7819 B 2726.2: 13.Assume that no temperature change occurs during the liquid compression.822 kJ mol Calculate the heat exchanger heat duty.77 degC Tsat 273.9 K Tsat Estimate the heat of vaporization at Tsat using Watson's method From Table B.2 For benzene from A Table B.78 10 6 0 Q 260 .72 kJ mol Tsat Tc Tr1 ( 80 273. 3 37.572 Tsat A B ln P2 kPa C degC Tsat 142. (4.747 67. Therefore: T2 T1 Estimate the saturation temperature at P = 5 bar using the Antoine Equation and values from Table B.2 Hlv At 80 C: 30.15) K Tc Tr1 0.81 C 217.628 Tr2 Tr2 0.

75 Calculate the compressor inlet temperature.2bar P2 1.72 kJ mol 261 From Table B.2: 13. Estimate the saturation temperature at P = 1. T2.15K 134.2 For benzene from A Table B. In the exchanger the liquid is first heated to the saturation temperature at P1.21) and (7.54 T1 ( 25 273.7.7 K Estimate the heat of vaporization at Tsat using Watson's method From Table B.91 degC Calculate the compressor power Ws Cpv T3 T2 Ws 6. Note that the exchanger outlet temperature. Combining equations (7. The benzene enters the exchanger as a subcooled liquid. is equal to the compressor inlet temperature.06 K 1 P3 P2 1 T2 273.1 for benzene: Tc 562.2 bar using the Antoine Equation and values from Table B.2K .595 degC Tsat Tsat 273.15)K P3 5bar Cpv 105 J mol K 0. vaporized and finally the vapor is superheated to temperature T 2.834 kJ mol Ans.15)K P1 1. Calculate the heat exchanger duty.572 Tsat A B ln P1 kPa C degC Tsat 85.7819 B 2726.81 C 217.22) yields: T2 1 T3 R Cpv T2 408.2bar T3 ( 200 273.15K Tsat 358. (7.17).2 At 25 C: Hlv 30.

2bar T1 300K P2 6bar Cp 50.405 6 kJ mol R ICPH T1 Tsat 0.57 ndot 100 kmol hr P1 1. 262 . 7.96 10 Hlv2 Cpv T2 Tsat 37.952 C_compressor 307452 dollars Ans.15) K Tc Tr1 0.6 J mol K 0.70 Assume the compressor is adaiabatic.393 kJ mol Ans. (4.855 C_motor 32572 dollars Ans.Tr1 ( 80 273.641 kW 182.13) 3 Hlv2 30. 77) T2 Wdots Wdote 390. R Cp T2 Wdots Wdote P2 P1 T1 (Pg.638 Hlv2 Q Hlv 1 1 Tr2 Tr1 Eq.345 kW C_compressor 3040dollars Wdots kW 0.78 10 0 Q 44. C_motor 380dollars Wdote kW 0.812 K ndot Cp T2 Wdots T1 127.747 67.628 Tr2 Tsat Tc Tr2 0.38 0.

(6-94) along with MCPS function for the mean heat capacity and SRB function for the residual entropy. 263 . Tr2 T2 Tc Tr2 1.424 B 14. (6-94) S 22.024 A 1.474 K Ans.357 Pr2 P2 Pc Pr2 6 0.128 J mol K Ans. Find T2 such that H = 0. H = Cpmig T2 T1 HR2 HR1 Eq.394 10 3 C 4.392 10 D 0 a) For throttling process. Guess: T2 T1 Given 0 J mol = MCPH T1 T2 A B C D R T2 T1 T2 Pr2 R Tc HRB R Tc HRB Tr1 Pr1 Tc T2 Find T2 T2 365.59 T1 375K P1 18bar P2 1.7.328 Pr1 P1 Pc Pr1 0. (6-93) Use the MCPH function to calculate the mean heat capacity and the HRB function for the residual enthalpy. assume the process is adiabatic.40bar Tr1 T1 Tc Tr1 1.087 Tc 282.295 Calculate change in entropy using Eq. S R MCPS T1 T2 A B C D ln R SRB Tr2 Pr2 T2 T1 R SRB Tr1 Pr1 R ln P2 P1 Eq.2bar For ethylene: 0.3K Pc 50.

HR2 HRB Tr2 Pr2 R Tc HS R MCPH T1 T2 A B C D T2 T1 HRB Tr2 Pr2 R Tc HRB Tr1 Pr1 6. Guess: Given T2 T1 0 T2 P2 J R ln = R MCPS T1 T2 A B C D ln T1 mol K P1 T2 Pr2 SRB R R SRB Tr1 Pr1 Tc T2 Find T2 T2 219.779 Now calculate the isentropic enthalpy change. Given HS = MCPH T1 T2 A B C D R T2 T1 T2 Pr2 R Tc HRB R Tc HRB Tr1 Pr1 Tc T2 Find T2 T2 268. (6-94) with S = 0.b) For expansion process. Solve Eq. 264 . H HS H 4. 70% First find T2 for isentropic expansion.793 K Tr2 T2 Tc Tr2 Eq.423 10 3 J R Tc HS mol Calculate actual enthalpy change using the expander efficiency. (6-94) 0. HS.496 10 3 J mol Find T2 such that H matches the value above.536 K Ans.

The disadvantages are the extra capital and operating cost of the expander and the low temperature of the gas leaving the expander compared to the gas leaving the throttle valve.77 J mol K Ans.643 Ans. (6-94) S 7. This is because a significant portion of the energy lost by the gas is used to vaporize the oil. Calculate power produced by expander kJ Ans. P H P 3. F Cpgas T3 T1 D Hlv Coilp T3 T2 = 0 Solving for D/F gives: DF Cpgas T3 Hlv T1 T2 Cpoil T3 DF 0.Now recalculate S at calculated T2 S R MCPS T1 T2 A B C D ln R SRB Tr2 Pr2 T2 T1 R SRB Tr1 Pr1 R ln P2 P1 Eq. 265 . the overall energy balance is as follows. 7.147 mol The advantage of the expander is that power can be produced in the expander which can be used in the plant. For an adiabatic column. c) Using liquid oil to quench the gas stream requires a smaller oil flow rate.60 Hydrocarbon gas: T1 500degC Cpgas 200 J mol K 150 J mol K Hlv 35000 J mol Light oil: Exit stream: b) T2 T3 25degC Cpoil 200degC Assume that the oil vaporizes at 25 C.

9636 At point 4: Table F.1.Chapter 8 .1.9 Sliq For isentropic expansion. SI units.035 10 3 QH 3. Hliq H4 Hlv 2382.311 Ans.2. At point 2: Table F. 266 .3 At point 1: H1 H4 At point 3: Table F.Mathcad Solutions 8.3241 x'3 S'3 Sliq Slv x'3 0. H2 3531.9 x3 0. 8. 0.96 H3 Hliq x3 Hlv H3 2496.805 Ans. Ws H3 H2 QH H2 H1 Ws 1.322 10 3 Ws cycle QH cycle 0. H4 209.5 S2 6.855 H'3 Hliq x'3 Hlv H'3 2246 H3 turbine H2 H2 turbine H'3 0.7035 S'3 S2 Slv 7.1 With reference to Fig.Section A .1.

22 10 3 (kJ/s) (e) Wdot12 0 Wdot34 0 Wdot23 mdot ( H3 H2) Wdot23 873.3482 P1 3.617 (f) Wdot23 Wdot41 Qdot12 Note that the first law is satisfied: Q Qdot12 Qdot34 W Wdot23 Wdot41 Q W 0 267 . Thus by Eq.533 State 2.368 161. Step 1--2: Qdot12 mdot ( H2 H1) Qdot12 1.931 10 (kJ/s) (d) The rate of heat rejection. Wet Vapor at TC: Sliq 0. Sat.241 (c) The rate of heat addition.2 mdot 1. Vapor at TH: H2 2792. Sat.0 State 4. Step 3--4: H3 Hliq x3 ( Hvap Hliq) H4 Hliq x4 ( Hvap Hliq) H3 1.222 Wdot41 mdot ( H1 H4) Wdot41 0.0 (kg/s) The following property values are found by linear interpolation in Table F. 8. 6.3929 Svap 8.1: State 1.5200 P4 1616. Liquid at TH: H1 860.7 S1 2.8.533 State 3.741 x4 S1 Sliq Svap Sliq 3 x4 0.6 P3 1616.5 Hvap 2550.919 10 3 H4 699. (b) Steps 2--3 and 4--1 (Fig.0 S2 6.2) are isentropic.083 Qdot34 mdot ( H4 H3) Qdot34 1. Wet Vapor at TC: Hliq 112. for which S3=S2 and S1=S4.0 (a) The pressures in kPa appear above.4139 P2 3.82): x3 S2 Sliq Svap Sliq x3 0.

8 BTU lbm 268 .453 kJ kg 2609.9485 kJ kg K 3635.9013 kJ kg K 3529.8.2 and F.6 kg 6.9875 kJ kg K kJ 3475.6759 BTU lbm rankine Sat. liq.6595 BTU lbm rankine 1558.0 kJ kg 180. Enthalpies and entropies for superheated vapor. values from Tables F.9 kJ kg 191.2 and F.5 BTU lbm 69.3 The following vectors contain values for Parts (a) through (f).73 BTU lbm 1105.4 H2 kJ kg S2 6.8 kJ kg 251.9145 kJ kg K 1507.8 BTU lbm 1. 8.064 kg 2676.4): 3622.17 BTU lbm 1150.4 @ P2 and T2 (see Fig. and sat.832 Hliq kJ kg Hvap 2584.7 kJ kg 6.832 kJ kg 2584.8 kJ kg kJ 419. vap. Tables F.6 kJ kg 6.0 BTU lbm 1.4 @ P3 = P4: 191.

75 0.1326 BTU lbm rankine 1.017 gm 3 0.8321 kJ kg K 7.9094 kJ kg K 0.3069 kJ kg K 7.75 1.6493 Sliq kJ kg K 8.6493 kJ kg K 8.80 0.0167 ft 3 lbm 3 ft 0.80 0.78 0.75 0.80 0.010 gm 3 cm 1.80 turbine pump 0.1511 Svap kJ kg K 1.044 gm 3 0.010 Vliq cm gm 3 cm 1.75 0.0161 lbm 269 .9781 BTU lbm rankine cm 1.78 0.1511 kJ kg K 0.3554 kJ kg K 0.75 0.0.75 0.7568 BTU lbm rankine 0.3121 BTU lbm rankine 1.

43 108.33 kPa 14.29 kg sec 1 2 3 4 240705 355111 kJ 213277 sec 205061 QdotH QdotH QdotH QdotH QdotH mdot5 mdot6 145.598 sec 5 6 192801 BTU 228033 sec 270 .80 100 Wdot 70 50 50 80 10 kW 3 10000 kPa 7000 kPa P1 8500 kPa 6500 kPa 950 psi 1125 psi P4 10 kPa 20 kPa 10 kPa 101.733 lbm 153.13 67.7 psi 1 psi Wpump Vliq P1 pump P4 H4 Hliq H1 H4 Wpump S'3 = S2 x'3 S2 Svap Sliq Sliq H'3 Hliq x'3 Hvap Hliq H3 H2 turbine H'3 H2 Wturbine H3 H2 mdot Wdot Wturbine Wpump QdotH QdotC H2 QdotH H1 mdot Wdot Answers follow: mdot1 mdot2 mdot3 mdot4 QdotH 70.64 62.

332 160705 255111 kJ 0. 550.333 QdotC QdotC 143277 sec 155061 QdotC QdotC 8.0373 7.244 0.328 0.030 gm 3 H4 340.4 5 6 145410 BTU 152208 sec Subscripts refer to Fig.282 Wdot QdotH 0.911 The following vectors give values for temperatures of 450.9 kJ kg S2 7.24).6 H2 3565.5947 By Eq. (7.246 0.0912 Svap Wpump H1 7.3 3792. 8.0 kJ kg kJ kg K P1 Wpump 3. V 4 P4 kJ kg H1 H4 Wpump 343.3.QdotC QdotC 1 2 3 4 0.348 kJ kg Sliq 1. and 650 degC: 3340.564 kJ kg P4 P1 3300 kPa 50 kPa Saturated liquid and vapor at 50 kPa: Hliq H4 kJ kg K Hvap 2646.5891 kJ kg K 271 .3282 7. Saturated liquid at 50 kPa (point 4) V4 cm 1.

5 Subscripts refer to Fig.0526 6.381 H1 H4 Wpump H1 296. x'3 0. 7500. Saturated liquid at 30 kPa (point 4) V4 cm 1. 8.022 gm 3 H4 289. Wpump V 4 P4 P1 kJ kg 294.4 kJ kg 7.959 0.S'3 H'3 QH S2 Hliq H2 0.936 299.7 3622. (7.999 8.9013 kJ kg K .9441 Svap By Eq.914 x'3 x'3 Hvap H1 S'3 Svap Sliq Sliq H'3 H2 Wpump Hliq Wturbine Wturbine QH 0.7 272 7.314 0.2578 kJ kg S2 7.302 kJ kg P1 30 kPa Saturated liquid and vapor at 30 kPa: Hliq H4 kJ kg K Hvap 2625.491 The following vectors give values for pressures of 5000.5 H2 3643.3.7695 kJ kg K 5000 P4 7500 10000 kPa Sliq 0.332 Ans.297 0. and 10000 kPa at 600 degC 3664.24).

925 x'3 x'3 Hvap H1 S'3 Svap Sliq Sliq H'3 H2 Wpump Hliq Wturbine Wturbine QH 0. x'3 0.5 3040.386 Ans.873 8.895 0.6 From Table F.2 at four values for intermediate pressure P2: 725 P2 750 775 800 kPa 3023. and sat.89 kg 559.5 kg kJ kg 0.9 3049. liq.4 kJ kg S1 7.4939 W12 572.8321 kJ kg K 7.3 H2 kJ 3200.9 kJ kg kJ kg K 0. at 20 kPa: Hliq Sliq 251.9 H'2 3032.572 3194 S2 7.442 kJ 565.9094 The following enthalpies are interpolated in Table F.S'3 H'3 QH S2 Hliq H2 0.4797 kJ kg K 3206.375 0.453 kJ kg Hvap Svap 2609.4898 7.0 W12 H'2 H1 3187. vap.4851 7.8 273 .78 579.15 W12 H2 H1 7.359 0.2200 kJ kg K S'2 S1 For sat.2 at 7000 kPa and 640 degC: H1 3766.

x'3 S2 Svap Sliq Sliq H'3 W12 H'3 Hliq x'3 Hvap Hliq W23 W H2 W 20.073 17.where the entropy values are by interpolation in Table F.817 7.16 kPa (P2) Also needed are values of H2 and S2 at this pressure. The work calculations must be repeated for THIS case: W12 W12 H'3 H'3 H2 H1 kJ kg Hliq x'3 x'3 W23 W23 S2 Svap 0. This gives an intermediate steam temperature t2 of 366. and we interpolate linearly to find the value of P2 for which the work difference is zero: linterp W P2 0.9 kJ kg kJ kg K 7.6 degC.16 kPa 3197.2 at P2.9 kJ kg kJ kg K H2 S2 3197.16 kPa linterp P2 S2 765.0 kJ kg 765. Again we do linear interpolations: linterp P2 H2 765.4869 We can now find the temperature at this state by interplation in Table F.469 x'3 Hvap 10 3 kJ H'3 568.4869 7.723 kJ kg W23 The work difference is essentially linear in P2.94 Sliq Sliq 568.2.811 5.5 Hliq 2.46 H2 kJ kg kg 274 .

Work W12 W23 Work 1137 kJ kg For a single isentropic expansion from the initial pressure to the final pressure.2 kJ kg Whence the overall efficiency is: Work overall W' overall 0.8202 Ans.903 H'3 2. 275 . which yields a wet exhaust: x'3 S1 Svap Sliq Sliq H'3 Hliq x'3 Hvap Hliq x'3 0.38 10 3 kJ kg W' H'3 H1 W' 1386.

2 for steam at 4500 kPa and 500 degC: H2 3439.7 From Table F.6 H2 kJ kg H3 0. & vap.78 2.0311 kJ kg K S'3 S2 By interpolation at 350 kPa and this entropy.3 kJ kg S2 7.8321 kg K 7.918 10 3 kJ WI kg WI H'3 521. liq.586 H2 kJ kg WI Isentropic expansion to 20 kPa: S'4 Hliq Sliq S2 251.453 kJ kg kJ Exhaust is wet: for sat.8.9094 276 . H'3 H3 2770.: Hvap Svap 2609.9 kJ kg kJ kg K 0.

liq.2): H7 584.317 x'4 Hvap 10 3 kJ Hliq kg H'4 H2 3 H4 2.841 kJ kg 257.87 (degC) We need the enthalpy of compressed liquid at point 1.26 kPa Vsat.270 kJ kg t7 138.073 cm 3 gm Also by approximation.liq 9.15 K t1 132.017 P5 cm gm H6 H6 P5 20 kPa P6 4500 kPa Wpump Wpump H5 Wpump kJ kg 5. where the pressure is 4500 kPa and the temperature is: t1 138.x'4 x'4 H4 S'4 Svap 0.liq kJ 558.87 At this temperature.1 gives: Hsat.564 10 3 kJ kg H5 Hliq V5 V 5 P6 1.32 10 1.083 20 4 1 1.294 For sat.5 kg Psat 294. 132.87 6 T1 t1 273. interpolation in Table F.liq 1.876 H2 Sliq Sliq H'4 H'4 Hliq 2.87 degC. at 350 kPa (Table F. the definition of the volume expansivity yields: 1 Vsat.063 cm gm K 3 P1 P6 K 277 .

3 kJ QH H2 H1 1 kg QH 2878 kJ Wnet QH 0. (7.567 kJ Wnet WI Wpump 1 kg WII Wnet 823. Work in 2nd section of turbine: WII ( kg 1 mass) H4 H3 WII 307.4 for steam at 650(psia) & 900 degF: H2 1461.2 BTU lbm S2 1. H'3 1180. 8.liq Vsat.By Eq. Although entropy values are not needed for most points in the process. From Table F.8.2861 Ans.8 Refer to figure in preceding problem.78 WI H'3 H2 H3 H2 WI H3 1242.7431 BTU lbm rankine 278 .305 kJ kg By an energy balance on the feedwater heater: mass H1 H3 H6 H7 kg mass 0.6671 BTU lbm rankine S'3 S2 By interpolation at 50(psia) and this entropy.13028 kg Ans. H1 Hsat.2 BTU lbm WI 219.liq 1 T1 P1 Psat H1 561. they are recorded here for future use in Problem 15.25).024 BTU lbm S3 1.4 BTU lbm 0.

liq.489 BTU lbm P6 650 psi H6 H5 Wpump H6 72.944 S4 1.67 rankine t1 270.01 279 .8 BTU lbm x4 H4 Hvap Hliq Hliq S4 Sliq x4 Svap Sliq x4 P5 0.9781 BTU lbm rankine x'4 S'4 Svap Sliq Sliq H'4 Hliq x'4 Hvap Hliq x'4 0.4): H7 250.Isentropic expansion to 1(psia): S'4 S2 Exhaust is wet: for sat. at 50(psia) (Table F.219 BTU lbm For sat.73 BTU lbm Hvap 1105.21 BTU lbm t7 281. where the pressure is 650(psia) and the temperature is t1 281.831 H'4 931.1326 BTU lbm rankine Svap 1.: Hliq 69.01 11 T1 t1 459. liq.01 S7 0.204 BTU lbm H4 H2 H'4 H2 H4 1047.8748 BTU lbm rankine V5 ft 0. & vap.8 BTU lbm Sliq 0.0161 lbm 3 1 psi H5 Hliq Wpump V 5 P6 P5 Wpump 2.4112 BTU lbm rankine We need the enthalpy of compressed liquid at point 1.

At this temperature.25) and (7.1717 ft 3 lbm BTU lbm rankine Ssat.26).87 psi 238.6 0.liq 4.397 By an energy balance on the feedwater heater: mass H1 H3 H6 H7 lbm mass 0.3 gives: Psat Hsat.95 10 0.liq P1 T1 Psat P1 Psat H1 S1 257.liq 0.liq Ssat.18687 lbm Ans.liq Vsat.586 BTU 1.204 10 BTU 3 Wpump 1 lbm H1 1 lbm 0. 270. 280 . H1 S1 Hsat.3112 Ans. interpolation in Table F.liq 1 Vsat.01709 ft 3 lbm rankine P1 P6 1 rankine BTU lbm BTU lbm rankine By Eq. Work in 2nd section of turbine: WII Wnet QH 1 lbm WI H2 Wnet QH mass H4 H3 WII WII Wnet QH 158.01726 20 5 0.01 degF.3960 The definition of the volume expansivity yields: 1 Vsat.liq 0.liq 41.96 BTU lbm Vsat. (7.051 BTU 374.

6 H2 kJ kg WI kg From Table F. from Table F.1258 kJ kg K P2 6500 kPa At point 3 the pressure must be such that the steam has a condensation temperature in feedwater heater I of 195 degC.244 10 3 kJ WI WI H'3 407.8. Its saturation pressure. S'3 H'3 H3 S2 3142.1 kJ kg S2 7.0 kPa.1.2. and if expansion from P2 to P3 is isentropic. 5 deg higher than the temperature of the feed water to the boiler at point 1.2: H2 3652.80 3. kJ kg H3 H10 0. The steam at point 3 is superheated vapor at this pressure. is 1399.9 Steam at 6500 kPa & 600 degC (point 2) Table F.1: 829.9 kJ kg 281 .6 H2 By double interpolation in Table F. corresponding to 195 degC.

1: 1 Vliq 5. vap.023 20 10 4 1 1.238 kJ kg H67 Wpump We apply Eq.8321 kJ kg K Hvap Svap 2609. and its properties from Table F.9 kJ kg kJ kg K Vliq 1.017 cm 3 gm 7. They can be estimated from data in Table F. the properties of sat. we have saturated liquid at 20 kPa.24)] 8. liq.9094 If we find t7.2 are: tsat H6 60.2 kJ kg K K CP kJ kg K Solving Eq. (7.012 cm 3 gm K CP 272. At point 6.15 K P6 20 kPa Wpump Wpump [Eq.0 10 4. (7.18 230.Similar calculations are required for feedwater heater II. then t8 is the mid-temperature between t7 and t1(190 degC). At the exhaust conditions of 20 kPa. For this we need values of the heat capacity and volume expansivity of water at about 60 degC.453 kg 0. are: Hliq Sliq kJ 251.408 1. (7. and that fixes the pressure of stream 4 so that its saturation temperature is 5 degC higher.25) for the calculation of the temperature change from point 6 to point 7.09 Hliq V 6 P2 P6 Tsat V6 tsat Vliq 273.678 K t7 tsat T67 K t9 190 2 282 t7 t7 t8 t9 5 . and sat.25) for delta T gives: T67 H67 Vliq 1 CP Tsat P2 P6 T67 0.

1 at saturation temperatures t9 and t1: Hsat.t7 60.691 kJ kg At points 9 and 1.1 V9 kJ 807.768 t8 130.128) gm T 20 K 1 9 V9 T 1 1 Vsat.9 kJ kg T1 ( 273.15 190)K T1 1 T1 463. and we find the effect of pressure on the liquid by Eq. (7. .38 T9 273.089 kJ kg Now we can make an energy balance on feedwater heater I to find the mass of steam condensed: mI H1 H3 H9 H10 kg 283 mI 0.142 gm 3 Psat.226 10 3 1 K H9 Hsat.38 From Table F.9 Vsat.9 kJ kg H7 Hliq H67 t9 125.6 kg Vsat.1 H1 810.9 234.11563 kg Ans.1: H8 547.1 1 P2 Psat.056) gm V1 cm 1.9 1 9 T9 P2 Psat.1 Vsat.9 kPa Hsat.1 kPa 3 cm 1. the streams are compressed liquid (P=6500 kPa).5 kg ( 1. Values by interpolation in Table F.15 t9 K H7 259.92 10 4 1 K 1 1.9 kJ 526.1 V1 T Vsat.9 H9 530.156 1255.9 9 8.065 gm 3 Psat.1 ( 1.1 3 cm 1.15 K H1 Hsat.9 cm 1.25).075 Vsat.

Isentropic expansion of steam from the initial conditions to this pressure results in a slightly superheated vapor.842 10 kJ 3 Wturbine Wturbine Wpump 1 kg QH 0.1 is 273.3265 Ans.38 (see above) is the saturation temperture in feedwater heater II. where the exhaust is wet.2 kJ kg Then H4 H4 H2 2. x'5 x'5 Then S2 Svap 0. for which by double interpolation in Table F.941 H'4 10 3 kJ H2 kg We can now make an energy balance on feedwater heater II to find the mass of steam condensed: mII H9 H7 1 kg H4 mI H10 H8 H8 mII 0.349 x'5 Hvap 10 3 kJ Hliq kg H5 2609. The saturation pressure by interpolation in Table F.28 kPa. The final stage of expansion in the turbine is to 20 kPa. 284 . For isentropic expansion.2 kJ QH H2 H1 1 kg QH 2.4 kJ kg H5 H2 H'5 H2 The work of the turbine is: Wturbine WI 1 kg 1 kg mI H4 H3 1 kg mI mII H5 H4 936.09971 kg Ans.The temperature at point 8.889 Sliq Sliq H'5 H'5 Hliq 2.2: H'4 2763. t8 = 130.

853 10 3 11.92) combined with Eq.853 10 K 3 C 11. with HRB at the above T: Hig R ICPH T0 T 1.123 Use generalized second-virial correlation: The entropy change is given by Eq.15 K P0 4800 kPa P 450 kPa S 0 J mol K For the heat capacity of isobutane: A 1.48 bar 0.0 Hig 1.677 37.1 K Pc 36.3158 0. Then T0 533. (5.3064 Pr0 Pr P0 Pc P Pc Pr0 Pr 1.141 10 4 J mol 285 . (6. (6.49 K Tr T Tc Tr 1.181 For isentropic expansion in the turbine.15) with D = 0: 0.945 10 K 2 6 Tr0 T0 Tc Tr0 1. let the initial state be represented by symbols with subscript zero and the final state by symbols with no subscript.8.10 Isobutane: Tc 408.945 10 6 0.8 (guess) Given S = R A ln SRB B T0 T0 Tc C T0 2 1 2 1 ln P P0 Pr SRB Tr0 Pr0 Find 0.91).114 The enthalpy change for this final temperature is given by Eq.677 B 37.852 T T0 T 454.

853 10 286 3 11.7 mol Zc 2 0.59 mol sec Ans.15 K b.282 Trsat Tsat Tc 3 Trsat 0. and for this we need an estimate of the molar volume of isobutane as a saturated liquid at 450 kPa.15 K: Hig R ICPH T Tsat 1.775 Cvp 274.945 10 6 0. The saturation temperature at 450 kPa is given by the Antoine equation solved for t degC: VP Avp 450 kPa 14.Hturbine Hturbine Hig 8850. (3.24). For saturated vapor at 307. This is given by Eq.57100 Bvp Cvp 2606.15 K Enthalpy change of cooling: HRB at the initial state has already been calculated. The enthalpy change of the isobutane in the cooler/condenser is calculated in two steps: a.0 .362 mol 488.677 37.72).753 Vliq Wpump V c Zc 1 T rsat 7 Vliq P Wpump cm 112.48 to 307.8 Vliq P0 J mol The flow rate of isobutane can now be found: mdot 1000 kW Wturbine Wpump mdot 119. (7.068 tsat Avp Bvp VP ln kPa 3 tsat 34 Tsat Tsat tsat 273. Condensation of the vapor at 307.15 K 307.15 K Vc cm 262.6 R Tc HRB Tr Pr J mol HRB Tr0 Pr0 Wturbine Hturbine The work of the pump is given by Eq. Cooling of the vapor from 454.

let the initial (inlet) state be represented by symbols with subscript zero and the final (exit) state by symbols with no subscript.756 Hig 18082 10 4 J mol HRB Tr Pr R Tc HRB Trsat Pr J mol For the condensation process. we estimate the latent heat by Eqs.013 Tn Tc Trn 0.118 10 4 J mol Hb Qdotout Hn 1 1 Trsat Trn Ha Hb Hb Qdotout 18378 J mol mdot Qdotin Qdotout Wturbine 4360 kW Wpump mdot Qdotin 1000 kW Qdotin 0.13): Tn 261.641 R Tn 1. Then T0 S 413.092 ln Hn 0.123 gm mol 287 . 5360 kW 8.12) and (4.48 bar 0.181 For isentropic expansion in the turbine. (4.15 K 0 J mol K P0 3400 kPa P 450 kPa molwt 58.187 Ans.38 Trn 1.930 Hn 2.Hig Ha Ha 1.11 Isobutane: Tc 408.4 K Pc bar Trn 0.1 K Pc 36.

08 K 0. (6.853 10 9.15) with D = 0: 0.945 10 6 0.945 10 K 2 6 Tr0 Tr0 Pr0 Pr P0 Pc P Pc Pr0 Pr 0.530 SRLK0 1. (5. with HRB at the above T: Hig Hig Hturbine Hturbine R ICPH T0 T 1.123 Use Lee/Kesler correlation for turbine-inlet state.92) combined with Eq. designating values by HRLK and SRLK: HRLK0 1. (6.3 10 3 J 3 11.8 Given (guess) S = R A ln SRB T0 Tc B T0 Pr C T0 2 1 2 1 ln P P0 SRLK0 Find 0.91).6 HRLK0 Wturbine Hturbine .0 mol R Tc HRB Tr Pr J mol 288 Hig 4852.0124 3 C 11.For the heat capacity of isobutane: A 1.160 The entropy change is given by Eq.677 T0 Tc B 37.809 T Tr T0 T Tc T Tr 334.932 0.819 The enthalpy change for this final temperature is given by Eq.677 37.853 10 K 1.

15 K it was found in Problem 8.15 K b.36 cm 3 mol Wpump Vliq P0 P Wpump 331.753 6 R ICPH T Tsat 1. For saturated vapor at 307. .817 kJ mol R Tc HRB Trsat Pr J mol 0.The work of the pump is given by Eq.15 K Enthalpy change of cooling: HRB at the initial state has already been calculated.677 37. and the required value for the molar volume of saturated-liquid isobutane at 450 kPa (34 degC) is the value calculated in Problem 8. (7. The enthalpy change of the isobutane in the cooler/condenser is calculated in two steps: a.10: Hb 18378 J mol Qdotout Qdotout 289 mdot Ha Hb 27553 kW Ans. Cooling of the vapor from 334.0 Ha Ha Hig 2975 HRB Tr Pr For the condensation process.15K Trsat Tsat Tc 3 Trsat 11. the enthalpy change was found in Problem 8.462 J mol For the cycle the net power OUTPUT is: mdot kg 75 molwt sec Wdot Wdot mdot Wturbine 5834 kW Wpump Ans.07 to 307.945 10 0.10 as: Tsat Hig Hig 307.853 10 2.10: Vliq 112.24). Condensation of the vapor at 307.

i.134 Ans.175 We now recalculate results for a cycle for which the turbine and pump each have an efficiency of 0. The work of the turbine is 80% of the value calculated above.8 Wturbine W'turbine 3882 J mol The work of the pump is: W'pump Wdot Wpump 0.8 mdot W'turbine W'pump W'pump Wdot 414. Wdot Qdotin 290 . W'turbine 0.3 J mol Ans. The increase in pump work shows up as a decrease in the heat added in the heater/boiler. Thus Qdotin Qdotin W'pump Wpump mdot 0.8.e. Thus Qdotout Qdotout Qdotout 28805 kW Wturbine W'turbine mdot Ans. Ans. Wdot Qdotin 0. 4475 kW The decrease in the work output of the turbine shows up as an increase in the heat transferred out of the cooler condenser. Qdotin 33280 kW Ans..For the heater/boiler: Qdotin Wdot Qdotout Qdotin 33387 kW Ans.

8.341 0.845 K re = VB VA = VC VA = PC R TA PA PA PD re T C PA T A PC re 8. 3 Ratio 5 7 9 Eq. Eq.15 K PD 5 bar 1.30b): TD TC PD PC TA QDA CP QDA 1500 J mol QDA = CP TA TD R TC TD TA 515. 1 1 Ratio 291 . CP 7 R 2 PC 1 bar TC 293.14 2.434 Ans.10.4 By Eq.12) now becomes: 1 Ratio = PB PA 1.35 0.8.248 0.396 0.13 Refer to Fig. (3.157 Ans.841 Ans. (3. (8.30c): 1 PC V C = PD V D 1 VC VD = PD PC or r 1 PD PC r 3.

552 292 . (7.22) R CP 2 WAB = CP TA PB PA 1 = CP TA cr 7 1 WCD = CP TC PD PC R CP 2 1 = CP TC er 7 1 where cr is the compression ratio and er is the expansion ratio.5 2 7 er 0.16 Figure shows the air-standard turbojet power plant on a PV diagram.8. cr 6. Since the two work terms are equal but of opposite signs.15 K R CP 2 By Eq. 7 TA 303.15 K TC 1373.5 (guess) 2 7 Given TC er 1 = TA cr 1 er er Find er) ( 0.

15K 582K 3.589 bar Ans.8 Assume air to be an ideal gas with mean heat capacity (final temperature by iteration): Cpmair MCPH 298.By Eq.4 m sec Ans.921 J mol K 293 .05bar PB 7.18): TD = TC PD PC 2 7 R CP This may be written: TD TC er 1 By Eq. 8. (7.355 0. (7.17 TA 305 K PA 1.11) uE 2 uD = 2 2 PD V D 1 1 PE PD (A) We note the following: er = PD PC cr = PB PA = PC PE cr er = PD PE The following substitutions are made in (A): uD = 0 1 = 2 R = 7 CP PD V D = R T D molwt 29 PE PD gm mol = 1 cr er Then 2 7 uE 2 R 7 TD 1 2 molwt 1 cr er uE 843.5bar 0.0 0.016 10 5 R Cpmair 29. PE 1 bar PD cr er PE PD 3.575 10 3 0.

470 3.217 R ( 298.217*R.292 10 3 J mol TA TB 582. Because the combustion is adiabatic. For methane the temperature change is very small. Assume a value for N until the above energy balance is satisfied.638 (This is the final value after iteration) 582.121 0. The value for air is given above.21N-2) mol O2 1 n 2 .896 10 5 J mol The product stream contains: 1 mol CO2.15 4.15 300)K Cpmair N ( 298.639 B 1.1 for 298 K: 4.457 A 2 3.045 1.280 3.79 N .21 N i 1 4 5.593 0.126 K Combustion: CH4 + 2O2 = CO2 + 2H2O Basis: Complete combustion of 1 mol CH4.157 D 0.450 0. use the value given in Table C. 0.79N mol N2. the basic equation is: HR H298 HP = 0 For H_R.506 10 3 1.040 0. the mean heat capacities for air and methane are required. (a) TC HR HR 1000K N 57. Reactants are N mol of air and 1mol CH4. 2mol H2O.Compressor: R Cpmair Wsair TB Cpmair TA Wsair Cpmair PB PA 1 Wsair 8.227 10 5 294 . and (0. The solution process requires iteration for N.03)K 4.

Ans. to 1.) mol Thus.3872 10 10 6 J mol From Ex. Assume expansion of the combustion products in the turbine is to 1(atm).0361 0.0133 bar: PD 1. The mean heat capacity is that of the combustion gases.036 D 1.7: H298 HP 136. . B.517 0.638 moles of air per mole of methane fuel.223 802625 HR H298 J (This result is sufficiently close to zero. and D have the final values determined above.12K 198.517 0. This calculation yields an exhaust temperature of about 390 K.ni i 58. i.638 moles of combustion product: R Cpm Ws 58.5bar The pertinent equations are analogous to those for the compressor. For an initial calculation use the mean heat capacity already determined.638 Cpm TC PD PC 1 Ws 1.292 J mol 1.387 5 10 R MCPH 298. Cpm Cpm MCPH 1000K 343.15K 1000.) Ans. Thus iteration starts with this value.0133bar PC 7.0 1.214 10 6 J mol TD TC Ws Cpm TD 343.K 198.15K HP 1.849 10 3 1.517 B 0.0361 0.e. and depends on the temperature of the exhaust gases from the turbine. Parameters A. N = 57..638 A i ni Ai B i ni Bi D i ni D i 5 A CpmP HP 198.123 K 295 (Final result of iteration. 4.0 CpmP TC 298.3872 10 5 R J mol K For 58. which must therefore be found by iteration.

8.365 10 5 TD 5 343.629 0.19 TC 111.4K TH 300K Hnlv HE 8.05 cents kW hr Ans.651 kJ QC QH 1 HE QC 1. This is about 1/2 to 1/3 of the typical cost charged to residential customers.35 me 0. with the following results: (b) TC 1200 N 37.07 Wsnet 5.00 dollars GJ Cost_electricity tm Cost_fuel 1 me ( line_losses) Cost_electricity 0.651 kJ W 0.18 tm 0.Wsnet Ws Wsair N Wsnet 7. (J per mole of methane) Parts (b) and (c) are solved in exactly the same way.123 (c) TC 1500 N 24.7519 10 TD 598.6 Carnot 0.95 line_losses 20% Cost_fuel 4.48 Wsnet 7.206 Carnot 1 TC TH Carnot kJ mol HE 0.201 mol kJ Ans. 296 .94 8.377 Assume as a basis: W 1kJ QH QC Hnlv W HE QH 2.364 10 5 J mol Ans.

Candidates that provide reasonable pressures at the required temperature levels include ammonia.20 TH ( 27 273. n-butane.6 2 3 actual 0. and propane. 297 . This argues for working fluids that are relatively inexpensive.028 Ans.07 Ans. c) The thermal efficiency is low and high fluid rates are required to generate reasonable power.8.15)K a) Carnot 1 TC TH Carnot 0.15)K TC (6 273. b) actual Carnot 0.

118 Q43 ( H3 H4) 298 Q43 59.83 138.21868 P1 P2 138.83 State 2.03408 Svap 0.3) 0.302 (c) Heat addition.971 x4 S1 Sliq Svap Sliq x4 0. Sat. Liquid at TH: H1 44.4 Basis: 1 lbm of tetrafluoroethane The following property values are found from Table 9. for which S3=S2 and S1=S4.15) K TH 293.2) are isentropic. Thus by Eq.797 Wdot QdotC (9. Wet Vapor at TC: Sliq 0.888 H4 42.943 S1 0.Mathcad Solutions 9. Wet Vapor at TC: Hliq 116.15 K TC ( 20 273.15 K QdotC Carnot 125000 kJ day TC TH TC (9.09142 0. Sat.1: State 1.15) K TC 253. (b) Steps 3--2 and 1--4 (Fig. 8.77 (Btu/lbm) .183 dollars yr Ans.187 Hvap 104.617 (a) The pressures in (psia) appear above. 6.617 State 4.6 Carnot 3. Vapor at TH: H2 State 3. Step 4--3: H3 Hliq x3 ( Hvap Hliq) H4 Hliq x4 ( Hvap Hliq) H3 101.2) Wdot 0.82): x3 S2 Sliq Svap Sliq x3 0.381 kW Cost 0. 9.2 TH ( 20 273.22418 P4 26.Section A .471 P3 26.Chapter 9 .166 S2 15.08 kW hr Wdot Cost 267.

Step 2--1: Q21 ( H1 H2) Q21 71.3): T'C Carnot T'H T'C Carnot 10. (9.43 By Eq.689 kJ sec Ans. Given that: 0.8): Carnot Carnot 0. (5.15 K (Engine) (Refrigerator) T'C 273.(d) Heat rejection.926 By definition: = Wengine QH = Q'C Q'C Wrefrig 35 kJ sec But Wengine = Wrefrig QH Q'C Carnot Carnot Whence QH 7. 299 .15 K T'H 298.825 (f) Q43 W14 W32 5.15 K 1 TC TH By Eq.448 kJ sec Ans.6 Carnot 6.278 W14 ( H4 H1) W14 2.223 (Btu/lbm) (e) W21 0 W43 0 W32 ( H2 H3) W32 14.556 QH Q'C QH 20.6 Carnot 0.15 K TH 523.219 Note that the first law is satisfied: Q Q21 Q43 W W32 W14 Q W 0 9.7 TC 298.

67 479.79 0.78 0. 489.75 QdotC 600 500 400 300 200 Btu sec 107.15)K TH 313.5 kW QC W 2.22325 S2 0.8 (a) QC 4 kJ sec W 1.75 K Ans.1.1 for sat. liquid S'3 = S2 (isentropic compression) 300 .15 K TC TH 1 TC 227.22525 0.67 rankine 459.978 Btu lbm Btu lbm rankine T4 539.320 105. Values of H2 and S2 for saturated vapor come from Table 9. (b) QH QC W QH 5.77 0.542 Btu lbm 0.67 0. 9.471 103.9.667 Ans.015 101.22418 0.4 degC 9.76 0.9 The following vectors contain data for parts (a) through (e).907 H2 104.67 T2 469.67 449.67 rankine From Table 9. (c) = TC TH TC TH ( 40 273.5 kJ sec Ans. Subscripts refer to Fig.1. or -45.22647 H4 37.22244 0.

084 30.1 is 101.22 (H=114) and at S=0.098 kJ kg 273.336 283.146 lbm sec Ans.711 276. 689. For isentropic compression. This leads to the following values (rounded to 1 decimal): 115.5 116. Wdot mdot H23 Wdot 99. The most satisfactory procedure is probably to read an enthalpy at S=0.026 286.24 (H=126) and interpolate linearly for intermediate values of H.6 595.613 3.2 90.5 100. G.361 mdot 6. This cannot be done with much accuracy.0 H'3 116.1 268.37(psia).4 kW Ans.438 H3 279.732 mdot QdotC H2 H1 7.8 72.5 117.653 kJ kg H1 88. from Point 2 to Point 3'.2 at this pressure and at the entropy values S2.414 50.6 94.9 Btu lbm H23 H'3 H2 H3 H1 H2 H4 H23 24. 301 .2 117.337 kJ kg H23 36.337 43. we must read values for the enthalpy at Point 3' from Fig.The saturation pressure at Point 4 from Table 9.016 4.918 8.5 Ans.2 Btu sec QdotH mdot H4 H3 QdotH 494 386.

15)K 1200 kJ kg T4 H2 ( 34 273.1 is 5.1. T2 ( 4 273.4 S'2 = S2 (isentropic compression) The saturation pressure at Point 4 from Table F.76 9.995 Carnot TH TC Carnot 6. This requires double interpolation.10 Subscripts in the following refer to Fig.793 7.25 4.2 the enthalpy (Point 3') at this pressure and at the entropy S2.15)K kJ kg S2 0. The pressure lies between entries for pressures of 1 and 10 kPa. changes very little with P and can be interpolated linearly.71 5.368 302 . and linear interpolation with P is unsatisfactory.697 QdotC Wdot 5.996 Ans. and interpolation must be in accord with this relation.0526 kJ kg K QdotC H4 kJ sec 2508.6.256 3. All property values come from Tables F.7 kJ kg H23 H23 H'3 H2 kJ kg H1 H4 402. 9. TC T2 TC TH T4 9. on the other hand. We must find in Table F. Linear interpolation with temperture is satisfactory in either case. Steam is here very nearly an ideal gas.746 4. The result of interpolation is H'3 2814. The enthalpy. 9.1 and F. for which the entropy is linear in the logarithm of P.914 Ans.9 142.318 kPa.2.485 2.

238 Ans.H3 mdot H2 H23 QdotC H3 mdot 2.911 10 3 kJ kg H2 H1 H3 0.881 T4 T2 Carnot 9.11 Parts (a) & (b): subscripts refer to Fig.507 kg Ans. 9.505 Btu lbm Hvap 303 100. QdotH Wdot mdot H4 mdot H23 QdotH Wdot 1404 204 kW Ans. vapor from Table 9. sec Ans.799 Btu lbm H2 Hvap . liquid and sat.667(psia)] for sat. QdotC Wdot T2 Carnot 5.1: Hliq 7.1 At the conditions of Point 2 [t = -15 degF and P = 14. sec kJ Ans. 9.

liquid at Point 4 (80 degF): H4 37.37(psia) H3 118.07892 Btu lbm rankine (a) Isenthalpic expansion: H1 H4 QdotC 5 Btu sec mdot QdotC H2 H1 mdot 0.5896 Ans.3 Btu lbm Eq. .262 Btu lbm rankine mdot QdotC H2A H4 mdot 0. (9.978 Btu lbm S4 0. (b) Isentropic expansion: S1 S4 x1 S1 Svap Sliq Sliq H1 Hliq x1 Hvap Hliq H1 34. vapor at Point 2.01733 Btu lbm rankine Svap 0.Sliq 0.0796 lbm sec Ans. G. vapor from the evaporator is superheated in the heat exchanger to 70 degF at a pressure of 14. (c) The sat. (d) For isentropic compression of the sat.5 Btu lbm S2A 0.0759 lbm sec Ans. Property values for this state are read (with considerable uncertainty) from Fig. G.4) may now be applied to the two cases: In the first case H1 has the value of H4: H2 a H4 H2 a 304 H3 3.667(psia).2: H2A 117.0629 lbm sec Ans. S3 Svap and from Fig.22714 Btu lbm rankine For sat.892 BTU lbm mdot QdotC H2 H1 mdot 0.2 at this entropy and P=101.

634 lbm sec QdotC 2000 Btu sec mdot QdotC H2 H1 305 .12 Subscripts: see figure of the preceding problem. vapor.907 Btu lbm S2 0. t = 20 degF and P = 33. In Part (c).22325 Btu lbm rankine At Point 2A we have a superheated vapor at the same pressure and at 70 degF.2435 Btu lbm rankine Btu lbm R For sat.885 BTU lbm mdot 25.7659 Ans. liquid at Point 4 (80 degF): H4 37. G.978 S4 0. Again from Fig.2: H3 138 Btu lbm Wdot Wdot H3 1.289 H2A mdot BTU sec (Last calculated value of mdot) QdotC c Wdot c 3.In the second case H1 has its last calculated value [Part (b)]: H2 b H1 H2 b H3 3.2: H2A 116 Btu lbm Btu lbm S2A 0.110(psia)] from Table 9. compression is at constant entropy of 0. G.1: H2 105. From Fig.07892 Energy balance.8791 Ans. heat exchanger: H1 H4 H2A H2 H1 27. At the conditions of Point 2 [sat. 9.262 to the final pressure.

13 Subscripts refer to Fig.471 Btu lbm S2 0.2435 to the final pressure of 101. G.087. vapor @ 10 degF] from Table 9.3 H'3 116.1. 9.032 kW Ans.239 H4 37. liquid at Point 4 come from Table 9. 9. 80.1 and H values for Point 3` come from Fig.2: H'3 127 Btu lbm 0. 14.For compression at constant entropy of 0.5 119.22325 to P = 101.2.1: H2 104. and compression is at a constant entropy of 0.75 Hcomp H'3 H2A Wdot mdot Hcomp 25. 31. G. At Point 2 [sat. & 138.37(psia). mdot QdotC H2 H4 H'3 116 Btu lbm Hcomp Hcomp H'3 H2 Wdot mdot Hcomp lbm sec 13.37. then H1 = H4.978 44.667 Btu lbm mdot If the heat exchanger is omitted. & 100 degF at pressures of 72. Points 2A & 2 coincide. The vectors following give values for condensation temperatures of 60.943 Btu lbm 113.3 Btu lbm H1 H4 306 . by Fig.66 kW Hcomp Ans.443 Wdot 418. 101.37(psia).634 lbm sec Wdot 396.22418 Btu lbm R S'3 S2 H values for sat.83(psia) respectively.457 Btu lbm mdot 29.

011 Ans. 9.528 4.4): H2 H'3 H1 H2 8.4) now becomes H2 H1 H 6. (9. (9.75 TH TC TC TC Find TC 268.75 TH TH TC Wdot = QdotH TH TC Given 250 (Guess) TH TC Wdot = TH 0.294 5.(a) By Eq.146 3.75 Eq.15 Wdot 1.94 K Ans.21 degC 307 . (b) H H'3 0. Minimum t = -4.5 TC QdotH = 0.14 WINTER TH 293.221 4.014 H2 Since H = H3 H2 Ans.

15 and 9.4 kJ kg By Eq. H4 1033. Maximum t = 49.75 TH TC TH TC Wdot = TC QdotC TH 300 (Guess) Given Wdot 0.15 and 9.16 come from Perry's Handbook.3 kJ kg H9 284.17 0.67 rankine QC 50000 Btu hr WCarnot QC 308 TH TC TC WCarnot 12253 Btu hr . 9.15 0.17 Advertized combination unit: TH ( 150 459.8): z H4 H9 H15 H15 z 0.57 K Ans.SUMMER TC QdotC 298.7 1056.67)rankine TH 609.67 rankine TC 489.16 Data in the following vectors for Pbs.351 Ans. 9.7 kJ kg H15 1186.42 degC 9. 7th ed.75 TH TC = TH TC TC TH Find TH TH 322.67)rankine TC ( 30 459. (9.5 785.

The amount of heat rejected at the higher temperature of 150 degF is QH WI QC QH 68380 Btu hr For the conventional water heater. WI + WII.5 WCarnot WI 18380 Btu hr This is the TOTAL power requirement for the advertized combination unit. For the conventional cooling unit. to the r Carnot work: 9. This problem is just a reworking of Example 9.67) rankine WCarnot QC TH TC TC WCarnot 9190 Btu hr Work 1.WI 1. 309 .65 TC T'H TC II 0.5 WCarnot Work 13785 Btu hr The total power required is WII QH Work WII 82165 Btu hr NO CONTEST 9. (9. It could be useful as a group project.18 TC 210 T'H 260 T'C 255 TH 305 By Eq.3): TC TH TC I 0. TH ( 120 459.3 with different values of x. this amount of energy must be supplied by resistance heating. which requires power in this amount.65 T'C TH T'C WCarnot = QC WI = QC I WII = QC II Define r as the ratio of the actual work.19 1 I 1 II r 1.477 Ans.

063 Ans.196 bar PH Given ln PH bar = 45.40kW TC Carnot TH TC 6.536 kW 310 .15) K T2 T1 Calculate the high and low operating pressures using the given vapor pressure equation Guess: PL 1bar PH 4104.25 3 2 65% Carnot 4.0 bar T4 K 2 PH Find PH PH 11.9.67 T1 K 2bar PL Given ln PL bar = 45.025 kW Follow the notation from Fig.22 TH 290K TC 250K Carnot Ws 0. QC 9.133 6. 9.146 ln T4 K 615.15) K T2 ( 20 273.15) K Using values from Table C.79 10 3 16.327 5.0 bar T1 K 2 PL Find PL PL 6.3 QdotC ndottoluene R ICPH T1 T2 15.23 Ws QC 1.15) K T4 ( 30 273.67 T4 K 5.327 4104.35 10 6 0 QdotC 177.703 bar Calculate the heat load ndottoluene 50 kmol hr T1 ( 100 273.625 -3 Q 10 kgm sec H Ws QC QH 2.1 With air at 20 C and the specification of a minimum approach T = 10 C: T1 ( 10 273.146 ln T1 K 615.

078 For the evaporator H12 = H2 H1 = H1vap H1liq x1 Hlv = 1 x1 Hlv H12 ndot 1 x1 Hlv H12 ndot 311 19.34 kJ mol Tr ( 20 273.80bar Zc 0.75 10 3 192.71 10 6 0 Hliq41 1.621 kJ mol x1 Hliq41 Hlv x1 0.698 Hlv Hliq41 Hlvn Vliq PH 1 1 PL Tr1 Trn 0.Since the throttling process is adiabatic: H4 = H1 But: Hliq4 = Hliq1 x1 Hlv1 so: Hliq4 T4 Hliq1 = x1 Hlv and: Hliq4 Hliq1 = Vliq P4 P1 T1 Cpliq ( T) dT Estimate Vliq using the Rackett Eqn. 0.5 mol Tn 239.591 Trn Tc Tc Tr1 kJ mol 0.38 Hlv 20.112 mol Estimate Hlv at 10C using Watson correlation T1 Tn Tr1 Trn 0.177 kJ mol Ans.258 mol sec .253 Tc 405.7K Hlvn 23.242 Vc cm 72. QdotC H12 9.15)K Tc 2 Tr 0.798 R ICPH T1 T4 22.7K Pc 3 112.723 3 Vliq V c Zc 1 Tr 7 Vliq cm 27.626 100.

545 Ans.156 kPa Ans. P) ⎜ ⎝P⎠ (b) Given: y1 := 0. P := 120⋅ kPa Guess: y1 := 0. T = 103.Chapter 10 .5 P := 100⋅ kPa x1⋅ Psat1 ( T) + ( 1 − x1) ⋅ Psat2 ( T) = P x1⋅ Psat1 ( T) = y1⋅ P ⎛ y1 ⎞ := Find ( y1 .33 P := 100⋅ kPa x1⋅ Psat1 ( T) + ( 1 − x1) ⋅ Psat2 ( T) = P x1⋅ Psat1 ( T) = y1⋅ P ⎛ x1 ⎞ := Find ( x1 .7819 A2 := 13. T) ⎜ T⎠ ⎝ y1 = 0.Mathcad Solutions 10.9320 A1 − B1 T degC +C1 B1 := 2726.81 B2 := 3056.33 Given y1 = 0. P = 92.542 312 Ans.572 C2 := 217. P = 109.307 degC Ans.33 Given x1 = 0.625 Psat1 ( T) := e ⋅ kPa Psat2 ( T) := e Guess: +C2 ⋅ kPa (a) Given: x1 := 0. P) ⎜ ⎝P⎠ (c) Given: x1 := 0. .169 Ans.96 A2 − B2 T degC C1 := 217.5 T := 100⋅ degC x1⋅ Psat1 ( T) + ( 1 − x1) ⋅ Psat2 ( T) = P x1⋅ Psat1 ( T) = y1⋅ P ⎛ y1 ⎞ := Find ( y1 .33 Given T := 100⋅ degC y1 := 0. T := 100⋅ degC Guess: x1 := 0.Section A .303 kPa Ans.1 Benzene: Toluene: A1 := 13.

484 V := 0.484 Ans. 313 . Therefore one would expect little chemical interaction between the components.33 T := 100⋅ degC x1⋅ Psat1 ( T) + ( 1 − x1) ⋅ Psat2 ( T) = P x1⋅ Psat1 ( T) = y1⋅ P ⎛ x1 ⎞ := Find ( x1 . The temperature is high enough and pressure low enough to expect ideal behavior.33 Guess: Given x1 = 0.131 degC Ans. T := 105⋅ degC P := 120⋅ kPa Guess: x1⋅ Psat1 ( T) + ( 1 − x1) ⋅ Psat2 ( T) = P x1⋅ Psat1 ( T) = y1⋅ P x1 := 0.5 z1 = L⋅ x1 + V⋅ y1 L+V = 1 y1 = 0.(d) Given: y1 := 0.33 y1 := 0. y1 = 0. T) ⎜ T⎠ ⎝ (e) Given: Given x1 = 0. Benzene and toluene are both non-polar and similar in shape and size.173 Ans.238 L = 0.282 L := 0.5 ⎛ x1 ⎞ := Find ( x1 .282 Ans. Ans.762 Ans.33 Given P := 120⋅ kPa Guess: x1 := 0. V) ⎜ ⎝V ⎠ (g) Vapor Fraction: Liquid Fraction: V = 0. y1) ⎜ y1 ⎠ ⎝ (f) z1 := 0.5 ⎛L ⎞ := Find ( L . T = 109. x1 = 0.

t⎤ ⎣ ⎦ y'1 ( x1) := x1⋅ Psat1 ( T ( x1) ) + ( 1 − x1) ⋅ Psat2 ( T ( x1) ) x1⋅ Psat1 ( T ( x1) ) x1 := 0 .572 C2 := 212.81 B2 := 3259.9726 Psat1 ( T) := exp ⎜ A1 − B1 := 2726.5 1 314 .2 Pressures in kPa. y'1 ( x1 ) 0.05 . Ethylbenzene=2 A1 := 13. y1 ( x1 ) 0.300 ⎛ ⎝ B2 ⎞ ⎛ Psat2 ( T) := exp ⎜ A2 − T + C2 ⎠ ⎝ P-x-y diagram: T := 90 y1 ( x1) := x1⋅ Psat1 ( T) P ( x1 ) P ( x1) := x1⋅ Psat1 ( T) + ( 1 − x1) ⋅ Psat2 ( T) T-x-y diagram: P' := 90 B1 ⎞ T + C1 ⎠ Guess t for root function: t := 90 T ( x1) := root ⎡x1⋅ Psat1 ( t) + ( 1 − x1) ⋅ Psat2 ( t) − P' .0 150 140 130 P ( x1 ) P ( x1 ) 50 100 120 T ( x1 ) 110 100 T ( x1 ) 90 80 70 0 0 x1 .7819 A2 := 13. 1. 0.10. temperatures in degC (a) Antoine coefficients: Benzene=1..5 1 60 0 x1 .93 C1 := 217.

33 P ( x1 ) P ( x1 ) 66.(b) Antoine coefficients: 1-Chlorobutane=1. t⎤ ⎣ ⎦ y'1 ( x1) := x1⋅ Psat1 ( T ( x1) ) + ( 1 − x1) ⋅ Psat2 ( T ( x1) ) x1⋅ Psat1 ( T ( x1) ) x1 := 0 .5 1 x1 . 0.67 107. 1.5 T ( x1 ) 100 T ( x1 ) 92.78 B1 ⎞ T + C1 ⎠ C1 := 218..5 85 77.265 C2 := 211. Chlorobenzene=2 A1 := 13.73 B2 := 3174.5 20 0 0. y1 ( x1 ) x1 .5 115 113.05 . y'1 ( x1 ) 315 .7965 A2 := 13.5 1 70 0 0.700 Psat2 ( T) := exp ⎜ A2 − ⎛ ⎝ ⎛ ⎝ B2 ⎞ T + C2 ⎠ P-x-y diagram: T := 90 y1 ( x1) := x1⋅ Psat1 ( T) P ( x1 ) P ( x1) := x1⋅ Psat1 ( T) + ( 1 − x1) ⋅ Psat2 ( T) T-x-y diagram: P' := 90 Guess t for root function: t := 90 T ( x1) := root ⎡x1⋅ Psat1 ( t) + ( 1 − x1) ⋅ Psat2 ( t) − P' .8635 Psat1 ( T) := exp ⎜ A1 − B1 := 2723.0 160 130 122.

5 0 0.3 Pressures in kPa.8 0.5 y1 := y1 = 0.6 0.65 z1 0.5: x1 := 0.432 Psat2 ( T) := exp ⎜ A2 − ⎛ ⎝ B1 ⎞ T + C1 ⎠ ⎛ ⎝ B2 ⎞ T + C2 ⎠ T := 55 P := ⎜ ⎛ Psat1 ( T) + Psat2 ( T) ⎞ 2 ⎝ ⎠ x1⋅ Psat1 ( T) P P = 104. x1 must be 0.7667 A2 := 13. at the specified P.75 0.5 0. Material balance: z1 = x1⋅ ( 1 − V) + y1⋅ V z1 := x1 . x1 + 0.26 C1 := 232.01 .45 0.8622 Psat1 ( T) := exp ⎜ A1 − B1 := 2451. temperatures in degC (a) Antoine coefficinets: n-Pentane=1. z1 ranges from the liquid composition at the bubble point to the vapor composition at the dew point. n-Heptane=2 A1 := 13. y1 V is obviously linear in z1: 1 x1 y1 V ( z1) := z1 − x1 y1 − x1 V ( z1 ) 0.55 0.89 For a given pressure.88 B2 := 2911.85 316 .014 C2 := 216..349 Since for Raoult's law P is linear in x.7 0.10.

5 y := 0.572 C2 := 212.3.7819 B1 := 2726. y .(b) At fixed T and z1. and is worked in exactly the same way.5 p := ⎜ ⎛ Psat1 ( T) + Psat2 ( T) ⎞ 2 ⎝ ⎠ Three equations relate x1. 0.300 B2 T degC +C2 Ethylbenzene A2 := 13. the Mathcad solution for Problem 10.81 B2 := 3259. All that is involved is a change of numbers. y1.3 can be converted into the solution for any part of this problem simply by changing one number. y1 and P as functions of fraction vapor (V).1 .5 V 1 0 0 0.5 V 1 10. Benzene: A1 := 13.4 Each part of this problem is exactly like Problem 10.9726 A1 − B1 T degC +C1 Psat1 ( T) := e ⋅ kPa 317 Psat2 ( T) := e ⋅ kPa . x1 and y1 vs. 1. p) x1 ( V) := f ( V) 1 y1 ( V) := f ( V) 2 P ( V) := f ( V) 3 V := 0 . In fact.5 Guess: Given x := 0.93 A2 − 10. z1 := 0.. calculate x1.7 C1 := 217. & P for given V: p = x⋅ Psat1 ( T) + ( 1 − x) ⋅ Psat2 ( T) y⋅ p = x⋅ Psat1 ( T) z1 = ( 1 − V) ⋅ x + V⋅ y f ( V) := Find ( x . vapor fraction (V) 150 100 P ( V) 50 x1 ( V) y1 ( V) 0. the temperature.5 0 0 0.0 1 Plot P.

96 ⎟ ⎜ 3259. the process must be operated under vacuum conditions.625 ⎟ ⎜ 212. 10.44⋅ deg_C P = 118.35 Given y1 := 0.72⋅ kPa P = 66. The temperatures are well within the bounds of typical steam and cooling water temperatures. (b) T = 111.02⋅ kPa (d) T = 72.9726 ⎠ ⎝ (a) n := rows ( A) Ai− ⎛ 2726. P) ⎝P ⎠ T = 134.(a) Given: x1 := 0.300 ⎠ ⎝ zi := 1 n i := 1 .7819 ⎞ (1) = benzene ⎜ A := ⎜ 13.88⋅ deg_C (c) T = 91. T) := e ⋅ kPa ki := Psat ( i . P = 207.93 ⎠ ⎝ ⎛ 217.572 ⎞ ⎜ C := ⎜ 217.9 ⎛ 13.70 Guess: T := 116⋅ degC P := 132⋅ kPa x1⋅ Psat1 ( T) + ( 1 − x1) ⋅ Psat2 ( T) = P x1⋅ Psat1 ( T) = y1⋅ P ⎛T ⎞ ⎜ := Find ( T ..1 degC Ans. one must know the composition of the feed.46 kPa Ans. For parts (c) and (d).5 318 .43⋅ deg_C To calculate the relative amounts of liquid and vapor phases. the temperature and pressure of the process must be lowered.9320 ⎟ (2) = toluene (3) = ethylbenzene ⎜ 13.81 ⎞ ⎜ B := ⎜ 3056. (c) and (d) use the same structure.8 To increase the relative amount of benzene in the vapor phase. Set the defined variables and change the variables in the Find statement at the end of the solve block. T) P Guess: V := 0.38⋅ kPa P = 36. 10. For parts (b). n Bi T degC +Ci T := 110⋅ degC P := 90⋅ kPa Psat ( i .

293 ⎞ ⎜ x = ⎜ 0.312 ⎟ ⎜ 0.16) ⎛ 0.10 As the pressure increases.417 ⎠ ⎝ ⎛ 0. (b) T = 110⋅ deg_C P = 100⋅ kPa (c) T = 110⋅ deg_C P = 110⋅ kPa V = 0.146 10. (10.352 (d) T = 110⋅ deg_C P = 120⋅ kPa V = 0.334 ⎟ ⎜ 0.339 ⎟ ⎜ 0.29 ⎠ ⎝ ⎛ 0. (10.441 ⎞ ⎜ y = ⎜ 0.18 ⎠ ⎝ ⎛ 0. xi := Ans.284 ⎟ ⎜ 0.836 zi⋅ ki = 1 Eq.371 ⎞ ⎜ y = ⎜ 0.Given i=1 ∑ n 1 + V⋅ ( ki − 1) V = 0.345 ⎟ ⎜ 0.478 ⎠ ⎝ ⎛ 0. yi := 1 + V⋅ ( ki − 1) yi⋅ P Psat ( i .333 ⎟ ⎜ 0.572 ⎞ ⎜ y = ⎜ 0.508 ⎞ ⎜ y = ⎜ 0.17) V := Find ( V) Ans.188 ⎞ ⎜ x = ⎜ 0.342 ⎟ ⎜ 0.575 ⎛ 0.144 ⎠ ⎝ V = 0. the mole fraction of benzene in both phases increases and the the mole fraction of ethylbenzene in both phases decreases.226 ⎠ ⎝ ⎛ 0.306 ⎟ ⎜ 0.142 ⎞ ⎜ x = ⎜ 0. 319 .238 ⎞ ⎜ x = ⎜ 0. the fraction of vapor phase formed (V) decreases.366 ⎠ ⎝ Ans. T) zi⋅ ki Eq.552 ⎠ ⎝ ⎛ 0.

8950 ⎠ ⎝ 3413.5 i=1 ∑ n 1 + V⋅ ( ki − 1) V = 0.741 r = 0..644 Ans.678 y1 = 0.11 (a) (1) = acetone A := ⎜ B := ⎜ C := ⎜ (2) = acetonitrile ⎝ 14.624 r = 0. n T := ( 340 − 273.547 V = 0.10 ⎠ ⎝ 250.75 z2 := 1 − z1 Ai− Bi T degC +Ci i := 1 . (10. r = 0.16) 1 + V⋅ ( ki − 1) yi⋅ P Psat ( i .805 Ans. Eq. xi := x1 = 0.639 320 .3145 ⎞ ⎛ 2756.17) V := Find ( V) Eq. T) := e Guess: Given ⋅ kPa ki := Psat ( i .060 ⎞ 10.340 r = 0.183 x1 = 0. (10.682 zi⋅ ki y1 = 0. T) P V := 0.656 yi := zi⋅ ki = 1 Ans.487 V = 0.⎛ 14. T) y1⋅ V z1 y1 = 0.469 Ans.523 ⎠ n := rows ( A) z1 := 0.15) ⋅ degC P := 115⋅ kPa Psat ( i .22 ⎞ ⎛ 228.705 V = 0.285 x1 = 0.320 y1 = 0. r := (b) (c) (d) x1 = 0.

x2) := exp A⋅ x2 ( 2 ) ( 2 ) P ( x1 . x2) ⋅ Psat1 + x2⋅ γ 2 ( x1 .864 Ans. 1 − x1) ⋅ Psat1 P' = x1⋅ γ 1 ( x1 . x2) DEW P calculation: Guess: Given x1 := 0. x2) := exp A⋅ x1 z1 := 0... 1 − x1) ⋅ Psat2 ⎛ x1 ⎞ := Find ( x1 . + ( 1 − x1) ⋅ γ 2 ( x1 .10⋅ bar P := 1⋅ bar Assume at 1 bar that the vapor is an ideal gas.10. .14 A := 0. Then: y1⋅ P = H1⋅ x1 x1 + x2 = 1 Solve for x1 and y1: x1 := P − Psat2 H1 − Psat2 −3 y2⋅ P = x2⋅ Psat2 P = H1⋅ x1 + ( 1 − x1) ⋅ Psat2 P = y1⋅ P + y2⋅ P y1 := H1⋅ x1 P Ans.9 10.13 H1 := 200⋅ bar Psat2 := 0. P') ⎜ Pdew ⎠ ⎝ 321 Pdew = 43.65 γ 1 ( x1 . 1 − x1) ⋅ Psat1 .67 γ 2 ( x1 .745 y1 := z1 P' := x2 := 1 − x1 Ans. x2) := x1⋅ γ 1 ( x1 . x1 = 4.16 Pressures in kPa Psat1 := 32. y2 := 1 − y1 Psat1 + Psat2 2 y1⋅ P' = x1⋅ γ 1 ( x1 . The vapor-phase fugacities are then equal to the partial presures. Assume the Lewis/Randall rule applies to concentrated species 2 and that Henry's law applies to dilute species 1.5 x1 := z1 Pbubl = 56.502 × 10 y1 = 0.27 Psat2 := 73. x2) ⋅ Psat2 (a) BUBL P calculation: Pbubl := P ( x1 .

x2) := x1⋅ γ 1 ( x1 . y2 := 1 − y1 Psat1 + Psat2 2 (a) BUBL P calculation: Pbubl := P ( x1 .05 Pbubl = 47. there is no azeotrope.1 y1 := 0. 10.The pressure range for two phases is from the dewpoint to the bubblepoint: From 43. α 12.892 Ans. x2) ⋅ Psat2 y1 ( x1) := x1⋅ γ 1 ( x1 . x2) := exp A⋅ x2 ( 2 ) ( 2 ) P ( x1 . x2) 322 .862 α 12.17 Psat1 := 79.1 = 0. 1) ⋅ Psat1 Psat2 α 12. 1 − x1) ⋅ Psat1 P ( x1 .226 Since alpha does not pass through 1.0 = 0. x2) ⋅ Psat1 + x2⋅ γ 2 ( x1 . 1 − x1) x1 := 0. 1 − x1) x1 := 0.864 to 56. 0) ⋅ Psat2 α 12.971 y1 ( x1) = 0.0 := γ 1 ( 0 . x2) = 51.95 γ 2 ( x1 .5 A := 0.379 P ( x1 .3(e).196 (b) DEW P calculation: Guess: x1 := 0. (c) See Example 10.1 := Psat1 γ 2 ( 1 .8 Psat2 := 40.0 for 0<x1<1. x2) := exp A⋅ x1 γ 1 ( x1 .75 x2 := 1 − x1 x1⋅ γ 1 ( x1 . 1 − x1) ⋅ Psat1 The fraction vapor.05 P' := x2 := 1 − x1 Ans.745 kPa (b) BUBL P calculation: y1 ( x1) := P ( x1 . by material balance is: V := y1 ( x1) − x1 z1 − x1 V = 0.

Psat2 := 31..857 ⎞ ⎜ ⎜ yaz ⎟ = ⎜ 0.18 Psat1 := 75. 1 − x1) ⋅ Psat1 . 1 − x1) ⋅ Psat2 ⎛ x1 ⎞ := Find ( x1 .191 x1 = 0. 1 − x1) ⋅ Psat1 + ( 1 − x1) ⋅ γ 2 ( x1 .66⋅ kPa y1 = x1 γ2 γ1 = Psat1 Psat2 2 and x1 := 0. 1 − x1) ⋅ Psat1 P' = x1⋅ γ 1 ( x1 .0998 x2 − x1 x2 := 1 − x1 323 .366 ⎠ ⎠ ⎝ Ans.. y .Given y1⋅ P' = x1⋅ γ 1 ( x1 . 1 − x1) ⋅ Psat2 ⎛ xaz1 ⎞ ⎜ ⎜ yaz ⎟ := Find ( x . 1 − x1) ⋅ Psat1 P P = x1⋅ γ 1 ( x1 . P) 1 1 ⎜ 1⎟ ⎜ Paz ⎠ ⎝ 10.20⋅ kPa At the azeotrope: Therefore lnγ1 = A⋅ x2 2 ⎛ xaz1 ⎞ ⎜ ⎛ 0. + ( 1 − x1) ⋅ γ 2 ( x1 .294 ln ⎜ γi = P Psati x2 := 1 − x1 lnγ2 = A⋅ x1 ln ⎜ ⎛ γ2⎞ ⎝ γ1⎠ = A⋅ x1 − x2 ( 2 2 ) ⎛ Psat1 ⎞ ⎝ Psat2 ⎠ 2 2 Whence For A := x1 := 0.8 Pdew = 42.6 A = 2. y1 := x1 P := x1 ≥ 0 Psat1 + Psat2 2 x1 ≤ 1 x1 = y1 x1⋅ γ 1 ( x1 .0104 Ans.857 ⎟ ⎜ 1⎟ ⎜ ⎜ Paz ⎝ 81. P') ⎜ Pdew ⎠ ⎝ (c) Azeotrope Calculation: Guess: Given y1 = x1 := 0.

P) ⎜ ⎝P⎠ ⎛ x1 ⎞ ⎛ 0.104 kPa Psat1 := 1.6013 By a material balance. y1 . (a) Azeotrope calculation: x1 := 0.673 ⎠ Ans. V= (c) Guess: z1 − x1 y1 − x1 For 0≤V ≤1 x1⋅ γ 1⋅ Psat1 P Answer to Part (b) 0.6 y1 := x1 P := Psat1 + Psat2 2 2 γ 1 ( x1) := exp ⎡ A⋅ ( 1 − x1) ⎤ ⎣ ⎦ γ 2 ( x1) := exp A⋅ x1 ( 2 ) Given P = x1⋅ γ 1 ( x1) ⋅ Psat1 + ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2 x1 ≥ 0 x1 ≤ 1 x1 = y1 y1 = x1⋅ γ 1 ( x1) ⋅ Psat1 P ⎛ x1 ⎞ ⎜ ⎜ y1 ⎟ := Find ( x1 .65 ( 2 ) P := x1⋅ γ 1⋅ Psat1 + x2⋅ γ 2⋅ Psat2 y1 = 0. x1⋅ γ 1⋅ Psat1 P 10.6013 ≤ z1 ≤ 0.701 Psat2 := 0.89 x2 := 1 − x1 γ 2 := exp A⋅ x1 y1 := Ans.8 γ 1 := exp A⋅ x2 ( 2 ) P = 1.65 Ans.592 ⎞ ⎜ ⎜ ⎜ y1 ⎟ = ⎜ 0.19 Pressures in bars: A := 1.671 ( 2 ) P := x1⋅ γ 1⋅ Psat1 + x2⋅ γ 2⋅ Psat2 y1 = 0.592 ⎟ ⎜ ⎜ ⎝ P ⎠ ⎝ 1.24 x1 := 0. 324 .γ 1 := exp A⋅ x2 y1 := ( 2 ) γ 2 := exp A⋅ x1 P = 90.

27 C1 := 228. T) := Guesses: Given F= L+V z1⋅ F = x1⋅ L + y1 ( x1 .060 C2 := 239.. T) x1⋅ γ 1 ( x1 . T) ⋅ V p = P ( x1 .3145 A2 := 16.431 ⎞ ⎜ ⎜ ⎜ V ⎟ = ⎜ 0.5 ⎛L ⎞ ⎜ ⎜ V ⎟ := Find ( L . 1 − x1) ⋅ P2sat ( T) y1 ( x1 .5785 P in kPa.531 ⎠ y1 ( x1 . T) = 0.64 x1 := 0.25 p := 100 (kPa) γ 1 ( x1 .531 (degC) ⎛ L ⎞ ⎛ 0. T ) F := 1 T := 100 V := 0..307 Ans.10. x2) := exp A⋅ x2 ( 2 ) γ 2 ( x1 .569 ⎟ ⎜T ⎜ ⎝ ⎠ ⎝ 59. T) := x1⋅ γ 1 ( x1 . 1 − x1) ⋅ P1sat ( T) . V . x2) := exp A⋅ x1 ( 2 ) P ( x1 . + ( 1 − x1) ⋅ γ 2 ( x1 .22 B2 := 3638. T) ⎜T ⎝ ⎠ T = 59.20 Antoine coefficients: Acetone(1): Methanol(2): A1 := 14. 325 .5 L := 0.175 z1 := 0. T in degC B1 := 2756. 1 − x1) ⋅ P1sat ( T) P ( x1 .500 P1sat ( T) := exp ⎜ A1 − ⎛ ⎝ B1 ⎞ T + C1 ⎠ P2sat ( T) := exp ⎜ A2 − ⎛ ⎝ B2 ⎞ T + C2 ⎠ A := 0.

10.93 ⋅ x2 2 ⎛T⎞ ⎜ ⎝ K ⎠ ⋅ bar γ 2 := e 0. P := x1⋅ γ 1⋅ Psat1 ( T) y1 P = 0.63 Psat1 ( T) := e x2 := 1 − x1 Given ⎛T⎞ ⎜ ⎝ K ⎠ ⋅ bar y2 := 1 − y1 = x2⋅ γ 2⋅ y1 x1⋅ γ 1⋅ y2 Psat2 ( T) := e γ 1 := e 0.0 B1 Guess: T := 300⋅ K B2 := 6254.0 A2 − B2 A2 := 11.95 B1 := 2572.137 bar Ans. 326 .93 ⋅ x1 2 Psat1 ( T) Psat2 ( T) T := Find ( T) T = 376.22 x1 := 0.08 A1 − y1 := 0.453 K Ans.002 A1 := 10.

200 0.615 0.824 bar) ANSWER Ki yi=Ki*xi Ki yi=Ki*xi Ki yi=Ki*xi 5.168 SUM = 1.520 0.552 4.600 0.800 0.085 5.380 0.450 0.342 0.730 0.445 0.11 C) P=200 psia P=250 psia P=215 psia (14.450 0.100 0.680 0.900 SUM = 1.600 0.650 0.25 to 10.178 0.210 327 .182 0.050 0.962 SUM = 1.430 0.700 0.008 close enough Component methane ethylene ethane yi 0.600 0.971 SUM = 1.460 0.120 4.500 0.564 0.008 close enough Component methane ethylene ethane xi 0.250 0.529 0.380 0.083 4.250 c) BUBL T P=250 psia (17.350 0.588 4.433 SUM = 0.900 0.24 bar) T=-50 F T=-60 F T=-57 F (-49.33 C) ANSWER Ki xi=yi/Ki Ki xi=yi/Ki Ki xi=yi/Ki 5.515 0.089 0.405 0.460 5.467 0.543 0.004 close enough P=250 psia (17.400 0.570 0.480 0.560 4.740 0.486 0.194 SUM = 1.150 0.288 0.076 SUM = 0.44 C) ANSWER xi Ki yi=Ki*xi Ki yi=Ki*xi Ki yi=Ki*xi 0.450 0.700 0.25 a) BUBL P T=-60 F (-51.272 0.088 SUM = 0.246 0.24 bar) T=-40 F T = -50 F T = -45 F (-27.500 0.900 0.357 0.084 SUM = 1.445 0.Problems 10.79 bar) ANSWER Ki xi=yi/Ki Ki xi=yi/Ki 5. Problem 10.088 5.485 0.562 SUM = 0.216 0.400 b) DEW P T=-60 F (-51.700 0.404 0.11 C) P=190 psia P=200 psia (13.228 0.325 0.900 0.937 SUM = 1.420 0.005 close enough Component methane ethylene ethane d) DEW T Component methane ethylene ethane yi 0.575 0.085 0.34 have been solved using MS-EXCEL 2000 We give the resulting spreadsheets.152 0.680 0.360 0.600 0.

12 c) BUBL T P=15 bar (217.760 0.950 0.124 2.700 0.325 1.130 0.500 0.010 close enough Component ethane propane isobutane isopentane yi 0.42 0.25 0.26 a) BUBL P T=60 C (140 F) P=200 psia P=50 psia P=80 psia (5.800 0.048 SUM = 0.525 0.25 0.680 4.234 0.073 1.15 0.205 0.25 0.15 0.274 0.208 0.168 0.010 close enough Component ethane propane isobutane isopentane xi 0.620 0.500 0.970 SUM = 1.006 close enough Component ethane propane isobutane isopentane xi 0.295 0.350 0.12 0.475 0.14 0.27 0.26 0.520 0.585 0.195 0.430 SUM = 1.097 6.48 d) DEW T P=15 bar (217.760 0.500 SUM = 1.071 6.197 0.749 3.000 0.12 1.475 0.56 psia) T=220 F T=150 F T=145 F (62.56 psia) T=150 F Ki xi=yi/Ki 3.045 SUM = 1.27 0.197 0.077 0.13 328 .481 SUM = 0.475 0.205 0.255 0.406 SUM = 1.475 0.585 bar) ANSWER Ki xi=yi/Ki Ki xi=yi/Ki Ki xi=yi/Ki 4.125 0.192 1.475 0.30 0.30 0.Problem 10.268 0.800 0.122 2.760 0.800 0.516 bar) ANSWER Ki yi=Ki*xi Ki yi=Ki*xi Ki yi=Ki*xi 2.615 SUM = 1.203 1.410 1.950 0.600 0.44 C) ANSWER Ki xi=yi/Ki Ki xi=yi/Ki 3.169 2.740 0.720 0.071 0.114 3.986 T=145 F T=148 F (64.720 0.050 0.120 SUM = 1.082 0.57 0.40 b) DEW P T=60 C (140 F) P=80 psia P=50 psia P=52 psia (3.197 0.369 0.050 0.700 0.780 0.111 1.525 0.495 0.800 0.10 0.13 0.190 0.013 close enough Component ethane propane isobutane isopentane yi 0.48 0.202 6.111 1.180 0.716 SUM = 1.25 0.198 1.000 0.203 0.20 0.560 0.78 C) ANSWER Ki yi=Ki*xi Ki yi=Ki*xi Ki yi=Ki*xi 5.780 0.534 SUM = 0.560 0.015 0.050 SUM = 1.532 3.800 0.200 0.192 0.028 0.518 2.

21 0.51 0.266 Ki yi 2.437 0.3825 0.0005 Close enough Component n-butane n-hexane xi 0.50 0.7 0.45 0.152 SUM = 1.150 0.575 2.000 329 .5 0.675 2.30 V= 0.39 psia) T = 200 F (93.0575 SUM = 1.145 ANSWER xi=yi/Ki 0.73 ANSWER xi=yi/Ki 0.108 0.28 First calculate equilibrium composition T=95 C (203 F) P=80 psia P=65 psia P=69 psia (4.000 Problem 10.45 0.347 ANSWER Problem 10.058 0.25 0.3675 SUM = 0.001 Component methane ethane propane n-butane zi 0.25 0.75 Now calculate liquid fraction from mole balances z1= x1= y1= L= 0.354 SUM = 1.83 bar) ANSWER Ki yi=Ki*xi Ki yi=Ki*xi Ki yi=Ki*xi 2.20 0.3375 0.000 Component n-pentane n-hexane n-heptane zi 0.412 0.25 0.49 0.00 atm (29.960 0.075 0.29 FLASH P = 2.191 0.25 0.81 C) P=250 psia (17.052 0.275 0.187 0.20 V= 0.5625 2.680 0.27 FLASH T=80 F (14.6 0.616 SUM = 1.455 0.129 SUM = 1.633 0.24 bar) Fraction condensed L= 0.855 Ki yi 10.3 C) Fraction condensed L= 0.430 0.000 0.Problem 10.9000 SUM = 1.10 0.633 0.

034 bar) xi=yi/Ki Ki yi xi=yi/Ki 0.508 1.610 0.045 4.44 V= 0.012 Component ethane propane n-butane V= 0.002 1.343 0.419 0.071 Component ethane propane i-butane n-butane zi 0.35 1.400 0.246 1.700 0.400 0.620 0.039 3.982 SUM = 0.925 0.982 SUM = 1.05 0.047 0.373 0.11 C) Fraction condensed L= 0.036 2.457 0.227 1.810 0.485 1.004 0.413 0.660 0.525 0.20 P=50 psia Ki yi 7.907 ANSWER P=44 psia (3.150 0.004 8.255 0.Problem 10.80 P=40 psia xi=yi/Ki Ki yi 0.219 0.900 0.060 0.037 0.700 0.50 0.034 0.464 0.558 0.540 0.023 SUM = 1.60 P=110 psia zi Ki yi 0.691 0.000 330 .740 0.312 SUM = 0.107 0.220 0.101 0.900 0.001 Problem 10.370 1.50 0.01 0.367 0.223 0.699 0.041 4.472 0.094 0.15 5.035 0.000 0.494 0.470 0.921 SUM = 1.999 1.40 P=100 psia xi=yi/Ki Ki yi 0.30 FLASH T=40 C (104 F) Fraction condensed L= 0.660 0.400 0.500 0.31 FLASH T=70 F (21.300 0.274 bar) xi=yi/Ki Ki yi xi=yi/Ki 0.053 ANSWER P=120 psia (8.004 9.032 2.432 0.524 0.653 0.398 SUM = 1.

085 0.1855 Ki yi 5.30 0.424 SUM = 0.982 Component methane ethane propane n-butane zi 0.352 0.30 0.30 L= 0.30 0.420 0.162 0.794 1.30 L= 0.200 0.000 331 .073 0.092 0.135 0.000 SUM = 1.086 Target: y1=0.047 0.10 0.017 SUM = 1.129 0.820 0.32 FLASH T=-15 C (5 F) P=300 psia V= 0.2535 L= 0.125 0.103 0.376 0.360 0.8145 xi=yi/Ki 0.079 P=150 psia V= 0.10 0.616 bar) V= 0.802 0.373 0.906 0.900 0.30 0.960 Component methane ethane propane n-butane zi 0.Problem 10.088 0.086 0.364 SUM = 0.600 0.8 Component methane ethane propane n-butane zi 0.900 0.103 0.3150 Ki yi 10.230 0.200 0.10 0.6850 xi=yi/Ki 0.30 0.031 SUM = 1.395 SUM = 1.020 0.30 0.30 P=270 psia (18.074 0.7465 ANSWER Ki yi xi=yi/Ki 6.070 0.0495 0.

116 SUM = 1.253 1.180 0.924 0.006 close enough P=250 psia xi=yi/Ki Ki yi 0.78 1.40 P=350 psia zi Ki yi 0.890 0.948 0.217 SUM = 0.33 First calculate vapor composition and temperature on top tray BUBL T: P=20 psia T=70 F T=60 F T=69 F (20.675 1.775 0.929 bar) xi=yi/Ki Ki yi xi=yi/Ki 0.943 SUM = 0.22 0.137 SUM = 1. calculate composition out of condenser FLASH P=20 psia (1.071 8.983 Problem 10.905 T=60 F (15.660 0.013 SUM = 0.235 0.007 ANSWER xi=yi/Ki 0.855 SUM = 0.092 0.245 0.50 7.360 0.50 Component n-butane n-pentane L= 0.085 xi=yi/Ki 0.914 0.350 0.50 T=70 F zi Ki yi 0.995 close enough Component n-butane n-pentane xi 0.602 0.56 C) ANSWER Ki yi=Ki*xi Ki yi=Ki*xi Ki yi=Ki*xi 1.224 0.450 0.450 0.575 0.56 C) Ki yi 1.303 0.360 0.097 11.440 0.350 0.786 0.400 0.379 bar) V= 0.871 0.225 0.788 1.986 ANSWER P=325 psia (7.038 332 .50 Using calculated vapor composition from top tray.768 0.550 0.60 Component methane n-butane L= 0.900 0.220 SUM = 1.290 0.50 0.50 0.996 1.324 0.575 0.34 FLASH T=40 C (104 F) V= 0.Problem 10.000 0.021 SUM = 1.772 0.

The value is Table 10. (2) Solving to eliminate P gives: Hi By definition: Mi = ni ns Ms Eq.22 T degC 228. (3) and (4) gives: Hi = 1 xs Ms ki If xi is small.35 a) The equation from NIST is: Mi = ki yi P Eq.5 333 .060 Psat1 ( ) T e 14.8950 kPa 3413. then x s is approximately equal to 1 and: Hi = b) For water as solvent: Ms 18. = Mi Dividing by the toal number of moles gives: Mi = xi xs Ms Eq.015 For CO2 in H2O: ki 0.034 gm mol mol 1 Ms ki Eq.1 is 1670 bar. 10. (4) Combining Eqs. (3) ki xi where M is the molar mass and the subscript s refers to the solvent. (1) The equation for Henry's Law is:i Hi = yi P x Eq. (5) kg bar Hi By Eq.3145 2756.36 Acetone: 14. (5): Hi 1 Ms ki 1633 bar Ans.10 T degC 250.523 Acetonitrile Psat2 ( ) T e kPa a) Find BUBL P and DEW P values T 50degC x1 0. The values agree within about 2%.5 y1 0.10.

573 atm Ans.37 Calculate x and y at T = 90 C and P = 75 kPa 13.3 C and 51.625 Toluene: Psat2 ( T) e kPa a) Calculate the equilibrium composition of the liquid and vapor at the flash T and P T 90degC P 75kPa Guess: x1 0.BUBLP x1 Psat1 ( T) 1 x1 Psat2 ( T) BUBLP 0.5atm x1 0.478 atm Ans.572 Benzene: Psat1 ( T) e 13.5 y1 0.5 y1 0.7819 2726.9320 kPa 3056.573 atm b) Find BUBL T and DEW T values P 0.2 C 10.96 T degC 217. two phases will form between T = 46.5 Guess: T 50degC Given x1 Psat1 ( T) 1 x1 Psat2 ( T) = P BUBLT Find ( T) x1 Psat1 ( T) = y1 P Find x1 T BUBLT 1 46.478 atm and 0. y1 P Given x1 DEWT x1 Psat2 ( T) = 1 51. DEWP 1 y1 Psat1 ( T) 1 y1 DEWP 0. Psat2 ( T) At T = 50 C two phases will form between P = 0. DEWT At P = 0.238 degC Ans.5 334 .5 atm.316 degC Ans.81 T degC 217.

3872 100degC 3885. Since air will not dissolve in the liquid to any significant extent.2919 x2 1 x1 x2 0. Conclusion: An air leak is consistent with the measured compositions.608 y3 0.1604 y1 0.7288 yCO21 0. b) Assume that the measured values are correct.38 yO21 0.8396 Now calculate the composition of the vapor.1 Ans.170 PsatH2O ( ) T e kPa 335 .Given x1 Psat1 ( )= y1 P T Find x1 y1 1 x1 Psat2 ( )= 1 T y1 0.1550 ndot 10 kmol hr T1 16.458 y1 P x1 y1 x1 0.70 T degC T2 25degC P 1atm 230. 10. x1 0. y3 represents the mole fraction of air in the vapor.0775 yH2O1 0. Guess: y2 0.5 y3 1 y2 y1 Given 1 x1 Psat2 ( )= 1 T Find y2 y3 y1 y3 P y1 y2 y3 = 1 y2 y3 y2 0.0387 yN21 0. the mole fractions of toluene in the liquid can be calculated.252 The equilibrium compositions do not agree with the measured values.

0315 This is less than the mole fraction of water in the feed. Assume that two streams leave the process: a liquid water stream at rate ndotliq and a vapor stream at rate ndotvap. yH2O2 PsatH2O T2 P yH2O2 0. Therefore.031 yCO22 .276 0.044 kmol hr yN22 ndotvap 0. Apply mole balances around the cooler to calculate the exit composition of the vapor phase.0775 ndot = ndotliq Overall balance O2 balance N2 balance CO2 balance Summation equation ndot yO21 = ndotvap yO22 ndot yN21 = ndotvap yN22 ndot yCO21 = ndotvap yCO22 yO22 yN22 yCO22 yH2O2 = 1 ndotliq ndotvap yO22 yN22 yCO22 ndotliq yO22 Find ndotliq ndotvap yO22 yN22 yCO22 1.0387 ndotliq yN22 ndotvap ndot 2 0.724 kmol hr 0.089 yH2O2 0.7288 yCO22 0. Guess: ndotvap yO22 Given ndot 2 0.Calculate the mole fraction of water in the exit gas if the exit gas is saturated with water. some of the water will condense.835 336 8.

470 1.14 at pressure: xC3 xC4 xC5 P 18psia Ans.895 kW Ans.Apply an energy balance around the cooler to calculate heat transfer rate.227 10 ndotvap yN22 R ICPH T1 T2 3. 0 0.040 10 0 1.15K 5 5 5 ndotvap yO22 R ICPH T1 T2 3. 0.539 10 ndotvap yCO22 R ICPH T1 T2 5.23 The vapor mole fractions must sum to 1.85 0.004 337 .39 Assume the liquid is stored at the bubble point at T = 40 F Taking values from Fig 10. xC3 KC3 xC4 KC4 xC5 KC5 1.10 KC3 KC4 KC5 3.506 10 0 3 3 3 0.639 0.66 kJ mol T1 T1 273.045 10 ndotvap yH2O2 R ICPH T1 T2 3.450 10 HlvH2O ndotliq Qdot 19.925 0.15K T2 3 T2 273.121 10 10.05 0. HlvH2O Qdot 40.157 10 5 0 0.457 1.280 0.9 0.

3872 3885.170 P 1atm T2 70degC PsatH2O ( ) T e kPa a) Calculate the mole fraction of H2O and SO2 in the exiting vapor stream assuming vapor is saturated with H2O yH2Ovap ySO2 1 PsatH2O T2 P yH2Ovap yH2Ovap 0. hr 338 . ySO2 0. b) Calculate the vapor stream molar flow rate using balance on SO 2 ndotvap ndotSO2 ySO2 ndotvap 14.40 H2S + 3/2 O2 -> H2O + SO2 By a stoichiometric balance. Calculate the liquid H2O flow rate using balance on H2O ndotH2Ovap ndotvap yH2Ovap ndotH2Ovap 4.10.692 Ans.461 kmol hr Ans.461 kmol hr ndotH2Oliq ndotH2O ndotH2Ovap ndotH2Oliq 5.70 T degC Exit conditions: 230. calculate the following total molar flow rates Feed: Products ndotH2S 10 kmol hr ndotO2 3 ndotH2S 2 ndotSO2 ndotH2S ndotH2O ndotH2S 16.308 Ans.539 kmol Ans.

3872 Tdp1 20degC Tdp2 10degC P 1atm 3885.606 kPa Ans.207 degF Ans.170 MH2O 18.023 y2 PsatH2O Tdp2 P y2 0.41 NCL 0.42 ndot1 50 kmol hr 16.01 kg kg MH2O 18.0161 yH2O YH2O 1 YH2O yH2O 0.70 T degC 230.004 degC yH2O P = PsatH2O ( ) Tdp T Tdp Tdp 32degF Tdp 57. 10.10.70 T degC 230.170 c) PsatH2O ( ) T e kPa Guess: T Find ( ) T 20degC Given Tdp 14.01 PsatH2O ( ) T e kPa gm mol y1 PsatH2O Tdp1 P y1 0. b) P 1atm ppH2O 16.01 gm mol Mair 29 gm mol a) YH2O NCL Mair MH2O YH2O 0.3872 yH2O P ppH2O 1.0158 Ans.012 By a mole balances on the process Guess: ndot2liq ndot1 ndot2vap ndot1 339 . 3885.

Com ponent1 Benzene 2.572 220.7 7 65.7819 13.559 kmol hr mdot2liq ndot2liq MH2O mdot2liq 10.Given ndot1 y1 = ndot2vap y2 ndot2liq H2O balance ndot1 = ndot2vap ndot2liq Overall balance ndot2liq ndot2vap ndot2vap Find ndot2liq ndot2vap 49.44 C1 C2 217.81 2723.43Benzene: Cyclohexane: A1 A2 13.3 8 .6 64 .618 Psat1 ( T) exp A1 B1 T degC C1 Psat2 ( T) exp A2 B2 T degC kPa C2 Guess: T 66degC Given Psat1 ( T) = Psat2 ( T) T Find ( T) The Bancroft point for this system is: Psat1 ( T) 39. 10.2 60 .441 kmol hr ndot2liq 0.6568 B1 B2 kPa 2726.8 P ( Pa) k 39.321 degC Ans.t Bu anol Acet ti oni le r Com ponent2 Cyclohexane W at er Et hanol T (C) 52.074 kg hr Ans.6 340 .591 kPa T 52.

First calculate the equilibrium T and P.7m 3 N2 (2): x2 0.Chapter 11 .15 K i 1 2 ntotal nN2 nAr x1 nN2 ntotal x2 nAr ntotal x1 0.15 K TAr 403.885 J K Ans.Mathcad Solutions 11. for an ideal gas.385 CvAr 3 R 2 CvN2 5 R 2 CpAr CvAr R CpN2 CvN2 R Find T after mixing by energy balance: T TN2 2 TAr (guess) Given nN2 CvN2 T TN2 = nAr CvAr TAr 341 T T Find T) ( .15)K] 273.342 mol S nR i xi ln xi S 204.615 x2 0.7 V1 0.5 mol TN2 TAr [75 ( ( 130 273. Also.15) K P n i Vi RT n 40. 11. nN2 nAr 4 mol 2.Section A . fixed-volume system. U = Cv T.15)K PN2 PAr 30 bar 20 bar TN2 348.1 For an ideal gas mole fraction = volume fraction CO2 (1): x1 0.3 V2 0. adiabatic. U =0.2 For a closed.3m 3 i 1 2 P 1bar T ( 25 273.

3 mdotN2 molwtN2 2 kg sec gm mol mdotH2 molwtH2 0.016 molarflowN2 molarflowtotal mdotN2 molwtN2 molarflowN2 molarflowH2 mdotH2 molwtH2 319.38 bar Calculate entropy change by two-step path: 1) Bring individual stream to mixture T and P.T 273.15 K 90 degC Find P after mixing: P PN2 2 PAr (guess) Given nN2 nAr R T P = nN2 R TN2 PN2 nAr R TAr PAr P Find ( P) P 24.006 J K S SN2 SAr Smix S 38.014 2. 2) Then mix streams at mixture T and P. SN2 nN2 CpN2 ln T TN2 T TAr R ln P PN2 P PAr SN2 11.5 kg sec gm mol i 1 2 28.409 mol sec molarflowH2 molarflowtotal 342 .27 Ans.806 J K J K SAr nAr CpAr ln R ln SAr 9. 11.547 Smix ntotal R i xi ln xi J K Smix 36.

0 MCPHmix 0.776 S R molarflowtotal i yi ln yi S 1411 J secK Ans.561 10 6 0.131 19.15 K P1 3 3 bar P2 6 1 bar For methane: MCPHm MCPH T1 T2 1.081 10 2. (11.225 10 3 5.702 9. y1 0.225 10 3 5.5 The last term is the entropy change of UNmixing J T 300 K S 15.164 10 6 0.79 t 0.y1 molarflowN2 molarflowtotal y1 0.05 T 300 K Assume ideal gases.0 MCPHe MCPH T1 T2 1.164 10 0.15 K T2 308.26).5 MCPHe MCPHmix MCPSmix 6. For UNmixing of a binary mixture it becomes: 343 .5 MCPSm 0.5 MCPSe T1 R ln P2 P1 R MCPHmix T2 H 7228 J mol S R MCPSmix ln T2 T1 R 2 0. 11.5 MCPHm 0.224 y2 molarflowH2 molarflowtotal y2 0.081 10 3 2.0 MCPSm For ethane: MCPS T1 T2 1.21 6.5 Basis: 1 mole entering air.21 y2 0.702 9.131 19.0 MCPSe MCPS T1 T2 1. then H= 0 The entropy change of mixing for ideal gases is given by the equation following Eq.561 10 6 0.161 MCPSmix H 0. 11.813 mol K Wideal H T S Wideal 2484 J mol Ans.5 ln ( ) 0.4 T1 448.

Ai i Fi Fi 1 Pi 2 Pi 1 ln i ln i 1 i Pi Ai exp ln i fi Generalized correlation for fugacity coefficient: For CO2: Tc 304.2 K Pc 73.391 exp Pc Tr B0 Tr B1 Tr 344 fG ( P) G ( P) P . (5.282 10 mol By Eq.913 Z 0. (11.762 0.765 0.15) K Tr T Tc Tr 1.28): Work Wideal t Work 25638 J mol Ans.000 0.910 Fi Zi Pi 1 ln 1 0 1 1 end rows ( P) i 2 end Fi is a well behaved function.27): Wideal T S Wideal 1.16 0 10 20 40 60 P 80 100 200 300 400 500 bar 1.824 0.885 0.83 bar 0.942 0.35) numerically. (5.985 0. 11.273 J mol K 3 J By Eq.869 0.224 T P G ( P) ( 150 273.S R y1 ln y1 y2 ln y2 S 4.970 0. use the trapezoidal rule to integrate Eq.

4 0 200 Pi 400 600 0 200 Pi bar 400 600 bar Agreement looks good up to about 200 bar (Pr=2.698 0.896 0.332 71.949 0.6 bar 100 0 0.167 153.973 55.7 @ Tr=1.922 0.393 Pc P Pr 78.555 37.925 19. we see from Fig.17 For SO2: Tc T 430. 345 .805 For the given conditions.8 K 600 K 1.Pi bar Calculate values: 10 20 40 60 80 100 200 300 400 500 fi i 0.84 bar 300 bar P Pc Pr 0.978 0.14 that the Lee/Kesler correlation is appropriate.77 0.993 0.872 0.636 bar 9.377 317.964 209.656 0.39) 11.8 i G Pi f G Pi 0.676 87. 3.299 262.245 Tr T Tc Tr 3.96 400 fi bar 300 200 0.

2335 0 1 f P 0.196 0.15 & E.0 0. f PHIB Tr ( )Pr ( ) T P P T ( 280 f 18.16 and by Eq.16 and Eq.18 Isobutylene: Tc 417.5 P At these conditions use the Lee/Kesler correlation.4 266.5 P At these conditions use the generalized virial-coeffieicnt correlation. 0 0.724 f P GRRT ln f 217. (11.67).83 K T K P bar Psat bar .354 0 1 0. (11.9 K Pc 40.00 bar 0.15)K P 20 bar Tr ( ) T T Tc Tr ( ) 1. Tables E.323 Ans.8 420.76 bar 273.15)K Ans.02 40.3236 T Pr ( ) 2.191 Zc Vc Tn 322.273 0.267 25. P 100 bar b) At 280 degC and 100 bar: Tr ( ) 1.277 383.67): 0 0.169 bar Ans.732 f 73.672 1 1.15 K Pc 45.7025 1 1.3236 T Pr ( ) P P Pc Pr ( ) 0.15 393. 11.3 275 34 346 bar cm mol 3 0.15 & E.19 The following vectors contain data for Parts (a) and (b): (a) = Cyclopentane.Data from Tables E.9 5.194 a) At 280 degC and 20 bar: T ( 280 273.43 258 239. (b) = 1-butene Tc 511. 11.14 bar GRRT 0.

Tr T Tc Tr 0.44): 2 Vsat V c Zc 1 Tr 7 Vsat 107.78 20.44) with satPsat = fsat r exp Vsat P RT Psat r 1.900 (b) PHIB Tr Psatr 2 2 2 0.15 K Equation Eq.21 Table F.749 0.084 r= f fsat = 1.29 Psat exp Vsat ( Psat) P RT f bar Ans.117 0.9361 Psatr Psat Pc Psatr 0.084 Ans.68): (a) PHIB Tr Psatr 1 1 1 0.091 cm molwt gm 3 3 T ( 150 273.546 cm3 133.00 kPa molwt 18 gm mol Vsat 1.7486 0.72).76 Eq. (11.1.299 mol f PHIB Tr Psatr 11. 11. (11.638 mol T 423. (3.15)K P 150 bar Vsat cm 19. the Rackett equation: Tr T Tc Tr 0. (11.936 Eq.6389 Calculate the fugacity coefficient at the vapor pressure by Eq. 150 degC: Psat 476. 347 .

194 0.9 K 420. (b) 50(psia) & 800 degF: T2 3275.270 Zc 0.7 Tc 417.6 lbm 1. and (c): (a) = n-pentane (b) = Isobutylene (c) = 1-Butene: 469.9 239.9 K mol .277 cm 3 309.0 Pc 33.275 0.252 bar 0.0 Vc 238.0377 (b) r= = 0.0338 J gm K Btu 1431.9227 Btu lbm rankine Eq.11.2915 S1 J gm K H1 Btu 1389.3 348 0.0377 0.3 266.70 40.67) rankine J gm 6.2: (a) 300 kPa & 400 degC.191 0. (a) r= f2 f1 = 0.15) K 459. (b) 1000(psia) & 800 degF: T1 ( 400 ( 800 3121.23 The following vectors contain data for Parts (a). (b).43 313.22 The following vectors contain data for Parts (a) and (b): molwt 18 gm mol Table F.0542 11.0542 Ans.7 lbm 1.2: (a) 9000 kPa & 400 degC.2 H2 J gm S2 8.2 Tn 266.2 273.0 40. (A) on page 399 may be recast for this problem as: r exp molwt R H2 T1 H1 S2 S1 f2 f1 r 0.5677 Btu lbm rankine T1 Table F.

(11.293 Vc cm 239.01325 bar 1.801 Psat exp Vsat ( Psat) P R Tn Ans.6355 Psat 1.0251 Tr Tn Tc Calculate the fugacity coefficient at the nbp by Eq.72): Vsat V c Zc Eq.4 K Pc 3 54.0301 Pr Psat Pc Pr 0.01325 1.44): f PHIB Tr Pr 2. (3.445 f 3.72 bar 0. (3.2857 Eq.9572 2 2 0.0 mol Tn 334.222 Zc 0. 11.9618 (c) PHIB Tr Pr 3 3 3 0.68): (a) (b) PHIB Tr Pr 1 1 PHIB Tr Pr 2 1 0.882 2 Trn Tn Tc Trn 0.24 (a) Chloroform: Tc 536.15 K Tr T Tc Tr 0.326 bar 1.27 bar T 473.72): Vsat V c Zc 1 Trn 7 Vsat cm 94.200 P 300 bar 150 0.9620 1 Tr 0.623 3 Eq.41 mol 349 .3 K Psat 22.6583 Tr 0.0253 0. (11.6372 0.01325 0.

5 bar 40 bar 40 Psat bar ( P) Psat bar f ( P) bar 30 0.72): V c Zc 1 Trn 7 cm 102.6 10 0 0 20 40 0.4 0 20 P bar 40 P P bar bar (b) Isobutane Zc T Tc Vc Tr 408.181 Psat 5.282 cm mol Tr Tn 0.48 bar 261. (11.1 K 262.68): P Pc if P Psat Pr ( P ) Tr Pr ( P ) ( P) exp B0 Tr B1 Tr f ( P) ( P) P ( Psat) Psat exp Vsat ( P Psat) RT ( P) P if P Psat ( P) ( Psat) Psat P exp Vsat ( P RT Psat) 0 bar 0.Calculate fugacity coefficients by Eqs.4 K Tn Tc Vsat 0.8 P bar 20 0. (3.15 K Trn Trn 0.28 bar 0.767 2 313.7 T Tc Vsat Pc 3 36.107 mol 350 .641 3 Eq.

6 0 0 5 10 0.6 K Pc 50.4 0 5 P bar 10 P P bar bar 11. (11.3 365.40 46.35 y2 k 1 1 n y1 j 1 n .68): Pr ( ) P P Pc if P Psat ( )P P () P exp Pr ( ) P Tr B0 Tr B1 Tr fP) ( ( )Psat exp Psat Vsat ( Psat) P RT () P P if P Psat () ( ) P Psat Psat P exp Vsat ( P RT Psat) 0 bar 0. Propylene = species 2 Tc 282.Calculate fugacity coefficients by Eq.5 bar 10 bar 10 Psat bar 0.4 y1 T n 423.25 Ethylene = species 1.15 K 2 30 bar 1 n 351 0.65 bar cm mol 3 w 0.087 0.8 Psat bar fP) ( bar P bar 5 () P 0.281 0.140 Zc 0.0 188.289 Vc P i 131.

085 0.157 50.189 0. .261 Pc 321.189 46.499 1.875 352 fhat 10.059 bar Ans.114 0.4 mol 131 0.14 Tc 282.By Eqs.43 mol Bi j R Tc i j B0i j Pc i j B By Eq.96 0 0 hatk exp Bk k 1 2 i j yi y j 2 i k i j fhatk hatk yk P hat 0. (11.6 0.189 48.114 0.96 cm3 mol 20.74) wi i j wj 2 1 3 Tc i j Tci Tc j Zc Zci 2 Zc j i j Vc Vci Vc j 1 3 3 Zc Pc i j i j i j 2 T R Tc i j Vc i j Tr i j Tc Tr 1.053 17.3 321.085 0.285 0.108 0.181 99.251 i j B1i j B1 0.181 cm3 159.892 99.285 0. (11.627 K Zc bar i j Vc 157.966 188.317 1.345 48.64): i j 2 Bi j Bi i P RT Bj j 20.66): B0i j B0 B0 Tr 0.289 By Eqs. (3.281 0.087 0.65) and (3.70) through (11.966 cm3 157.189 i j B1i j B1 Tr i j 0.317 1.957 0.261 365.138 0.046 59.

286 w 0. Alternatively.873 11.873 fhatid 9.48 Vc 145. Pr P i j Pr idk exp k k k k Pc i j Tr B0k k k k B1k k id 0.36 T 373.012 P 35 bar 0.For an ideal solution .95 0.5 200.70) through (11.6 cm mol 3 190.022 bar Ans.595 0.978 17.43 0.6 Tc 305.0 n 3 i 1 n j 1 n k 1 n By Eqs.276 98.15 K 0.95 0.100 0.279 0. id = pure species Pr P k Pck Pr 0.3 K 369.74) wi i j wj 2 1 3 Tc i j Tci Tc j Zc Zci 2 Zc j i j Vc Vci Vc j 1 3 3 Zc Pc i j i j i j 2 R Tc i j Vc i j 353 .643 Pr idk exp Tr k B0k k k k B1k k k k fhatid k idk yk P id 0.27 Methane = species 1 Ethane = species 2 Propane = species 3 0. (11.8 Pc 48.152 45.72 bar 42.99 Zc 0.21 y 0.

533 120.276 265.254 bar 9.286 0.8 0. (11.282 0.378 145.082 0.259 45.006 K 369.406 1.442 cm 3 mol 107.111 1.281 Zc 0.809 0 23.428 190.6 Vc 120.006 By Eqs.547 1.005 43.958 1.279 0.226 265.056 0.152 0.482 0 2 Bi j Bi i Bj j 30.111 1.009 i j 98.019 0.775 354 7.406 Tr T i j Tc Tr 1.6 Tc 241.1 0.012 0.442 107.533 143.5 171.65) and (3.222 1. (3.1.66): B0i j B0 Tr B1i j i j B1 Tr i j Bi j R Tc i j B0i j Pc i j i j B1i j By Eq.126 0.881 0.281 0.378 171.308 200 cm 3 mol 143.005 48.64): i j 0 30. .488 336.809 23.488 305.3 336.253 bar 43.082 0.491 fhat 13.282 0.278 0.308 45.126 0.056 0.764 Ans.253 42.226 241.672 45.547 1.964 47.482 hatk exp P RT Bk k 1 2 i j yi y j 2 i k i j fhatk hatk yk P hat 1.278 0.259 Pc 47.

15) & (11.4 x1 1.251 bar 9. (11.8 ln 2 = 2 x1 2 x1 1.977 fhatid k idk exp Prk Tr k k B0k k k k B1k k 7.8 x1 x1 2 GE = RT 0.16) for M = GE/RT: ln 1 = GE RT d 1 x1 GE RT dx1 ln 2 = GE RT d x1 GE RT dx1 d GE RT dx1 = 1.569 Ans.4 x1 2 3 1.759 11.100): GE = x1 RT 1.6 x1 1.182 fhatid 13. (b) Apply Eq. (11.8 1 x1 2 x1 x1 2 1.88 0.824 0.8 x1 1.6 x1 3 3 1. idk yk P id 0.8 x2 x1 x2 Substitute x2 = 1 . id = pure species 0.6 x1 Ans.For an ideal solution .x1: .4 x1 2 2 ln 1 = 1.6 x1 3 1.8 x1 1 x1 = 1.761 Prk P Pck Pr 0.8 2 x1 2.6 x1 This reduces to the initial condition: 355 .8 x1 3 Apply Eqs.28 Given: (a) GE RT = 2.718 0.

6 x1 3 ln 2 () 1 2.0 356 . = 0 Q.8 x1 4.8 x1 2 d ln 1 = 2 x1 dx1 d ln 1 = 1 dx1 2. of Part (c) that (e) DEFINE: g = GE/RT g x1 ln 1 x1 ln 2 x1 ln 1 () 0 d ln 1 dx1 d ln 2 dx1 = 0 Q.8 x1 4.8 2 x1 2 0.4 x1 3 1. we see from the 3rd eq.8 x1 3 2 2 x1 1. (d) When x1 = 1.8 x1 1. 1.8 x1 2 d ln 2 = 2 x1 dx1 3 4.E.8 x1 2 These two equations sum to zero in agreement with the Gibbs/Duhem equation.(c) Divide Gibbs/Duhem eqn.D.8 x1 1. we see from the 2nd eq.100) by dx1: d ln 1 dx1 x1 x2 d ln 2 dx1 = 0 Differentiate answers to Part (a): d ln 1 = 2 dx1 x1 2 2.E.8 x1 x2 x1 2 x1 4.6 x1 1. (11.D.1 1.6 x1 0 0. of Part (c) that When x1 = 0.

6 417.7 276.93287 0.72792 0.0 357 0.9 190.6 0.1 VE 321.32760 0.82954 0.0 g x1 ln 1 x1 ln 2 x1 1 0 ln 1 ( ) 2 ln 2 ( ) 1 3 0 H H1bar H2bar 0.2 0.5 265.56689 0.1 347.09329 0.7 421.4 98.66233 0.69984 0.17490 0.4 252.6 10.01 1 .4 0.02715 11.4 534.8 x1 0.4 37.86835 0.32 87.7 178.40244 0.1 138.98233 253 n rows x1 i 1 n x1 0 0.77514 0.5 531.63128 x1 0.79243 0.

202 10 244.6 0.2 0.615 3 x1 1 600 VEi x1 ( 1 x1) a b x1 c ( x1) 2 400 200 0 0 0. Then use x1 to find VEmax.(a) Guess: x1 1 F x1 x1 2 a x1 x1 x1 a b c 3000 b 3000 c a 250 3. 3.4 i 0.5 3 (c b) ( x1) x1 2 2 (b a) x1 a= 0 Find ( x1) 0.448 10 3 3 1 linfitx1 VE F b c Ans.353 Ans. 358 . set dVE/dx1 = 0 and solve for x1. Guess: Given 4 c ( x1) x1 3 x1 0.8 x1 x1 By definition of the excess properties V = x1 x2 a E b x1 c x1 3 (c 2 d 3 E V = 4 c x1 dx1 Vbar1 E b) x1 2 2 (b 2 a) x1 a = x2 = x1 2 a 2 b x1 3 c x1 Vbar2 E 2 a b 2 (b c) x1 3 c x1 2 (b) To find the maximum.

2 0.61): B i 359 yi y j Bi j j B 504. b) Interior extrema come in pairs: VEbar min for species 1 occurs at the same x1 as VEbar max for species 2. (c) VEbar1 ( ) x1 ( 1 x1) a 2 2 b x1 VEbar2 ( ) x1 x1 0 0.6 0. (11. 11.15)K 466 809 cm mol 3 P n 2 bar 2 y1 i 0.33 Propane = 1.25 cm 3 mol . n-Pentane = 2 T B ( 75 273. c) At the point where the VEbar lines cross.VEmax x1 ( 1 x1) a b x1 2 c x1 2 VEmax 3c( ) x1 2 536.4 x1 x1 0. the VE plot shows a maximum.294 Ans. and both occur at an inflection point on the VE vs. x1 plot.8 Discussion: a) Partial property for species i goes to zero WITH ZERO SLOPE as xi -> 1.01 1 4000 ( ) a x1 b 2( b c)x1 3c( ) x1 2 2000 VEbar 1 ( ) x1 x1 VEbar 2 ( ) 0 2000 0 0.5 1 n y2 j 1 1 n y1 276 466 By Eq.

085 SR SRR R V 13968 cm 3 mol HR 348.92 mol K 3 3 Differentiate Eq.15 K 323.18 5. (6. .61): dBdT i j yi y j dBdTi dBdT j cm 3.15 K 373.18 d B22 ( T) dT cm 3.15 t 348.55 mol K By Eq.037 360 J mol SR 0. (3.15 3 interp ( vs11 t b11 T) B11 ( T) cm 276 mol vs22 lspline ( t b22) B22 ( T) interp ( vs22 t b22 T) B22 ( T) cm 809 mol 3 vs12 lspline ( t b12) B12 ( T) interp ( vs12 t b12 T) B12 ( T) cm 466 mol 3 dBdT d d B12 ( T) B11 ( T) dT dT d dT B12 ( T) dBdT 1.38): Z 1 BP RT Z 0. (11. (6.55): HRRT By Eq.92 3.71 J mol K Ans.12 HR SRR P dBdT R 0.965 V ZR T P HRRT R T By Eq.56): P R B T dBdT HRRT SRR 0.Use a spline fit of B as a function of T to find derivatives: 331 b11 276 235 cm 3 980 b22 809 684 cm 3 558 b12 466 399 cm 3 mol mol mol 50 t 75 100 vs11 lspline ( t b11) B11 ( T) 273.

1 1.95 0.63b): hat1 ( ) y1 exp P B1 1 RT ( 1 2 y1) 1 2 2 hat2 ( ) y1 y1 exp P B2 2 RT y1 1 2 0 0.15)K 466 809 cm 3 P 2 bar n y1 2 0.2 0.0 1 0.34 Propane = 1. (11.96 0.99 0.94 0 0.97 hat2 ( ) y1 0.63a) and (11.4 y1 361 0.11.8 .98 hat1 ( ) y1 0.5 y2 1 y1 276 466 i 1 n mol j 1 n ij 2 Bi j Bii B j j By Eqs.6 0. n-Pentane = 2 T B ( 75 273.

7621 0.01 a 539.2 0.6 118.01 1 (a) Guess: x1 1 F x1 x1 2 3 a x1 x1 x1 b 100 c 0.8181 0.2 191.4 i 0.6 500 a b c 0 0.0 116.2624 0.3472 x1 0.6 176.1 141.2 144.8650 0.5163 0.0.5 86. x1 HEi x1 ( 1 x1) a b x1 c ( x1) 2 100 200 300 0 0.6 43.1177 0.36 23.1510 0.011 10 913.3 45.4158 0.6156 0.0426 11.8 x1 x1 362 .122 3 1 1 linfit x1 HE F b c Ans.7 174.7 66.6810 0.9624 n x1 rows x1 i 1 n 0 0.5 22.6 HE 195.6 0.2107 0.653 1.7 204.8 85.0817 0.9276 0.

c x1 2 2( b x1 x1) a HEmin (c) HEmin 204. Then use x1 to find HEmin.4 x1 363 0.By definition of the excess properties H = x1 x2 a d dx1 E E b x1 3 c x1 3( c 2 H = 4 c x1 E b) x1 2 2( b 2 a)x1 a Hbar1 = x2 = x1 2 a 2 b x1 3 c x1 Hbar2 E 2 a b 2( b c)x1 3 c x1 2 (b) To find the minimum.401 Ans.512 b x1 x1 ( 1 2 x1) a a)x1 b x1 a= 0 c x1 4c( ) x1 Find ( ) x1 x1 ( 1 b)( ) x1 Ans.2 0.5 3 HE ( ) x1 3( c 0. set dHE/dx1 = 0 and solve for x1. HEbar1 ( ) x1 HE ( ) ( x1 1 d x1) HE ( ) x1 dx1 HEbar2 ( ) x1 x1 0 0.01 1 500 0 500 HE ( ) x1 x1 d HE ( ) x1 dx1 HEbar 1 ( ) x1 x1 HEbar 2 ( ) 1000 0 0.6 0.8 . Guess: Given x1 2 x1 0.

x1 plot.25 0.104 45.2 0 K Eq.48 0 Note: the calculated pure species Pc values in the matrix above do not agree exactly with the values in Table B.082 508.851 425.15) K Vc P 209 170 kPa cm mol 3 w n 2 0.71) Tci j Tc Tc i j 1 ki j Tc 464.013 42. (11.37 (a) (1) = Acetone (2) = 1. b) Interior extrema come in pairs: HEbar min for species 1 occurs at the same x1 as HEbar max for species 2.Discussion: a) Partial property for species i goes to zero WITH ZERO SLOPE as xi -> 1.152 464.276 209 0 214.3-butadiene y1 0.267 0. c) At the point where the HEbar lines cross. (11. 11.70) i j 0.2485 0.4 200 0 cm mol 47.233 0.25 j Zc 1 3 0.126 0.826 bar 42. 364 .2 0.65 3 Vc Eq.267 220.73) Zci j i Zc 2 1 0.74) Vci j 3 i Vc 3 j 2 Vc 214.126 0. (11.307 0. and both occur at an inflection point on the H E vs.190 0.2 T K Zc ( 60 273. (11.72) Pci j Zci j R Tci j Vci j Pc 45.307 0.013 Eq.2 425.851 369. the HE plot shows a minimum.4 i 1 n wi wj 2 j 1 n ki j 0 0.233 0.2485 0.65 220.8 Zc Eq.28 y2 Tc 1 y1 508.1 due to round-off error in the calculations. (11.082 Eq.19 0.

61) B i 1 j 1 yi y j Bi j B 598.74636 B0 0.558 0.6 0. (6.717 0.874 B1 0.717 0.6361 0.656 0.028 0.2 Eq.04 0.34 0. (3. 0.5405 0.038 Pr 0.38) Z V 1 BP RT Z V 0.036 0. (3.66) B1i j B1 Tri j 0.188 cm3 499. (3.5694 10 3 4 cm RT Z P mol Ans.027 Eq.824 0 Tr Eq.188 n 665.89) dB0dTri j Eq.558 0.65) 0.784 B0i j B0 Tri j Pri j P Pci j 0. (11.6361 0.028 0. (11.098 0.Tri j T Tci j 0.90) dB1dTri j 365 .722 Tri j 5.69a) + (11.524 mol Eq.16178 0. (6.527 mol cm 3 Eq.69b) Bi j R Tci j B0i j Pci j i j B1i j B n 910.33295 0.278 665.963 1.675 Tri j 2.038 0.27382 0.098 0.27382 0.16178 Eq.

Differentiating Eq.3 J mol (d) V = 80972 cm 3 mol HR = 36.666 mol J mol J SR = 0.097 J mol K 3 GR = 8.96 J mol SR = 0.322 GR = 125. (b) cm V = 15694 mol SR = 1.051 Eq.2 J mol 366 . (6. mol Ans.48 J mol SR = 0. (6.61) and using Eq.1 J mol J mol K 3 J mol (c) V = 24255 cm HR = 175. (11.727 J mol J Ans.006 HR = 450.69b) n n dBdT i 1 j 1 yi y j R dB0dTri j Pci j i j dB1dTri j Eq.7 mol K J Ans.56) SR P dBdT SR 0. (6.55) HR PT B T dBdT HR 344.41 mol K GR = 53. Eq. (11.647 J mol K GR = 85.69a) + (11.54) GR BP 3 GR 101.1 J mol (e) cm V = 56991 mol HR = 277.

3 150. (3.817 Pr P Pc Tr T Tc Tr 1.023 Tc 308.98 48.99 34.11.206 11.00 .38 .40 325 200 575 T 350 300 525 225 200 P 15 100 40 35 50 10 25 75 1.40 30.034 1.9 562.133 0.081 0.25 45.544 2.474 0.000 .028 0.847 2.98 73.038 0.187 .54) q 3.992 0.02 0.53) 0.08664 0.504 4.585 Pr 0.012 .210 .6 190.Data for Problems 11.244 2.121 q Tr 1.18 1.473 Guess: z 1 367 .04 0.325 1. (3.2 282.998 4.38 Redlich/Kwong Equation: 0.331 0.063 1.691 3.5 Eq.2 304.39 48.151 1.77 0.6 126.054 1.087 .559 3.234 4.036 0.42748 4.224 .069 Pr Tr Eq.042 0.2 Pc 61.83 50.301 .3 507.

480 1. (3.036 0.859 1 ln Z i qi Ii Eq.887 0.081 0.73 0.53) 0.254 63.85 fi 13.952 31.737 q Eq.62 3.069 1 c 1 Tr 4.749 0.881 0.362 36.89 0. (3.827 2.028 0.02 0.352 29.37) fi Z i 0.42748 2 c 0.121 3.925 0.504 8.891 0.202 4.39 Soave/Redlich/Kwong Equation 2 0.54) q Pr Tr Eq.08664 0.133 0.9 0. (11.744 0.468 4.722 0.176 0. (3.52) Z q Find z () i 1 8 Ii i qi ln Z Z i qi i qi i qi i Eq.04 0.304 Tr Guess: z 1 368 .5 0.93 0.574 0.743 11.944 74.49 3.998 22.65) i exp Z i Pi i qi 0.896 0.79 4.668 0.639 0.Given z= 1 q z z z Eq. (6.

881 i qi 1 i qi Ii Eq.729 0.751 0.53) 0.073 0.903 0.748 0.062 1 c 1 Tr 0.Given z= 1 q z z z Eq.882 0.036 0.108 q Tr Eq.946 5.274 65.26992 0.(3.40 Peng/Robinson Equation 1 2 1 2 2 0.5 5. (11. (3. (6.65) i exp Z i Pi i qi 0.598 5.359 5.12 0.54226 0.893 0.37464 1.018 0.646 0.155 11.07779 0.896 0.869 fi 13.025 0.(3.902 0.646 2.733 0.931 0.924 369 .383 3.927 0.527 4.54) q 4.45724 2 c 0.018 22.05 31.891 0.66 9.52) Z q Find z () i 1 8 Ii ln Z Z ln Z i qi i qi i qi i Eq.658 Pr Tr Eq.965 74.032 0.673 0.37) fi Z i 0.618 36.753 30.

(d).66) 370 . (3.647 0.89 0.301 .865 0. (3.69 0.881 0.845 ln Z i qi i i qi Ii Eq.465 8.363 BY GENERALIZED CORRELATIONS Parts (a). and (g) --.83 30.224 .65) i exp Z i Pi i qi 1 i qi 0.876 0.882 0.25 45.709 0.73 0.142 35.6 P 15 35 10 25 Pc 61.2 507.617 0.842 71. (11.711 0.197 31.923 0. (f).3 304.012 Tr Pr P Pc Evaluation of : B0 B0 ( Tr) Eq.91 21. (3.52) Z q Find ( z) Given z = 1 i 1 8 Ii 1 2 2 ln Z Z i qi i qi i i Eq.113 29.832 13.891 0.65) B1 B1 ( Tr) Eq.37) fi fi Z 0.6 190.99 .187 .895 62.918 0. (6.Virial equation: 325 T 350 525 225 T Tc Tc 308.39 73.Guess: z 1 q z z z Eq.

43 ndot1 x1 2 kmol hr ndot2 x1 4 kmol hr x2 ndot3 1 x1 ndot1 x2 ndot2 0.7454 0 .746 0.DB0 0.13 . and (h) --.333 a) Assume an ideal solution since n-octane and iso-octane are non-polar and very similar in chemical structure.932 Pr B0 exp Tr B1 Eq. (6.9883 1.7316 .6 Eq.9634 0. there is no heat of mixing therefore the heat transfer rate is zero. (e).087 0.731 0.000 0. b) St R x1 ln x1 x2 ln x2 ndot3 St 8.895 (a) (d) (f) (g) Parts (b).862 (b) (c) (e) (h) 11.8554 1 1. (11.67): 0.7517 .667 ndot1 ndot3 0.Lee/Kesler correlation: Interpolate in Tables E.904 0.16: .722 Tr 5.675 Tr 2.038 0. (11.1842 0.210 0. 371 .60) 0. (6.903 0. For an ideal solution.89) DB1 0.90) 0.82 W K Ans.E.2071 0.2 Eq.745 0 1 Eq. (c).

For an ideal gas there is no heat of mixing. treat the process in two steps: 1. c) To calculate the entropy change. Mix the N2 and combined O2 to produce the enhanced air Entropy change of demixing S12 R xO21 ln xO21 xN21 ln xN21 Entropy change of mixing S23 R xO22 ln xO22 xN22 ln xN22 Total rate of entropy generation: SdotG ndotair S12 ndot2 S23 SdotG 152.354 mol sec Ans.21 xN21 0.5 xN22 0. Demix the air to O2 and N2 2.919 W K Ans. b) Assume ideal gas behavior.44 For air entering the process: xO21 0. the heat transfer rate is zero. ndotO2 18.646 mol sec Ans.5 ndot2 50 mol sec a) Apply mole balances to find rate of air and O2 fed to process Guess: ndotair 40 mol sec ndotO2 10 mol sec Given xO21 ndotair ndotO2 = xO22 ndot2 Mole balance on O 2 xN21 ndotair = xN22 ndot2 ndotair ndotO2 Find ndotair ndotO2 Mole balance on N2 ndotair 31. 372 .79 For the enhanced air leaving the process: xO22 0. therefore.11.

GE and T*SE at 25 C using a. mol J Ans.10 11.4 845.15K 932.9 J mol Assume Cp is constant.2 HE 893.242 K GE ( ) T a T ln T K T bT ( c GE [25 273.155 1. b and c values.848 K 373 .559 13.15) ] 378.1 J mol 30 K 50 GE 513. HE ( ) T aT c J Ans.544 J mol K 10 3 J mol T bT c GE is of the form: GE = a T ln T K Rearrange to find b using estimated a and c values along with GE and T data.394 K J Ans.15) ] 901.15) ] 522. Then HE is of the form: Find a and c using the given HE and T values. mol HE [25 ( 273.50 T 544.549 J mol K Now calculate HE. a c HE = c aT slope ( HE) T intercept ( HE) T a c 2.543 B 13. mol TSE ( ) T HE ( ) GE ( ) T T TSE [25 ( 273. GE B a T ln T T K T c 13.0 273.545 J mol K Use averaged b value 3 Bi b i 1 3 b 13.0 494.

652 60.953 kPa Calculate EXPERIMENTAL values of activity coefficients and excess Gibbs energy.562 kPa Psat2 19.1686 0.15 K 0.9141 n 10 i 1 n Number of data points: Calculate x2 and y2: n x2 rows ( ) P 1 x1 y2 1 y1 Vapor Pressures from equilibrium data: Psat1 84.784 P 56.852 52.Section A .832 kPa T 333.1 Methanol(1)/Water(2)-.7742 0.3039 0.6804 0.924 70.6943 0.7345 y1 0.8922 0.VLE data: 39.5714 0.229 72.5282 0.8383 0.2167 0.Chapter 12 .998 67.614 63.6044 0.3681 x1 0.6268 0.223 42.984 48. y1 P 1 y2 P 2 x1 Psat1 x2 Psat2 GERT x1 ln 1 x2 ln 2 374 .Mathcad Solutions 12.7255 0.7776 0.8085 0.4461 0.8733 0.

271 0.382 1.683 Intercept Intercept A21 A21 Slope 0.385 0.104 0.097 1.5 0.012 2 i 1.208 Intercept 0.087 0.2 0.41 ln 1 i 0.013 1.148 0.32 1.278 0.233 1.148 0.012 ln 2 i 0.3 0.475 375 .163 1.049 0.209 0.452 0.157 1. by linear least squares: VXi x1 i VYi GERTi x1 x2 i i intercept ( VX VY) 0.683 A12 Ans.073 0.2 0.311 1.3 0.324 0.6 0.026 1.22 0.4 0.135 0.4 ln 1 i ln 2 i GERT i 0. Slope Slope A12 A12 slope ( VX VY) 0.47 1.031 0.246 1.35 1.075 1.086 0.021 1.148 0.i 1 2 3 4 5 6 7 8 9 10 1 i 1.136 0.013 0.031 1.112 1.093 0.026 0.117 0.343 GERTi 0.106 0.021 0.05 1.146 0.8 x1 i (a) Fit GE/RT data to Margules eqn.104 0.151 0.1 0 0 0.572 1.

90 80 Pi kPa 70 60 50 j Pi kPa pcalc kPa 40 j pcalc kPa 30 20 10 0 0.01 X2 j 1 X1 j pcalc j X1 j 1 X1 X2 Psat1 j j j X2 j 2 X1 X2 Psat2 j j X1 Y1calc j 1 X1 X2 Psat1 j j pcalc j P-x. fit to GE/RT data.2 0.y Diagram: Margules eqn.6 j 0.4 i i j 0.8 x1 y1 X1 Y1calc P-x data P-y data P-x calculated P-y calculated 376 .The following equations give CALCULATED values: 1 ( x2) x1 2 ( x2) x1 j 1 101 exp x2 exp x1 2 2 A12 A21 2 A21 2 A12 A12 x1 A21 x2 X1 j .01 j .

by linear least squares: VXi Slope Slope a12 a12 x1 i VYi x1 x2 i i GERTi intercept ( VX VY) 1.641 1 Intercept 0. 1 ( x1 x2) exp a12 1 2 ( x1 x2) exp a21 1 X1 X2 a21 x2 a12 x1 j 1 101 j j .485 2 Ans.01 j 1 X1 .00999 j (To avoid singularities) 377 .418 slope ( VX VY) 0.705 Intercept Intercept a21 a21 a12 x1 a21 x2 2 1 ( Slope Intercept) 0.Pcalc i x1 1 x1 x2 Psat1 i i i x1 1 x1 x2 Psat1 i i i Pcalc i x2 2 x1 x2 Psat2 i i i y1calc i RMS deviation in P: Pi RMS i Pcalc n 2 i RMS 0.399 kPa (b) Fit GE/RT data to van Laar eqn.

6 j 0.2 i 0.4 i j 0.454 kPa 378 . 90 80 Pi kPa 70 60 50 j Pi kPa pcalc kPa 40 j pcalc kPa 30 20 10 0 0.8 1 x1 y1 X1 Y1calc P-x data P-y data P-x calculated P-y calculated RMS deviation in P: Pi RMS i Pcalc n 2 i RMS 0.pcalc j X1 j 1 X1 X2 Psat1 j j X2 j 2 X1 X2 Psat2 j j Pcalc i x1 1 x1 x2 Psat1 i i i x2 2 x1 x2 Psat2 i i i X1 Y1calc j j 1 X1 X2 Psat1 j j pcalc j y1calc i x1 1 x1 x2 Psat1 i i i Pcalc i P-x. fit to GE/RT data.y Diagram: van Laar eqn.

Guesses: SSE 12 0.026 Ans. Minimize the sum of the squared errors using the Mathcad Minimize function. by non-linear least squares.5 GERTi 21 1.(c) Fit GE/RT data to Wilson eqn.476 1. 21 12 exp x2 1 ( x2) x1 21 12 x1 x2 x1 x2 12 x1 21 x2 12 exp 2 ( x2) x1 x1 21 12 x1 x2 x2 x2 21 x1 21 x1 j 1 101 X1 X1 j .0 x2 2 12 21 i x1 ln x1 i i i i 12 21 x2 ln x2 i i x1 12 21 Minimize SSE 12 12 21 0.01 X2 X2 j 1 X1 j pcalc Pcalc j j 1 X1 X2 Psat1 j j j 2 X1 X2 Psat2 j j i x1 1 x1 x2 Psat1 i i i X1 x2 2 x1 x2 Psat2 i i i x1 1 x1 x2 Psat1 i i i Pcalc i Y1calc j 1 X1 X2 Psat1 j j j pcalc j y1calc i 379 .01 j .

y diagram: Wilson eqn. 90 80 Pi kPa 70 60 50 j Pi kPa pcalc kPa 40 j pcalc kPa 30 20 10 0 0.P-x. 1 x1 x2 A 12 A 21 2 x1 x2 A 12 A 21 exp ( ) A12 x2 exp ( ) A21 x1 2 2 2 A21 2 A12 A12 x1 A21 x2 380 .8 1 x1 y1 X1 Y1calc P-x data P-y data P-x calculated P-y calculated RMS deviation in P: Pi RMS i Pcalc n 2 i RMS 0.2 i 0. Guesses for parameters: answers to Part (a).48 kPa (d) BARKER'S METHOD by non-linear least squares.6 j 0. fit to GE/RT data.4 i j 0. Margules equation.

167 kPa 381 . Guesses: SSE A12 A21 i A12 0.758 0.0 2 x1 x2 A12 A21 Psat1 i 1 i i i x2 2 x1i x2i A 12 A 21 Psat2 A12 A21 A12 Minimize SSE A12 A21 0.435 Ans.Minimize the sum of the squared errors using the Mathcad Minimize function. A21 pcalc j X1 j j 1 X 1 j X 2 j A 12 A 21 Psat1 2 X 1 j X 2 j A 12 A 21 Psat2 1 X 1 j X 2 j A 12 A 21 Psat1 X2 X1 Y1calc j j pcalc j Pcalc i x1 i i 1 x1i x2i A 12 A 21 Psat1 2 x1i x2i A 12 A 21 Psat2 1 x1i x2i A 12 A 21 Psat1 x2 x1 y1calc i i Pcalc i RMS deviation in P: Pi RMS i Pcalc n 2 i RMS 0.5 Pi x1 A21 1.

2 i 0. Margules eqn.P-x-y diagram.5 0 0.5 y1 y1calc 100 i i 0 0.6 0.2 0.6 j 0.4 i j 0.8 x1 Pressure residuals y1 residuals i 382 . by Barker's method 90 Pi kPa 80 70 60 50 j Pi kPa pcalc kPa 40 j pcalc kPa 30 20 10 0 0.8 1 x1 y1 X1 Y1calc P-x data P-y data P-x calculated P-y calculated Residuals in P and y1 1 Pi Pcalc kPa i 0.4 0.

(e) BARKER'S METHOD by non-linear least squares.01 j . j 1 101 X1 j .0 2 x1 x2 a12 a21 Psat1 i 1 i i i x2 2 x1i x2i a12 a21 Psat2 a12 a21 Minimize SSE a12 a21 a12 a21 0.83 0. Guesses: SSE a12 a21 i a12 0. van Laar equation. Guesses for parameters: answers to Part (b).00999 a12 x1 a21 x2 2 X2 j 1 X1 j 1 x1 x2 a12 a21 exp a12 1 2 x1 x2 a12 a21 exp a21 1 a21 x2 a12 x1 2 Minimize the sum of the squared errors using the Mathcad Minimize function. pcalc j X1 j j 1 X 1 j X 2 j a12 a21 Psat1 2 X 1 j X 2 j a12 a21 Psat2 1 X 1 j X 2 j a12 a21 Psat1 X2 X1 Y1calc Pcalc j j pcalc x1 i i j i 1 x1i x2i a12 a21 Psat1 2 x1i x2i a12 a21 Psat2 1 x1i x2i a12 a21 Psat1 x2 x1 y1calc i i Pcalc i 383 .468 Ans.5 Pi x1 a21 1.

6 j 0.286 kPa P-x.y diagram.4 i j 0.RMS deviation in P: Pi RMS i Pcalc n 2 i RMS 0.8 1 x1 y1 X1 Y1calc P-x data P-y data P-x calculated P-y calculated 384 . van Laar Equation by Barker's Method 90 80 70 Pi kPa 60 Pi kPa pcalc kPa 50 j pcalc kPa j 40 30 20 10 0 0.2 i 0.

4 0. 1 Pi Pcalc kPa i 0. Guesses for parameters: answers to Part (c).8 x1 Pressure residuals y1 residuals i (f) BARKER'S METHOD by non-linear least squares.5 0 0. Guesses: 12 0.5 21 385 1.0 .5 y1 y1calc 100 i i 0 0.Residuals in P and y1.01 x2 x2 12 12 X2 j 1 X1 j ln x1 x2 x1 21 12 x2 x1 21 2 x1 x2 12 21 exp ln x2 x1 x1 x1 x2 21 12 12 21 x2 x1 21 Minimize the sum of the squared errors using the Mathcad Minimize function. Wilson equation.01 j exp .6 0. j 1 101 1 x1 x2 12 21 X1 j .2 0.

198 Ans. 21 pcalc j X1 j j 1 X1 j X2 j 2 X1 j X2 j 12 12 21 Psat1 21 Psat2 X2 X1 Y1calc j j 1 X1 j X2 j 12 j 21 Psat1 pcalc Pcalc i x1 i i 1 x1i x2i 2 x1i x2i 12 12 21 Psat1 21 Psat2 x2 x1 y1calc i i 1 x1i x2i 12 i 21 Psat1 Pcalc RMS deviation in P: 2 i Pi RMS i Pcalc n RMS 0.SSE 12 21 i Pi x1 x1 x2 i 1 i i i 12 12 21 Psat1 21 Psat2 2 x2 2 x1i x2i 12 21 Minimize SSE 12 12 21 0.305kPa 386 .348 1.

6 0.y diagram.6 j 0. Wilson Equation by Barker's Method 90 Pi kPa 80 70 60 50 j Pi kPa pcalc kPa 40 j pcalc kPa 30 20 10 0 0.P-x.8 x1 Pressure residuals y1 residuals i 387 .2 0.4 i j 0. 1 Pi Pcalc i kPa 0.5 0 0.5 y1 y1calc 100 i i 0 0.8 1 x1 y1 X1 Y1calc P-x data P-y data P-x calculated P-y calculated Residuals in P and y1.4 0.2 i 0.

0287 0.4480 0.1046 0.811 99.206 95.4184 0.799 kPa T 328.4779 0.951 82.7383 0.6174 0.467 100.4050 x1 0.528 86.3 Acetone(1)/Methanol(2)-.5512 0.5135 y1 0.7729 0.0570 0.2190 0.278 100.524 78.9080 0.279 77.9448 0.VLE data: 72.7876 0.15 K 0.950 100.5432 0.0858 0.059 99.1295 0.1848 0.646 98.12.885 kPa Psat2 68.365 97.0647 0.017 P 96.2173 0.9336 n y2 20 1 y1 i 1 n Number of data points: Calculate x2 and y2: n x2 rowsP) ( 1 x1 Vapor Pressures from equilibrium data: Psat1 96.1452 0.3579 0.7124 0.462 99.877 99.3633 0.2787 0.5844 0.7752 0.6945 0.999 101.6772 0.088 93.6926 0.8959 0.728 kPa 388 .762 90.7922 0.5052 0.6605 0.278 75.6332 0.7327 0.2694 0.

243 1.358 0.497 1.139 0.285 1.534 0.52 0.151 0.485 1. y1 P 1 y2 P 2 x1 Psat1 1 1 2 3 4 5 6 7 8 9 x2 Psat2 2 i 1.133 0.144 0.039 0.044 0.544 0.036 0.155 1.017 1.224 1.103 1.097 0.027 1.166 1.162 0.108 0.706 1.568 0.458 0.407 0.13 1.098 0.045 1.396 1.013 1.06 0.013 0.202 0.218 0.275 0.018 ln 1 i 0.163 0.278 1.152 0.128 0.082 1.747 GERT x1 ln 1 x2 ln 2 i i 1.043 0.026 1.058 0.027 0.027 0.765 1.061 0.039 1.317 1.123 0.503 1.245 0.161 0.334 0.048 10 11 12 13 14 15 16 17 18 19 20 389 .011 1.682 1.017 0.644 1.062 1.113 0.145 0.182 0.815·10-3 1.497 0.317 0.006 1.431 1.002 1.177 0.018 ln 2 i 0.052 0.58 1.374 1.153 0.723 1.026 0.119 0.089 0.404 0.055 0.057 1.395 0.975·10-3 0.Calculate EXPERIMENTAL values of activity coefficients and excess Gibbs energy.558 GERTi 0.165 0.131 0.011 5.037 1.102 1.2 1.193 1.14 1.079 0.25 0.

708 Intercept Intercept A21 A21 Slope 0.6 0.708 A12 Ans.2 0 0 0.0.4 0.01 j .01 X2 A21 x2 X2 j 1 X1 j pcalc j j 1 X1 X2 Psat1 j j j j 2 X1 X2 Psat2 j j X1 Y1calc j 1 X1 X2 j j Psat1 pcalc j 390 .8 (a) Fit GE/RT data to Margules eqn. by linear least squares: VXi Slope Slope A12 A12 x1 i VYi GERTi x1 x2 i i intercept ( VX VY) 0.69 The following equations give CALCULATED values: 1 ( x2) x1 exp x2 2 A12 2 A21 A12 x1 2 ( x2) x1 j 1 101 X1 exp x1 2 A21 X1 j 2 A12 . slope ( VX VY) 0.018 Intercept 0.6 ln 1 i ln 2 i GERTi 0.4 x1 i 0.2 0.

851 kPa 391 .y Diagram: Margules eqn.6 j 0.4 i i j 0.2 0. 105 100 Pi kPa 95 90 85 j Pi kPa pcalc kPa 80 j pcalc kPa 75 70 65 0 0. fit to GE/RT data.P-x.8 x1 y1 X1 Y1calc P-x data P-y data P-x calculated P-y calculated Pcalc i x1 1 x1 x2 Psat1 i i i x2 2 x1 x2 Psat2 i i i y1calc i x1 1 x1 x2 Psat1 i i i Pcalc i RMS deviation in P: Pi RMS i Pcalc n 2 i RMS 0.

1 ( x2) x1 exp a12 1 2 ( x2) x1 exp a21 1 X1 X2 a21 x2 a12 x1 j 1 101 j j .442 1 ( Slope 0.693 Intercept Intercept a21 a21 a12 x1 a21 x2 2 Intercept) Ans.015 1 Intercept 0.01 j 1 X1 .00999 j (To avoid singularities) pcalc Pcalc j X1 j 1 X1 X2 j j Psat1 X2 j 2 X1 X2 j j Psat2 i x1 1 x1 x2 Psat1 i i i x2 2 x1 x2 Psat2 i i i X1 Y1calc j j 1 X1 X2 Psat1 j j pcalc j y1calc i x1 1 x1 x2 Psat1 i i i Pcalc i 392 .686 2 slope ( VX VY) 0.(b) Fit GE/RT data to van Laar eqn. by linear least squares: x1 x2 VXi Slope Slope a12 a12 x1 i VYi i i GERTi intercept ( VX VY) 1.

y Diagram: van Laar eqn.8 1 x1 y1 X1 Y1calc P-x data P-y data P-x calculated P-y calculated RMS deviation in P: Pi RMS i Pcalc n 2 i RMS 0.6 j 0.5 21 1. by non-linear least squares.701 kPa (c) Fit GE/RT data to Wilson eqn.2 i 0.4 i j 0. 105 100 Pi kPa 95 90 85 j Pi kPa pcalc kPa 80 j pcalc kPa 75 70 65 0 0. Minimize the sum of the squared errors using the Mathcad Minimize function. fit to GE/RT data.0 SSE 12 21 i GERTi x1 ln x1 i i x2 ln x2 i i x2 2 i i 12 21 x1 393 .P-x. Guesses: 12 0.

12 21 Minimize SSE 12 12 21 0. 21 12 exp x2 1 ( x2) x1 21 12 x1 x2 x1 x2 12 x1 21 x2 12 exp 2 ( x2) x1 x1 21 12 x1 x2 x2 x2 21 x1 21 x1 j 1 101 X1 j .71 0.01 j .681 Ans.01 X2 j 1 X1 j pcalc j X1 j 1 X1 X2 Psat1 j j X2 j 2 X1 X2 Psat2 j j Pcalc i x1 1 x1 x2 Psat1 i i i x2 2 x1 x2 Psat2 i i i X1 Y1calc j 1 X1 X2 Psat1 j j j pcalc j y1calc i x1 1 x1 x2 Psat1 i i i Pcalc i 394 .

y diagram: Wilson eqn. Margules equation. Guesses for parameters: answers to Part (a).361 kPa (d) BARKER'S METHOD by non-linear least squares.2 i 0.P-x.4 i j 0. 1 x1 x2 A 12 A 21 2 x1 x2 A 12 A 21 exp ( x2) exp ( x1) 2 2 A12 A21 2 A21 2 A12 A12 x1 A21 x2 395 . fit to GE/RT data. 105 100 Pi kPa 95 90 85 j Pi kPa pcalc kPa 80 j pcalc kPa 75 70 65 0 0.8 1 x1 y1 X1 Y1calc P-x data P-y data P-x calculated P-y calculated RMS deviation in P: Pi RMS i Pcalc n 2 i RMS 0.6 j 0.

644 0.5 Pi x1 A21 1.365 kPa 396 .672 Ans. Guesses: SSE A12 A21 i A12 0.Minimize the sum of the squared errors using the Mathcad Minimize function. A21 pcalc j X1 j j 1 X 1 j X 2 j A 12 A 21 Psat1 2 X 1 j X 2 j A 12 A 21 Psat2 1 X 1 j X 2 j A 12 A 21 Psat1 X2 X1 Y1calc j j pcalc j Pcalc i x1 i i 1 x1i x2i A 12 A 21 Psat1 2 x1i x2i A 12 A 21 Psat2 1 x1i x2i A 12 A 21 Psat1 x2 x1 y1calc i i Pcalc i RMS deviation in P: Pi RMS i Pcalc n 2 i RMS 0.0 2 x1 x2 A12 A21 Psat1 i 1 i i i x2 2 x1i x2i A 12 A 21 Psat2 A12 A21 A12 Minimize SSE A12 A21 0.

6 0.2 i 0.2 0.4 i j 0.8 1 x1 y1 X1 Y1calc P-x data P-y data P-x calculated P-y calculated Residuals in P and y1 2 Pi Pcalc kPa i 1 y1 y1calc 100 i i 0 1 0 0.6 j 0.8 Pressure residuals y1 residuals 397 . by Barker's method 105 Pi kPa 100 95 90 85 j Pi kPa pcalc kPa 80 j pcalc kPa 75 70 65 0 0.P-x-y diagram.4 x1 i 0. Margules eqn.

00999 a12 x1 a21 x2 2 X2 j 1 X1 j 1 x1 x2 a12 a21 exp a12 1 2 x1 x2 a12 a21 exp a21 1 a21 x2 a12 x1 2 Minimize the sum of the squared errors using the Mathcad Minimize function. van Laar equation.5 Pi x1 a21 1. Guesses for parameters: answers to Part (b).0 2 x1 x2 a12 a21 Psat1 i 1 i i i x2 2 x1i x2i a12 a21 Psat2 a12 a21 Minimize SSE a12 a21 a12 a21 0. pcalc j X1 j j 1 X 1 j X 2 j a12 a21 Psat1 2 X 1 j X 2 j a12 a21 Psat2 1 X 1 j X 2 j a12 a21 Psat1 X2 X1 Y1calc Pcalc j j pcalc x1 i i j i 1 x1i x2i a12 a21 Psat1 2 x1i x2i a12 a21 Psat2 1 x1i x2i a12 a21 Psat1 x2 x1 y1calc i i Pcalc i 398 .644 0. Guesses: SSE a12 a21 i a12 0. j 1 101 X1 j .01 j .(e) BARKER'S METHOD by non-linear least squares.672 Ans.

6 j 0.4 i j 0.2 i 0.RMS deviation in P: Pi RMS i Pcalc n 2 i RMS 0.364 kPa P-x.8 1 x1 y1 X1 Y1calc P-x data P-y data P-x calculated P-y calculated 399 . van Laar Equation by Barker's Method 105 100 95 Pi kPa 90 Pi kPa pcalc kPa 85 j pcalc kPa j 80 75 70 65 0 0.y diagram.

6 0.4 x1 i 0.Residuals in P and y1.8 Pressure residuals y1 residuals (f) BARKER'S METHOD by non-linear least squares.5 1 y1 y1calc 100 i i 0 0.5 21 400 1. Guesses for parameters: answers to Part (c). Wilson equation.5 0 0.0 .5 1 Pi Pcalc kPa i 0. 1 101 X1 12 21 j j . Guesses: 12 0. 1.01 j .2 0.01 x2 x2 12 12 X2 j 1 X1 j 1 x1 x2 exp ln x1 x2 x1 21 12 x2 x1 21 2 x1 x2 12 21 exp ln x2 x1 x1 x1 x2 21 12 12 21 x2 x1 21 Minimize the sum of the squared errors using the Mathcad Minimize function.

732 0.663 Ans.SSE 12 21 i Pi x1 x1 x2 i 1 i i i 12 12 21 Psat1 21 Psat2 2 x2 2 x1i x2i 12 21 Minimize SSE 12 12 21 0. 21 pcalc j X1 j j 1 X1 j X2 j 2 X1 j X2 j 12 12 21 Psat1 21 Psat2 X2 X1 Y1calc j j 1 X1 j X2 j 12 j 21 Psat1 pcalc Pcalc i x1 i i 1 x1i x2i 2 x1i x2i 12 12 21 Psat1 21 Psat2 x2 x1 y1calc i i 1 x1i x2i 12 i 21 Psat1 Pcalc RMS deviation in P: Pi RMS i Pcalc n 2 i RMS 0.35 kPa 401 .

Wilson Equation by Barker's Method 105 Pi kPa 100 95 90 85 j Pi kPa pcalc kPa 80 j pcalc kPa 75 70 65 0 0.P-x.2 i 0.4 x1 i 0.2 0.y diagram.4 i j 0.8 Pressure residuals y1 residuals 402 .6 0.6 j 0. 2 Pi Pcalc kPa i 1 y1 y1calc 100 i i 0 1 0 0.8 1 x1 y1 X1 Y1calc P-x data P-y data P-x calculated P-y calculated Residuals in P and y1.

1975 y1 0.5749 0.5036 0.7176 0.265 kPa Psat1 49.719 72.442 68.455 49.1314 0.833 53.6 Methyl t-butyl ether(1)/Dichloromethane--VLE data: T 83.096 59.0253 0.0579 0.926 49.0330 0.9002 0.7676 0.6736 0.9502 0.9093 0.3880 0.720 x2 1 x1 kPa 308. y1 P 1 y2 P 2 x1 Psat1 x2 Psat2 GERT x1 ln 1 x2 ln 2 GERTx1x2 GERT x1 x2 n rows ( ) P n 14 i 1 n 403 .1665 0.620 50.0804 0.202 80.481 76.2457 0.651 56.8238 0.4564 0.005 P 65.3686 0.402 82.0141 0.12.15 K 0.689 51.8476 0.9529 y2 Psat2 1 y1 85.5882 0.0924 0.3322 x1 0.624 kPa Calculate EXPERIMENTAL values of activity coefficients and excess Gibbs energy.0416 0.2482 0.

Guesses: A12 0.01 j .01 1 X1 j GERTx1x2 i GeRTx1x2 X1 X2 j j 0 0.4 j i 0.1 0. Minimize sum of the squared errors using the Mathcad Minimize function.336 0.2 C x1 x2 i i SSE A12 A21 C i GERTi x1 x2 i 2 i A12 A21 C Minimize SSE A12 A21 C A12 A21 C 0.6 0 0.3 A21 0.(a) Fit GE/RT data to Margules eqn.6 j i 0.2 ln 1 i ln 1 X1 X2 j j 0.535 0. (b) Plot data and fit GeRTx1x2 ( x2) x1 GeRT ( x2) x1 ln 1 ( x2) x1 A21 x1 A12 x2 C x1 x2 GeRTx1x2 ( x2)x1 x2 x1 x2 2 A12 2 A21 A12 C x1 3 C x1 2 ln 2 ( x2) x1 j 1 101 x1 2 A21 2 A12 X1 j A21 C x2 3 C x2 X2 j 2 . by nonlinear least squares.3 0.2 i 0.5 A21 x1 i C A12 x2 i 0.195 Ans.4 ln 2 i ln 2 X1 X2 j j 0.5 0.8 j x1 X1 x1 X1 x1 X1 404 .

(c) Plot Pxy diagram with fit and data 1 ( x1 x2) exp ln 1 ( x1 x2) 2 ( x1 x2) exp ln 2 ( x1 x2) j Pcalc j X1 1 X1 X2 Psat1 j j j X2 j 2 X1 X2 Psat2 j j X1 y1calc j 1 X1 X2 Psat1 j j Pcalc j P-x.4 i i j 0.2 0.y Diagram from Margules Equation fit to GE/RT data.6 j 0. 90 Pi kPa 80 Pi kPa 70 j Pcalc kPa 60 j Pcalc kPa 50 40 0 0.8 x1 y1 X1 y1calc P-x data P-y data P-x calculated P-y calculated (d) Consistency Test: GERTi 1i 2 i GeRT x1 x2 i i GERTi ln 1 2i ln 1 x1 x2 i i 2 x1 x2 i i ln 405 .

0.5 C 0.004 0 0.23 Ans.004 0 GERTi 0 ln 1 2i 0. Guesses: A12 0.391 10 mean ln 1 2 0.5 1 x1 i x1 i Calculate mean absolute deviation of residuals 4 mean GERT 9.025 0.364 0.521 0.5 1 0.021 (e) Barker's Method by non-linear least squares: Margules Equation 1 x1 x2 A 12 A 21 C exp ( ) A12 x2 2 2 A21 2 A12 C x1 3 C x1 2 x1 x2 A 12 A 21 C exp ( ) A21 x1 2 2 A12 2 A21 C x2 3 C x2 Minimize sum of the squared errors using the Mathcad Minimize function.3 Pi i A21 x1 0.2 2 SSE A12 A21 C x1 x2 A12 A21 C Psat1 i 1 i i i x2 2 x1i x2i A 12 A 21 C Psat2 A12 A21 C Minimize SSE A12 A21 C A12 A21 C 0.05 0 0. 406 .

Pcalc j X1 j j 1 X 1 j X 2 j A 12 A 21 C Psat1 2 X 1 j X 2 j A 12 A 21 C Psat2 X2 X1 y1calc j j 1 X 1 j X 2 j A 12 A 21 C Psat1 Pcalc 90 j Pi kPa 80 Pi kPa 70 j Pcalc kPa 60 j Pcalc kPa 50 40 0 0.4 i i j 0.6 j 0.2 0.y diagram for Margules Equation with parameters from Barker's Method.Plot P-x.8 x1 y1 X1 y1calc P-x data P-y data P-x calculated P-y calculated Pcalc i x1 i i 1 x1i x2i A 12 A 21 C Psat1 2 x1i x2i A 12 A 21 C Psat2 x2 x1 y1calc i i 1 x1i x2i A 12 A 21 C Psat1 Pcalc i 407 .

068 kPa 408 .2 i i 0 0.4 y1 y1calc 100 0.8 0.2 0 0.5 1 x1 i Pressure residuals y1 residuals RMS deviations in P: Pi RMS i Pcalc n 2 i RMS 0.Plot of P and y1 residuals. 0.6 Pi Pcalc i kPa 0.

4187 x1 0.12.049 1.016 1.600 1.2233 0.7832 0.032 1.001 1.247 Intercept 0.006 1.022 1.076 1.8 (a) Data: 0.129 1.295 1.6469 0. by linear least-squares procedure: Xi Slope Slope A12 A12 x1 i Yi slope ( Y) X GERTi x1 x2 i i intercept ( Y) X 0.004 1.170 1.1299 0.024 1.092 1.180 1.2764 0.9813 1 1.393 1.286 exp x2 exp x1 2 2 Slope 0. Intercept Intercept A21 A21 0.102 1.120 1.5001 0.202 1.404 n rows x1 x1 ln 1 i i x2 i 1 x1 i GERTi x2 ln 2 i i (b) Fit GE/RT data to Margules eqn.307 1.9388 0.3482 0.5637 0.298 1.534 1 ( x2) x1 2 ( x2) x1 A12 A21 2 A21 2 A12 A12 x1 A21 x2 GeRT ( x2) x1 x1 ln 1 ( x2) x1 x2 ln 2 ( x2) x1 409 .234 1.8576 0.003 i 1 n n 13 2 1.228 1.286 A12 Ans.0523 0.002 1.

3 0.4 0.5 GERT i GeRT x1 x2 i i ln 1 i ln 1 x1 x2 i i ln 2 i ln 2 x1 x2 i i 0.6 0.1 0 0 0.2 0.4 x1 i 0.Plot of data and correlation: 0.8 (c) Calculate and plot residuals for consistency test: GERTi GeRT x1 x2 i i GERTi 1i 2 i ln 1 2i ln 1 x1 x2 i i 2 x1 x2 i i ln 410 .2 0.

2909 0.168 0.1818 0.236·10-4 ln 1 2i 0.22·10-3 -2.553 35.8145 0.0940 0.174·10-3 -1.068 36.0455 0.998·10-3 -2.874·10-3 -2.3980 x1 0.1829 0.021 0.025·10-5 4.6157 0.VLE data T 318. the data show a high degree of consistency 12.962·10-5 9.372 32.742·10-4 2.5458 0.14·10-3 -2.1 0.978 36.GERTi 3.7869 0.038 kPa 0.5946 0.264·10-3 -3.331 30.4274 31.153·10-5 -0.3607 0.2783 0.028 -9.028 -0.9 Acetonitrile(1)/Benzene(2)-.4885 0.05 ln 1 2i 0 0 0.314·10-3 -2.8972 0.026 -0.934·10-3 0.1056 0.957 33.139·10-3 -5.457 36.098 -9.011 0.5098 0.15 K 0.9573 411 y1 0.8916 .553·10-3 -8.5 x1 i 1 Calculate mean absolute deviation of residuals: mean GERT 1.59·10-3 9.792 34.285 36.03 Based on the graph and mean absolute deviations.778 35.6913 0.996 P 37.019 5.617·10-4 -0.944·10-4 5.615 10 3 mean ln 1 2 0.7206 0.5375 0.5069 0.

778 kPa y2 1 y1 Psat2 29.155 0. by nonlinear least squares.x2 Psat1 1 x1 27.01 j .819 kPa Calculate EXPERIMENTAL values of activity coefficients and excess Gibbs energy.53 Ans. (b) Plot data and fit GeRTx1x2 ( x2) x1 GeRT ( x2) x1 ln 1 ( x2) x1 A21 x1 A12 x2 C x1 x2 GeRTx1x2 ( x2)x1 x2 x1 x2 2 A12 2 A21 A12 C x1 3 C x1 2 ln 2 ( x2) x1 j 1 101 x1 2 A21 2 A12 X1 j A21 C x2 3 C x2 X2 j 2 .5 C 0.3 A21 0. Guesses: A12 0.2 SSE A12 A21 C i GERTi A21 x1 i A12 x2 i C x1 x2 i i x1 x2 i i 2 A12 A21 C Minimize SSE A12 A21 C A12 A21 C 1.01 1 X1 j 412 . Minimize sum of the squared errors using the Mathcad Minimize function. y1 P 1 y2 P 2 x1 Psat1 x2 Psat2 GERT x1 ln 1 x2 ln 2 GERTx1x2 GERT x1 x2 n rows ( ) P n 12 i 1 n (a) Fit GE/RT data to Margules eqn.128 1.

1.6 j i 0.4 j i 0.2 i 0.8 j x1 X1 x1 X1 x1 X1 (c) Plot Pxy diagram with fit and data 1 ( x1 x2) exp ln 1 ( x1 x2) 2 ( x1 x2) exp ln 2 ( x1 x2) j Pcalc j X1 1 X1 X2 j j Psat1 X2 j 2 X1 X2 j j Psat2 X1 y1calc j j 1 X1 X2 Psat1 j j Pcalc j 413 .4 0.8 0.2 GERTx1x2 i GeRTx1x2 X1 X2 j j 1 0.6 ln 1 i ln 1 X1 X2 j j ln 2 i ln 2 X1 X2 j j 0.2 0 0 0.

8 x1 y1 X1 y1calc P-x data P-y data P-x calculated P-y calculated (d) Consistency Test: GERTi 1i 2 i GeRT x1 x2 i i GERTi ln 1 2i ln 1 x1 x2 i i 2 x1 x2 i i ln 0.004 0 0.y Diagram from Margules Equation fit to GE/RT data.5 1 0.2 0.4 i i j 0.004 0 GERTi 0 ln 1 2i 0.025 0.5 1 x1 i x1 i 414 .05 0 0.6 j 0. 38 Pi kPa 36 Pi kPa 34 Pcalc kPa 32 j 30 Pcalc kPa j 28 26 0 0.P-x.

3 Pi i A21 x1 0.5 C 0.2 2 SSE A12 A21 C x1 x2 A12 A21 C Psat1 i 1 i i i x2 2 x1i x2i A 12 A 21 C Psat2 A12 A21 C Minimize SSE A12 A21 C A12 A21 C 1.114 1.Calculate mean absolute deviation of residuals 4 mean GERT 6. Guesses: A12 0.098 0.237 10 mean ln 1 2 0.025 (e) Barker's Method by non-linear least squares: Margules Equation 1 x1 x2 A 12 A 21 C exp ( ) A12 x2 2 2 A21 2 A12 C x1 3 C x1 2 x1 x2 A 12 A 21 C exp ( ) A21 x1 2 2 A12 2 A21 C x2 3 C x2 Minimize sum of the squared errors using the Mathcad Minimize function.387 Ans. Plot P-x.y diagram for Margules Equation with parameters from Barker's Method. Pcalc j X1 j j 1 X 1 j X 2 j A 12 A 21 C Psat1 2 X 1 j X 2 j A 12 A 21 C Psat2 1 X 1 j X 2 j A 12 A 21 C Psat1 X2 X1 y1calc j j Pcalc j 415 .

2 0.8 x1 y1 X1 y1calc P-x data P-y data P-x calculated P-y calculated Pcalc i x1 i i 1 x1i x2i A 12 A 21 C Psat1 2 x1i x2i A 12 A 21 C Psat2 x2 x1 y1calc i i 1 x1i x2i A 12 A 21 C Psat1 Pcalc i 416 .4 i i j 0.6 j 0.38 Pi kPa 36 Pi kPa 34 Pcalc kPa 32 j Pcalc kPa 30 j 28 26 0 0.

4 Pi Pcalc i kPa 0.2 0 0.04 kPa 417 .Plot of P and y1 residuals.2 0.6 0. 0.4 y1 y1calc 100 i i 0 0.5 1 x1 i Pressure residuals y1 residuals RMS deviations in P: Pi RMS i Pcalc n 2 i RMS 0.

07 mol 1351.90 3 a12 cal mol a21 cal mol 12 ( ) T a12 V2 exp RT V1 12 ( ) T x1 21 ( ) T a21 V1 exp RT V2 21 ( ) T x1 21 ( ) T exp x2 1 ( x2 T) x1 x2 12 ( ) x2 T x1 x2 12 ( ) T exp 2 ( x2 T) x1 x1 12 ( ) T x1 x2 12 ( ) x2 T x2 x1 418 21 ( ) T x1 21 ( ) T 21 ( ) T .67 K 3885.mcd reproduces the table of Wilson parameters on Page 474 and includes the necessary Antoine coefficients.1154 16.70 K C1 C2 205.807 K 230.15 K) C1 kPa Psat2 ( ) T exp A2 (T B2 273.12 It is impractical to provide solutions for all of the systems listed in the table on Page 474 we present as an example only the solution for the system 1-propanol(1)/water(2).170 K Psat1 ( T) exp A1 (T B1 273. Solutions for the other systems can be obtained by rerunning the following Mathcad program with the appropriate parameter values substituted for those given.15 K) C2 kPa Parameters for the Wilson equation: V1 cm 75. The file WILSON.48 3 V2 cm 18.12. Antoine coefficients: 1-Propanol: Water: A1 A2 16.14 mol 775.3872 B1 B2 3483.

P-x.y diagram at T ( 60 273.466 0.453 0.491 25.148 30.3 0.441 0.97 31.315 0.45 0.6 0.526 0.275 419 .413 0.646 0.483 0.496 31.9 0.421 0.182 31.55 0.404 0.363 0.85 0.35 0.355 29.718 0.05 1.2 0.05 0.4 0.556 0.009 30.594 0.769 23.437 20.5 0.65 0.95 1 yeq x) ( 0 0.759 27.1 0.15 0.825 1 Peq x) ( kPa 20.15) K Guess: P 70 kPa Given P = x1 1 ( x1 1 x1 T) Psat1 ( T) ( 1 x1) 2 ( x1 1 x1 T) Psat2 ( T) Peq x1) ( Find P) ( yeq x1) ( x1 1 ( x1 1 x1 T) Psat1 ( T) Peq x1) ( x 0 0.51 31.75 0.331 31.7 0.8 0.431 0.639 30.435 31.25 0.324 30.467 31.827 30.686 28.353 31.502 0.007 28.395 0.0 x 0 0.383 0.

Solutions for the other systems can be obtained by rerunning the following Mathcad program with the appropriate parameter values substituted for those given.6 0.15 K) C2 420 Psat2 ( ) T exp A2 ( T kPa .2 0.1154 16. we present as an example only the solution for the system 1-propanol(1)/water(2).70 K kPa C1 C2 205.8 x yeq x) ( 12.807 K 230.x.y Diagram at T 32 333.15 K) C1 B2 273.67 K 3885.4 0. Antoine coefficients: 1-Propanol: A1 Water: Psat1 ( ) T 16.170 K A2 exp A1 ( T B1 273.P.3872 B1 B2 3483.mcd reproduces the table of Wilson parameters on Page 474 and includes the necessary Antoine coefficients. The file WILSON.15 K 30 28 Peq x) ( kPa Peq x) ( kPa 26 24 22 20 0 0.13 It is impractical to provide solutions for all of the systems listed in the table on Page 474.

y diagram at P Guess: Given 101.Parameters for the Wilson equation: V1 75.15) K T ( 90 P = x1 1 ( x1 1 x1 T) Psat1 ( T) ( 1 x1) 2 ( x1 1 x1 T) Psat2 ( T) Find T) ( x1 1 ( x1 1 x1 Teq ( x1) ) Psat1 ( Teq ( x1) ) P Teq ( x1) yeq ( x1) x 0 0.33 kPa 273.90 12 ( T) a12 V2 exp RT V1 exp x2 12 ( T) x1 21 ( T) a21 V1 exp RT V2 21 ( T) 1 ( x1 x2 T) x2 12 ( T) x1 x2 x2 12 ( T) x1 21 ( T) exp 2 ( x1 x2 T) x1 12 ( T) x1 x2 12 ( T) x2 x1 21 ( T) x2 x1 21 ( T) 21 ( T) T-x.0 421 .07 cm 3 mol cal mol a12 775.05 1.14 cm 3 mol cal mol V2 18.48 a21 1351.

858 1 Teq x () K 373.626 370.809 362.3 0.85 0.7 0.429 0.5 0.95 1 yeq x () 0 0.35 0.555 0.6 0.136 364.468 0.159 362.364 363.45 0.358 0.8 1 x yeq x) ( 422 .75 0.2 0.4 0.6 0.x.985 360.407 0.9 0.504 0.15 0.911 360.y Diagram at P 375 101.836 361.395 0.44 0.25 0.33 kPa Teq( ) 370 x K Teq( ) x K 365 360 0 0.149 364.527 0.759 0.644 367.99 361.264 361.476 361.05 0.453 0.195 365.686 0.418 0.304 0.484 0.101 360.381 0.881 360.2 0.65 0.1 0.904 360.349 T.8 0.x 0 0.4 0.154 361.631 0.49 361.589 0.55 0.418 361.

807 K 230. Solutions for the other systems can be obtained by rerunning the following Mathcad program with the appropriate parameter values substituted for those given.67 K 3885.70 K kPa C1 C2 205.15 K) C2 kPa Parameters for the NRTL equation: b12 500. The file NRTL.14 It is impractical to provide solutions for all of the systems listed in the table on Page 474.mcd reproduces the table of NRTL parameters on Page 474 and includes the necessary Antoine coefficients.1154 16. Antoine coefficients: 1-Propanol: A1 Water: Psat1 ( T) 16.40 b12 RT exp 12 ( T) cal mol b21 1636.57 cal mol b21 RT exp 2 0.3872 B1 B2 B1 273.15 K) 3483.5081 12 ( T) G12 ( T) 21 ( T) G21 ( T) 21 ( T) 1 ( x1 x2 T) exp x2 2 21 ( T) G21 ( T) x1 x2 G21 ( T) G12 ( T) 12 ( T) x1 G12 ( T) ) 2 ( x2 2 ( x1 x2 T) exp x1 2 12 ( T) G12 ( T) 2 x2 x1 G12 ( T) G21 ( T) 21 ( T) x2 G21 ( T) ) 423 ( x1 2 .12. we present as an example only the solution for the system 1-propanol(1)/water(2).170 K A2 exp A1 (T C1 Psat2 ( T) exp A2 (T B2 273.

479 0.382 0.085 30.124 20.271 29.15 0.531 0.459 0.836 1 Peq x () kPa 20.783 30.05 0.85 0.75 0.404 0.65 0.442 0.606 0.386 0.45 0.876 30.922 30.95 1 yeq x () 0 0.659 0.7 0.503 0.007 28.03 28.959 31.427 0.373 0.395 0.39 0.1 0.74 29.256 23.25 0.P-x.48 30.0 x 0 0.4 0.657 30.892 30.9 0.275 424 .163 31.05 1.127 31.732 0.048 31.35 0.y diagram at T ( 60 273.6 0.095 26.414 0.2 0.5 0.868 25.55 0.8 0.3 0.33 0.15)K Guess: P 70 kPa Given P = x1 1 ( 1 x1 T)Psat1 ( ) x1 T ( x1) 2 ( 1 x1 T)Psat2 ( ) 1 x1 T Peq x1) ( Find P) ( yeq x1) ( x1 1 ( 1 x1 x1 T)Psat1 ( ) T Peq x1) ( x 0 0.564 0.172 31.

mcd reproduces the table of NRTL parameters on Page 474 and includes the necessary Antoine coefficients.y Diagram at T 35 333.15 K) C2 kPa Parameters for the NRTL equation: b12 500.15 K) C1 Psat2 ( T) exp A2 (T B2 273.57 425 cal mol 0.3872 (T B1 273.1154 Water: Psat1 ( T) B1 B2 3483.x.40 cal mol b21 1636. Antoine coefficients: 1-Propanol: A1 16.15 K Peq ( x) kPa 30 Peq ( x) kPa 25 20 0 0. we present as an example only the solution for the system 1-propanol(1)/water(2).15 It is impractical to provide solutions for all of the systems listed in the table on Page 474. The file NRTL.6 0.4 x yeq ( x) 0.170 K A2 exp A1 16.70 K kPa C1 C2 205. Solutions for the other systems can be obtained by rerunning the following Mathcad program with the appropriate parameter values substituted for those given.5081 .807 K 230.P.2 0.67 K 3885.8 12.

33 kPa Guess: T ( 90 273.y diagram at P 101.15)K Given P = x1 1 ( 1 x1 T)Psat1 ( ) x1 T ( x1) 2 ( 1 x1 T)Psat2 ( ) 1 x1 T Teq x1) ( Find T) ( yeq x1) ( x1 1 ( 1 x1 x1 Teq x1) Psat1 ( ( ) ( ) Teq x1 ) P 426 .12 ( ) T b12 RT 21 ( ) T b21 RT G12 ( ) T exp 12 ( ) T G21 ( ) T exp 2 21 ( ) T 1 ( x2 T) x1 exp x2 2 G21 ( ) T 21 ( ) T x1 x2 G21 ( ) T G12 ( ) 12 ( ) T T ( x2 x1 G12 ( ) T) 2 2 ( x2 T) x1 exp x1 2 G12 ( ) T 12 ( ) T x2 x1 G12 ( ) T G21 ( ) 21 ( ) T T ( x1 x2 G21 ( ) T) 2 2 T-x.

745 361.697 360.215 362.8 1 .066 360.349 T.606 361.843 360.447 0.2 0.5 0.65 0.629 0.7 0.0 x 0 0.408 0.394 0.3 0.15 0.55 0.x 0 0.95 1 yeq ( x) 0 0.149 363.415 0.25 0.5 0.524 0.1 0.66 362.853 1 Teq ( x) K 373.985 361.012 365.33 kPa Teq ( x) 370 K Teq ( x) K 365 360 0 0.424 0.442 367.6 0.434 0.y Diagram at P 375 101.946 360.45 0.676 360.05 0.974 364.807 360.48 0.377 0.x.757 360.253 361.75 0.709 360.9 0.682 0.402 0.85 0.262 361.05 1.32 0.8 0.552 0.449 370.4 x yeq ( x) 427 0.6 0.754 0.462 0.2 0.586 0.4 0.35 0.

Antoine coefficients: 1-Propanol: Water: Psat1 ( ) T A1 A2 exp A1 16.1154 16.67 K 3885.48 3 V2 cm 18.mcd reproduces the table of Wilson parameters on Page 474 and includes the necessary Antoine coefficients. The file WILSON.807 K 230.16 It is impractical to provide solutions for all of the systems listed in the table on Page 474.70 K kPa C1 C2 205. we present as an example only the solution for the system 1-propanol(1)/water(2).170 K ( T B1 273.15 K) C1 Psat2 ( ) T exp A2 ( T B2 273.15 K) C2 kPa Parameters for the Wilson equation: V1 cm 75.12.3872 B1 B2 3483.14 mol 775. Solutions for the other systems can be obtained by rerunning the following Mathcad program with the appropriate parameter values substituted for those given.07 mol 1351.90 3 a12 cal mol a21 cal mol 12 ( ) T a12 V2 exp RT V1 21 ( ) T a21 V1 exp RT V2 exp x2 1 ( x2 T) x1 12 ( ) T x1 x2 12 ( ) x2 T x1 x2 12 ( ) T 21 ( ) T x1 21 ( ) T exp 2 ( x2 T) x1 x1 12 ( ) T x1 x2 12 ( ) x2 T x2 x1 428 21 ( ) T x1 21 ( ) T 21 ( ) T .

5 x1 y1 0.3 y2 1 y1 Guess: Given P 101.15) K y1 0.33 kPa y1 0.(a) BUBL P: T ( 60 273.15) K x1 0.3 Guess: V 0.1 0.15) K z1 0. (c) P.587 Ans.413 y2 0.1 x2 y2 1 1 y1 x1 Given y1 = x1 1 ( x1 x2 T) Psat1 ( T) P x1 x2 = 1 y2 = x2 2 ( x1 x2 T) Psat2 ( T) P 429 y1 y2 = 1 .1 x1 x2 x2 = 1 1 x1 y1 P = x1 1 ( x1 x2 T) Psat1 ( T) y2 P = x2 2 ( x1 x2 T) Psat2 ( T) Pdew x1 x2 Pdew 27.T-flash Calculation P Pdew 2 Pbubl T ( 60 273.3 x2 1 x1 Guess: P 101.33 kPa Find ( P y1 y2) y1 0.958 Ans.79 kPa Find ( P x1 x2) x1 0.33 kPa x1 0. (b) DEW P: T ( 60 273.042 x2 0.4 y2 1 y1 Given y1 P = x1 1 ( x1 x2 T) Psat1 ( T) y1 y2 P = x2 2 ( x1 x2 T) Psat2 ( T) y2 = 1 Pbubl y1 y2 Pbubl 31.

4386 430 y1 0. .08 Find x1 x2 y1 y2 V) ( x2 0.4386 Ans. 10.511 kPa Find x1 x2 y1 y2 P) ( x1 0.581 121 Psat1 ( ) T 2 ( 0 T)Psat2 ( ) 1 T 121 0.92 y1 0.813 (d) Azeotrope Calculation Test for azeotrope at: T ( 60 273.3 x2 y2 1 1 y1 x1 Given y1 P = x1 1 ( x2 T)Psat1 ( ) x1 T y2 P = x2 2 ( x2 T)Psat2 ( ) x1 T x1 x2 = 1 y1 y2 = 1 x1 = y1 x1 x2 y1 y2 Paz Paz 31.3 0.296 0 2 ( 0 T) 4.216 Since one of these values is >1 and the other is <1. an azeotrope exists.3(e) Guess: P 101. See Ex.15) x1 x2 y1 y2 V x1 0.683 1 120 1 ( 1 T)Psat1 ( ) 0 T Psat2 ( ) T 120 21.351 y2 0. (10.x1 ( 1 V) y1 V = z1 Eq.33 kPa x1 y1 0.649 V 0.15)K 1 ( 1 T) 21.

17 It is impractical to provide solutions for all of the systems listed in the table on Page 474.3872 B1 B2 B1 273.5081 12 ( T) 21 ( T) G21 ( T) G12 ( T) 21 ( T) 1 ( x1 x2 T) exp x2 2 21 ( T) G21 ( T) x1 x2 G21 ( T) G12 ( T) 12 ( T) x1 G12 ( T) ) 2 ( x2 2 ( x1 x2 T) exp x1 2 12 ( T) G12 ( T) 2 x2 x1 G12 ( T) G21 ( T) 21 ( T) x2 G21 ( T) ) 431 ( x1 2 .40 b12 RT exp 12 ( T) cal mol b21 1636. we present as an example only the solution for the system 1-propanol(1)/water(2). The file NRTL.57 cal mol b21 RT exp 2 0.1154 16.15 K) 3483.mcd reproduces the table of NRTL parameters on Page 474 and includes the necessary Antoine coefficients.807 K 230.70 K kPa C1 C2 205.67 K 3885.15 K) C2 kPa Parameters for the NRTL equation: b12 500. Solutions for the other systems can be obtained by rerunning the following Mathcad program with the appropriate parameter values substituted for those given. Antoine coefficients: 1-Propanol: A1 Water: Psat1 ( T) 16.170 K A2 exp A1 (T C1 Psat2 ( T) exp A2 (T B2 273.12.

5 x1 y1 0.3 Guess: V 0.1 0.4 y2 1 y1 Given y1 P = x1 1 ( x2 T)Psat1 ( ) x1 T y1 y2 P = x2 2 ( x2 T)Psat2 ( ) x1 T y2 = 1 Pbubl y1 y2 Pbubl 31. (b) DEW P: T ( 60 273.81 kPa Find ( x1 x2) P x1 0.15)K x1 0.(a) BUBL P: T ( 60 273.05 kPa Find ( y1 y2) P y1 0.1 x2 y2 1 1 y1 x1 Given y1 = x1 1 ( x2 T)Psat1 ( ) x1 T P x1 x2 = 1 y2 = x2 2 ( x2 T)Psat2 ( ) x1 T P y1 y2 = 1 x1 ( 1 V) y1 V = z1 Eq. (c) P.T-flash Calculation P Pdew 2 Pbubl T ( 60 273.15)K z1 0.15) 432 .33 kPa x1 0.33 kPa y1 0.963 Ans.037 x2 0.395 y2 0.1 x2 1 x1 Given y1 P = x1 1 ( x2 T)Psat1 ( ) x1 T x1 y2 P = x2 2 ( x2 T)Psat2 ( ) x1 T x2 = 1 Pdew x1 x2 Pdew 27.15)K y1 0.3 y2 1 y1 Guess: P 101.605 Ans.3 x2 1 x1 Guess: P 101. (10.

.307 120 1 ( 0 1 T) Psat1 ( T) Psat2 ( T) 120 20. Guess: P 101.18 kPa Find ( x1 x2 y1 y2 P) x1 0.15) K 1 ( 0 1 T) 19.94 y1 0.235 Since one of these values is >1 and the other is <1.129 121 Psat1 ( T) 2 ( 1 0 T) Psat2 ( T) 121 0. an azeotrope exists.863 2 ( 1 0 T) 4.655 V 0.3 x2 y2 1 1 x1 x1 Given y1 P = x1 1 ( x1 x2 T) Psat1 ( T) y2 P = x2 2 ( x1 x2 T) Psat2 ( T) x1 x2 = 1 y1 y2 = 1 x1 = y1 x1 x2 y1 y2 Paz Paz 31.06 Find ( x1 x2 y1 y2 V) x2 0. 10.4187 433 y1 0.843 (d) Azeotrope Calculation Test for azeotrope at: T ( 60 273.4187 Ans.345 y2 0.x1 x2 y1 y2 V x1 0.3 0.33 kPa x1 y1 0.3(e). See Ex.

15 K) C2 kPa Parameters for the Wilson equation: V1 cm 75.807 K 230.mcd reproduces the table of Wilson parameters on Page 474 and includes the necessary Antoine coefficients.12. Solutions for the other systems can be obtained by rerunning the following Mathcad program with the appropriate parameter values substituted for those given.1154 16.14 mol 775. The file WILSON.07 mol 1351.3872 B1 B2 3483.18 It is impractical to provide solutions for all of the systems listed in the table on Page 474.70 K kPa C1 C2 205. we present as an example only the solution for the system 1-propanol(1)/water(2).15 K) C1 Psat2 ( ) T exp A2 ( T B2 273.90 3 a12 cal mol a21 cal mol 12 ( ) T a12 V2 exp RT V1 21 ( ) T a21 V1 exp RT V2 21 ( ) T x1 21 ( ) T exp x2 1 ( x2 T) x1 12 ( ) T x1 x2 12 ( ) x2 T x1 x2 12 ( ) T exp 2 ( x2 T) x1 x1 12 ( ) T x1 x2 12 ( ) x2 T x2 x1 21 ( ) T 21 ( ) T x1 21 ( ) T 434 .170 K ( T B1 273.67 K 3885. Antoine coefficients: 1-Propanol: Water: Psat1 ( ) T A1 A2 exp A1 16.48 3 V2 cm 18.

1 K Find ( T y1 y2) y1 0.33 kPa y1 0.1 x1 x2 x2 = 1 1 y1 Given y1 P = x1 1 ( x1 x2 T) Psat1 ( T) y2 P = x2 2 ( x1 x2 T) Psat2 ( T) Tdew x1 x2 Tdew 364.3 y2 1 y1 Given y1 P = x1 1 ( x1 x2 T) Psat1 ( T) y1 y2 P = x2 2 ( x1 x2 T) Psat2 ( T) y2 = 1 Tbubl y1 y2 Tbubl 361.33 kPa x1 0.1 0.T-flash Calculation T Tdew 2 Tbubl P 101. (10.15) K x1 0.3 y2 1 x1 Guess: T ( 60 273.28 K Find ( T x1 x2) x1 0. (b) DEW T: P 101.(a) BUBL T: P 101.418 y2 0.582 Ans.952 Ans.15) 435 . (c) P.3 Guess: V 0.15) K y1 0.1 x2 y2 1 1 y1 x1 Given y1 = x1 1 ( x1 x2 T) Psat1 ( T) P x1 x2 = 1 y2 = x2 2 ( x1 x2 T) Psat2 ( T) P y1 y2 = 1 x1 ( 1 V) y1 V = z1 Eq.048 x2 0.5 x1 y1 0.33 kPa z1 0.3 x2 1 x1 Guess: T ( 60 273.

459 0 2 ( 0 Tb1) 3.807 (d) Azeotrope Calculation Test for azeotrope at: P 101.65 V 0.x1 x2 y1 y2 V x1 0. Guesses: T ( 60 273. See Ex.33 kPa C1 273.09 Find x1 x2 y1 y2 V) ( x2 0.281 Since one of these values is >1 and the other is <1.149 K 1 ( 1 Tb2) 16.91 y1 0.35 y2 0.349 K Tb2 C2 273.15 K Tb2 373.15 K Tb1 A1 B1 P ln kPa B2 A2 P ln kPa Tb1 370.4 x2 1 y1 y1 x2 = 1 y2 = 1 x1 = y1 0.506 121 P 2 ( 0 T)Psat2 ( ) 1 Tb1 0. 10.15)K x1 0.3(e).4 y2 1 x1 Given y1 P = x1 1 ( x2 T)Psat1 ( ) x1 x1 T y2 P = x2 2 ( x2 T)Psat2 ( ) y1 x1 T 436 . an azeotrope exists.779 1 120 1 ( 1 T)Psat1 ( ) 0 Tb2 P 120 121 19.

67 K 3885.x1 x2 y1 y2 Taz Taz 360. The file NRTL.70 K kPa C1 C2 205.3872 B1 B2 B1 273.4546 Ans.4546 y1 0. we present as an example only the solution for the system 1-propanol(1)/water(2).19 It is impractical to provide solutions for all of the systems listed in the table on page 474.170 K A2 exp A1 (T C1 Psat2 ( T) exp A2 (T B2 273.5081 21 ( T) 12 ( T) G21 ( T) 21 ( T) 437 .57 cal mol b21 RT exp 0.881 K x1 0.807 K 230. Find ( x1 x2 y1 y2 T) 12. Solutions for the other systems can be obtained by rerunning the following Mathcad program with the appropriate parameter values substituted for those given.mcd reproduces the table of NRTL parameters on Page 474 and includes the necessary Antoine coefficients.1154 16. Antoine coefficients: 1-Propanol: A1 Water: Psat1 ( T) 16.40 b12 RT exp cal mol b21 1636.15 K) C2 kPa Parameters for the NRTL equation: b12 12 ( T) G12 ( T) 500.15 K) 3483.

042 x2 0.958 Ans.3 Ans.33 kPa x1 0.84 K P Find ( y1 y2) T y1 0.415 y2 y1 0.27 K Find ( x1 x2) T x1 0.05 x2 1 y1 Given y1 P = x1 1 ( x2 T)Psat1 ( ) x1 T y2 P = x2 2 ( x2 T)Psat2 ( ) x1 T x1 x2 = 1 Tdew x1 x2 Tdew 364.15)K x1 0.1 ( x2 T) x1 exp x2 2 21 ( ) T G21 ( ) T x1 x2 G21 ( ) T G12 ( ) 12 ( ) T T x1 G12 ( ) T) 2 2 ( x2 2 ( x2 T) x1 exp x1 2 12 ( ) T G12 ( ) T x2 x1 G12 ( ) T G21 ( ) 21 ( ) T T x2 G21 ( ) T) 2 2 ( x1 (a) BUBL T: P 101.3 y2 1 y1 Given y1 P = x1 1 ( x2 T)Psat1 ( ) x1 T y1 y2 P = x2 2 ( x2 T)Psat2 ( ) x1 T y2 = 1 Tbubl y1 y2 Tbubl 360. 438 .15)K y1 0.33 kPa y2 1 x1 Guess: T ( 90 273.585 0.3 x2 1 x1 Guess: T ( 60 273. (b) DEW T: 101.

T-flash Calculation T Tdew 2 Tbubl P 101.15 K Tb1 370.931 y1 0.648 V 0.15 K Tb2 373.352 y2 0.069 V) y1 V = z1 Eq.699 C1 273.149 K 1 ( 0 1 Tb2) 2 ( 1 0 Tb1) 4.33 kPa z1 0.5 x1 y1 0.349 K Tb2 C2 273.(c) P.15) Find ( x1 x2 y1 y2 V) x2 0.3 Guess: V 0.1 x2 y2 1 1 y1 x1 Given y1 = x1 1 ( x1 x2 T) Psat1 ( T) P x1 x2 = 1 y2 = x2 2 ( x1 x2 T) Psat2 ( T) P y1 y2 = 1 x1 ( 1 x1 x2 y1 y2 V x1 0.33 kPa Tb1 A1 B1 P ln kPa B2 A2 P ln kPa 14.05 439 . (10.1 0.816 (d) Azeotrope Calculation Test for azeotrope at: P 101.

170 Psat ( T) i exp Ai Bi T K T ( 65 273.07 A 14.15)K x1 0.38 0 cal mol Wilson parameters: a 583.88 291.500 230.05 V 40.73 18.060 C 239. See Ex.27 3885.3145 16. 12.3872 B 2756.676 K x1 0.55 440 .27 0 107.70 kPa Ci 0 228.20 Molar volumes & Antoine coefficients: 74.15 161. Guesses: T ( 90 273.578 121 P 2 ( 0 T)Psat2 ( ) 1 Tb1 121 0.27 Since one of these values is >1 and the other is <1.5785 16.4461 y1 Find x1 x2 y1 y2 T) ( y2 = 1 x1 = y1 0.4 x2 1 y1 y1 0. 10.11 1448.3(e).120 1 ( 1 T)Psat1 ( ) 0 Tb2 P 120 17.4 y2 1 x1 Given y1 P = x1 1 ( x2 T)Psat1 ( ) x1 x1 T x2 = 1 y2 P = x2 2 ( x2 T)Psat2 ( ) y1 x1 T x1 x2 y1 y2 Taz Taz 360.01 469.15) K 273.22 3638.4461 Ans. an azeotrope exists.

( i j T) Vj Vi exp ai j RT i 1 3 j 1 3 p 1 3 (a) BUBL P calculation: No iteration required.527 y 0.4 0. x1 0.2 y3 x3 1 1 y1 x1 y2 x2 P Pbubl x1 P y1 = x1 ( 1 x T) Psat ( 1 T) P y3 = x3 ( 3 x T) Psat ( 3 T) x1 x2 x3 Pdew 441 P y2 = x2 ( 2 x T) Psat ( 2 T) xi = 1 i Find x1 x2 x3 P .367 0.1 kPa Ans.3 0.106 (b) DEW P calculation: Pbubl 117. y1 Guess: Given 0.3 x2 0.4 x3 1 x1 x2 ( i x T) exp 1 ln j xj xp p j ( i j T) ( p i T) ( p j T) xj Pbubl i xi ( i x T) Psat ( i T) yi xi ( i x T) Psat ( i T) Pbubl 0.05 y2 x2 0.

3 V z2 0.4 z1 z2 Use x from DEW P and y from BUBL P as initial guess.426 0.0. .183 442 V 0.775 (c) P. P z3 Pdew 2 1 Pbubl T 338.T-flash calculation: z1 Guess: Given P y1 = x1 ( x T)Psat1 T) 1 ( P y2 = x2 ( x T)Psat2 T) 2 ( P y3 = x3 ( x T)Psat3 T) 3 ( xi = 1 i i Pdew 69.391 y 0.677 Ans.15 K 0.19 0.345 0.14 kPa Ans. x1 ( 1 x2 ( 1 x3 ( 1 V) y1 V = z1 V) y2 V = z2 V) y3 V = z3 yi = 1 x1 x2 x3 y1 y2 y3 V 0.035 x 0.546 Find x1 x2 x3 y1 y2 y3 V 0.109 x 0.5 0.

443 .170 kPa Ci 273.060 C 239.22 3638.5343 0.12.70 exp Ai Bi T K 228.2994 0 0 b 222.3 kPa Ans.3145 16.4 x3 1 x1 x2 exp i j i j j i G j i xj ( i x T) exp j Gl i xl l xk k j G k j x j Gi j j l k i j l Gl j xl G l j xl Pbubl i xi ( i x T) Psat ( i T) 0.15)K A 14.3084 0.05 0 253.3084 0.21 bi j RT i 1 3 j 1 3 i j Gi j l 1 3 k 1 3 (a) BUBL P calculation: No iteration required.70 631.15 NRTL parameters: 0 0.37 0.500 230.525 yi xi ( i x T) Psat ( i T) Pbubl y 0.105 Pbubl 115.5343 0 0. x1 0.64 184.05 V 40.2994 1197.5785 16.3 x2 0.41 845.27 3885.3872 Psat ( i T) B 2756.07 T ( 65 273.88 0 cal mol 0.73 18.21 Molar volumes & Antoine coefficients: Antoine coefficients: 74.

77 (c) P.(b) DEW P calculation: y1 0.T-flash calculation: Find x1 x2 x3 P Pdew 68.4 z3 1 z1 z2 Guess: V 0.4 y3 1 y1 y2 Guess: x1 0.15 K z1 0.2 x3 1 x1 x2 P Pbubl Given 2 ( P y1 = x1 ( x T)Psat1 T) P y2 = x2 ( x T)Psat2 T) 1 ( P y3 = x3 ( x T)Psat3 T) 3 ( xi = 1 i x1 x2 x3 Pdew 0.3 y2 0.038 x 0.5 Use x from DEW P and y from BUBL P as initial guess.192 0.3 z2 0.9 kPa Ans. 1 ( Given P y1 = x1 ( x T)Psat1 T) x1 ( 1 V) y1 V = z1 P y2 = x2 ( x T)Psat2 T) 2 ( x2 ( 1 V) y2 V = z2 P y3 = x3 ( x T)Psat3 T) 3 ( x3 ( 1 V) y3 V = z3 xi = 1 i yi = 1 i 444 .05 x2 0. P Pdew 2 Pbubl T 338.

3145 16.534 Find x1 x2 x3 y1 y2 y3 V 0.11 161.4 x3 445 1 x1 x2 .15 0 Wilson parameters: a 583.183 V 0.73 18.426 0.88 291.x1 x2 x3 y1 y2 y3 V 0.391 y 0.07 A 14.347 0.27 0 107.500 230.55 ( i j T) Vj Vi exp ai j RT i 1 3 j 1 3 p 1 3 (a) x1 BUBL T calculation: 0.3 x2 0.667 Ans.70 kPa Ci 228.060 C 239.170 Psat ( i T) exp Ai Bi T K P 101.01 469.3872 B 2756.38 0 cal mol 1448.33kPa 273. 12.118 x 0.5785 16.22 3638.22 Molar volumes & Antoine coefficients: 74.27 3885.05 V 40.

102 (b) DEW T calculation: y1 Guess: Given P y1 = x1 ( x T)Psat1 T) P y2 = x2 ( x T)Psat2 T) 1 ( 2 ( P y3 = x3 ( x T)Psat3 T) 3 ( i Tbubl 334.2 y3 x3 1 1 y1 x1 y2 x2 T Tbubl x1 xi = 1 446 . 0.361 0.3 y3 1 y1 y2 P y1 = x1 ( x T)Psat1 T) 1 ( P y3 = x3 ( x T)Psat3 T) 3 ( y1 y2 y3 Tbubl Find y1 y2 y3 T P y2 = x2 ( x T)Psat2 T) 2 ( P= i xi ( x T)Psati T) i ( 0.536 y 0.4 0.05 y2 x2 0.( x T) i exp 1 ln j xj xp p j ( j T) i ( i T) p ( j T) p xj Guess: Given T 300K y1 0.08K Ans.3 0.3 y2 0.

75 K 0.T-flash calculation: z1 Guess: Tdew 347.5 0.x1 x2 x3 Tdew Find x1 x2 x3 T 0.204 0.043 x 0.2 z1 z2 Use x from DEW P and y from BUBL P as initial guess.3 V z2 0. T z3 Tdew 2 1 Tbubl T 340. x1 ( 1 x2 ( 1 x3 ( 1 Given P y1 = x1 ( 1 x T) Psat ( 1 T) P y2 = x2 ( 2 x T) Psat ( 2 T) P y3 = x3 ( 3 x T) Psat ( 3 T) xi = 1 i i V) y1 V = z1 y2 V = z2 y3 V = z3 V) V) yi = 1 x1 x2 x3 y1 y2 y3 V 447 Find x1 x2 x3 y1 y2 y3 V .753 (c) P.4 K Ans.

3084 0.5343 0.125 x 0.23 Molar volumes & Antoine coefficients: Antoine coefficients: 74.70 exp Ai Bi T K 228.22 3638.5343 0 0.27 3885.5785 16.73 18.241 0.64 184.15 NRTL parameters: 0 0.21 l exp i k 1 3 1 3 j 1 3 1 3 ( j T) i i j G ( j T) i ( j T) i (a) BUBL T calculation: x1 0.705 0.2994 0 0 b 222.17 0.41 845.3145 16.05 V 40.0.170 kPa Ci 273.536 y 0.426 Ans.70 631.500 230.2994 1197.3084 0.07 P 101.223 V 0.060 C 239.88 0 bi j RT cal mol 0.4 x3 1 x1 x2 ( i T)G ( i T)x j j j ( x T) i exp j G ( i T)xl l l xk ( j T)G ( j T) k k x j G ( j T) i j l ( j T) i k G ( j T)xl l l G ( j T)xl l 448 .3 x2 0.3872 Psati T) ( B 2756.05 0 253. 12.33kPa A 14.

3 0.749 449 Find x1 x2 x3 T Tdew 347.3 y3 1 y1 y2 Given P y1 = x1 ( 1 x T) Psat ( 1 T) P y2 = x2 ( 2 x T) Psat ( 2 T) P y3 = x3 ( 3 x T) Psat ( 3 T) P= i xi ( i x T) Psat ( i T) y1 y2 y3 Tbubl 0.05 y2 0.046 x 0.102 (b) DEW T calculation: Tbubl 334. y1 Guess: 0.205 0. .6 K Find y1 y2 y3 T Ans.4 y3 1 y1 y2 x1 x2 0.5 K Ans.365 0.3 y2 0.Guess: T 300K y1 0.2 x3 1 x1 x2 T Tbubl Given P y1 = x1 ( 1 x T) Psat ( 1 T) P y2 = x2 ( 2 x T) Psat ( 2 T) P y3 = x3 ( 3 x T) Psat ( 3 T) xi = 1 i x1 x2 x3 Tdew 0.533 y 0.

011 K 0.T-flash calculation: z1 Guess: T z3 Tdew 2 1 Tbubl T 341.238 0.5 0.537 y 0.173 0.694 Find x1 x2 x3 y1 y2 y3 V 0. x1 ( 1 x2 ( 1 x3 ( 1 Given P y1 = x1 ( x T)Psat1 T) 1 ( P y2 = x2 ( x T)Psat2 T) 2 ( P y3 = x3 ( x T)Psat3 T) 3 ( xi = 1 i i V) y1 V = z1 V) y2 V = z2 V) y3 V = z3 yi = 1 x1 x2 x3 y1 y2 y3 V 0.414 Ans. 450 .133 x 0.225 V 0.(c) P.2 z1 z2 Use x from DEW P and y from BUBL P as initial guess.3 V z2 0.

15) & (11.12.92 cm 3 mol By Eq.92 cm mol 3 OK 12.256 mol 3 VE x1 x2 1.27): V x1 x2 VE x1 x2 x1 V1 x2 V2 V x1 x2 105. V VE x1 V1 451 x2 V 2 V 88.136 cm 3 mol . Vbar2 Vbar2 V x1 x2 x1 d dx1 V x1 x2 Check by Eq.68 cm mol 3 3 Ans.63 mol V2 3 cm 118.26 x1 0. (12.455 mol x1 moles1 moles x1 0.503 cm mol 3 x2 1 x1 cm 0.46 mol moles1 750 cm V1 moles2 1500 cm V2 3 moles moles1 moles2 moles 25.27 V1 cm 58.28 mol 49.16): Vbar1 V x 1 x2 d x2 V x1 x2 dx1 Vbar1 cm 190.27).92 cm 3 mol By Eqs. (12. (11.220 x1 x2 VE By Eq.11): V x1 Vbar1 3 x2 Vbar2 V 3 105. (11.026 0.4 x2 1 x1 V1 110 cm 3 mol V2 90 cm 3 mol VE x1 x2 x1 x2 45 x1 25 x2 cm 3 mol VE x1 x2 7.

6 kJ) (Fig.5 H2O) -----> HCl + 4. 12.2H2O + 8 H2O(l) ---> LiCl(10 H2O) H1 ( 1012650)J (Table C. For an ideal solution. (11.2 kJ Ans. 452 .25 H2O) H1 2 ( 50.81) applies: Vtotal x1 V 1 x2 V2 moles Vtotal 2250 cm 3 Ans. 457) (Table C.4) H H1 H2 H3 H 589 J (On the basis of 1 mol of solute) Since there are 11 moles of solution per mole of solute.28 LiCl. 12. the result on the basis of 1 mol of solution is H 11 53.55 J Ans.2H2O ---> Li + 1/2 Cl2 + 2 H2 + O2 (1) Li + 1/2 Cl2 + 10 H2O ---> LiCl(10 H2O) (2) 2(H2 + 1/2 O2 ---> H2O) (3) -------------------------------------------------------------------LiCl. 12.25) H2 62 kJ (Fig.5 H2O) + HCl -----> 2 HCl(2.14 @ n=4.14 @ n=2.4) H2 H3 441579 J 2 ( 285830 J) (Pg.25 H2O -----> HCl(2.Vtotal V moles Vtotal 2243 cm 3 Ans.25 H2O)) (1) HCl(4. 12. Eq.5 with sign change) H H1 H2 H 39.5 H2O (2) ---------------------------------------------HCl(4.29 2(HCl + 2.

2949 LiCL(21. Assume 3 steps in the process: 1. 12. Unmix 1 mole (0.7667(LiCl + 8.8 moles water + 0.18 H2O) (1) 0.2949(LiCl(21.31 Basis: 1 mole of 20% LiCl solution entering the process. 12. n=21.18 Moles of LiCl added: n'LiCl 0.015 kmol 3 0.9 125 18.4718 LiCl ---> 0. n=8.245 10 mol 20 kmol 42.18 H2O) ---> LiCl + 21. Mix (M1 + 0.15 H2O ---> LiCl(8.18 H2O) + 0.472 kmol Mole ratio.295 kmol 6.7667 LiCl(8.14.8) moles of water and 0. 12.145 H2O) H1 nLiCl 35 kJ mol (Fig.39 21. Heat M1 moles of water from 10 C to 25 C 2.2 moles of LiCl 453 .15 nLiCl n'LiCl 0.39 kmol nH2O nH2O n'LiCl nH2O nLiCl 0.15) Q H2 14213 kJ Ans.14.2 moles LiCl) of 20 % LiCl solution 3.15 H2O)) (2) --------------------------------------------------------------------------------------0.30 Calculate moles of LiCl and H2O in original solution: nLiCl nLiCl 0.1 125 42.12. original solution: Mole ratio.7667 kmol 0. final solution: nH2O nLiCl n'LiCl 8.18) H2 nLiCl H1 n'LiCl Q 32 kJ mol (Fig.

8 1.99 kJ kg 18.015 kg mol H1 1. Continue to guess M1 until H =0 for adiabatic process. M1 1.3 mol n3 n3 H H x 0.2 mol M1 1 mol 0.14 with n = 4 moles H2O/mole solute: H2 25.H LiCl in 3 mol H2O) From Figure 12.5 M1 0.905 J Ans.087 Ans.16 kJ mol M1 H1 0. 12. 12.132 kJ kg 41.2 mol H2 0.Step 1: From Steam Tables H1 H1 104.14. 457 ( H LiCl(s) .2 mol 454 25.01 kJ gm 18. Calculate H for process.14 H3 0.509 kJ mol 20.015 kg kmol kJ mol Step 2: From Fig.756 From p.061 kJ 0.2 mol H3 33.8 mol 10.5 H1 kJ mol H2 H 646. .32 H2O @ 5 C -----> H2O @ 25 C (1) LiCl(3 H2O) -----> LiCl + 3 H2O (2) LiCl + 4 H2O -----> LiCl(4 H2O) (3) -------------------------------------------------------------------------H2O @ 5 C + LiCl(3 H2O) -----> LiCl(4 H2O) H1 H2 H3 H 104.8 kJ kg kJ mol 21.5 kJ mol Step 3: Guess M1 and find H3 solution from Figure 12.2 mol H3 Close enough x 0.

1 kJ Ans.2 mol kJ mol H1 From Figure 12.2 mol H 5.472 kJ Ans. (b) LiCl(3 H2O) -----> LiCl + 3 H2O (1) LiCl + 4 H2O -----> LiCl(4 H2O) (2) ----------------------------------------------------LiCl(3 H2O) + H2O -----> LiCl(4 H2O) H1 20.5 kJ From Figure 12.756 kJ mol From p.H LiCl in 3 mol H2O) H2 25.14 H2 H3 H4 H 1. 457 for LiCl.12.83 408.949 kJ Ans. (c) LiCl*H2O -----> Li +1/2 Cl2 + H2 + 1/2 O2 (1) H2 + 1/2 O2 -----> H2O (2) Li + 1/2 Cl2 -----> LiCl (3) LiCl + 4 H2O -----> LiCl(4 H2O) (4) ---------------------------------------------------------------------LiCl*H2O + 3 H2O -----> LiCl(4 H2O) H1 H2 H3 H4 H (d) 712. 457 ( H LiCl(s) .14 mol 0.58 kJ mol kJ mol kJ mol From p.5 0.5 kJ From Figure 12. 457 for LiCl 285.14 mol H 0. LiCl + 4 H2O -----> LiCl(4 H2O) (1) 4/9 (LiCl(9 H2O) -----> LiCl + 9 H2O) (2) --------------------------------------------------------------5/9 LiCl + 4/9 LiCl(9 H2O) -----> LiCl(4 H2O) 455 .33 (a) LiCl + 4 H2O -----> LiCl(4H2O) H 25.2 mol H1 H2 H 0.4 Hf H2O(l) From p.61 25.H2O From Table C.

4 Hf H2O(l) ( 285.5 kJ mol H1 From p. 5/6 (LiCl(3 H2O) -----> LiCl + 3 H2O) (1) 1/6 (LiCl(9 H2O) -----> LiCl + 9 H2O) (2) LiCl + 4 H2O -----> LiCl(4 H2O) (3) -----------------------------------------------------------------------5/6 LiCl(3 H2O) + 1/6 LiCl(9 H2O) -----> LiCl(4 H2O) H1 H2 H3 kJ 5 ( 20.22 kJ Ans.2 mol H2 H3 H 0.14 From Figure 12.14 ( ) 32.14 H (f) 0.H LiCl in 3 mol H2O) From Figure 12.5 4 9 kJ mol kJ mol H1 From Figure 12.14 0.H1 H2 H (e) 25.4 From Figure 12. 457 ( H LiCl(s) .83) kJ mol 456 .H2O From Table C. 5/8 (LiCl*H2O -----> Li +1/2 Cl2 + H2 + 1/2 O2) (1) 5/8 (H2 + 1/2 O2 -----> H2O) (2) 3/8 (LiCl(9 H2O) -----> LiCl + 9 H2O) (3) 5/8 (Li + 1/2 Cl2 -----> LiCl (4) LiCl + 4 H2O -----> LiCl(4 H2O) (5) ---------------------------------------------------------------------------------------5/8 LiCl*H2O + 3/8 LiCl(9 H2O) -----> LiCl(4 H2O) kJ 5 ( 712. 457 for LiCl.58) mol 8 5 8 H1 H2 From p.2 mol H2 H 2.756) mol 6 kJ 1 ( ) 32.561 kJ Ans.4 mol 6 25.

14 H4 5 8 ( 408.5 kJ mol From Figure 12.833 n2 kmol sec 26.84 kJ H H1 H2 H3 H4 H 45.6H2O ---> Cu + N2 + 6 O2 + 6 H2 (3) Cu(NO3)2 + 20. during which the following are mixed: (1) 12 kg hydrated (6 H2O) copper nitrate (2) 15 kg H2O n1 12 kmol 295.2 mol H1 H2 H3 H4 H5 H 0.51 H2O ---> Cu(NO3)2(20.61) kJ mol From p.8 kJ) H4 47.041 kmol sec n2 15 kmol 18.14 H 0.51 H2O(l) ---> Cu(NO3)2(20.61 sec 0.6H2O + 14.34 BASIS: 1 second.403 kJ Ans.83 kJ) (Table C.4) H2 302.51 Mole ratio.H3 kJ 3 ( 32.4) mol 8 From Figure 12.51 H2O) H1 6 ( 285. 457 for LiCl H5 25.015 sec n1 n2 6 n1 0. final solution: n1 6(H2 + 1/2 O2 ---> H2O(l)) Cu + N2 + 3 O2 ---> Cu(NO3)2 (1) (2) Cu(NO3)2. 12.08 kJ 457 .51 H2O) (4) -----------------------------------------------------------------------------------------------Cu(NO3)2.9 kJ H3 ( 2110.

805 kJ) H4 ( 439.2H2O ---> Li + 1/2 Cl2 + 2H2 + O2 (3) -------------------------------------------------------------------------------------LiCl.2H2O + n H2O ---> LiCl(n+2 H2O) H2 2 ( 285.83 kJ) H3 1012. H= H1 H2 H3 Since it is also adiabatic. H 19. 458 .3H2O ---> 2 LiCl(5H2O) H1 1311. kJ H Ans. H= 0 Therefore.This value is for 1 mol of the hydrated copper nitrate.288 kJ) (Pg.4) H3 2 ( 436.3H2O ---> Li + 1/2 Cl2 + 3H2 + 3/2 O2 (1) 3(H2 + 1/2 O2 ---> H2O(l)) (2) 2(Li + 1/2 Cl2 + 5 H2O ---> LiCl(5H2O)) (3) LiCl(7H2O) ---> Li + 1/2 Cl2 + 7 H2O (4) ------------------------------------------------------------------------------LiCl(7H2O) + LiCl.4) Since the process is isothermal.878 xLiCl 0.99 kJ Interpolation in the table on pg.36 Li + 1/2 Cl2 + (n+2)H2O ---> LiCl(n+2 H2O) (1) 2(H2 + 1/2 O2 ---> H2O) (2) LiCl.878 mol H2O. xLiCl 1 9. H1 H2 H3 H1 440.3 kJ H2 3 ( 285.488 kJ Q H Q 19. 457) H H1 H2 H3 H4 Ans. 457 shows that the LiCl is dissolved in 8.35 LiCl. Q 1830 Q n 1 sec mol 12. On the basis of 1 second.83 kJ) (Table C.1012 Ans.488 kJ 12.65 kJ (Table C.

07 Hf 872.85 870.79 875.12.06 871.82 874.37 Data: 10 15 20 25 n 50 100 300 500 1000 862.74 867.91 kJ 873.8 kJ Ca + Cl2 + n H2O ---> CaCl2(n H2O) CaCl2(s) ---> Ca + Cl2 -------------------------------------------CaCl2(s) + n H2O ---> CaCl2(n H2O) From Table C.4: i 1 rows ( n) 65 HfCaCl2 70 Hf i HfCaCl2 kJ 75 80 10 100 ni 459 1 10 3 .54 Hf HfCaCl2 Htilde 795.13 875.

8 kJ (Table C.6H2O + 28.6H2O(s) ---> Ca + Cl2 + 6 H2 + 3 O2 (1) Ca + Cl2 + 34.5 H2O) H1 795.4) H2 871.37) H298 H1 H2 H3 for reaction at 25 degC H298 21.911 H2O) H1 2607.8 kJ (Pb.6H2O dissolved CaCl2.5 H2O ---> CaCl2(12.991 H2O --->CaCl2(34.38 CaCl2 ---> Ca + Cl2 (1) 2(Ca + Cl2 + 12.4) H2 2 ( 865.908 gm 460 .12 kJ msoln ( 110.83 kJ) (Table C.911 H2O) (2) 6(H2 + 1/2 O2 ---> H2O) (3) --------------------------------------------------------------------------------------CaCl2. The two steps together are adiabatic and the overall enthalpy change is 0. 12.9 kJ H3 6 ( 285.015)gm msoln 739.986 n 34.295 kJ) H3 871.986 34.015 n 15 110.12.911 Moles of H2O per mol CaCl2 in final solution.911 H2O ---> CaCl2(34. 12.39 The process may be considered in two steps: Mix at 25 degC.911 Basis: 1 mol of Cacl2.911 18. Moles of water added per mole of CaCl2.72 kJ Ans. Calculate moles H2O needed to form solution: 85 18.07 kJ H H1 H2 H3 Q H Q 63.5 H2O) (2) CaCl2(25 H2O) ---> Ca + Cl2 + 25 H2O (3) -----------------------------------------------------------------------------------CaCl2(25 H2O) + CaCl2 ---> 2 CaCl2(12.6H2O: n 6 28. then heat/cool solution to the final temperature.

CP 3.17) Q m3 H3 m1 H1 m2 H2 Q 38150 BTU Ans.28 kJ kg degC H298 CP T = 0 T H298 msoln CP T 8.5 % (Final soln.) m3 m1 m2 H3 90 BTU lbm (Fig. at 200 degF) H1 100 BTU lbm H2 152 BTU lbm (Fig.39 % (Final soln) m3 m1 m2 H3 41 BTU lbm (Fig.) H1 8 BTU lbm H2 23 BTU lbm (Fig.17.19) 35 % m1 m1 10 % m2 m2 27. 12. 12. 12.5 x2 1 x1 H 69 BTU lbm (50 % soln) H1 20 BTU lbm (pure H2SO4) H2 108 BTU lbm (pure H2O) HE H x1 H1 x2 H2 HE 133 BTU Ans. lbm 12.44 Enthalpies from Fig.17) 100 % m1 m1 25 % m2 m2 47. 12. at 130 degF) m2 175 lbm (10% soln.19) 461 .298 degC Ans.45 (a) m1 400 lbm (35% soln.702 degC T 25 degC T T 16. 12. 12. x1 0.43 m1 150 lb (H2SO4) m2 350 lb (25% soln. 12.

Q

m3 H3

m1 H1

m2 H2

Q

43025 BTU Ans.

(b) Adiabatic process, Q = 0.

H3

m1 H1

m2 H2

m3

H3

115.826

BTU lbm

From Fig. 12.19 the final soln. with this enthalpy has a temperature of about 165 degF.

12.46 m1

25

lbm sec

(feed rate)

x1

0.2

H1

24

BTU lbm

(Fig. 12.17 at 20% & 80 degF)

H2

55

BTU lbm

(Fig. 12.17 at 70% and 217 degF) [Slight extrapolation]

x2

0.7

H3

1157.7

BTU lbm

(Table F.4, 1.5(psia) & 217 degF]

m2

x1 m1 x2
m2 H2

m2

7.143

lbm sec

m3

m1

m2

m3

17.857

lbm sec

Q

m3 H3

m1 H1

Q

20880

BTU sec

Ans.

12.47 Mix m1 lbm NaOH with m2 lbm 10% soln. @ 68 degF. BASIS: m2

1 lbm

x3

0.35

x2

0.1

m1

1 lbm

(guess)

m3

m1

m2

Given

m1

m2 = m3

m1
m1

x2 m2 = x3 m3
0.385 lbm

m1 m3
Find m1 m3

m3

1.385 lbm

462

From Example 12.8 and Fig. 12.19
H1 478.7 BTU lbm
m2 H2

H2

43

BTU lbm
BTU lbm

H3

m1 H1

m3

H3

164

From Fig. 12.19 at 35% and this enthalpy, we find the temperature to be about 205 degF.

12.48 First react 1 mol SO3(l) with 1 mol H2O(l) to form 1 mol H2SO4(l): SO3(l) + H2O(l) ---> H2SO4(l) With data from Table C.4: H298 [ 813989 ( 441040 285830) ]J
H298
mH2SO4 0.5

8.712

10 J

4

Mix 1 mol or 98.08 gm H2SO4(l) with m gm H2O to form a 50% solution. mH2SO4
mH2O

98.08 gm
msoln mH2SO4

msoln

Data from Fig. 12.17:
HH2SO4
HH2O
Hsoln
Hmix
Hmix
Q

0

BTU lbm

[pure acid @ 77 degF (25 degC)]

45

BTU lbm
BTU lbm

[pure water @ 77 degF (25 degC)]

70

[50% soln. @ 140 degF (40 deg C)] mH2SO4 HH2SO4 mH2O HH2O

msoln Hsoln
18.145 kg
H298 msoln

BTU lbm
Q 283 BTU lbm
Ans.

Hmix

463

12.49

m1

140 lbm

x1

0.15

m2

230 lbm

x2

0.8

H1

65

BTU lb

(Fig. 12.17 at 160 degF)

H2

102

BTU lb

(Fig. 12.17 at 100 degF)

m3

m1

m2

x3

m1 x1

m2 x2

m3

x3

55.4 %

Q

20000 BTU

H3

Q

m1 H1 m3

m2 H2

H3

92.9

BTU lbm

From Fig. 12.17 find temperature about 118 degF

12.50 Initial solution (1) at 60 degF; Fig. 12.17:
m1 1500 lbm

x1

0.40

H1

98

BTU lbm

Saturated steam at 1(atm); Table F.4:

m3 m2

m1

m2

H2

1150.5

BTU lbm

x3 m2

x1 m1 m1 m2

H3 m2

m1 H1

m2 H2

m3 m2

m2

125 lbm

x3 m2

36.9 %

H3 m2

2

BTU lbm

The question now is whether this result is in agreement with the value read from Fig. 12.17 at 36.9% and 180 degF. It is close, but we make a second calculation:

m2

120 lbm

x3 m2

37%

H3 m2

5.5

BTU lbm

This is about as good a result as we can get.

464

12.51 Initial solution (1) at 80 degF; Fig. 12.17:

m1

1 lbm

x1

0.45

H1

95

BTU lbm

Saturated steam at 40(psia); Table F.4:

m3 m2

m1

m2

H2

1169.8

BTU lbm

x3 m2

x1 m1 m1 m2

H3 m2

m1 H1

m2 H2

m3 m2

m2

0.05 lbm

x3 m2

42.9 %

H3 m2

34.8

BTU lbm

The question now is whether this result is in agreement with the value read from Fig. 12.17 at 36.9% and 180 degF. It is close, but we make a second calculation:

m2

0.048 lbm

x3 m2

42.9 %

H3 m2

37.1

BTU lbm

This is about as good a result as we can get.

12.52 Initial solution (1) at 80 degF; Fig. 12.19:

m1

1 lbm

x1

0.40

H1

77

BTU lbm

Saturated steam at 35(psia); Table F.4:

H2

1161.1

BTU lbm

x3

0.38

m2

x1 m1 x3

m1

m3

m1

m2

m3

1.053 lbm

m2

0.053 lbm

H3

m1 H1 m2 H2 m3

H3

131.2

BTU lbm

We see from Fig. 12.19 that for this enthalpy at 38% the temperature is about 155 degF.

465

12.53 Read values for H, H1, & H2 from Fig. 12.17 at 100 degF:

H

56

BTU lbm

H1

8

BTU lbm

H2

68

BTU lbm

x1

0.35

x2

1

x1

H

H

x1 H 1

x2 H2

H

103

BTU lbm

Ans.

12.54 BASIS: 1(lbm) of soln. Read values for H1 & H2 from Fig. 12.17 at 80 degF:

H1
Q=

4

BTU lbm
x1 H 1

H2

48

BTU lbm

x1

0.4

x2

1

x1

H= H

x2 H2 = 0

H

x1 H 1

x2 H2

H

30.4

BTU lbm

From Fig. 12.17, for a 40% soln. to have this enthalpy the temperature is well above 200 degF, probably about 250 degF.

12.55 Initial solution:

x1

2 98.08 2 98.08 15 18.015

x1

0.421

Final solution:

x2

3 98.08 3 98.08 14 18.015

x2

0.538

Data from Fig. 12.17 at 100 degF:

HH2O

68

BTU lbm

HH2SO4

9

BTU lbm

H1

75

BTU lbm

H2

101

BTU lbm

466

Unmix the initial solution:

Hunmix
Hunmix

x1 HH2SO4
118.185 BTU lbm

1

x1 HH2O

H1

React 1 mol SO3(g) with 1 mol H2O(l) to form 1 mol H2SO4(l). We neglect the effect of Ton the heat of reaction, taking the value at 100 degF equal to the value at 77 degF (25 degC)
J mol
J mol
HfH2O HfSO3
Hrx 1.324 10
5 J

HfSO3
HfH2SO4
Hrx

395720

HfH2O

285830

J mol

813989

HfH2SO4

mol

Finally, mix the constituents to form the final solution:

Hmix
Q

H2

x2 HH2SO4

1

x2 HH2O

Hmix

137.231

BTU lbm

Hunmix ( 98.08 2 1 lbmol Hrx Hmix ( 98.08 3

15 18.015)lb 14 18.015)lb

Q

76809 BTU

Ans.

12.56 Read values for H(x1=0.65), H1, & H2 from Fig. 12.17 at 77 degF:
H 125 BTU lbm
x2

H1
1

0

BTU lbm

H2
H

45

BTU lbm
x1 H 1
BTU lbm

x1

0.65

x1

H

x2 H2
Ans.

H

140.8

467

From the intercepts of a tangent line drawn to the 77 degF curve of Fig. 12.17 at 65%, find the approximate values:

Hbar1

136

BTU lbm

Hbar2

103

BTU lbm

Ans.

12.57 Graphical solution: If the mixing is adiabatic and water is added to bring the temperature to 140 degF, then the point on the H-x diagram of Fig. 12.17 representing the final solution is the intersection of the 140-degF isotherm with a straight line between points representing the 75 wt % solution at 140 degF and pure water at 40 degF. This intersection gives x3, the wt % of the final solution at 140 degF:

x3

42 %

m1

1 lb

By a mass balance:

x3 =

0.75 m1 m1 m2

m2

0.75 m1 x3

m1

m2

0.786 lbm

Ans.

12.58 (a) m1
x1

25 lbm
0

m2
x2

40 lbm
1

m3

75 lbm

x3

0.25

Enthalpy data from Fig. 12.17 at 120 degF:

H1

88

BTU lbm

H2

14

BTU lbm

H3

7

BTU lbm

m4

m1

m2

m3

m4

140 lbm

x4

x1 m1

x2 m2 m4

x3 m3

x4

0.42

H4

63

BTU lbm

(Fig. 12.17)

Q

m4 H4

m1 H1

m2 H2

m3 H3

Q

11055 BTU Ans.

468

(b) First step: m1

40 lb

x1

1

H1

14

BTU lbm

m2

75 lb

x2

0.25

H2

7

BTU lbm

m3

m1

m2

x3

x1 m1

x2 m2

m3

H3

Q

m1 H1 m3

m2 H2

x3

0.511

H3

95.8

BTU lbm

From Fig. 12.17 at this enthalpy and wt % the temperature is about 100 degF.

12.59 BASIS: 1 mol NaOH neutralized. For following reaction; data from Table C.4: NaOH(s) + HCl(g) ---> NaCl(s) + H2O(l)
H298 [ 411153 285830
5

( 425609

92307) ]J

H298

1.791

10 J

NaOH(s) + HCl(g) ---> NaCl(s) + H2O(l) (1) NaOH(inf H2O) ---> NaOH(s) + inf H2O (2) HCl(9 H2O) ---> HCl(g) + 9 H2O(l) (3) NaCl(s) + inf H2O ---> NaCl(inf H2O) (4) ---------------------------------------------------------------------------------------NaOH(inf H2O) + HCl(9 H2O) ---> NaCl(inf H2O)

H1

H298

H2

44.50 kJ

H3

68.50 kJ

H4

3.88 kJ

H

H1

H2

H3

H4

Q

H

Q

62187 J

Ans.

469

12.60 First, find heat of solution of 1 mole of NaOH in 9 moles of H2O at 25 degC (77 degF). Weight % of 10 mol-% NaOH soln:
x1
HH2O
Hsoln

1 40.00 1 40.00 9 18.015
45 BTU lbm
BTU lbm
BTU lbm

x1

19.789 %

(Table F.3, sat. liq. at 77 degF)

35

(Fig. 12.19 at x1 and 77 degF)

HNaOH

478.7

[Ex. 12.8 (p. 468 at 68 degF]

Correct NaOH enthalpy to 77 degF with heat capacity at 72.5 degF (295.65 K); Table C.2: T 295.65 K
molwt
3

40.00

gm mol

Cp

R molwt

0.121

16.316 10 K

T

Cp

0.245

BTU lbm rankine
BTU lbm

HNaOH

HNaOH

Cp ( 77

68)rankine

HNaOH

480.91

H
H

Hsoln
0.224

x1 HNaOH
kJ gm

1

x1 HH2O

This is for 1 gm of SOLUTION.

However, for 1 mol of NaOH, it becomes:
H H x1

molwt

H

45.259

kJ mol

470

Now, on the BASIS of 1 mol of HCl neutralized: NaOH(s) + HCl(g) ---> NaCl(s) + H2O(l) (1) HCl(inf H2O) ---> HCl(g) + inf H2O (2) NaOH(9 H2O) ---> NaOH(s) + 9 H2O (3) NaCl + inf H2O ---> NaCl(inf H2O) (4) --------------------------------------------------------------------------------------HCl(inf H2O) + NaOH(9 H2O) ---> NaCl(inf H2O) H1
H2
H3
H4
H

179067 J
74.5 kJ
45.259 kJ
3.88 kJ
H1 H2

(Pb. 12.59)
(Fig. 12.14 with sign change)
(See above; note sign change)
(given) H3 H3
Q H
Q 14049 J Ans.

12.61 Note: The derivation of the equations in part a) can be found in Section B of this manual.

0.1 0.2 0.3 0.4 0.5 x1 0.6 0.7 0.8 0.85 0.9 0.95
HE

73.27 144.21 208.64 262.83 302.84 323.31 320.98 279.58 237.25 178.87 100.71
kJ kg HE x1 x2

x2

1

x1

H

471

In order to take the necessary derivatives of H, we will fit the data to a HE 3 2 third order polynomial of the form H = = a bx.1 c x1 d x1 . x1 x2

Use the Mathcad regress function to find the parameters a, b, c and d.

w w n a b c d
2 3
H

w w n
regress x1 kJ kg

3 3 3 735.28 824.518 195.199 914.579

3

a b c d kJ kg

H

x1

a

b x1

c x1

d x1

Using the equations given in the problem statement and taking the derivatives of the polynomial analytically:

HEbar1 x1

1

x1

2

H

x1

x1

b

2 c x1

3 d x1

2

kJ kg
kJ kg

HEbar2 x1

x1

2

H

x1

1

x1

b

2 c x1

3 d x1

2

472

0

500

1000
(kJ/kg)

1500

2000

2500

0

0.2
H/x1x2 HEbar1 HEbar2

0.4
x1

0.6

0.8

12.62 Note: This problem uses data from problem 12.61

0.1 0.2 0.3 0.4 0.5 x1 0.6 0.7 0.8 0.85 0.9 0.95 HE

73.27 144.21 208.64 262.83 302.84 323.31 320.98 279.58 237.25 178.87 100.71
kJ kg

x2

1

x1

H

HE x1 x2

473

Fit a third order polynomial of the form

HE x1 x2

= a

bx.1

c x1

2

d x1

3

.

Use the Mathcad regress function to find the parameters a, b, c and d. w w n a b c d
regress x1
H

w w n
kJ kg

3 3 3 735.28 824.518 195.199 914.579

3

a b c d

By the equations given in problem 12.61
H

x1

a
H

b x1

c x1

2

d x1

3

kJ kg

H x1 Hbar1 x1

x1 x1 1 1 x1
2
2

x1 x1 x1 b 2 c x1 3 d x1
2

H

kJ kg

Hbar2 x1

x1

H

x1

1

x1

b

2 c x1

3 d x1

2

kJ kg

At time , let: x1 = mass fraftion of H2SO4 in tank m = total mass of 90% H2SO4 added up to time H = enthalpy of H2SO4 solution in tank at 25 C H2 = enthalpy of pure H2O at 25 C H1 = enthalpy of pure H2SO4 at 25 C H3 = enthalpy of 90% H2SO4 at 25 C Material and energy balances are then written as: x1 ( 4000
Q=

m) = 0.9m
m) H

Solving for m:

m x1

( 4000kg)x1 0.9 x1

Eq. (A)

Ht = ( 4000

4000H2

m H3
474

x1 H1 x2 H2 and since T is constant at 25 C, we set H1 = H2 = 0 at this T, making H = H. The energy balance then becomes: Eq. (B) Q= ( 4000 m) H m H3
Since H = H
Applying these equations to the overall process, for which: 6hr
x1 0.5
H3
H
Define quantities as a function of x 1

H( ) 0.9

H3
H

178.737

kJ kg
kJ kg

H( ) 0.5

303.265

Q x1
m x1
Qtx1

4000kg
( 4000kg) 1 x 0.9 x1

m x1

H x1

m x1 H3
m ( ) 5000 kg 0.5
6

4000kg

m x1

H

m x1 H3

Qt0.5) (

1.836

10 kJ

Since the heat transfer rate q is constant:
q Qtx1
Q x1 q

and

x1

Eq. (C)

The following is probably the most elegant solution to this problem, and it leads to the direct calculation of the required rates, dm r= d
When 90% acid is added to the tank it undergoes an enthalpy change equal to: 0.9Hbar1+0.1Hbar2-H3, where Hbar1 and Hbar2 are the partial enthalpies of H2SO4 and H2O in the solution of mass fraction x1 existing in the tank at the instant of addition. This enthalpy change equals the heat required per kg of 90% acid to keep the temperature at 25 C. Thus,
r x1 q 0.9 Hbar1 x1 0.1 Hbar2 x1
475

H3

17 x2 x3 0.5 140degF a) Use mass balances to find feed rate of cold water and product rate.5 1100 1000 r x1 kg hr 900 800 700 600 0 1 2 3 x1 hr 4 5 6 12. 12. Guess: Given mdot2 mdot1 mdot1 mdot2 = mdot3 mdot3 2mdot1 Total balance H2SO4 balance mdot1 x1 mdot2 x2 = mdot3 x3 476 .Plot the rate as a function of time 1200 x1 0 0.8 T1 T2 T3 120degF H1 H2 H3 92 BTU lb Enthalpies from Fig.0 40degF 7 BTU lb 70 BTU lb 0.64 mdot1 20000 lb hr x1 0.01 0.

hr b) Apply an energy balance on the mixer Qdot mdot3 H3 mdot1 H1 mdot2 H2 Qdot 484000 BTU hr Since Qdot is negative. dL = Vdot dt d L x1 An unsteady state species balance on water yields: = y1 Vdot dt An unsteady state mole balance yields: Expanding the derivative gives: L dx1 dt dx1 dt dx1 dt dx1 dt dx1 x1 dL = Vdot y1 dt Substituting -Vdot for dL/dt: L x1 ( Vdot)= y1 Vdot Rearranging this equation gives: L = x1 = y1 = dL L y1 Vdot x1 dL dt Substituting -dL/dt for Vdot: L Eliminating dt and rearranging: y1 477 x1 . c) For an adiabatic process.875 BTU lb mdot3 From Fig.17.65 Let L = total moles of liquid at any point in time and Vdot = rate at which liquid boils and leaves the system as vapor. 12. Qdot is zero. this corresponds to a temperature of about 165 F 12.mdot2 mdot3 Find mdot2 mdot3 mdot2 12000 lb mdot3 hr 32000 lb Ans. heat is removed from the mixer. Solve the energy balance to find H3 H3 mdot1 H1 mdot2 H2 H3 54.

071 kPa K1 Psat1 inf1 P 15. 478 .459 Lf norg0 norg0 L0 exp L0 1 1 K1 x10 1 ln x1f x10 Lf norgf norgf 0.70 T degC K1 kPa 230.842 mole Lf 1 x1f 0.At low concentrations y1 and x1 can be related by: y1 = Psat1 inf1 P x1 = K1 x1 dx1 K1 1 x1 where: dL L K1 = inf1 Psat1 P Substituting gives: = Integrating this equation yields: ln Lf L0 = 1 K1 1 ln x1f x10 where L0 and x10 are the initial conditions of the system For this problem the following values apply: L0 T 1mol x10 P 600 10 6 x1f 50 10 6 130degC 1atm inf1 5.3872 3885. The water can be removed but almost 16% of the organic liquid will be removed with the water.744 % Ans.8 Psat1 exp 16.842 mole %lossorg norg0 %lossorg 15.170 Psat1 270.999 mole norg0 norgf 0.

611 ln inf2 12 21 exp 21 ln inf2 0.73 cm 3 mol V2 12 V1 exp a12 RT ln inf1 12 21 V2 21 exp 21 0. 12. 445 ln inf2 ln 21 1 12 ln inf2 0.88 cal mol a21 cal 583.12.Acetone 2.3048 b12 RT 0.613 Ans.9 (b) 479 .62 ln inf2 = 0.15) K For Wilson equation a12 161. 12.288 b21 21 RT 21 0.Methanol T ( 50 273.347 G12 exp 12 G12 21 0.916 12 exp G21 12 exp 21 G21 0.9(b) For NRTL equation ln inf1 = 0.70 cal mol b21 12 222.64 cal mol 0.708 V1 74.11 mol 0.05 V1 cm 3 mol a21 RT V2 40.69 1 . 446 ln inf1 ln inf1 0.733 ln 12 1 ln inf1 0.600 Both estimates are in close agreement with the values from Fig.9 From p. From p. From Fig.603 Ans.61 b12 12 184.

10a) and (12. From Margules Equation: GE = x1 x2 A21 x1 RT 2 A12 x2 Eq.10b) to Guess: A12 0. (12.12.253 and Eqs.478 exp 1 2 x1 2 A12 2 A21 A21 A12 x1 1 x1 2 x1 exp x1 A21 2 A12 480 .7kPa x1 0. 1 y1 P 1 x1 Psat1 1 1.456 P 139.71 Psat1 183.367 1 2 y1 P x1 Psat2 2 1 1.635 kPa Since PRL<P. we need a model for GE/RT. (12.4kPa Psat2 96. (12. Therefore. (12. and 2 at x1=0.10a) Eq.10b) A21 2 A12 A12 A12 A21 1 x1 Find A12 A21 0.1kPa Check whether or not the system is ideal using Raoult's Law (RL) PRL x1 Psat1 1 1 x1 Psat2 2 PRL 118.5 A21 0.253 from the given data.5 Given ln 1 = 1 ln 2 = x1 2 x1 2 A12 2 A21 A21 A12 x1 1 x1 Eq.644 A21 0.10a) Eq. A two parameter model will work. (12.10b) ln 1 = x2 ln 2 = x1 Find 1 A12 A21 2 A21 2 A12 A12 x1 A21 x2 2 and 2 at x1=0. and are not equal to 1.253 y1 0.048 Use the values of find A12 and A21.

A one parameter model will work. we need a model for GE/RT.9kPa Check whether or not the system is ideal using Raoult's Law (RL) PRL x1 Psat1 1 1 x1 Psat2 2 PRL 91.148 kPa Ans. b) 1inf exp A12 1inf Psat1 1inf 1. we must use the following equation to find A: P = x1 1 Psat1 x2 2 Psat2 481 .614 120 Since Psat2 12 120 3.911 kPa Since PRL < P.904 2inf exp A21 2inf 1. P x1 1 x1 Psat1 1 x1 2 x1 Psat2 P 160.743 Ans. and are not equal to 1.5 y1 x1 1 x1 Psat1 P y1 0. 12.6kPa x1 0.389 T ( 35 273.72 P 108. Assume a model of the form: GE = A x1 x2 RT 2 1 = exp A x2 2 = exp A x.a) x1 0.175 remains above a value of 1.2kPa Psat2 73.612 121 Psat1 2inf Psat2 121 1. an azeotrope is unlikely based on the assumption that the model of GE/RT is reliable.15) K Psat1 120.1 2 Since we have no y1 value. Therefore.

482 .554 2 x1 Psat2 x1 1 x1 Psat1 exp ( A) 1inf Psat1 x1 110.228 kPa 2inf Ans.677 1 x1 exp A 1 x1 1 x1 Psat1 P x1 2 2 x1 exp A x1 Ans. 1.826 Since 12 ranges from less than 1 to greater than 1 an azeotrope is likely based on the assumption that our model is reliable.201 121 121 0.968 2inf exp ( A) Psat1 2inf Psat2 Psat2 120 3.968 1. P 2 a) y1 b) P c) 1inf 120 y1 1 1inf 0.Use the data to find the value of A Guess: A 1 Given P = x1 exp A 1 A x1 2 Psat1 1 x1 exp A x1 2 Psat2 A Find A) ( 0.

Section A .13 at 1000 K: T 1000 kelvin G 1 2 ( 395790) RT 2 1 2 ln J mol 1 2 ( 192420 2 200240) J mol 2 2 ln 2 Guess: Given d d e e 0.Mathcad Solutions Note: For the following problems the variable kelvin is used for the SI unit of absolute temperature so as not to conflict with the variable K used for the equilibrium constant 13. (A) and with data from Example 13.3 0.45308 0.31 0.082 2.086 2.5 e = 0 G J mol e Find e e 0. (13.084 G 10 5 2.4 0.5 0.2 0.Chapter 13 .088 0.6 483 .4 H2(g) + CO2(g) = H2O(g) + CO(g) = i i= 1 1 1 1= 0 1 2 n0 = 1 1= 2 By Eq.3 0.5). yH = yCO = 2 2 yH2O = yCO = 2 By Eq.6 2.

65 484 . yH = yCO = 2 2 yH2O = yCO = 2 By Eq.5 0.5).13.103 2.5 e = 0 G J mol e Find e e 0.55 0.106 2.107 0.35 0.6 0.104 G 10 5 2. (A) and with data from Example 13. 0.36 0.105 2.5 (a) H2(g) + CO2(g) = H2O(g) + CO(g) = i i= 1 1 1 1= 0 1 2 n0 = 1 1= 2 By Eq.102 2. (13.13 at 1100 K: T 1100 kelvin G 1 2 ( 395960) RT 2 1 2 ln J mol 1 2 ( 187000 2 209110) J mol 2 2 ln 2 Guess: Given d d e e 0.502 Ans.3 0.35 0.65 2.4 0.45 0.

7 2.53988 Ans.123 G 10 5 2.121 2.7 485 . (13. yH = yCO = 2 2 yH2O = yCO = 2 By Eq.122 2. (A) and with data from Example 13.(b) = H2(g) + CO2(g) = H2O(g) + CO(g) i= i 1 1 1 1= 0 1 2 n0 = 1 1= 2 By Eq.55 0.1 e = 0 G J mol e Find e e 0.4 0.124 2.127 0.125 2.6 0.13 at 1200 K: T 1200 kelvin G 1 2 ( 396020) J RT 2 1 2 ln mol 1 2 ( 181380 2 217830) J mol 2 2 ln 2 Guess: Given d d e e 0.126 2.5).41 0. 0.35 0.45 0.65 0.5 0.4 0.

5 0.6 0.4 0.57088 Ans.7 486 .146 2.35 0.55 0.41 0.45 0.6 J mol Given G e = 0 e Find e e 0. (A) and with data from Example 13.(c) = H2(g) + CO2(g) = H2O(g) + CO(g) i= i 1 1 1 1= 0 1 2 n0 = 1 1= 2 By Eq.148 0. (13.13 at 1300 K: T 1300 kelvin G 1 2 ( 396080) RT 2 1 2 ln J mol 1 2 ( 175720 2 226530) J mol 2 2 ln 2 Guess: d d e e 0. 0.7 2.144 2. yH = yCO = 2 2 yH2O = yCO = 2 By Eq.5).142 G 10 5 2.14 2.4 0.65 0.

the following vectors represent values for Parts (a) through (d): 1000 T 1100 1200 1300 kelvin 3130 G 150 3190 6170 J mol Combining Eqs.4531 exp G RT 0.5399 0.5). (13.11a). (13.6 H2(g) + CO2(g) = H2O(g) + CO(g) = i i= 1 1 1 1= 0 1 2 n0 = 1 1= 2 By Eq.13.28) gives 2 2 1 2 2 1 2 = 1 2 = K = exp G RT 0. (13.13. yH = yCO = 2 2 yH2O = yCO = 2 With data from Example 13. and (13.15 kelvin J mol T0 298.5). 0.15 kelvin G298 75948 487 .5709 13.11 4HCl(g) + O2(g) = 2H2O(g) + 2Cl(g) = 1 H298 n0 = 6 114408 J mol T 773.5021 1 Ans.

28).089 10 3 0.5) 1 6 yHCl = yH2O = 5 6 2 6 4 yO2 = yCl2 = 2 6 Apply Eq.623 0.344 10 5 i 1 end i Bi i A B D i i Di A 0.5 4 (guess) Find Given 5 6 2 5 4 6 1 4 = 2K 0.0397 yH2O 488 0. (13. (13.506 1.151 D 0.793 yHCl yO2 1 6 yH2O 2 6 yCl2 2 6 yHCl 0. 0.267 10 4 J mol K 7.470 4.The following vectors represent the species of the reaction in the order in which they appear: 4 1 2 2 end rowsA) ( i Ai i 3.439 B 8 10 5 C 0 D 8.3048 yCl2 0.227 0.3048 Ans.639 3.3508 yO2 0.23 10 4 G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D G 1.156 A 3. .450 0.18041 K exp G RT By Eq.442 B 0.121 0.

191 10 5 T 923.01464 By Eq. 489 .173 10 3 C 0 D 0. (13.5). and 13. find the following values: H298 42720 J mol G298 39430 J mol A 0. 0. 4. 4.22(x).12 N2(g) + C2H2(g) = 2HCN(g) = 0 n0 = 2 This is the reaction of Pb.4715 yC2H4 0.4715 yHCN 0.21(x). (13.057 Ans.5 (guess) Given 1 2 2 1 2 = K Find 0.7(x). P has no effect on the equilibrium composition.28).13. From the answers for Pbs.15 kelvin T0 298. Given the assumption of ideal gases.057 yN2 yC2H4 1 2 yHCN yN2 0.15 kelvin G H298 H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D T G 3.242 10 4 J mol K exp G RT K 0.060 B 0. 4. yN2 = 1 2 yC2H4 = 1 2 yHCN = 2e 2 = By Eq.21(x).

4.7064 By Eq.5 K 3.15 kelvin G H298 H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D T G 6. .1968 yH2 0.13.5 2. From the answers for Pbs.156 10 D 0.5 1 1.601 10 3 C 0. If the pressure is reduced to 1 bar. (13.5). (13.28).5 = 1K Find 0.4053 yC2H5OH 0.7(r).3387 Ans. find the following values: H298 68910 J mol G298 39630 J mol 6 A 1.5 yCH3CHO 0. 4.5 yC2H5OH 2.5 2.22(r).15 kelvin T0 298.424 B 1.4867 Ans.5 2. and 13. Given 0.5 K exp G RT 1.5 yC2H5OH 2.5 (guess) Find 1 1.13 CH3CHO(g) + H2(g) = C2H5OH(g) = 1 n0 = 2.5 = 3K 0.108 yH2 0.5 yH2 1.083 10 5 T 623.5 2.5 yH2 1.21(r).5 By Eq. Given 2.5 This is the reaction of Pb. 4.4645 490 yC2H5OH 0.5 yCH3CHO 0. yCH3CHO = yH2 = yC2H5OH = 2.787 10 3 J mol 1 2.633 yCH3CHO 1 2.21(r).818 yCH3CHO 1 2.

5196 yC6H5C2H5 0.15 kelvin G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D G 2.5 1 1.5 = 1.814 10 D 0.C2H5(g) = 1 n0 = 2. find the following values: H298 117440 J mol G298 3 83010 J mol 6 A 4.5 yC6H5CHCH2 0. (13.0133 K Find 0.5 2.14 C6H5CH:CH2(g) + H2(g) = C6H5.13.5 K 1.2794 yH2 0.5 This is the REVERSE reaction of Pb.5 (guess) Given 2. From the answers for Pbs.5). 4. yC6H5CHCH2 = yH2 = 1.418 yC6H5CHCH2 1 2.28).15 kelvin T0 298.5 yC6H5C2H5 2.5 2.766 10 C 1.21(y).22(y). 491 . 4. 4. and 13.175 B 4. (13.201 Ans.5 yC6H5C2H5 = 2.21(y).398 10 3 J mol K exp G RT 1 2.5 By Eq.36672 By Eq.5 yH2 1. 0.083 10 5 T 923.7(y) WITH OPPOSITE SIGNS.

2 0. Given 1 0.15 Basis: 1 mole of gas entering.03675 By Eq.506 10 1.056 3 1.5).5 From data in Table C.15 1 0.015 D 0.5 0.20 1 0. (13.1455 .804 10 4 J mol K exp 0.20 mol O2.15 kelvin G H298 H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D T G 2.5 ySO3 = 1 0.699 A 3. containing 0.639 8.65 mol N2.5O2 = SO3 = 0.13.15 kelvin T0 298.28).15 mol SO2.5 0. H298 98890 J mol G298 70866 J mol The following vectors represent the species of the reaction in the order in which they appear: 1 0.060 B 0. SO2 + 0.5 0.5 n0 = 1 By Eq.5415 B 2 10 6 C 0 D 8.028 5 i B i 1 end i Bi A D i i Di A 0.15 0.995 10 4 T 753. and 0.227 10 2. ySO2 = 0.5 0. (13.5 1 end rowsA) ( i Ai i 5.801 0.4.1 G RT (guess) K 88. 0.5 492 = K Find 0.5 yO2 = 0.

213 A 1.4).785 14.702 B 28. By Eq.31 10 3 C 2.4) nC3H8 = 1 Fractional conversion of C3H8 = n0 nC3H8 n0 = 1 1 1 = By Eq.913 B 5.424 1. mol 13. H298 82670 J mol G298 42290 J mol The following vectors represent the species of the reaction in the order in which they appear: 1 1 1 end rowsA) ( i Ai i 1.1455 By Eq. yC3H8 = 1 1 yC2H4 = 1 yCH4 = 1 From data in Table C.5). nSO3 = = 0.4.268 10 6 D 0 (a) T 625 kelvin T0 298.164 6 i 1 end i Bi i A B C i i Ci A 1. (13.392 10 2. (13.081 3 8.16 C3H8(g) = C2H4(g) + CH4(g) = 1 Basis: 1 mole C3H8 feed.18).15 kelvin 493 .By Eq.394 10 9. (13. (4. H753 H298 R IDCPH T0 T A B C D H753 98353 J mol Q H753 Q 14314 J Ans.824 C 4.

G H298 H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D T G 2187. 2 (b) 0. 2 0.8 K Ans.5 From data in Table C. It is not difficult to find T by trial. This leads to the value: T = 646.5).5 yH = 1. n0 = 1. yC2H6 = 1 1. The problem now is to find the T which generates this value.777 This value of epsilon IS the fractional conversion.5 By Eq.52356 By Eq. (13. (13.5 yC2H4 = 1.604 G R T ln ( K) G Ans. Ans.9 J mol K exp G RT (guess) K 1.85 K 1 4972.5 mol H2O.5 Given 1 1 = K Find 0. 13. H298 136330 J mol G298 100315 J mol The following vectors represent the species of the reaction in the order in which they appear: 494 .17 C2H6(g) = H2(g) + C2H4(g) = 1 Basis: 1 mole entering C2H6 + 0.4.28).3 1 J mol K 2.

3 10 3 T 1100 kelvin T0 298.225 B 0.083 10 0. (guess) Given 1. nC2H6 = 1 nH2 = nC2H4 = n= 1 yC2H6 1 1 yH2 1 yC2H4 1 yC2H6 0.1 1 1 A 1.422 14.561 C 0.542 B 4.81048 By Eq. (13.0 4.249 1.4551 Ans.4551 yH2 0.15 kelvin G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D G 5.131 3.409 10 3 C 1.4).0 D 0.394 0.169 10 6 D 8.429 10 3 J mol 0. (13. 495 .392 10 6 19.5 2 K exp G RT K 1.424 5.28).0899 yC2H4 0.83505 By Eq.0 5 10 3 end rowsA) ( i Ai i i 1 end i Bi A B i C i i Ci D i i Di A 3.5 1 = K Find 0.

3 10 3 298.5). H298 109780 J mol G298 79455 J mol The following vectors represent the species of the reaction in the order in which they appear: 1 1 1 A 1.18 C2H5CH:CH2(g) = CH2:CHCH:CH2(g) + H2(g) (1) (2) (3) = 1 Number the species as shown.10 From data in Table C. Basis is 1 mol species 1 + x mol steam.15 kelvin H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D T 496 . (13.0 6 31.734 3.630 B 26.422 10 T0 3 C 9.4.786 10 0.0 D 0.13.0 0.91 10 7 D 8. n0 = 1 x y1 = 1 1 x y2 = y3 = 1 x By Eq.249 9.882 10 0.422 3 0.083 10 5 end A rows ( A) i Ai i i B i 1 end i Bi C i i Ci D i i Di A T G 4.873 C 8.016 950 kelvin H298 B 4.967 2. = 0.

1 0.10 1 x = K K 0. y1 = 1 1 x 2 y2 = 1 x 2 = 0. (13.28).24 H298 235030 J mol G298 166365 J mol The following vectors represent the species of the reaction in the order in which they appear: 1 1 2 A 1.249 B 36.0186 yH2O ysteam 0.4.2 y1 y1 0.53802 By Eq.5894 7.G 4.10 1 x 6.786 10 0.12 From data in Table C.935 2.5894 (a) y1 1 1 x yH2O 1 0.843 x 0. (13.896 10 3 J mol K exp G RT x K 0.5894 13. (b) ysteam 6.5).7814 0.734 3. Basis is 1 mol species 1 + x mol steam entering.19 C4H10(g) = CH2:CHCH:CH2(g) + 2H2(g) (1) (2) (3) = 2 Number the species as shown.8682 Ans.1 1 = K Since 0. n0 = 1 x By Eq.915 26.422 3 497 . ( )( ) 1 0. y3 = 2 y2 = 0. Ans.10 0.

52 10 6 D 1.3151 5.12) ( 0.66 10 4 T 925 kelvin T0 298.3151 0.3151 ysteam 0.0 0.402 C 8.812 Ans.023 yH2O 0. ( 0.083 10 5 i 1 end i Bi i A B C i i Ci D i i Di A 7.839 (a) y1 1 1 x 2 yH2O 1 0.0 end rows ( A) i Ai i 0.242 10 3 J mol K exp G RT 2 K 1 x 2 0.28).24) 1 = K Because 0.285 10 3 C 2.36 y1 y1 0.12 1 2 x 4.297 B 9.30066 By Eq. 498 .12 1 x 2 = K K ( 0.15 kelvin G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D G 9.0 10 6 D 0. (b) ysteam 4.617 Ans. (13.11.24) 2 x 0.882 0.

627 10 4 J mol 1 K exp G RT K 679.22(a). 4.5 0. 3/2 mol H2 feed n0 = 2 This is the reaction of Pb.0905 10 C 0 D 0.9664 2 yNH3 0.21(a) with all stoichiometric coefficients divided by two. 13.9 for ideal gases: 1 yNH3 1 1. and 13.15 kelvin G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D G P 1 1.299 K P P0 0. find the following values: H298 46110 J mol G298 16450 3 J mol A 2.9355 B 2.1586 499 .57 P0 From Pb. (b) For yNH3 = 0.299 K 6.7(a) ALL DIVIDED BY 2. 4.5 by the preceding equation 2 3 Solving the next-to-last equation for K with P = P0 gives: 1 K 1 2 1 1. 4. From the answers to Pbs.3305 10 5 (a) T 300 kelvin T0 298.13.20 1/2N2(g) + 3/2H2(g) = NH3(g) = 1 Basis: 1/2 mol N2.21(a).9349 Ans.

2kelvin 34.061 3 0 500 . which can be evaluated by the generalized second-virial correlation.887 Tr1 For N2(2): T Tc1 Tr1 1. (d) Eq.038 Tr2 583 126. (13.06159 Another solution by trial for T yields T = 577.7kelvin Pc1 112. (3.5 44.59) Tc3 1 43.5 kelvin Ans.437 Pc2 Pr1 2 Tc2 126.0 Pr2 2.757 bar Pr3 P Pc3 Pr3 5.6 kelvin Ans. estimate critical constants using Eqns. and requires fugacity coefficients.806 K Tr3 T Tc3 Tr3 13. the preceding equation becomes 1 K 1 2 1 129.8bar Pr1 P Pc1 1 0.27) applies.62 Pc3 1 20.62 Pr2 100 34.016 T kelvin kelvin Tc3 42.8 2. Since iteration will be necessary.9 K 0.Find by trial the value of T for which this is correct.0bar 0.016 kelvin bar Pc3 19.2 T 2.941 For H2(3).253 0.58) and (3. It turns out to be T = 399.2 Tr2 4. we assume a starting T of 583 K for which: T 583kelvin P 100bar For NH3(1): Tc1 405. (c) For P = 100.6 21.

135 10 5 300 kelvin 298.21 CO(g) + 2H2(g) = CH3OH(g) Basis: 1 mol CO. Of course.07292 Another solution by trial for T yields T = 568.15 kelvin 501 .815 10 T0 3 C 3.034 1.924 1.4.029 1 i 0.9 1.5 i i 1.6. and several trials were in fact made.5 1. 13. 142 from which: A (a) T 7. 4. but not shown here.45 10 6 D 0.184 The expression used for K in Part (c) now becomes: 1 K 1 2 1 K 129. i 1 3 1 2 3 PHIB Tr1 Pr1 PHIB Tr2 Pr2 PHIB Tr3 Pr3 0. without reproducing them. = 2 n0 = 3 H298 90135 J mol G298 24791 J mol This is the reaction of Ex. The trials are made by simply changing numbers in the given expressions.663 B 10.184 0. the INITIAL assumption made for T was not so close to the final T as is shown here. Pg.6 K Ans. 2 mol H2 feed From the data of Table C.Therefore.

(13.28).47 kelvin Ans. By the preceding equation 0. with the species numbered in the order in which they appear in the reaction. 502 .439 10 4 J mol 1 K exp G RT K 1.9752 y3 (b) 3 y3 2 0. It turns out to be: T = 364.75 Solution of the equilibrium equation for K gives K 3 4 1 2 2 3 K 27 Find by trial the value of T for which this is correct. y1 = 1 3 2 y2 = 2 3 2 2 y3 = 3 2 By Eq.G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D G P 1 2.5 3 y3 2 y3 1 y3 0.5).762 10 4 P0 By Eq.9291 Ans. 0.8 (guess) Given 3 4 1 2 2 3 = P P0 2 K Find 0. (13.

235 By Eq. and requires fugacity coefficients.9kelvin Pc1 34.27) applies.16.5933 .99bar 1 0. 3 0.612 For H2(2).15 & E. Since iteration will be necessary. (11.7 10 3 Another solution by trial for T yields T = 516.(c) For P = 100 bar.032 1 0.612 i i i 503 0. (13.97bar 3 0.6206 0.67) and data from Tables E. assume a starting T of 528 K. the preceding equation becomes K 3 4 1 2 2 100 3 2 K 2. for which: T 528kelvin P 100bar For CO(1): Tc1 132.973 Pr1 P Pc1 Pr1 2.6kelvin Pc3 80.048 Tr1 T Tc1 Tc3 Tr1 3.03 Pr P Pc3 Pr 1.48 kelvin Ans.9763 3 3 0.0 0. (d) Eq.858 For CH3OH(3): 512.564 Tr T Tc3 Tr 1.612 1 2 1 1. the reduced temperature is so large that it may be assumed ideal: Therefore: i 1 3 1 PHIB Tr1 Pr1 1.

16 10 4 298. H298 178321 J mol G298 130401 J mol The following vectors represent the species of the reaction in the order in which they appear: 1 1 1 A 12. If the pure CO2 is assumed an ideal gas at 1(atm).011 1151. Eq.83 kelvin B 1. For the two species existing as solid phases.443 10 1.157 i Bi 5 i 1 3 A i B i D i i Di A T 1.045 i Ai 3 3. 13. for which the activity is f/f0. then for CO2 the activity is f/f0 = P/P0 = P (in bar).637 0. (13.104 5.149 10 T0 3 C 0 D 9. and the activity is unity.4.047 10 1.0133.572 6.593 K 1.10) becomes K = P = 1. and we must find the T for which K has this value.7 kelvin Ans.22 CaCO3(s) = CaO(s) + CO2(g) Each species exists PURE as an individual phase.15 kelvin G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D 504 .The expression used for K in Part (c) now becomes: 3 4 1 2 2 K 100 3 2 0.457 B 2. As a result. From the data of Table C.6011 10 3 Another solution by trial for T yields: T = 528. f and f0 are for practical purposes the same.120 D 1.

A handbook value for this temperature is 1171 K.5 bar.105 3.10) becomes K = (0. only the final trial is shown.5 10 G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D 505 . (13.0133 Thus T = 1151.578 3.75)(0. If the equimolar mixture of NH3 and HCl is assumed an ideal gas mixture at 1.97 kelvin B 0.23 NH4Cl(s) = NH3(g) + HCl(g) The NH4Cl exists PURE as a solid phase.0 10 3 D 0.012462 T0 298.324 J mol K exp G RT K 1.020 0. H298 176013 J mol G298 91121 J mol The following vectors represent the species of the reaction in the order in which they appear: 1 1 1 A 5. Although a number of trials were required to reach this result.156 B 16.15 kelvin C 0 D 3.5625 .939 3. then with f0 = 1 bar the activity of each gas species is its partial pressure.186 10 0. and we must find the T for which K has this value.795 623.4. 13.G 126. the activity is unity.5)(1.75. As a result.151 5 i 1 3 A i B i i Bi D i i Di 3 A T 0.83 kelvin Ans. Eq. for which the activity is f/f0.623 i Ai 0.5) = 0. From the given data and the data of Table C. Since f and f0 are for practical purposes the same. (0.75) = 0.

5 yNO2 yNO yO2 0.26 C2H4(g) + (1/2)O2(g) = <(CH2)2>O(g) = 0. only the final trial is shown.21 0. Moles O2 entering: nO2 1.5 See Example 13.25 NO(g) + (1/2)O2(g) = NO2(g) = 0. Pg. G298 K 1.307 10 6 Find yNO yNO2 12 This is about 7 10 6 ppm (a negligible concentration) Ans.5 10 6 Given yNO yNO2 yNO2 = ( ) 0.5 = yNO2 yNO ( ) 0. Although a number of trials were required to reach this result.25 0.21 K yNO yNO2 yNO yNO = 5 10 7.5 = K T 298.5624 T = 623.97 K Ans. 13.9.15 kelvin From the data of Table C. 13. H298 105140 J mol G298 81470 J mol Basis: 1 mol C2H4 entering reactor.G Thus 2.4. 508-510 From Table C.4.986 10 3 J mol K exp G RT K 0.493 (guesses) 35240 J mol K yNO exp 10 G298 RT 12 10 6 yNO2 0.5 Moles N2 entering: nN2 nO2 79 21 506 .

639 0.3) & (4.1: Guess: 1 n nO2 0.8 1. (4.040 0.280 0.506 23. we combine Eqs.5 1 0 kelvin i 1 4 A i n i Ai B i n i Bi C i n i Ci D i n i Di y n n0 0. For the product stream.394 B 0. 507 .5).5 0.463 0. (13.0 10 6 2 14.385 3. The three equations together provide the energy balance. data from Table C.n0 1 nO2 nN2 n0 3.0 9.0 0.424 A 3.5 K i y i i K 15.947 The energy balance for the adiabatic reactor is: H298 HP = 0 For the second term.976 Index the product species with the numbers: 1 = ethylene 2 = oxygen 3 = ethylene oxide 4 = nitrogen The numbers of moles in the product stream are given by Eq.227 0.593 10 kelvin 3 nN2 4.392 C 0.7).296 0.0 D 1 10 kelvin 5 2 0.

23(g): A D Guess: 3.11a) & (13.21(g).629 0.417 B 2 T0 2 2 1 C 3 H298 T0 1 D T0 H298 idcps 1 K = exp G298 1 T0 R T0 R T0 0.15 kelvin idcph B 2 T0 2 2 1 C 3 T0 1 D T0 1 idcps A ln B T0 C T0 D 2 1 2 2 1 T0 idcph Given H298 = R A T0 1 3 3 130.114 10 kelvin 3 A T0 1 3 3 5 2 B T0 8. 4. (13.88244 3.182 kelvin idcps 0. 4.18374 idcph Find 508 . apply a combination of Eqs.904 10 6 2 kelvin 298.18).For the equilibrium state.816 10 3 kelvin C 4. for which the following values are given in Pb.The reaction considered here is that of Pb.

702 1.23 kelvin Ans.081 B 0. 13.164 6 9.2496 0. Thus we leave it out of consideration.867 10 0. From the data of Table C.249 2.0333 y 0.0 10 i 1 3 C 0.0 D 0.0 0. Ans.164 10 6 D 7. H298 74520 J mol G298 50460 J mol The following vectors represent the species of the reaction in the order in which they appear: 1 1 2 A 1.083 5 A i i Ai B i i Bi C i i Ci D i i Di A T 6.01 10 4 923.052 0.27 CH4(g) = C(s) + 2H2(g) = 1 (gases only) The carbon exists PURE as an individual phase.567 B 7.15 kelvin 298.15 kelvin 509 .466 10 T0 3 C 2.88244) ( 0.771 3.422 3 0.4.771 10 0.0.6651 T T0 T 949. for which the activity is unity.

8 (guess) Given 2 2 2 1 = K Find 0.5).2392 By Eq. yCH4 = yH2 = 2 2 2 1 (a) By Eq.8354 n0 = 2 Ans.7173 (fraction decomposed) yCH4 1 1 yH2 2 1 yCH4 0. By Eq.7893 (fraction decomposed) yCH4 1 2 yH2 2 2 yN2 1 yCH4 yH2 yH2 0. . 0. (13.0756 yN2 0. 510 . (13. 2 1 1 = 4 1 = K K 4 K 0.G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D G 1.28).5659 yCH4 0. (13.1646 yH2 (b) For a feed of 1 mol CH4 and 1 mol N2.28).109 10 4 J mol n0 = 1 K exp G RT 1 1 2 K 4.3585 Ans.

280 3.22(n).21(n).15 kelvin 511 .15 kelvin G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D 4 J G 6.85 10 4 T 2000 kelvin T0 298.639 4. H298 33180 J mol G298 51310 J mol The following vectors represent the species of the reaction in the order in which they appear: 0. 4.4. find the following values: H298 90250 J mol G298 86550 3 J mol 5 A 0.506 10 1.792 i Bi 5 A i i Ai B i D i i Di A 0.195 3 0.7(n) ALL DIVIDED BY 2.0795 10 C 0 D 0.593 0.1075 10 T 2000 kelvin T0 298.982 B 0.0725 B 0. and 13.227 10 0.5 1 1 i 1 3 A 3. From the answers to Pbs.13.02004 (2) 1/2N2(g) + O2(g) = NO2(g) From the data of Table C.28 1/2N2(g) + 1/2O2(g) = NO(g) = 0 (1) This is the reaction of Pb.040 D 0. 4.925 10 4 C 0 D 5.501 10 mol K1 exp G RT = 0.5 K1 0. 4.21(n) with all stoichiometric coefficients divided by two.297 B 3.

7 0. = 1 From the given data and the data of Table C.5 yNO 3. for which the activity is f/f0.592 mol K2 exp G RT K2 6. H298 145546 J mol G298 89830 J mol 512 .5 = ( ) 0.7 ( ) 0.5 K2 yNO2 P P0 0.05 0.5 = yNO ( ) 0.4.05 200 0.7 P0 1 0.5 = K1 yNO (2) K1 ( ) 0.5 yO2 0.74962 10 3 Ans. P yNO2 yN2 0.05 0.5 ( ) 0.5 = yO2 yNO2 ( ) 0.28): (1) yN2 yNO 0. and it is omitted from the equilibrium equation. 13.9373 10 5 With the assumption of ideal gases.5 ( ) 0.5 P P0 0.7 0.29 2H2S(g) + SO2(g) = 3S(s) + 2H2O(g) The sulfur exists PURE as a solid phase.104 10 5 Ans. (13. we apply Eq.5 K2 ( ) 0.05 yNO2 4. the activity is unity.G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D 10 5 J G 1. Thus for the gases only. Since f and f0 are for practical purposes the same.

931 5.470 B 1.15 kelvin G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D 4 J G 1.801 1.015 0.28). gases only: n0 = 3 yH2S = 2 3 2 ySO2 = 1 3 yH2O = 2 3 By Eq.The following vectors represent the species of the reaction in the order in which they appear: 2 1 3 2 i 1 4 A 3.699 4.232 D 1.114 3.065 10 3 C 0 D 6.721 B 6.5 2 (guess) Given 2 2 2 3 2 = 8K 1 Find 0.728 1. (13. (13.538 10 mol K exp G RT (basis) K 12.490 0. (13.9169 By Eq.5).450 10 3 0.121 10 5 A i i Ai B i i Bi D i i Di A 5.783 0.15 kelvin T0 298.767 Percent conversion of reactants = PC PC = ni0 ni0 ni 100 = i ni0 100 [By Eq. 0.28 10 4 T 723.4)] 513 .

4241 Ans.667 Ans.203 10 5 G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D G 3.7031 514 .1 provide the following values: H298 57200 J mol G298 5080 J mol T0 298.Since the reactants are present in the stoichiometric proportions.696 B 0.911 Basis: 1 mol species (a) initially. for each reactant. (b) P 1 P0 1 K 4P K 0.968 10 3 J mol K exp G RT K 3.30 N2O4(g) = 2NO2(g) (a) (b) = 1 Data from Tables C.4 and C.4044 ya 1 1 ya 0.133 10 C 0 D 1.15 kelvin T 350 kelvin 3 A 1. 13. Then ya = 1 1 yb = 2 1 2 1 2 1 K 4P K = P P0 1 K (a) P 5 P0 1 0. ni0 = i Whence PC 100 PC 76.

(13.1 2 xA Ans.1 xA xA xA 2 exp 0.1 xB ln b = 0.1 2 xA J mol 1 K = exp G RT G 1000 T 298.4044 0.1 xA xB K= 1 xA xA exp 0. 515 .18).32). 13.299 Whence Q H Q 17021 J mol Ans.31 By Eq.By Eq. the exponential term is unity: Given 1 xA xA = exp G RT xA Find xA xA 0. Ans. 1 = exp G RT xA Find xA 0.15 kelvin xA .1 xA 1 = Whence 2 2 K= 1 xA xA exp 0.3955 For an ideal solution.0050. which is 0. (4.5 (guess) Given xA 1 xA xA exp 0.7031 0. 2 2 K= xB B xA A 1 = 2 xA xA A B ln a = 0.4005 This result is high by 0. at 350 K: H H298 R IDCPH T0 T A B C D H 56984 J mol This is Q per mol of reaction.1 xB exp 0.

From the problem statement.96 1.).941 Let z = w/2 = moles H2O/mole "Water gas". nCO nCO nH2 nCO2 = 0.4).27837 (a) No. K decreases with increasing T.540 10 C 0 D 1.02 0.02 By Eq. (13. (13. at low pressures P has no effect (b) No. nCO = 1 nH2 = 1 NCO2 = 1 1 1 = 1 2 = 0. (The standard heat of reaction is negative.32 H2O(g) + CO(g) = H2(g) + CO2(g) = 0 From the the data of Table C.15 kelvin T 800 kelvin 3 A 1.860 B 0. 1 mol H2. yH2O = 2z w = 2 2z 2 w yCO = 1 2 2z yH2 = 1 2 2z 516 . H298 41166 J mol G298 28618 J mol T0 298.5).13. By Eq. (c) Basis: 1 mol CO.668 10 mol = 0 K exp G RT K 4.4.164 10 5 G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D 3 J G 9. w mol H2O feed.02 0. Since .

(13.1: H298 172459 J mol G298 120021 J mol D 1.962 10 5 A G 0. 517 . no reaction is possible.1 Ans.4 and C.092 yCO 5.476 H298 B 0. If the ACTUAL value of this ratio is GREATER than this value. the reaction tries to shift left to reduce the ratio. and certainly no carbon is formed.28) z 2 (guess) Given 1 2z 1 = K z Find z () z 4.775 10 3 No carbon can deposit from the equilibrium mixture.28). (13.702 10 3 C 0 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D G 3. (d) 2CO(g) = CO2(g) + C(s) = 1 (gases) Data from Tables C. The actual value of the ratio in the equilibrium mixture of Part (c) is yCO2 2 2z yCO 1 2 2z yCO2 0.7 for the reaction AT EQUILIBRIUM.yCO2 = 2 2z By Eq. with P = P0 = 1 bar yCO2 yCO 2 = K = 101.767 10 3 RATIO yCO2 yCO 2 RATIO 2. But if no carbon is present. gases only.7 By Eq.074 10 4 J mol K exp G RT K 101.

339 10 4 J mol K1 exp G RT = 0 K1 6.470 B 0.031 0.21.663 B 10.376 3.749 (2) 10 4 H2(g) + CO2(g) = CO(g) + H2O(g) From the the data of Table C.13. H298 41166 J mol G298 28618 J mol T 550 kelvin T0 298. where the following parameter values are given: H298 90135 J mol G298 24791 J mol T 550 kelvin T0 298.164 10 5 .557 1.33 CO(g) + 2H2(g) = CH3OH(g) = 2 (1) This is the reaction of Pb.45 10 6 D 0.457 3.249 5.4 10 4 518 C 0 D 1.4.450 i Ai 0.083 10 3 D 1.045 0.121 10 5 A i B i i Bi D i i Di A 1.135 10 5 G H298 H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D T G 3.422 1.86 B 5.815 10 3 C 3.15 kelvin A 7.157 0. 13.15 kelvin The following vectors represent the species of the reaction in the order in which they appear: 1 1 1 1 i 1 4 A 3.

1 2 0.G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D 4 J G 1.05 yCO2 = 1 2 1 yCH3OH = 1 2 1 yH2O = 2 1 2 1 P 100 P0 1 1 By Eq.1 (guesses) Given 1 1 2 1 2 2 = 1 2 0.05 mol N2.75 mol H2. Stoichiometric numbers. (13.856 10 mol K2 exp G RT K2 0.15 yCO = 1 1 2 2 1 1 0.40).75 2 1 0.15 mol CO.7) 0.05 = K2 1 2 Find 1 2 519 . (13.15 P P0 2 K1 2 2 2 2 0.15 1 2 0.01726 Basis: 1 mole of feed gas containing 0.75 yH2 = 1 2 1 2 1 2 2 0.05 mol CO2.75 2 1 0. and 0. 0. 0. 0.j i= j 1 2 H2 CO CO2 CH3OH H2O _______________________________________________ -2 -1 -1 1 0 -1 1 0 0 1 By Eq. i.

6606 yCO 0.1186 2 8.422 10 3 i 1 4 A i i Ai B i i Bi C i i Ci D i i Di A 7.0528 yCO2 0.164 10 6 D 9.75 yH2 1 2 1 2 1 2 2 0.557 0.8812 10 3 0.1555 yH2O 0.121 0.081 B 1. = 2 (1) H298 205813 J mol G298 141863 J mol The following vectors represent the species of the reaction in the order in which they appear: 1 1 1 3 2.1 0.0 0.0655 13.34 CH4(g) + H2O(g) = CO(g) + 3H2(g) From the the data of Table C.702 A 3.083 10 5 9.0 D 0.031 0.0 0.450 0.249 0.7 10 3 .15 yCO 1 1 2 2 1 1 0.708 10 3 C 520 2.0116 yN2 0.164 C 0.05 yCO2 1 2 1 yCH3OH 1 2 1 yH2O 2 1 2 1 yN2 1 yH2 yCO yCO2 yCH3OH yH2O yH2 0.0539 Ans.951 B 8. yCH3OH 0.0 10 6 1.470 3.4.376 3.

no H2O then remains for reaction (2).540 10 G298 3 28618 J mol D 1.15 kelvin T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D 10 5 J G 1. Primary reaction (1) shifts left with increasing P. moles H2/moles CO is very nearly equal to 3. With a feed equimolar in CH4 and H2O.32. In this event the ratio. 521 . (b) No.T G 1300 kelvin H298 T0 298. Primary reaction (1) shifts left with increasing T.164 10 5 1.860 H298 B C 0.0.892 mol K2 exp G RT K2 0. where parameter values are given: H298 A G H2O(g) + CO(g) = H2(g) + CO2(g) 41166 J mol 0.0 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D 10 3 J G 5. (c) The value of K1 is so large compared with the value of K2 that for all practical purposes reaction (1) may be considered to go to completion.031 mol K1 exp G RT K1 13845 = 0 (2) This is the reaction of Pb. 13.5798 (a) No.

(e) One practical way is to add CO2 to the feed.15 kelvin A 0.0 D 1. from which we get the necessary parameter values: H298 172459 J mol G298 120021 J mol For T = 1300 K.28).(d) With H2O present in an amount greater than the stoichiometric ratio. for reaction (2) at equilibrium by Eq.702 10 3 C 0. reaction (1) for all practical purposes still goes to completion. On the basis of 1 mol CH4 and 2 mol H2O initially.5): yCO = yH2O = 1 5 yCO2 = 5 yH2 = 3 5 By Eq. However. (13. Some H2 then reacts with the CO2 by reaction (2) to form additional CO and to lower the H2/CO ratio. Part (d). and may be considered to provide the feed for reaction (2). reaction (2) becomes important. 0. 1 mol CO. (f) 2CO(g) = CO2(g) + C(s) = 1 (gases) This reaction is considered in the preceding problem. Thus. T 1300 kelvin T0 298.476 B 0.962 10 5 G H298 T H298 G298 T0 R IDCPH T0 T A B C D R T IDCPS T0 T A B C D 522 . n0 = 5.638 Ans. (13.1375 Ratio = yH2 yCO Ratio 3 1 Ratio 3. what is left as feed for reaction (2) is: 1 mol H2O.5 (guess) Given 3 1 2 = K2 Find 0. and 3 mol H2.

Thus in Part (c). in Part (d) there can be no carbon deposition.673 10 4 J mol K exp G RT K 5.j CH4 H2O CO CO2 H2 j _________________________________________________ 3 1 2 0 .37 Formation reactions: C + 2H2 = CH4 H2 + (1/2)O2 = H2O C + (1/2)O2 = CO C + O2 = CO2 Elimination first of C and then of O2 leads to a pair of reactions: CH4 + H2O = CO + 3H2 CO + H2O = CO2 + H2 (1) (2) There are alternative equivalent pairs. there is danger of carbon deposition. there can be no carbon deposition.255685 10 3 As explained in Problem 13.G 5. where the CO2 mole fraction approaches zero. because Ratio > K: Ratio 1 5 2 Ratio 0. However. but for these: Stoichiometric numbers.924 13. the question of carbon deposition depends on: RATIO = yCO2 yCO 2 When for ACTUAL compositions the value of this ratio is greater than the equilibrium value as given by K.32(d). i= j 1 2 -1 0 -1 -1 1 -1 0 1 523 i.

(13.7): 2 yCH4 = yCO2 = 1 3 yH2O = yH2 = 1 2 5 2 1 2 5 2 1 2 yCO = 1 2 5 2 1 3 1 5 5 2 1 2 1 By Eq. n0 = 5.14.For initial amounts: 2 mol CH4 and 3 mol H2O.8304 2 0. and by Eq.457 G2 RT K1 1 27.3211 2 yCH4 5 1 3 yH2O 5 524 1 2 2 1 2 1 yCO 1 2 5 2 1 . G1 27540 J mol G2 3130 J mol T 1000 kelvin K1 exp G1 RT K2 K2 exp 1. with P = P0 = 1 bar yCO yH2 = k1 yCH4 yH2O 3 yCO2 yH2 yCO yH2O = k2 From the data given in Example 13. (13.5 2 1 2 (guesses) 3 1 1 2 1 2 Given 2 1 3 2 1 3 2 5 2 1 2 = K1 2 3 1 1 2 3 = K2 1 2 Find 1 2 1 1.453 1.40).

k= y1 3 x3 P P0 = 2 x2 x3 y1 x2 T 298.14.0196 yH2O 0.0 y3 = 0.0371 yH2 0.166 kPa (steam tables) Ethylene glycol(3): Psat3 = 0.33 kPa x1 = x2 = y1 P 415kPa y2 P Psat2 Water(2): x2 Psat2 = y2 P Psat2 3.1743 yCO2 0.CH2OH(l) By Eq. k exp G298 RT 525 .yCO2 2 5 2 1 yH2 3 1 2 5 2 1 yCH4 0.39Phase-equilibrium equations: Ethylene oxide(1): p1 = y1 P = 415x1 P 101.0 Therefore.40) and the stated assumptions.15kelvin Data from Table C.4: G298 k 6.6711 These results are in agreement with those of Example 13.098 yCO 0. y2 = 1 y1 and x3 = 1 x2 x3 For the specified standard states: (CH2)2O(g) + H2O(l) = CH2OH.018 72941 10 12 J mol Ans. (13. 13.

05 n0 Given values: Guess: yB 0.3 %. y2 approaches unity.So large a value of k requires either y1 or x2 to approach zero. the water present is entirely reacted along with 1 mole of the ethylene oxide. For initial amounts of 3 moles of ethylene oxide and 1 mole of water. This means that for all practical purposes the reaction goes to completion.737 kmol hr 2 2.10 yC 0. Conversion of the oxide is therefore 33.7) yC = n03 n0 1 1 2 2 yD = n04 n0 1 2 2 yC yD Find yC yD 1 2 1 2 1 44. Thus x2 must approach zero. 1 13. which is impossible.632 kmol hr 526 . and the phase-equilibrium expression for water(2) makes x2 = 32. (13. If y1 approaches zero.41 a) Stoichiometric coefficients: 1 Initial numbers of n0 moles j 50 50 kmol hr 0 0 1 0 1 0 1 1 Number of components: i 1 4 Number of reactions: n0 n0i i 1 2 100 kmol hr vj i i j v yA 1 1 0.4 yD 0.4 1 1 kmol hr 2 1 kmol hr Given yA = n01 n0 1 1 2 2 yB = n02 n0 1 1 2 Eqn. and the phase-equilibrium equation requires y2 also to approach zero.

40 1 b) Stoichiometric coefficients: 1 2 0 1 Number of reactions: 1 1 0 Initial numbers of n0 moles 40 kmol hr 0 0 j 1 2 Number of components: i 1 4 vj i i j v 1 2 n0 n0i i n0 80 kmol hr Given values: yC 0.05 Ans.632 hr kmol n nA nB nC nD n 52.632 nB n02 1 nB 2 5.263 kmol hr kmol nC n03 1 nC 42.4 yB 0.52 yD 0. (ii) yC 0.04 Guess: yA 0.8 yD 0. (13.632 hr kmol hr Ans.4 1 1 kmol hr 2 1 kmol hr Given yA = n01 n0 1 1 2 2 2 1 yB = n02 n0 1 1 2 2 2 2 2 Eqn.7) yC = n03 n0 1 2 2 yD = n04 n0 1 2 2 527 .105 hr kmol nD n04 2 nD 2.(i) nA n01 1 2 nA 2.

yA yB 1 2 Find yA yB 1 2 1 26 kmol hr 2 2 kmol hr yA 0.1 Guess: yA 0. (13.7) yC = n03 n0 1 1 2 yD = n04 n0 1 2 2 528 . nD n04 2 nD 2 hr kmol hr 1 c) Stoichiometric coefficients: 1 1 0 1 Number of reactions: 100 1 1 0 Initial numbers of n0 moles 0 0 0 j kmol hr Number of components: i 1 4 1 2 vj i i j v 1 1 n0 n0i i n0 100 kmol hr Given values: yC 0.2 nA n01 1 2 nA 12 nB n02 1 2 2 nB 10 kmol hr kmol nC n03 1 nC 26 hr kmol Ans.3 yD 0.4 1 1 kmol hr 2 1 kmol hr Given yA = n01 n0 1 1 2 2 0 yB = n02 n0 1 1 2 2 Eqn.4 yB 0.24 yB 0.

5 kmol hr 2 12.2 nA n01 1 2 nA 50 nB n02 1 2 nB 25 kmol hr kmol nC n03 1 nC 37.20 Guess: yA 0.5 hr kmol hr 1 1 d) Stoichiometric coefficients: 1 1 0 1 1 Number of reactions: 40 1 0 0 Initial numbers of n0 moles 60 0 0 0 kmol hr Number of components: i 1 5 j 1 2 kmol hr vj i i j v 1 0 0.1 1 1 kmol hr 2 1 kmol hr 529 .4 yE 0.yA yB 1 2 Find yA yB 1 2 1 37.4 yB 0.2 yB 0. nD n04 2 nD 12.25 n0 i n0i n0 100 Given values: yC yD 0.5 kmol hr yA 0.5 hr kmol Ans.

7) yC = n03 n0 1 1 yD = n04 n0 2 1 yE = n05 n0 2 1 yA yB yE 1 2 Find yA yB yE 1 2 1 20 kmol hr 2 16 kmol hr (i) (ii) nA n01 1 2 nA nB n02 1 2 nB nC nD n03 n04 1 nC nD kmol hr kmol 24 hr kmol 20 hr 4 16 kmol hr kmol yA 0.25 0.Given yA = n01 n0 1 1 2 yB = n02 n0 1 1 2 Eqn.2 13.2 2 nE n05 2 nE 16 hr yE 0.3 Ans. yC yD 0.45 C2H4(g) + H2O(g) -> C2H5OH(g) T0 298.05 yB 0.15kelvin P0 1bar T 400kelvin P 2bar 1 = C2H4(g) H0f1 52500 J mol G0f1 68460 J mol 2 = H2O(g) H0f2 241818 J mol J G0f2 228572 3 = C2H5OH(g) H0f3 235100 mol G0f3 168490 J mol J mol 530 . (13.

002) 0 ]10 6 C 1.21 10 29.376 B [( 14.263 Ans.392) () ( 6.470) ( 3. (13.H0 H0f1 H0f2 H0f3 H0 45.22) K1 9.366 4 a) K0 exp G0 R T0 H0 1 R T0 Eqn.989 Eqn.157 10 3 C [ ( 4.782 G0 G0f1 G0f2 G0f3 G0 8.07 10 3 K2 exp 1 IDCPH T0 T A B C D T IDCPS T0 T A B C D K0 K1 K2 Eqn.23) K400 K400 0. b) K1 exp T0 T Eqn.121) () 0 ]10 5 D K0 1.518) A 3 1. (13. (13.20) K2 0.450) ( 20.394) ( 1.378 kJ mol kJ mol A ( 1.424) ( 3.61 10 6 D [ () ( 0 0.21) K298 K298 Ans. (13. c) Assume as a basis there is initially 1 mol of C2H4 and 1 mol of H2O 1 y1 = 2 e e 1 y2 = 2 e e y3 = e 2 e Assuming ideal gas behavior y3 y1 y2 = K P P0 e Substituting results in the following expression: 2 e 1 2 e 1 e 2 = K400 e e P P0 531 .001) ]10 B 4.

152 J mol kelvin S0H2O2 232.680 J mol kelvin J mol kelvin S0O2 S0O2 205.105 e Ans. T S0fH2O2 105.5 e Given 2 e 1 2 1 e 1 e 2 e e = K400 e e Find e e 0.46 H2(g) + O2(g) -> H2O2(g) H0fH2O2 S0H2 136.447 y3 y3 e 2 0.Solve for e using a Mathcad solve block.95 S0fH2O2 G0f S0H2 H0fH2O2 S0H2O2 S0fH2O2 G0f 102.1064 kJ mol T 298.191 1 y2 y2 y1 y1 e e 2 0.432 532 .447 2 0. d) Since a decrease in pressure will cause a shift on the reaction to the left and the mole fraction of ethanol will decrease. 13.15kelvin P 1bar 130.882 kJ mol J mol kelvin Ans. P P0 e Guess: e 0.

714 Eqn.2bar 1 = C3H8 (g) H0f1 104680 J mol G0f1 24290 J mol 2 = C3H6 (g) H0f2 19710 J mol G0f2 62205 J mol 3 = H2 (g) H0f3 0 J mol G0f3 0 J mol 4 = C2H4 (g) H0f4 52510 J mol G0f4 68460 J mol 5 = CH4 (g) H0f5 74520 J mol G0f5 50460 J mol Calculate equilibrium constant for reaction I: H0I H0f1 H0f2 H0f3 H0I 124. (13.637) ( 3.23) .083) ]10 5 DI KI0 KI1 KI2 8. (13.348 10 13 exp IDCPH T0 T AI BI CI DI T IDCPS T0 T AI BI CI DI 533 1.673 BI [( 28.785) ( 22.657 10 3 CI [ ( 8.915) () 0 ]10 6 CI 1.21) exp T0 T Eqn.22) 1.13.3 0 10 3 KI0 KI1 KI2 exp G0I R T0 H0I 1 R T0 1 Eqn.422) ]10 BI 5.909 10 6 DI [ () () ( 0 0 0.706) ( 0.495 kJ mol kJ mol AI ( 1.213) ( 1.249) AI 3 3.39 G0I G0f1 G0f2 G0f3 G0I 86. (13.48 C3H8(g) -> C3H6(g) + H2(g) (I) C3H8(g) -> C2H4(g) + CH4(g) (II) T0 298.15kelvin P0 1bar T 750kelvin P 1.824) ( 6.

213) ( 1.20) KII 21. (13.67 kJ mol kJ G0II G0f1 G0f4 G0f5 G0II 42. (13.164) ] 10 CII 2.702) AII 3 1.016 Calculate equilibrium constant for reaction II: H0II H0f1 H0f4 H0f5 H0II 82.KI KI0 KI1 KI2 Eqn. (13.328 Assume an ideal gas and 1 mol of C3H8 initially.21) exp T0 T Eqn.394) ( 9.322 10 10 8 8 KII0 KII1 KII2 exp G0II R T0 H0II 1 R T0 Eqn.268 10 6 DII [ ( 0) ( 0) ( 0) ] 10 5 DII KII0 KII1 0 3.392) ( 2.31 10 3 CII [ ( 8.23) KII KII0 KII1 KII2 Eqn.29 mol AII ( 1. (13.7) II I 1 I The equilibrium relationships are: y2 y3 P0 = KI P y1 y4 y5 y1 = KII P0 P Eqn.824) ( 4.081) ] 10 BII 6 5.424) ( 1. (13. 1 y1 = 1 I I II II y2 = I 1 y3 = II I I 1 I II y4 = II 1 y5 = II II Eqn.22) exp 1 IDCPH T0 T AII BII CII DII T IDCPS T0 T AII BII CII DII KII2 1.028 Eqn. (13.28) 534 .897 5.785) ( 14.913 BII [ ( 28.20) KI 0. (13.

5 I II Given I I II 1 1 = KI II P0 P P0 P 1 1 1 1 I I I I II II II II I II I II 1 I I II 1 = KII II I Find I II II I 0.4803 . Guess: 0.4803 y5 0.Substitution yields the following equations: I I 1 I II 1 I I II II I II 1 1 = KI P0 P II II 1 I II 1 I I II II I II 1 1 = KII P0 P Use a Mathcad solve block to solve these two equations for I and II. Note that the equations have been rearranged to facilitate the numerical solution.0132 y3 0.01298 y2 0.948 1 y1 1 I I II II II y2 I 1 y3 II II I I 1 I II y4 y1 1 y5 II I 1 I II 0.0132 y4 535 0.5 0.026 II 0.

a) K0 exp G0 R T0 H0 1 R T0 Eqn.945) ( ]10 6 C 5.034 0. T= y1 y2 y3 y4 y5 7 K 50 0. (13.A summary of the values for the other temperatures is given in the table below.402) ( 11.19 mol A 0.4407 0.49 n-C4H10(g) -> iso-C4H10(g) T0 298.00047 0.39 kJ mol kJ G0 G0f1 G0f2 G0 4.43 10 7 D [ () () 0 0 ]10 5 D K0 0 5.0132 0.258 A B ( 1. (13.364 K2 exp 1 IDCPH T0 T A B C D T IDCPS T0 T A B C D 536 K2 1 Eqn.38 10 4 C [11. (13.22) K1 0.23) .4407 13.421 Ans.21) b) K1 exp T0 T Eqn.677) [( 36.0130 0.853) ]10 3 B 9.48 03 1000 K 0.00006 0.059 3 0.15kelvin P0 1bar T 425kelvin P 15bar 1 = n-C4H10(g) H0f1 125790 2 = iso-C4H10(g) H0f2 134180 J mol J G0f1 16570 mol G0f2 20760 J mol J mol H0 H0f1 H0f2 H0 8.059 3 0.46 58 0.0132 0.935) ( 1.46 58 1250 K 0.915) ( 37.034 0.48 03 0.

In this case Eqn.20) Ke 1.200 Tc1 425.27) Substituting for yi yields: 1 e e 1 2 = K e= 2 2 This can be solved analytically for e to get: Ke 1 Calculate i for each pure component using the PHIB function. (13.395 PHIB Tr1 Pr1 0. b) Assume the gas is an ideal solution.974 Ans.48bar Tr2 T Tc2 Tr2 1.1kelvin Pc2 36. (13.041 Pr2 537 P Pc2 Pr2 0.336 Ans.664 y2 y2 0.872 For iso-C4H10: 2 0. (13. yi i = i P P0 K Eqn.27) applies.96bar Tr1 1 T Tc1 Tr1 1 1 Pr1 1 P Pc1 Pr1 0.181 Tc2 408. Assume as a basis there is initially 1 mol of n-C4H10(g) y1 = 1 e y2 = e a) Assuming ideal gas behavior y2 y1 = Ke e Substitution results in the following expression: 1 = Ke e e Solving for Ke yields the following analytical expression for 1 e 1 Ke e e 0.Ke K0 K1 K2 Eqn. For n-C4H10: 1 0.411 .1kelvin Pc1 37.336 e y1 1 y1 0.

661 y2 e y2 0. 538 .339 Ans. Therefore. The values of y1 and y2 calculated in parts a) and b) differ by less than 1%.2 PHIB Tr2 Pr2 e 2 2 0. the effects of vapor-phase nonidealities is here minimal.339 y1 1 e y1 0.884 e Solving for yields: 2 e 2 Ke 1 0.

731 y1 ( x1) = 0.1 A12 := 0.562 y1 ( x1) = 0.808 (b) BUBL P calculations with virial coefficients: B11 := −963⋅ cm 3 mol B22 := −1523⋅ cm 3 mol B12 := 52⋅ cm 3 mol δ 12 := 2⋅ B12 − B11 − B22 ⎡ B11⋅ ( P − Psat1) + P⋅ y22⋅ δ 12 ⎤ ⎥ Φ 1 ( P .5): Pbubl ( x1) := x1⋅ γ 1 ( x1) ⋅ Psat1 + ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2 y1 ( x1) := x1 := 0.Chapter 14 .31⋅ kPa BUBL P calculations based on Eq.25 x1 := 0. y1 .Mathcad Solutions 14.701 kPa y1 ( x1) = 0.37⋅ kPa (a) Psat2 := 37. (10.75 x1⋅ γ 1 ( x1) ⋅ Psat1 Pbubl ( x1) Pbubl ( x1) = 64. y2) := exp ⎢ R⋅ T ⎣ ⎦ ⎡ B22⋅ ( P − Psat2) + P⋅ y12⋅ δ 12 ⎤ ⎥ Φ 2 ( P . T . y2) := exp ⎢ R⋅ T ⎣ ⎦ 539 .42 2 T := ( 55 + 273.15) ⋅ K Margules equations: γ 1 ( x1) := exp ⎡ ( 1 − x1) ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ γ 2 ( x1) := exp ⎡ x1 ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ ( 1 − x1) ⎤ ⎤ ⎣ ⎣ ⎦⎦ 2 Psat1 := 82. y1 .533 kPa Pbubl ( x1) = 80.50 x1 := 0.59 A21 := 1.357 kPa Pbubl ( x1) = 85. T .Section A .

14 ⎠ ⎝ kPa ⎠ 540 . y1 .757 ⎠ ⎝ kPa ⎠ y1⋅ Φ 1 ( P . y1 . y2 . y1 . P) ⎜ ⎝P⎠ x1 := 0. y2) ⋅ P = x1⋅ γ 1 ( x1) ⋅ Psat1 y2⋅ Φ 2 ( P . y2) ⋅ P = x1⋅ γ 1 ( x1) ⋅ Psat1 y2⋅ Φ 2 ( P .267 ⎟ ⎜ P ⎟ ⎜ ⎜ ⎝ 79.Guess: x1 := 0. T .25 P := Psat1 + Psat2 2 Given y1 := 0. T . y1 .50 Given ⎛ y1 ⎞ ⎜ ⎛ 0. T .442 ⎟ ⎜ P ⎟ ⎜ ⎜ ⎝ 63. y2) ⋅ P = x1⋅ γ 1 ( x1) ⋅ Psat1 y2⋅ Φ 2 ( P .558 ⎞ y2 ⎟ ⎜ ⎜ = ⎜ 0. T . y2) ⋅ P = ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2 y2 = 1 − y1 ⎛ y1 ⎞ ⎜ ⎜ y2 ⎟ := Find ( y1 .188 ⎟ ⎜ P ⎟ ⎜ ⎜ ⎝ 85.621 ⎠ ⎝ kPa ⎠ y1⋅ Φ 1 ( P . y2) ⋅ P = ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2 y2 = 1 − y1 ⎛ y1 ⎞ ⎜ ⎜ y2 ⎟ := Find ( y1 . T . y2 . y2) ⋅ P = ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2 y2 = 1 − y1 ⎛ y1 ⎞ ⎜ ⎜ y2 ⎟ := Find ( y1 . y1 . T .812 ⎞ ⎜ ⎜ y2 ⎟ = ⎜ 0. y2 . y1 .5 y2 := 1 − y1 y1⋅ Φ 1 ( P . P) ⎜ ⎝P⎠ x1 := 0.733 ⎞ ⎜ ⎜ y2 ⎟ = ⎜ 0. P) ⎜ ⎝P⎠ ⎛ y1 ⎞ ⎜ ⎛ 0.75 Given ⎛ y1 ⎞ ⎜ ⎛ 0.

10a) that: ∞ ln ⎛ γ 1 ⎞ = A12 ⎝ ⎠ Combining this with Eq.7135 ⎠ ⎛ 12.118 Ans.92 ⎟ ⎜ 27.12 ⎠ x2 := 1 − x1 ⎛ 0.6096 ⎟ ⎜ ⎝ 0.01 ⎟ ⎜ ⎟ ⎜ 25.4565 ⎟ ⎜ ⎟ ⎜ 0.95 mol Assume Henry's law applies to methane(1) in the liquid phase.14.0895 ⎟ ⎜ 0.000 ⎞ ⎜ ⎜ 0.3 T := 200⋅ K H1 := 200⋅ bar P := 30⋅ bar B := −105⋅ cm 3 y1 := 0.4 Pressures in kPa Data: ⎛ 0.5119 ⎟ ⎜ 0.2716 ⎟ ⎜ 0. (11. and that the Lewis/Randall rule applies to the methane in the vapor: fhat1 = H1⋅ x1 By Eq.4232 ⎟ ⎜ ⎟ ⎜ 0.3193 ⎟ x1 := ⎜ 0.7440 ⎟ ⎜ 0.8050 ⎟ ⎜ ⎝ 0.5934 ⎟ y1 := ⎜ 0. 14.51 ⎟ ⎜ 18..1981 ⎟ ⎜ ⎟ ⎜ 0.10a) yields the required expression 541 . rows ( P) (a) It follows immediately from Eq.61 ⎟ ⎜ ⎟ ⎜ 21. (12.30 ⎞ ⎜ ⎜ 15.96 ⎟ ⎜ ⎝ 30.36): l fhat1 = y1⋅ φ 1⋅ P φ 1 := exp ⎛ ⎜ B⋅ P ⎞ ⎝ R⋅ T ⎠ φ 1 = 0.and vapor-phase fugacities and solve for x1: x1 := y1⋅ φ 1⋅ P H1 x1 = 0.000 ⎞ ⎜ ⎜ 0.63 ⎟ P := ⎜ 24.8639 ⎠ Psat2 := P1 i := 2 .6815 ⎟ ⎜ ⎟ ⎜ 0. (12.827 v Equate the liquid.

542 . A21) := exp ⎡ ( x2) ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ 2 2 γ 2 ( x1 . x2 . ⎥ i i i exp ( A12) ⎟⎥ ⎥ ⎢ dA12 ⎢ ⎜ ⎢ ⎢ ⎜ + x2i⋅ γ 2 x1i . γ 1 ( x1 . A21 ⋅ . A12 . Margules equation. A21 ⋅ Psat2 ⎥ ⎥ ⎠⎦ ⎦ ⎣ ⎣ ⎝ 0= ∑ i ( ( ) ) ⎛ A12 ⎞ ⎜ ⎜ A21 ⎟ := Find ( A12 . A21 ⋅ . A21 . The most satisfactory procedure for reduction of this set of data is to find the value of Henry's constant by regression along with the Margules parameters.2 A12 := 0. x2 .. x2i . A12 .(b) (c) Henry's constant will be found as part of the solution to Part (c) BARKER'S METHOD by non-linear least squares.4 Mininize the sums of the squared errors by setting sums of derivatives equal to zero. A12 .. A12 . A12 . A21 ⋅ Psat2 ⎥ ⎥ ⎠⎦ ⎦ ⎣ ⎣ ⎝ 2⎤ ⎡d ⎡ H1 ⎞⎤ ⎥ ⎛ ⎢ ⎢Pi − ⎜ x1 ⋅ γ 1 x1 .. A21 ⋅ . A12 . A21 ⋅ Psat2 ⎥ ⎥ ⎠⎦ ⎦ ⎣ ⎣ ⎝ ( ( ( ( ) ) ) ) 0= ∑ i 2⎤ ⎡d ⎡ H1 ⎞⎤ ⎥ ⎛ ⎢ ⎢Pi − ⎜ x1 ⋅ γ 1 x1 . A12 . x2 . x2i ..337 ⎠ Ans. Given 0= ∑ i 2⎤ ⎡d ⎡ H1 ⎞⎤ ⎥ ⎛ ⎢ ⎢Pi − ⎜ x1 ⋅ γ 1 x1 . x2 . H1) ⎜H ⎝ 1⎠ ⎛ A12 ⎞ ⎛ 0. A21) := exp ⎡ ( x1) ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤ ⎤ ⎣ ⎣ ⎦⎦ Guesses: H1 := 50 A21 := 0.. x2i .178 ⎟ ⎜ ⎜ ⎜H ⎝ 1 ⎠ ⎝ 51. ⎥ i i i exp ( A12) ⎟⎥ ⎥ ⎢ dH1 ⎢ ⎜ ⎢ ⎢ ⎜ + x2i⋅ γ 2 x1i . ⎥ i i i exp ( A12) ⎟⎥ ⎥ ⎢ dA21 ⎢ ⎜ ⎢ ⎢ ⎜ + x2i⋅ γ 2 x1i . x2 ..348 ⎞ ⎜ ⎜ A21 ⎟ = ⎜ 0. A12 .

x2 ⋅ i i i i ( ) exp( A12) + x2i⋅ γ2 ( x1i . x2) := exp ⎡ x22⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ γ2 ( x1 ..2 0 Pi−Pcalc i (y1i−y1calci)⋅ 100 0. − ⎛ A21⋅ x1 .6 0 0. by least squares: i := 2 .8 Pressure residuals y1 residuals Fit GE/RT data to Margules eqn...4 0. x2i) ⋅ Psat2 H1 y1calc := i H1 x1 ⋅ γ1 x1 ..(d) γ1 ( x1 ..2 0. x2) := exp ⎡ x1 ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤ ⎤ ⎣ ⎣ ⎦⎦ 2 Pcalc := x1 ⋅ γ1 x1 . rows ( P) Given 0= y2 := 1 − y1 y1 ⋅ Pi ⎞ ⎡⎛ ⎛ i d ⎢ ⎜ x1 ⋅ ln⎜ H1 ⎟ dA12 ⎢ ⎜ i ⎜ ⎜ x1i⋅ exp ( A ) ⎢⎜ 12 ⎠ ⎝ ⎢⎜ y ⋅P ⎢ ⎜ + x ⋅ ln⎛ 2i i ⎞ ⎜ ⎢ ⎜ 2i ⎜ x2 ⋅ Psat2 ⎣⎝ ⎝ i ⎠ 543 ∑ i ⎤ .2 0.4 x1 i 0. ⎞ ⋅ x1 ⋅ x2 ⎥ i i i⎥ ⎟ ⎜ ⎟ ⎜ + A12⋅ x2i ⎠ ⎥ ⎝ ⎟ ⎥ ⎟ ⎥ ⎥ ⎦ ⎠ ⎞ 2 .6 0. x2 ⋅ i i i exp ( A 12) Pcalc i ( ) 0.

A21 . x2) := exp ⎡ x2 ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ γ2 ( x1 . x2 ⋅ Psat2 i i i i exp ( A 12) i i i ( ) ( ) y1calc := i H1 x1 ⋅ γ1 x1 ..078 ⎠ Ans. − ⎛ A21⋅ x1 ...375 ⎞ ⎜ ⎜ ⎜ A21 ⎟ = ⎜ 0.148 ⎟ ⎜ ⎜H ⎝ 1 ⎠ ⎝ 53... − ⎛ A21⋅ x1 . ⎞ ⋅ x1 ⋅ x2 ⎥ i i i⎥ ⎟ ⎜ ⎟ ⎜ + A12⋅ x2i ⎠ ⎥ ⎝ ⎟ ⎥ ⎟ ⎥ ⎥ ⎦ ⎠ ⎞ 2 ⎞ 2 0= ∑ i ⎤ . x2 ⋅ i i i exp ( A 12) Pcalc i ( ) 544 . γ1 ( x1 . x2) := exp ⎡ x1 ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤ ⎤ ⎣ ⎣ ⎦⎦ H1 Pcalc := x1 ⋅ γ1 x1 .0= ∑ i y1 ⋅ Pi ⎞ ⎡⎛ ⎛ i d ⎢ ⎜ x1 ⋅ ln⎜ H1 ⎟ dA21 ⎢ ⎜ i ⎜ ⎜ x1i⋅ exp ( A ) ⎢⎜ 12 ⎠ ⎝ ⎢⎜ y ⋅P ⎢ ⎜ + x ⋅ ln⎛ 2i i ⎞ ⎜ ⎢ ⎜ 2i ⎜ x2 ⋅ Psat2 ⎣⎝ ⎝ i ⎠ y1 ⋅ Pi ⎞ ⎛ i d ⎡⎛ ⎢ ⎜ x1 ⋅ ln ⎜ H1 ⎟ dH1 ⎢ ⎜ i ⎜ x1 ⋅ ⎜ i exp ( A ) ⎢⎜ 12 ⎠ ⎝ ⎢⎜ y2 ⋅ Pi ⎞ ⎢ ⎜ + x ⋅ ln ⎛ i ⎜ ⎢ ⎜ 2i ⎜ x2 ⋅ Psat2 ⎣⎝ ⎝ i ⎠ ⎤ . H1) ⎜H ⎝ 1⎠ 2 2 ⎛ A12 ⎞ ⎛ 0.... ⎞ ⋅ x1 ⋅ x2 ⎥ i i i⎥ ⎟ ⎜ ⎜ + A12⋅ x2i ⎟ ⎝ ⎥ ⎠ ⎟ ⎥ ⎟ ⎥ ⎥ ⎦ ⎠ ⎛ A12 ⎞ ⎜ ⎜ A21 ⎟ := Find ( A12 . x2 ⋅ + x2 ⋅ γ2 x1 .

9048 ⎜ ⎟ ⎜ 0.8 Pressure residuals y1 residuals 14.12 ⎟ ⎜ ⎟ 31.6815 ⎟ ⎜ 0.5 Pressures in kPa Data: ⎛ 0.6096 ⎟ x1 := ⎜ ⎜ 0.9102 ⎟ ⎜ ⎝ 1.96 ⎟ P := ⎜ ⎜ 30.4232 ⎟ ⎜ 0.6 0. 7 (a) It follows immediately from Eq..7934 ⎜ ⎟ ⎜ 0.10a) yields the required expression.9590 ⎟ ⎜ ⎝ 1.7440 ⎟ ⎜ ⎟ 0.4 x1 i 0. 545 .7135 ⎟ ⎜ ⎟ 0.5934 ⎞ ⎜ ⎜ 0.8639 ⎟ ⎜ ⎟ 0.5119 ⎟ ⎜ ⎟ 0. (12.75 ⎜ ⎟ ⎜ 34.000 ⎠ x2 := 1 − x1 ⎛ 21.10a) that: ∞ ln ⎛ γ 2 ⎞ = A21 ⎝ ⎠ Combining this with Eq.15 ⎟ ⎜ ⎝ 36.63 ⎞ ⎜ ⎜ 24.8 0 0.8050 ⎟ y1 := ⎜ ⎜ 0.4 0. (b) Henry's constant will be found as part of the solution to Part (c).09 ⎠ ⎛ 0.0 0.92 ⎟ ⎜ ⎟ 27.000 ⎠ Psat1 := P8 i := 1 .3193 ⎞ ⎜ ⎜ 0. (12.2 0.01 ⎟ ⎜ 25.2 Pi−Pcalc i (y1i−y1calci)⋅ 100 0.6 0.

x2) := exp ⎡ x22⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ γ2 ( x1 .148 A12 := 0. A21 ⋅ Psat1 . A12 . A12 . A21 ⋅ exp ( A21) ⎥ ⎥ ⎠⎦ ⎦ ⎣ ⎣ ⎝ ( ) ( ( ) ) 0= ∑ ⎢ dA21 ⎡Pi − ⎛x1 ⋅γ 1 ( x1 . A12 .87 ⎠ Ans. A12 .. Margules equation. ⎢ ⎜ ⎥ ⎢ 12 ⎢ H2 ⎟⎥ ⎥ ⎜ ⎢ ⎢ ⎜ + x2i⋅ γ 2 x1i ..279 ⎟ ⎜ ⎜ ⎜H ⎝ 2 ⎠ ⎝ 14. A12 . x2 . A21) := exp ⎡ ( x1) ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤ ⎤ ⎣ ⎣ ⎦⎦ Guesses: H2 := 14 A21 := 0. ⎢ ⎜ ⎢ i ⎡d ⎢ ⎣ ⎢ ⎢ ⎣ H2 ⎜ + x2 ⋅ γ 2 x1 . The most satisfactory procedure for reduction of this set of data is to find the value of Henry's constant by regression along with the Margules parameters. x2i . γ 1 ( x1 . x2 .. x2i .. A21 ⋅ ⎜ i i i exp ( A21) ⎝ i i i ⎞⎤ ⎥ ⎟⎥ ⎥ ⎠⎦ 2⎤ ⎥ ⎥ ⎥ ⎦ 0= ∑ i ⎡d 2⎤ ⎞⎤ ⎥ ⎢ dH ⎡Pi − ⎛ x1i⋅ γ 1 x1i . ⎢ ⎜ ⎥ ⎢ 2⎢ H2 ⎟⎥ ⎥ ⎜ + x2 ⋅ γ 2 x1 . A21 ⋅ Psat1 .375 Mininize the sums of the squared errors by setting sums of derivatives equal to zero. (d) γ1 ( x1 . A12 . A21) := exp ⎡ ( x2) ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ 2 2 γ 2 ( x1 . x2i . A12 . Given 0 = ∑ i ⎡d 2⎤ ⎞⎤ ⎥ ⎢ dA ⎡Pi − ⎛ x1i⋅ γ 1 x1i . A21 ⋅ ⎢ ⎥ ⎢ ⎜ i i i exp ( A21) ⎠⎥ ⎦ ⎣ ⎣ ⎝ ⎦ ( ) ( ) ⎛ A12 ⎞ ⎜ ⎜ A21 ⎟ := Find ( A12 .469 ⎞ ⎜ ⎜ A21 ⎟ = ⎜ 0. x2) := exp ⎡ x1 ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤ ⎤ ⎣ ⎣ ⎦⎦ 2 546 . x2 .(c) BARKER'S METHOD by non-linear least squares. A12 . x2 . H2) ⎜H ⎝ 2⎠ ⎛ A12 ⎞ ⎛ 0. A21 .. A21) ⋅ Psat1 . x2 ..

H2 Pcalc := x1 ⋅ γ1 x1 ... x2 ⋅ Psat1 + x2 ⋅ γ2 x1 .6 x1 i 0. 7 Given 0= y2 := 1 − y1 ∑ i ⎡⎛ ⎛ y1 ⋅ Pi ⎞ d ⎢ ⎜ x1 ⋅ ln⎜ i .2 0.4 0. 1 0 Pi−Pcalc i 1 2 3 4 (y1i−y1calci)⋅ 100 0. x2 ⋅ i i i i i i i exp ( A 21) x1 ⋅ γ1 x1 .. by least squares: i := 1 . dA12 ⎢ ⎜ i ⎜ x1i⋅ Psat1 ⎝ ⎠ ⎢⎜ y2 ⋅ Pi ⎞ ⎛ i ⎢ ⎜ + x ⋅ ln⎜ ⎢ ⎜ 2i ⎜ H2 ⎟ x2 ⋅ ⎢⎜ ⎜ i exp ( A ) 21 ⎠ ⎣⎝ ⎝ ⎞ ⎤ − ⎛ A21⋅ x1 . ⎞ ⋅ x1 ⋅ x2 ⎥ i i i⎥ ⎟ ⎜ ⎟ ⎜ + A12⋅ x2i ⎠ ⎥ ⎝ ⎟ ⎥ ⎟ ⎥ ⎥ ⎦ ⎠ 2 547 .8 Pressure residuals y1 residuals Fit GE/RT data to Margules eqn.. no doubt because the data do not extend close enough to x1 = 0. x2 ⋅ Psat1 i i i y1calc := i Pcalc i ( ) ( ) ( ) The plot of residuals below shows that the procedure used (Barker's method with regression for H2) is not in this case very satisfactory..

H2) ⎜H ⎝ 2⎠ 2 2 ⎛ A12 ⎞ ⎛ 0.. ⎞ ⋅ x1 ⋅ x2 ⎥ i i i⎥ ⎟ ⎜ ⎜ + A12⋅ x2i ⎟ ⎝ ⎥ ⎠ ⎟ ⎥ ⎟ ⎥ ⎥ ⎦ ⎠ 2 2 0= ∑ i ⎛ y1 ⋅ Pi ⎞ d ⎡⎛ ⎢ ⎜ x1 ⋅ ln ⎜ i .0= ∑ i ⎡⎛ ⎛ y1 ⋅ Pi ⎞ d ⎢ ⎜ x1 ⋅ ln⎜ i . A21 .. x2 ⋅ Psat1 + x2 ⋅ γ2 x1 . ⎞ ⋅ x1 ⋅ x2 ⎥ i i i⎥ ⎟ ⎜ ⎟ ⎜ + A12⋅ x2i ⎠ ⎥ ⎝ ⎟ ⎥ ⎟ ⎥ ⎥ ⎦ ⎠ ⎛ A12 ⎞ ⎜ ⎜ A21 ⎟ := Find ( A12 ... γ1 ( x1 .. dH2 ⎢ ⎜ i ⎜ x1i⋅ Psat1 ⎝ ⎠ ⎢⎜ y2 ⋅ Pi ⎞ ⎛ i ⎢ ⎜ + x ⋅ ln ⎜ ⎢ ⎜ 2i ⎜ H2 ⎟ x2 ⋅ ⎢⎜ ⎜ i exp ( A ) 21 ⎠ ⎣⎝ ⎝ ⎤ − ⎛ A21⋅ x1 . dA21 ⎢ ⎜ i ⎜ x1i⋅ Psat1 ⎝ ⎠ ⎢⎜ y2 ⋅ Pi ⎞ ⎛ i ⎢ ⎜ + x ⋅ ln⎜ ⎢ ⎜ 2i ⎜ H2 ⎟ ⎢⎜ ⎜ x2i⋅ exp ( A ) 21 ⎠ ⎣⎝ ⎝ ⎞ ⎞ ⎤ − ⎛ A21⋅ x1 . x2) := exp ⎡ x1 ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤ ⎤ ⎣ ⎣ ⎦⎦ H2 Pcalc := x1 ⋅ γ1 x1 . x2 ⋅ i i i i i i i exp ( A 21) y1calc := i ( ) ( ) x1 ⋅ γ1 x1 .204 ⎟ ⎜ ⎜ ⎜H ⎝ 2 ⎠ ⎝ 15.37 ⎞ ⎜ ⎜ A21 ⎟ = ⎜ 0. x2 ⋅ Psat1 i i i ( ) Pcalc i 548 .. x2) := exp ⎡ x2 ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ γ2 ( x1 ...065 ⎠ Ans.

3615 ⎟ ⎟ ⎜ ⎜ 0.6718 ⎠ ⎛ 0.5555 ⎟ ⎜ ⎝ 0.9 1 Pressure residuals y1 residuals This result is considerably improved over that obtained with Barker's method.3691 ⎟ y1 := ⎜ ⎟ 0.10a) yields the required expression 549 .89 ⎟ P := ⎜ ⎟ 21.8378 ⎟ ⎜ ⎝ 0.1794 ⎟ ⎜ 0.8 0.6184 ⎟ ⎟ ⎜ ⎜ 0.80 ⎟ ⎜ ⎝ 42.0 ⎞ ⎜ ⎜ 0.95 ⎟ ⎟ ⎜ ⎜ 29.5 0.3 0.6 0.2 i (y1i−y1calci)⋅ 100 0.51 ⎟ ⎜ 18.2626 ⎟ ⎜ ⎜ 0.37 ⎟ ⎜ ⎜ 24. (12.9137 ⎠ i := 2 .1757 ⎟ ⎜ ⎜ 0.4750 ⎟ ⎜ 0.7 0.3302 ⎟ ⎜ ⎜ 0..0932 ⎟ ⎜ 0. rows ( P) (a) x2 := 1 − x1 Psat2 := P1 It follows immediately from Eq.0 Pi−Pcalc 0.30 ⎟ ⎜ ⎜ 19.7552 ⎟ ⎜ 0.6 Pressures in kPa Data: ⎛ 15.6 x1 i 0.79 ⎞ ⎜ ⎜ 17.2000 ⎟ x1 := ⎜ ⎟ 0.0 ⎞ ⎜ ⎜ 0.82 ⎟ ⎜ 34.2383 ⎟ ⎟ ⎜ 0. (12.4 0.4628 ⎟ ⎜ ⎜ 0. 14.4 0.15 ⎟ ⎟ ⎜ 19.10a) that: ∞ ln ⎛ γ 1 ⎞ = A12 ⎝ ⎠ Combining this with Eq.1248 ⎟ ⎟ ⎜ 0.10 ⎠ ⎛ 0.

27 A12 := −0. x2 . x2 . The most satisfactory procedure for reduction of this set of data is to find the value of Henry's constant by regression along with the Margules parameters. A12 . A21) := exp ⎡ ( x1) ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤ ⎤ ⎣ ⎣ ⎦⎦ Guesses: H1 := 35 A21 := −1.187 ⎟ ⎜ ⎜ ⎜H ⎝ 1 ⎠ ⎝ 32. A12 . x2 .. A21 ⋅ Psat2 ⎥ ⎥ ⎠⎦ ⎦ ⎣ ⎣ ⎝ ( ( ) ) 0= ∑ i 2⎤ ⎡d ⎡ H1 ⎞⎤ ⎥ ⎛ ⎢ ⎢Pi − ⎜ x1 ⋅ γ 1 x1 . x2i . A21 ⋅ Psat2 ⎥ ⎥ ⎠⎦ ⎦ ⎣ ⎣ ⎝ ( ( ) ) ⎛ A12 ⎞ ⎜ ⎜ A21 ⎟ := Find ( A12 . x2 . A21 ⋅ Psat2 ⎥ ⎥ ⎠⎦ ⎦ ⎣ ⎣ ⎝ ( ( ) ) 0= ∑ i 2⎤ ⎡d ⎡ H1 ⎞⎤ ⎥ ⎛ ⎢ ⎢Pi − ⎜ x1 ⋅ γ 1 x1 . A12 .731 ⎞ ⎜ ⎜ A21 ⎟ = ⎜ −1. A12 . A21 ⋅ . A12 .70 Mininize the sums of the squared errors by setting sums of derivatives equal to zero... x2i . ⎥ i i i exp ( A12) ⎟⎥ ⎥ ⎢ dA12 ⎢ ⎜ ⎢ ⎢ ⎜ + x2i⋅ γ 2 x1i .(b) Henry's constant will be found as part of the solution to Part (c) (c) BARKER'S METHOD by non-linear least squares. A21 ⋅ . A21 ⋅ . A12 . Given 0= ∑ i 2⎤ ⎡d ⎡ H1 ⎞⎤ ⎥ ⎛ ⎢ ⎢Pi − ⎜ x1 ⋅ γ 1 x1 .. Margules equation. A12 . ⎥ i i exp ( A12) ⎟⎥ ⎥ ⎢ dA21 ⎢ ⎜ i ⎢ ⎢ ⎜ + x2i⋅ γ 2 x1i . A12 . x2 . x2i . H1) ⎜H ⎝ 1⎠ 550 ⎛ A12 ⎞ ⎛ −0.065 ⎠ Ans. ⎥ i i i exp ( A12) ⎟⎥ ⎥ ⎢ dH1 ⎢ ⎜ ⎢ ⎢ ⎜ + x2i⋅ γ 2 x1i . A21 . A21) := exp ⎡ ( x2) ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ 2 2 γ 2 ( x1 . γ 1 ( x1 .. ..

3 x1 i 0.1 0.2 0. ⎞ ⋅ x1 ⋅ x2 ⎥ i i i⎥ ⎟ ⎜ ⎜ + A12⋅ x2i ⎟ ⎝ ⎥ ⎠ ⎟ ⎥ ⎟ ⎥ ⎥ ⎦ ⎠ ⎞ 2 . x2) := exp ⎡ x1 ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤ ⎤ ⎣ ⎣ ⎦⎦ 2 Pcalc := x1 ⋅ γ1 x1 .7 Pressure residuals y1 residuals Fit GE/RT data to Margules eqn..5 0 Pi−Pcalc i 0. x2) := exp ⎡ x2 ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ 2 γ2 ( x1 . − ⎛ A21⋅ x1 .. x2 ⋅ i i i i ( ) exp( A12) + x2i⋅ γ2 ( x1i . by least squares: i := 2 ... x2i) ⋅ Psat2 H1 y1calc := i H1 x1 ⋅ γ1 x1 .5 2 (y1i−y1calci)⋅ 100 0 0. rows ( P) Given 0= y2 := 1 − y1 ∑ i y1 ⋅ Pi ⎞ ⎡⎛ ⎛ i d ⎢ ⎜ x1 ⋅ ln⎜ H1 ⎟ dA12 ⎢ ⎜ i ⎜ x1 ⋅ ⎜ i exp ( A ) ⎢⎜ 12 ⎠ ⎝ ⎢⎜ y2 ⋅ Pi ⎞ ⎢ ⎜ + x ⋅ ln⎛ i ⎜ ⎢ ⎜ 2i ⎜ x2 ⋅ Psat2 ⎣⎝ ⎝ i ⎠ 551 ⎤ .6 0.5 0..4 0. x2 ⋅ i i i exp ( A 12) Pcalc i ( ) 0.5 1 1.(d) γ1 ( x1 .

.0= ∑ i y1 ⋅ Pi ⎞ ⎡⎛ ⎛ i d ⎢ ⎜ x1 ⋅ ln⎜ H1 ⎟ dA21 ⎢ ⎜ i ⎜ x1 ⋅ ⎜ i exp ( A ) ⎢⎜ 12 ⎠ ⎝ ⎢⎜ y2 ⋅ Pi ⎞ ⎢ ⎜ + x ⋅ ln⎛ i ⎜ ⎢ ⎜ 2i ⎜ x2 ⋅ Psat2 ⎣⎝ ⎝ i ⎠ y1 ⋅ Pi ⎞ ⎛ i d ⎡⎛ ⎢ ⎜ x1 ⋅ ln ⎜ H1 ⎟ dH1 ⎢ ⎜ i ⎜ ⎜ x1i⋅ exp ( A ) ⎢⎜ 12 ⎠ ⎝ ⎢⎜ y ⋅P ⎢ ⎜ + x ⋅ ln ⎛ 2i i ⎞ ⎜ ⎢ ⎜ 2i ⎜ x2 ⋅ Psat2 ⎣⎝ ⎝ i ⎠ ⎤ . ⎞ ⋅ x1 ⋅ x2 ⎥ i i i⎥ ⎟ ⎜ ⎜ + A12⋅ x2i ⎟ ⎝ ⎥ ⎠ ⎟ ⎥ ⎟ ⎥ ⎥ ⎦ ⎠ ⎞ 2 ⎞ 2 0= ∑ i ⎤ .356 ⎠ Ans.. γ1 ( x1 . x2) := exp ⎡ x2 ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ γ2 ( x1 . A21 .... x2 ⋅ y1calc := i i i i ( ) ( ) ( ) exp( A12) H1 i Pcalc 552 . ⎞ ⋅ x1 ⋅ x2 ⎥ i i i⎥ ⎟ ⎜ ⎟ ⎜ + A12⋅ x2i ⎠ ⎥ ⎝ ⎟ ⎥ ⎟ ⎥ ⎥ ⎦ ⎠ ⎛ A12 ⎞ ⎜ ⎜ A21 ⎟ := Find ( A12 .707 ⎞ ⎜ ⎜ A21 ⎟ = ⎜ −1. x2 ⋅ + x2 ⋅ γ2 x1 .. − ⎛ A21⋅ x1 . H1) ⎜H ⎝ 1⎠ 2 2 ⎛ A12 ⎞ ⎛ −0.. x2 ⋅ Psat2 i i i i exp ( A 12) i i i x1 ⋅ γ1 x1 .192 ⎟ ⎜ ⎜ ⎜H ⎝ 1 ⎠ ⎝ 33. x2) := exp ⎡ x1 ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤ ⎤ ⎣ ⎣ ⎦⎦ H1 Pcalc := x1 ⋅ γ1 x1 . − ⎛ A21⋅ x1 ..

4750 ⎟ x1 := ⎜ ⎟ ⎜ 0.37 ⎟ ⎟ ⎜ ⎜ 24.10 ⎟ ⎟ ⎜ 60.10a) yields the required expression.2000 ⎟ ⎜ 0.5 0.0000 ⎠ Psat1 := P10 i := 1 .6184 ⎟ ⎜ 0.0000 ⎠ x2 := 1 − x1 ⎛ 19.5 2 2.7552 ⎟ y1 := ⎜ ⎟ ⎜ 0.6718 ⎟ ⎟ ⎜ 0. (b) Henry's constant will be found as part of the solution to Part (c).6 0.5 Pi−Pcalc i 1 1..4628 ⎟ ⎟ ⎜ ⎜ 0.3615 ⎟ ⎜ 0.38 ⎟ ⎜ ⎜ 65.2626 ⎟ ⎟ ⎜ ⎜ 0.3 x1 i 0.80 ⎟ ⎜ 42. (12. 553 .3302 ⎞ ⎜ ⎜ 0.95 ⎟ ⎜ 29.0 0.9398 ⎟ ⎜ ⎝ 1.82 ⎟ P := ⎜ ⎟ ⎜ 34.7 Pressures in kPa Data: ⎛ 0.1757 ⎞ ⎜ ⎜ 0.9860 ⎟ ⎜ ⎜ 0.30 ⎞ ⎜ ⎜ 19.36 ⎠ ⎛ 0.8780 ⎟ ⎜ ⎜ 0.7 Pressure residuals y1 residuals 14.8378 ⎟ ⎜ 0.4 0.1 0.3691 ⎟ ⎜ 0.2 0.9945 ⎟ ⎜ ⎝ 1.5555 ⎟ ⎜ 0. (12.89 ⎟ ⎜ 21.5 (y1i−y1calci)⋅ 100 0 0.9137 ⎟ ⎟ ⎜ 0.10a) that: ∞ ln ⎛ γ 2 ⎞ = A21 ⎝ ⎠ Combining this with Eq.39 ⎟ ⎜ ⎝ 69. 9 (a) It follows immediately from Eq.

A12 . Margules equation. ⎢ ⎜ ⎢ i ⎡d ⎢ ⎣ ⎢ ⎢ ⎣ H2 ⎜ + x2 ⋅ γ 2 x1 . x2 . 554 . A12 . x2i .969 ⎠ Ans. γ 1 ( x1 .(c) BARKER'S METHOD by non-linear least squares. A12 .367 ⎟ ⎜ ⎜ ⎜H ⎝ 2 ⎠ ⎝ 3. A21) := exp ⎡ ( x2) ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ 2 2 γ 2 ( x1 . ⎢ ⎜ ⎥ ⎢ 21 ⎢ H2 ⎟⎥ ⎥ ⎜ ⎢ ⎢ ⎜ + x2i⋅ γ 2 x1i . x2 . A21 ⋅ Psat1 . A12 ..37 A12 := −0. A21 ⋅ ⎜ i i i exp ( A21) ⎝ i i i ( ) ⎞⎤ ⎥ ⎟⎥ ⎥ ⎠⎦ 2⎤ ⎥ ⎥ ⎥ ⎦ ⎛ A12 ⎞ ⎜ ⎜ A21 ⎟ := Find ( A12 .68 Mininize the sums of the squared errors by setting sums of derivatives equal to zero. A21 ⋅ ⎜ i i i exp ( A21) ⎝ i i i ( ) ⎞⎤ ⎥ ⎟⎥ ⎥ ⎠⎦ 2⎤ ⎥ ⎥ ⎥ ⎦ 0= ∑ i ⎡d 2⎤ ⎞⎤ ⎥ ⎢ dA ⎡Pi − ⎛ x1i⋅ γ 1 x1i . H2) ⎜H ⎝ 2⎠ ⎛ A12 ⎞ ⎛ −0.. A12 ... A21 . x2 . The most satisfactory procedure for reduction of this set of data is to find the value of Henry's constant by regression along with the Margules parameters. x2 . A21) ⋅Psat1 . x2i . A21 ⋅ exp ( A21) ⎥ ⎥ ⎠⎦ ⎦ ⎣ ⎣ ⎝ ( ) ( ) 0= ∑ ⎢ dH2 ⎡Pi − ⎛x1 ⋅ γ 1 ( x1 . A12 . ⎢ ⎜ ⎢ i ⎡d ⎢ ⎣ ⎢ ⎢ ⎣ H2 ⎜ + x2 ⋅ γ 2 x1 . x2 . x2 . A12 .. A21) := exp ⎡ ( x1) ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤ ⎤ ⎣ ⎣ ⎦⎦ Guesses: H2 := 4 A21 := −1. A21) ⋅ Psat1 . A12 .. Given 0= ∑ ⎢ dA12 ⎡Pi − ⎛x1 ⋅γ 1 ( x1 .679 ⎞ ⎜ ⎜ A21 ⎟ = ⎜ −1.

.8 Pressure residuals y1 residuals Fit GE/RT data to Margules eqn.4 x1 i 0. by least squares: i := 1 .(d) γ1 ( x1 . 9 Given 0= y2 := 1 − y1 ∑ i ⎡⎛ ⎛ y1 ⋅ Pi ⎞ d ⎢ ⎜ x1 ⋅ ln⎜ i . x2 ⋅ i i i i i i i exp ( A 21) y1calc := i ( ) ( ) x1 ⋅ γ1 x1 .2 0. dA12 ⎢ ⎜ i ⎜ x1i⋅ Psat1 ⎝ ⎠ ⎢⎜ y2 ⋅ Pi ⎞ ⎛ i ⎢ ⎜ + x ⋅ ln⎜ ⎢ ⎜ 2i ⎜ H2 ⎟ x2 ⋅ ⎢⎜ ⎜ i exp ( A ) 21 ⎠ ⎣⎝ ⎝ ⎞ ⎤ − ⎛ A21⋅ x1 ..6 0.. ⎞ ⋅ x1 ⋅ x2 ⎥ i i i⎥ ⎟ ⎜ ⎟ ⎜ + A12⋅ x2i ⎠ ⎥ ⎝ ⎟ ⎥ ⎟ ⎥ ⎥ ⎦ ⎠ 2 555 .. x2) := exp ⎡ x22⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ γ2 ( x1 .. x2) := exp ⎡ x1 ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤ ⎤ ⎣ ⎣ ⎦⎦ 2 H2 Pcalc := x1 ⋅ γ1 x1 . x2 ⋅ Psat1 + x2 ⋅ γ2 x1 . x2 ⋅ Psat1 i i i ( ) Pcalc 1 i Pi−Pcalc 0 i (y1i−y1calci)⋅ 100 1 2 0 0.

. x2) := exp ⎡ x1 ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2 ⎤ ⎤ ⎣ ⎣ ⎦⎦ H2 Pcalc := x1 ⋅ γ1 x1 .229 ⎟ ⎜ ⎜H ⎝ 2 ⎠ ⎝ 4. ⎞ ⋅ x1 ⋅ x2 ⎥ i i i⎥ ⎟ ⎜ ⎜ + A12⋅ x2i ⎟ ⎝ ⎥ ⎠ ⎟ ⎥ ⎟ ⎥ ⎥ ⎦ ⎠ 2 2 0= ∑ i ⎛ A12 ⎞ ⎜ ⎜ A21 ⎟ := Find ( A12 .. A21 . x2 ⋅ Psat1 + x2 ⋅ γ2 x1 .....0= ∑ i ⎡⎛ ⎛ y1 ⋅ Pi ⎞ d ⎢ ⎜ x1 ⋅ ln⎜ i .703 ⎠ Ans.. ⎞ ⋅ x1 ⋅ x2 ⎥ i i i⎥ ⎟ ⎜ ⎟ ⎜ + A12⋅ x2i ⎠ ⎥ ⎝ ⎟ ⎥ ⎟ ⎥ ⎥ ⎦ ⎠ ⎞ ⎤ − ⎛ A21⋅ x1 . γ1 ( x1 . dH2 ⎢ ⎜ i ⎜ x1i⋅ Psat1 ⎝ ⎠ ⎢⎜ y2 ⋅ Pi ⎞ ⎛ i ⎢ ⎜ + x ⋅ ln ⎜ ⎢ ⎜ 2i ⎜ H2 ⎟ ⎢⎜ ⎜ x2i⋅ exp ( A ) 21 ⎠ ⎣⎝ ⎝ ⎞ ⎤ − ⎛ A21⋅ x1 . dA21 ⎢ ⎜ i ⎜ x1i⋅ Psat1 ⎝ ⎠ ⎢⎜ y2 ⋅ Pi ⎞ ⎛ i ⎢ ⎜ + x ⋅ ln⎜ ⎢ ⎜ 2i ⎜ H2 ⎟ x2 ⋅ ⎢⎜ ⎜ i exp ( A ) 21 ⎠ ⎣⎝ ⎝ ⎛ y1 ⋅ Pi ⎞ d ⎡⎛ ⎢ ⎜ x1 ⋅ ln ⎜ i .845 ⎞ ⎜ ⎜ ⎜ A21 ⎟ = ⎜ −1. x2) := exp ⎡ x2 ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1 ⎤ ⎤ ⎣ ⎣ ⎦⎦ γ2 ( x1 . x2 ⋅ i i i i i i i exp ( A 21) y1calc := i ( ) ( ) x1 ⋅ γ1 x1 . H2) ⎜H ⎝ 2⎠ 2 2 ⎛ A12 ⎞ ⎛ −0. x2 ⋅ Psat1 i i i ( ) Pcalc i 556 ..

0895 ⎞ ⎜ 0.61 ⎟ ⎜ ⎜ 21.7440 ⎟ γ 1 := ⎜ ⎜ 0.30kPa T := ( 50 + 273.75 ⎟ ⎜ ⎝ 34.4232 ⎟ ⎟ ⎜ 0.92 ⎟ kPa x1 := ⎜ 27.12 ⎟ ⎜ 31.9048 ⎟ ⎜ ⎝ 0.5119 ⎟ y1 := ⎜ ⎜ 0.105 ⎟ ⎜ ⎜ 1.8050 ⎟ ⎟ ⎜ ⎜ 0.8639 ⎟ ⎜ 0.6 0. (10.01 ⎟ ⎟ ⎜ P := ⎜ 25.5): γ 1 := i y1 ⋅ Pi i x1 ⋅ Psat1 i γ 2 := i y2 ⋅ Pi i x2 ⋅ Psat2 i 557 .2716 ⎞ ⎜ 0.6815 ⎟ ⎟ ⎜ 0.010 ⎟ ⎜ 1.078 ⎟ ⎟ ⎜ 1.63 ⎟ ⎜ 24.997 ⎠ i i ⎛ 1.114 ⎟ ⎜ 1..3193 ⎟ ⎜ 0.268 ⎠ i i := 1 .9102 ⎠ n=9 ⎛ 0.2 0.044 ⎟ γ 2 := ⎜ ⎜ 1. n x2 := 1 − x1 y2 := 1 − y1 Psat2 := 12.51 ⎞ ⎜ 18.1 ⎛ 15.7135 ⎟ ⎜ 0.163 ⎟ ⎜ 1.8 Pressure residuals y1 residuals 14.009 ⎞ ⎜ 1.15)K Data reduction with the Margules equation and Eq.026 ⎟ ⎜ ⎜ 1.189 ⎟ ⎜ ⎝ 1.003 ⎟ ⎜ ⎝ 0.15 ⎠ n := rows ( P) Psat1 := 36.4 x1 i 0.023 ⎟ ⎟ ⎜ ⎜ 1.304 ⎞ ⎜ 1.071 ⎟ ⎟ ⎜ 1.188 ⎟ ⎜ ⎜ 1.9590 ⎠ i ⎛ 1.8 (a) Data from Table 12.6096 ⎟ ⎟ ⎜ ⎜ 0.135 ⎟ ⎟ ⎜ ⎜ 1.1 Pi−Pcalc 0 i (y1i−y1calci)⋅ 100 1 2 0 0.050 ⎟ ⎜ 1.96 ⎟ ⎟ ⎜ ⎜ 30.1981 ⎟ ⎜ ⎜ 0.09kPa ⎛ 0.5934 ⎟ ⎜ 0.7934 ⎟ ⎜ ⎝ 0.4565 ⎟ ⎜ ⎜ 0.

. A12 .374 A21 = 0.1 GERT i ⎡ A21⋅ x1+A12⋅ ( 1−x1) ⎤ ⋅ x1⋅ ( 1−x1) ⎣ ⎦ 0.i := 1 . n GERTi := x1 ⋅ ln γ 1 + x2 ⋅ ln γ 2 i i i i A12 := 0.. (14. 0.8 x1 .6 0.3 ( ) ( ( ) ) Guess: f ( A12 .197 Ans.01 . A21) ⎜ A21 ⎠ ⎝ A12 = 0.4 i 0. 1 0.05 0 0 0. A21) := i=1 ∑ n 2 ⎡ GERTi − A21⋅ x1i + A12⋅ x2i ⋅ x1i⋅ x2i ⎤ ⎣ ⎦ ⎛ A12 ⎞ := Minimize ( f .1 A21 := 0.033 × 10 −3 i=1 ∑ n 2 ⎡ GERTi − A21⋅ x1i + A12⋅ x2i ⋅ x1i⋅ x2i ⎤ ⎣ ⎦ ( ) n x1 := 0 . x1 Data reduction with the Margules equation and Eq.1): cm B11 := −1840 mol 3 cm B22 := −1800 mol 3 cm B12 := −1150 mol 3 δ 12 := 2⋅ B12 − B11 − B22 ⎡ ⎡ B11⋅ ( Pi − Psat1) + Pi⋅ y2 2⋅ δ 12 ⎤ ⎤ ⎢ i ⎦⎥ Φ 1 := exp ⎢ ⎣ ⎥ i R⋅ T ⎣ ⎦ 558 ( ) γ 1 := i y1 ⋅ Φ 1 ⋅ Pi i i x1 ⋅ Psat1 i . RMS Error: RMS := RMS = 1.2 0.

⎡ ⎡ B22⋅ ( Pi − Psat2) + Pi⋅ y1 2⋅ δ 12 ⎤ ⎤ ⎢ i ⎦⎥ Φ 2 := exp ⎢ ⎣ ⎥ i R⋅ T ⎣ ⎦
i := 1 .. n GERTi := x1 ⋅ ln γ 1 + x2 ⋅ ln γ 2 i i i i A12 := 0.1 A21 := 0.3

( )

γ 2 :=
i

y2 ⋅ Φ 2 ⋅ Pi
i i

x2 ⋅ Psat2
i

( )
(

( )
)

Guess: f ( A12 , A21) :=

i=1

n

2 ⎡ GERTi − A21⋅ x1i + A12⋅ x2i ⋅ x1i⋅ x2i ⎤ ⎣ ⎦

⎛ A12 ⎞ := Minimize ( f , A12 , A21) ⎜ A21 ⎠ ⎝
n

A12 = 0.379

A21 = 0.216

Ans.

RMS Error:

RMS :=
−4

i=1

2 ⎡ GERTi − A21⋅ x1i + A12⋅ x2i ⋅ x1i⋅ x2i ⎤ ⎣ ⎦

(

)

n

RMS = 9.187 × 10

x1 := 0 , 0.01 .. 1
0.1

GERT i

⎡ A21⋅ x1+A12⋅ ( 1−x1) ⎤ ⋅ x1⋅ ( 1−x1) ⎣ ⎦

0.05

0

0

0.5 x1 , x1
i

1

The RMS error with Eqn. (14.1) is about 11% lower than the RMS error with Eqn. (10.5). Note: The following problem was solved with the temperature (T) set at the normal boiling point. To solve for another temperature, simply change T to the approriate value.
559

14.9

(a) Acetylene: T := Tn

Tc := 308.3K Tr := T Tc

Pc := 61.39bar Tr = 0.614

Tn := 189.4K

For Redlich/Kwong EOS: σ := 1 ε := 0
−1

Ω := 0.08664

Ψ := 0.42748 α ( Tr ) ⋅ R ⋅ Tc
2 2

Table 3.1

α ( Tr) := Tr q ( Tr) :=

2

Table 3.1

a ( Tr) := Ψ ⋅ β ( Tr , Pr) := Guess:

Eq. (3.45)

Pc Ω ⋅ Pr Tr zv := 0.9 zv − β ( Tr , Pr) Eq. (3.53)

Ψ ⋅ α ( Tr ) Ω ⋅ Tr

Eq. (3.54)

Define Z for the vapor (Zv) Given Eq. (3.52)

zv = 1 + β ( Tr , Pr) − q ( Tr) ⋅ β ( Tr , Pr) ⋅ Zv ( Tr , Pr) := Find ( zv) Define Z for the liquid (Zl) Given Eq. (3.56)

( zv + ε ⋅ β ( Tr , Pr) ) ⋅ ( zv + σ ⋅ β ( Tr , Pr) )
zl := 0.01

Guess:

zl = β ( Tr , Pr) + zl + ε ⋅ β ( Tr , Pr) ⋅ zl + σ ⋅ β ( Tr , Pr) ⋅ ⎜

(

)(

)

⎛ 1 + β ( Tr , Pr) − zl ⎞ ⎝ q ( T r ) ⋅ β ( T r , Pr ) ⎠

To find liquid root, restrict search for zl to values less than 0.2, zl < 0.2 Zl ( Tr , Pr) := Find ( zl) Define I for liquid (Il) and vapor (Iv) Il ( Tr , Pr) := 1 σ−ε 1 σ−ε ⋅ ln ⎜

⎛ Zl ( Tr , Pr) + σ ⋅ β ( Tr , Pr) ⎞ ⎝ Zl ( Tr , Pr) + ε ⋅ β ( Tr , Pr) ⎠ ⎛ Zv ( Tr , Pr) + σ ⋅ β ( Tr , Pr) ⎞ ⎝ Zv ( Tr , Pr) + ε ⋅ β ( Tr , Pr) ⎠
560

Iv ( Tr , Pr) :=

⋅ ln ⎜

Eq. (6.65b)

lnφl ( Tr , Pr) := Zl ( Tr , Pr) − 1 − ln Zl ( Tr , Pr) − β ( Tr , Pr) − q ( Tr) ⋅ Il ( Tr , Pr) Eq. (11.37) lnφv ( Tr , Pr) := Zv ( Tr , Pr) − 1 − ln Zv ( Tr , Pr) − β ( Tr , Pr) − q ( Tr) ⋅ Iv ( Tr , Pr) Guess Psat: Psatr := Given 1bar Pc

(

)

(

)

lnφl ( Tr , Psatr) = lnφv ( Tr , Psatr) Zl ( Tr , Psatr) = 4.742 × 10 Psat = 1.6 bar Ans.
−3

Psatr := Find ( Psatr) Zv ( Tr , Psatr) = 0.965

Psatr = 0.026 Psat := Psatr⋅ Pc

The following table lists answers for all parts. Literature values are interpolated from tables in Perry's Chemical Engineers' Handbook, 6th ed. The last column shows the percent difference between calculated and literature values at 0.85Tc. These range from 0.1 to 27%. For the normal boiling point (Tn), Psat should be 1.013 bar. Tabulated results for Psat do not agree well with this value. Differences range from 3 to > 100%.
Tn (K) Psat (bar) 0.85 Tc (K) Psat (bar) Psat (bar) % Difference @ Tn @ 0.85 Tc Lit. Values 189.4 1.60 262.1 20.27 19.78 2.5% Acetylene 87.3 0.68 128.3 20.23 18.70 8.2% Argon 353.2 1.60 477.9 16.028 15.52 3.2% Benzene 272.7 1.52 361.3 14.35 12.07 18.9% n-Butane 0.92 113.0 15.2 12.91 17.7% Carbon Monoxide 81.7 447.3 2.44 525.0 6.633 5.21 27.3% n-Decane 169.4 1.03 240.0 17.71 17.69 0.1% Ethylene 371.6 2.06 459.2 7.691 7.59 1.3% n-Heptane 111.4 0.71 162.0 19.39 17.33 11.9% Methane 77.3 0.86 107.3 14.67 12.57 16.7% Nitrogen

14.10 (a) Acetylene: ω := 0.187 T := Tn

Tc := 308.3K

Pc := 61.39bar

Tn := 189.4K Tr := T Tc

Note: For solution at 0.85T c, set T := 0.85Tc.

For SRK EOS: σ := 1 ε := 0 Ω := 0.08664
561

Tr = 0.614 Ψ := 0.42748 Table 3.1

1⎞ ⎤ ⎡ ⎛ ⎢ 2 ⎜ 2 ⎥ α ( Tr , ω ) := ⎣ 1 + ( 0.480 + 1.574ω − 0.176ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

2

Table 3.1

α Tr , ω ⋅ R ⋅ Tc a ( Tr) := Ψ ⋅ Pc q ( Tr) := Ψ ⋅ α Tr , ω Ω ⋅ Tr

(

)

2

2

Eq. (3.45) β ( Tr , Pr) := Ω ⋅ Pr Tr

(

)

Eq. (3.54)

Eq. (3.53)

Define Z for the vapor (Zv) Given Eq. (3.52)

Guess:

zv := 0.9 zv − β ( Tr , Pr)

zv = 1 + β ( Tr , Pr) − q ( Tr) ⋅ β ( Tr , Pr) ⋅ Zv ( Tr , Pr) := Find ( zv) Define Z for the liquid (Zl) Given Eq. (3.56)

( zv + ε ⋅ β ( Tr , Pr) ) ⋅ ( zv + σ ⋅ β ( Tr , Pr) )

Guess:

zl := 0.01

zl = β ( Tr , Pr) + zl + ε ⋅ β ( Tr , Pr) ⋅ zl + σ ⋅ β ( Tr , Pr) ⋅ ⎜

(

)(

)

⎛ 1 + β ( Tr , Pr) − zl ⎞ ⎝ q ( T r ) ⋅ β ( T r , Pr ) ⎠

To find liquid root, restrict search for zl to values less than 0.2, zl < 0.2 Zl ( Tr , Pr) := Find ( zl) Define I for liquid (Il) and vapor (Iv) Il ( Tr , Pr) := 1 σ−ε 1 σ−ε ⋅ ln ⎜

⎛ Zl ( Tr , Pr) + σ ⋅ β ( Tr , Pr) ⎞ ⎝ Zl ( Tr , Pr) + ε ⋅ β ( Tr , Pr) ⎠ ⎛ Zv ( Tr , Pr) + σ ⋅ β ( Tr , Pr) ⎞ ⎝ Zv ( Tr , Pr) + ε ⋅ β ( Tr , Pr) ⎠
Eq. (6.65b)

Iv ( Tr , Pr) :=

⋅ ln ⎜

562

lnφl ( Tr , Pr) := Zl ( Tr , Pr) − 1 − ln Zl ( Tr , Pr) − β ( Tr , Pr) − q ( Tr) ⋅ Il ( Tr , Pr) Eq. (11.37) lnφv ( Tr , Pr) := Zv ( Tr , Pr) − 1 − ln Zv ( Tr , Pr) − β ( Tr , Pr) − q ( Tr) ⋅ Iv ( Tr , Pr) Guess Psat: Psatr := Given 2bar Pc

(

)

(

)

lnφl ( Tr , Psatr) = lnφv ( Tr , Psatr) Zl ( Tr , Psatr) = 3.108 × 10 Psat = 1.073 bar Ans.
−3

Psatr := Find ( Psatr) Zv ( Tr , Psatr) = 0.975

Psatr = 0.017 Psat := Psatr⋅ Pc

The following table lists answers for all parts. Literature values are interpolated from tables in Perry's Chemical Engineers' Handbook, 6th ed. The last column shows the percent difference between calculated and literature values at 0.85Tc. These range from less than 0.1 to 2.5%. For the normal boiling point (Tn), Psat should be 1.013 bar. Tabulated results for Psat agree well with this value. Differences range from near 0 to 6%.
Tn (K) Psat (bar) 0.85 Tc (K) Psat (bar) Psat (bar) % Difference @ Tn @ 0.85 Tc Lit. Values 189.4 1.073 262.1 20.016 19.78 1.2% 87.3 0.976 128.3 18.79 18.70 0.5% 353.2 1.007 477.9 15.658 15.52 0.9% 272.7 1.008 361.3 12.239 12.07 1.4% 81.7 1.019 113.0 12.871 12.91 -0.3% 447.3 1.014 525.0 5.324 5.21 2.1% 169.4 1.004 240.0 17.918 17.69 1.3% 371.6 1.011 459.2 7.779 7.59 2.5% 111.4 0.959 162.0 17.46 17.33 0.8% 77.3 0.992 107.3 12.617 12.57 0.3%

Acetylene Argon Benzene n-Butane Carbon Monoxide n-Decane Ethylene n-Heptane Methane Nitrogen

14.10

(b) Acetylene: ω := 0.187 T := Tn

Tc := 308.3K

Pc := 61.39bar

Tn := 189.4K Tr := T Tc

Note: For solution at 0.85T c, set T := 0.85Tc.

For PR EOS: σ := 1 + 2 ε := 1 − 2 Ω := 0.07779
563

Tr = 0.614 Ψ := 0.45724 Table 3.1

1⎞ ⎤ ⎡ ⎛ ⎢ 2 ⎜ 2 ⎥ Table 3.1 α ( Tr , ω ) := ⎣ 1 + ( 0.37464 + 1.54226ω − 0.26992ω ) ⋅ ⎝ 1 − Tr ⎠ ⎦

2

a ( Tr) := Ψ ⋅ q ( Tr) :=

α Tr , ω ⋅ R ⋅ Tc Pc

(

)

2

2

Eq. (3.45) β ( Tr , Pr) := Ω ⋅ Pr Tr

Ψ ⋅ α Tr , ω Ω ⋅ Tr

(

)

Eq. (3.54)

Eq. (3.53)

Define Z for the vapor (Zv) Given Eq. (3.52)

Guess:

zv := 0.9 zv − β ( Tr , Pr)

zv = 1 + β ( Tr , Pr) − q ( Tr) ⋅ β ( Tr , Pr) ⋅ Zv ( Tr , Pr) := Find ( zv) Define Z for the liquid (Zl) Given Eq. (3.56)

( zv + ε ⋅ β ( Tr , Pr) ) ⋅ ( zv + σ ⋅ β ( Tr , Pr) )

Guess:

zl := 0.01

zl = β ( Tr , Pr) + zl + ε ⋅ β ( Tr , Pr) ⋅ zl + σ ⋅ β ( Tr , Pr) ⋅ ⎜

(

)(

)

⎛ 1 + β ( Tr , Pr) − zl ⎞ ⎝ q ( T r ) ⋅ β ( T r , Pr ) ⎠

To find liquid root, restrict search for zl to values less than 0.2,zl < 0.2 Zl ( Tr , Pr) := Find ( zl) Define I for liquid (Il) and vapor (Iv) Il ( Tr , Pr) := 1 σ−ε 1 σ−ε ⋅ ln ⎜

⎛ Zl ( Tr , Pr) + σ ⋅ β ( Tr , Pr) ⎞ ⎝ Zl ( Tr , Pr) + ε ⋅ β ( Tr , Pr) ⎠ ⎛ Zv ( Tr , Pr) + σ ⋅ β ( Tr , Pr) ⎞ ⎝ Zv ( Tr , Pr) + ε ⋅ β ( Tr , Pr) ⎠
Eq. (6.65b)

Iv ( Tr , Pr) :=

⋅ ln ⎜

564

lnφl ( Tr , Pr) := Zl ( Tr , Pr) − 1 − ln Zl ( Tr , Pr) − β ( Tr , Pr) − q ( Tr) ⋅ Il ( Tr , Pr) Eq. (11.37) lnφv ( Tr , Pr) := Zv ( Tr , Pr) − 1 − ln Zv ( Tr , Pr) − β ( Tr , Pr) − q ( Tr) ⋅ Iv ( Tr , Pr) Guess Psat: Given Psatr = 0.018 Psat := Psatr⋅ Pc Psatr := 2bar Pc

(

)

(

)

lnφl ( Tr , Psatr) = lnφv ( Tr , Psatr) Zl ( Tr , Psatr) = 2.795 × 10 Psat = 1.09 bar Ans.
−3

Psatr := Find ( Psatr) Zv ( Tr , Psatr) = 0.974

The following table lists answers for all parts. Literature values are interpolated from tables in Perry's Chemical Engineers' Handbook, 6th ed. The last column shows the percent difference between calculated and literature values at 0.85Tc. These range from less than 0.1 to 1.2%. For the normal boiling point (Tn), Psat should be 1.013 bar. Tabulated results for Psat agree well with this value. Differences range from near 0 to 7.6%.
Tn (K) Psat (bar) 0.85 Tc (K) Psat (bar) Psat (bar) % Difference @ Tn @ 0.85 Tc Lit. Values 189.4 1.090 262.1 19.768 19.78 -0.1% 87.3 1.015 128.3 18.676 18.70 -0.1% 353.2 1.019 477.9 15.457 15.52 -0.4% 272.7 1.016 361.3 12.084 12.07 0.1% 81.7 1.041 113.0 12.764 12.91 -1.2% 447.3 1.016 525.0 5.259 5.21 0.9% 169.4 1.028 240.0 17.744 17.69 0.3% 371.6 1.012 459.2 7.671 7.59 1.1% 111.4 0.994 162.0 17.342 17.33 0.1% 77.3 1.016 107.3 12.517 12.57 -0.4%

Acetylene Argon Benzene n-Butane Carbon Monoxide n-Decane Ethylene n-Heptane Methane Nitrogen

14.12

(a)

van der Waals Eqn. ε := 0 Ψ ⋅ α ( Tr) Ω ⋅ Tr Ω :=

Tr := 0.7 1 8 Ψ := Ω ⋅ Pr Tr 27 64 α ( Tr) := 1

σ := 0 q ( Tr) :=

β ( Tr , Pr) :=

zv := 0.9 (guess) zv − β ( Tr , Pr) ( zv)
2

Given

zv = 1 + β ( Tr , Pr) − q ( Tr) ⋅ β ( Tr , Pr) ⋅

Eq. (3.52)

565

Zv ( Tr , Pr) := Find ( zv) zl := .01 Given (guess) zl = β ( Tr , Pr) + ( zl) ⋅
2 1 + β ( Tr , Pr) − zl

q ( Tr) ⋅ β ( Tr , Pr)

Eq. (3.56)

zl < 0.2

Zl ( Tr , Pr) := Find ( zl) Iv ( Tr , Pr) := β ( Tr , Pr) Zv ( Tr , Pr) Il ( Tr , Pr) := β ( Tr , Pr) Zl ( Tr , Pr) Case II, pg. 218.

By Eq. (11.39): lnφv ( Tr , Pr) := Zv ( Tr , Pr) − 1 − ln ( Zv ( Tr , Pr) − β ( Tr , Pr) ) − q ( Tr) ⋅ Iv ( Tr , Pr) lnφl ( Tr , Pr) := Zl ( Tr , Pr) − 1 − ln ( Zl ( Tr , Pr) − β ( Tr , Pr) ) − q ( Tr) ⋅ Il ( Tr , Pr) Psatr := .1 Given lnφl ( Tr , Psatr) − lnφv ( Tr , Psatr) = 0 Zl ( Tr , Psatr) = 0.05 Psatr := Find ( Psatr) Psatr = 0.2

Zv ( Tr , Psatr) = 0.839 lnφl ( Tr , Psatr) = −0.148 ω := −1 − log ( Psatr) (b)

lnφv ( Tr , Psatr) = −0.148 β ( Tr , Psatr) = 0.036 ω = −0.302 Ans.

Redlich/Kwong Eqn.Tr := 0.7 ε := 0
− .5

σ := 1 α ( Tr) := Tr q ( Tr) :=

Ω := 0.08664

Ψ := 0.42748

Ψ ⋅ α ( Tr) Ω ⋅ Tr

β ( Tr , Pr) :=

Ω ⋅ Pr Tr

Guess:

zv := 0.9

Given zv = 1 + β ( Tr , Pr) − q ( Tr) ⋅ β ( Tr , Pr) ⋅ Zv ( Tr , Pr) := Find ( zv) Guess: zl := .01

zv⋅ ( zv + β ( Tr , Pr) )

zv − β ( Tr , Pr)

Eq. (3.52)

566

Given zl < 0.2

zl = β ( Tr , Pr) + zl⋅ ( zl + β ( Tr , Pr) ) ⋅ Zl ( Tr , Pr) := Find ( zl)

1 + β ( Tr , Pr) − zl q ( Tr) ⋅ β ( Tr , Pr)

Eq. (3.55)

Iv ( Tr , Pr) := ln ⎜

⎛ Zv ( Tr , Pr) + β ( Tr , Pr) ⎞ Il ( Tr , Pr) := ln⎛ Zl ( Tr , Pr) + β ( Tr , Pr) ⎞ ⎜ Zv ( Tr , Pr) Zl ( Tr , Pr) ⎝ ⎠ ⎝ ⎠

By Eq. (11.39): lnφv ( Tr , Pr) := Zv ( Tr , Pr) − 1 − ln ( Zv ( Tr , Pr) − β ( Tr , Pr) ) − q ( Tr) ⋅ Iv ( Tr , Pr) lnφl ( Tr , Pr) := Zl ( Tr , Pr) − 1 − ln ( Zl ( Tr , Pr) − β ( Tr , Pr) ) − q ( Tr) ⋅ Il ( Tr , Pr) Psatr := .1 Given lnφl ( Tr , Psatr) = lnφv ( Tr , Psatr) Zl ( Tr , Psatr) = 0.015 Psatr := Find ( Psatr) Psatr = 0.087 β ( Tr , Psatr) = 0.011

Zv ( Tr , Psatr) = 0.913

lnφv ( Tr , Psatr) = −0.083 lnφl ( Tr , Psatr) = −0.083 ω := −1 − log ( Psatr) ω = 0.058 Ans.

14.15 (a) x1α := 0.1 Guess:

x2α := 1 − x1α A12 := 2
2

x1β := 0.9 A21 := 2

x2β := 1 − x1β

γ1α ( A21 , A12) := exp ⎡ x2α ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1α ⎤ ⎤ ⎣ ⎣ ⎦⎦ γ1β( A21 , A12) := exp ⎡ x2β ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1β ⎤ ⎤ ⎣ ⎣ ⎦⎦
2

γ2α ( A21 , A12) := exp ⎡ x1α ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2α ⎤ ⎤ ⎣ ⎣ ⎦⎦
2

γ2β( A21 , A12) := exp ⎡ x1β ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2β ⎤ ⎤ ⎣ ⎣ ⎦⎦
2

567

Given

x1α⋅ γ1α ( A21 , A12) = x1β⋅ γ1β( A21 , A12) x2α⋅ γ2α ( A21 , A12) = x2β⋅ γ2β( A21 , A12)

⎛ A12 ⎞ := Find ( A12 , A21) ⎜ A21 ⎠ ⎝
(b) x1α := 0.2 Guess:

A21 = 2.747

A12 = 2.747

Ans.

x2α := 1 − x1α A12 := 2
2

x1β := 0.9 A21 := 2

x2β := 1 − x1β

γ1α ( A21 , A12) := exp ⎡ x2α ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1α ⎤ ⎤ ⎣ ⎣ ⎦⎦ γ1β( A21 , A12) := exp ⎡ x2β ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1β ⎤ ⎤ ⎣ ⎣ ⎦⎦
2

γ2α ( A21 , A12) := exp ⎡ x1α ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2α ⎤ ⎤ ⎣ ⎣ ⎦⎦
2

γ2β( A21 , A12) := exp ⎡ x1β ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2β ⎤ ⎤ ⎣ ⎣ ⎦⎦
2

Given

x1α⋅ γ1α ( A21 , A12) = x1β⋅ γ1β( A21 , A12) x2α⋅ γ2α ( A21 , A12) = x2β⋅ γ2β( A21 , A12)

⎛ A12 ⎞ := Find ( A12 , A21) ⎜ A21 ⎠ ⎝
(c) x1α := 0.1 Guess:

A12 = 2.148

A21 = 2.781

Ans.

x2α := 1 − x1α A12 := 2
2

x1β := 0.8 A21 := 2

x2β := 1 − x1β

γ1α ( A21 , A12) := exp ⎡ x2α ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1α ⎤ ⎤ ⎣ ⎣ ⎦⎦ γ1β( A21 , A12) := exp ⎡ x2β ⋅ ⎡ A12 + 2⋅ ( A21 − A12) ⋅ x1β ⎤ ⎤ ⎣ ⎣ ⎦⎦
2

γ2α ( A21 , A12) := exp ⎡ x1α ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2α ⎤ ⎤ ⎣ ⎣ ⎦⎦
2

γ2β( A21 , A12) := exp ⎡ x1β ⋅ ⎡ A21 + 2⋅ ( A12 − A21) ⋅ x2β ⎤ ⎤ ⎣ ⎣ ⎦⎦
2

568

Given

x1α⋅ γ1α ( A21 , A12) = x1β⋅ γ1β( A21 , A12) x2α⋅ γ2α ( A21 , A12) = x2β⋅ γ2β( A21 , A12)

⎛ A12 ⎞ := Find ( A12 , A21) ⎜ A21 ⎠ ⎝
14.16 (a) x1α := 0.1 Guess: Given

A12 = 2.781

A21 = 2.148

Ans.

x2α := 1 − x1α a12 := 2

x1β := 0.9 a21 := 2

x2β := 1 − x1β

− 2⎤ − 2⎤ ⎡ ⎡ ⎛ a12⋅ x1α ⎞ ⎥ ⎛ a12⋅ x1β ⎞ ⎥ ⎢ ⎢ exp a12⋅ ⎜ 1 + ⋅ x1α = exp a12⋅ ⎜ 1 + ⋅ x1β ⎢ ⎢ a21⋅ x2α ⎠ ⎥ a21⋅ x2β ⎠ ⎥ ⎣ ⎝ ⎦ ⎣ ⎝ ⎦ − 2⎤ − 2⎤ ⎡ ⎡ ⎛ a21⋅ x2α ⎞ ⎥ ⎛ a21⋅ x2β ⎞ ⎥ ⎢ ⎢ exp a21⋅ ⎜ 1 + ⋅ x2α = exp a21⋅ ⎜ 1 + ⋅ x2β ⎢ ⎢ a12⋅ x1α ⎠ ⎥ a12⋅ x1β ⎠ ⎥ ⎣ ⎝ ⎦ ⎣ ⎝ ⎦

⎛ a12 ⎞ := Find ( a12 , a21) ⎜ a21 ⎠ ⎝
(b) x1α := 0.2 Guess: Given

a12 = 2.747

a21 = 2.747

Ans.

x2α := 1 − x1α a12 := 2

x1β := 0.9 a21 := 2

x2β := 1 − x1β

− 2⎤ − 2⎤ ⎡ ⎡ ⎛ a12⋅ x1α ⎞ ⎥ ⎛ a12⋅ x1β ⎞ ⎥ ⎢ ⎢ exp a12⋅ ⎜ 1 + ⋅ x1α = exp a12⋅ ⎜ 1 + ⋅ x1β ⎢ ⎢ a21⋅ x2α ⎠ ⎥ a21⋅ x2β ⎠ ⎥ ⎣ ⎝ ⎦ ⎣ ⎝ ⎦ − 2⎤ − 2⎤ ⎡ ⎡ ⎛ a21⋅ x2α ⎞ ⎥ ⎛ a21⋅ x2β ⎞ ⎥ ⎢ ⎢ exp a21⋅ ⎜ 1 + ⋅ x2α = exp a21⋅ ⎜ 1 + ⋅ x2β ⎢ ⎢ a12⋅ x1α ⎠ ⎥ a12⋅ x1β ⎠ ⎥ ⎣ ⎝ ⎦ ⎣ ⎝ ⎦

⎛ a12 ⎞ := Find ( a12 , a21) ⎜ a21 ⎠ ⎝

a12 = 2.199

a21 = 2.81

Ans.

569

(c)

x1α := 0.1 Guess:

x2α := 1 − x1α a12 := 2

x1β := 0.8 a21 := 2

x2β := 1 − x1β

Given

− 2⎤ − 2⎤ ⎡ ⎡ ⎛ a12⋅ x1α ⎞ ⎥ ⎛ a12⋅ x1β ⎞ ⎥ ⎢ ⎢ exp a12⋅ ⎜ 1 + ⋅ x1α = exp a12⋅ ⎜ 1 + ⋅ x1β ⎢ ⎢ a21⋅ x2α ⎠ ⎥ a21⋅ x2β ⎠ ⎥ ⎣ ⎝ ⎦ ⎣ ⎝ ⎦ − 2⎤ − 2⎤ ⎡ ⎡ ⎛ a21⋅ x2α ⎞ ⎥ ⎛ a21⋅ x2β ⎞ ⎥ ⎢ ⎢ exp a21⋅ ⎜ 1 + ⋅ x2α = exp a21⋅ ⎜ 1 + ⋅ x2β ⎢ ⎢ a12⋅ x1α ⎠ ⎥ a12⋅ x1β ⎠ ⎥ ⎣ ⎝ ⎦ ⎣ ⎝ ⎦

⎛ a12 ⎞ := Find ( a12 , a21) ⎜ a21 ⎠ ⎝

a12 = 2.81

a21 = 2.199

Ans.

14.18

(a) a := 975 T := 250 .. 450
2.1

b := −18.4 A ( T) :=

c := −3

a + b − c⋅ ln ( T) T

A ( T)

2

1.9 250

300

350 T

400

450

Parameter A = 2 at two temperatures. The lower one is an UCST, because A decreases to 2 as T increases. The higher one is a LCST, because A decreases to 2 as T decreases. Guess: Given x≥0 x := 0.25 A ( T) ⋅ ( 1 − 2⋅ x) = ln ⎛ ⎜ x ≤ 0.5 1 − x⎞ ⎝ x ⎠ Eq. (E), Ex. 14.5 x2 ( T) := 1 − x1 ( T)

x1 ( T) := Find ( x)
570

UCST := 300 (guess) Given A ( UCST) = 2 UCST := Find ( UCST) UCST = 272.93

LCST := 400 (guess) Given A ( LCST) = 2 LCST := Find ( LCST) LCST = 391.21

Plot phase diagram as a function of T T1 := 225 , 225.1 .. UCST T2 := LCST .. 450

500

T1 T1 T2 T2

400

300

200 0.2

0.3

0.4

0.5

0.6

0.7

0.8

x1 ( T1 ) , x2 ( T1 ) , x1 ( T2 ) , x2 ( T2 )

(b) a := 540 T := 250 .. 450
2.5

b := −17.1 A ( T) :=

c := −3

a + b − c⋅ ln ( T) T

A ( T)

2

1.5 250

300

350 T

400

450

Parameter A = 2 at a single temperature. It is a LCST, because A decreases to 2 as T decreases.
571

Guess: Given x≥0

x := 0.25 A ( T) ⋅ ( 1 − 2⋅ x) = ln ⎛ ⎜ x ≤ 0.5 1 − x⎞ ⎝ x ⎠ Eq. (E), Ex. 14.5

x1 ( T) := Find ( x)

LCST := 350 (guess) Given A ( LCST) = 2 LCST := Find ( LCST) LCST = 346

Plot phase diagram as a function of T
450

T := LCST .. 450

T T

400

350

300 0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

x1 ( T ) , 1−x1 ( T)

(c)

a := 1500 T := 250 .. 450

b := −19.9 A ( T) :=

c := −3

a + b − c⋅ ln ( T) T

3 2.5 A ( T) 2 1.5 250

300

350 T

400

450

Parameter A = 2 at a single temperature. It is an UCST, because A decreases to 2 as T increases.
572

14.8⋅ ( 1 − x1β) ⎤ ⎣ ⎦ ⎣ ⎦ x1α 1 − x1α + x1β 1 − x1β = 1 (Material balance) ⎛ x1α ⎞ := Find ( x1α .4⋅ ( 1 − x1α) ⎤ = x1β⋅ exp ⎡ 0.6 0. 1−x1 ( T) 14.20 Guess: Given x1α := 0.5 x1β := 0. (E).Guess: x := 0.371 x1β = 0.4 0.5 1 − x⎞ ⎝ x ⎠ Eq.291 Ans.25 A ( T) ⋅ ( 1 − 2⋅ x) = ln ⎛ ⎜ x ≤ 0.74) for species 1: 2 2 x1α⋅ exp ⎡ 0.5 Write Eq.2 0. Ex.5 Given x≥0 x1 ( T) := Find ( x) UCST := 350 (guess) Given A ( UCST) = 2 UCST := Find ( UCST) UCST = 339. 573 . (14. x1β) ⎜ x1β ⎠ ⎝ x1α = 0. 250 T T 300 250 0 0.8 x1 ( T ) ..66 Plot phase diagram as a function of T 350 T := UCST .

21(a)].14.69 281. Tstar + 0. 594-5 of text): Guess: Given T := 300 P = P1sat ( T) + P2sat ( T) Tstar := Find ( T) Tstar = 281.7 ⎞ T ⎠ 2048. pressures in kPa. Tstar + 0.97 ⎞ T ⎠ water P := 1600 SF6 P2sat ( T) := exp ⎛ 14. T2 y1II ( T) := 1 − 281.71 P2sat ( T) P P1sat ( T) TI := Tstar . Tstar + 6 y1I ( T) := P Because of the very large difference in scales appropriate to regions I and II [Fig.6511 − ⎜ Find 3-phase equilibrium temperature and vapor-phase composition (pp. showing regions I and II separately. P1sat ( T) := exp ⎛ 19. the txy diagram is presented on the following page in two parts.1478 − ⎜ ⎝ ⎝ 5363.. 14. y1II ( TII) ⋅ 10 574 .68 0 100 200 300 6 400 500 6 600 700 y1II ( TII) ⋅ 10 .68 P1sat ( Tstar) 6 y1star⋅ 10 = 695 P Find saturation temperatures of pure species 2: y1star := Guess: Given T := 300 P2sat ( T) = P T2 := Find ( T) T2 = 281.22 Temperatures in kelvins. TII := Tstar .01 .0001 ..7 TII Tstar 281.

y1I ( TI) ⋅ 10 14.288 286 TI Tstar 284 282 280 650 700 750 800 850 6 900 950 6 1000 1050 y1I ( TI) ⋅ 10 .3 For z1 < y1*.625 ⎠ Toluene P := 101.70 ⎞ P2sat ( T) := exp ⎛ 16. y1 = 1 − P2sat ( Tdew) P For z1 > y1*.855 Ans. C.3872 − ⎜ T + 230.444 Tstar = 84.9320 − ⎜ 3056.33 Water ⎝ 3885. first liquid is pure species 2. 575 . pressures in kPa P1sat ( T) := exp ⎛ 13. first liquid is pure species 1.2 Given Guess: Tdew := Tstar Tdew := Find ( Tdew) Tdew = 93.170 ⎠ ⎝ Find the three-phase equilibrium T and y: Guess: Given y1star := T := 25 P = P1sat ( T) + P2sat ( T) P1sat ( Tstar) P Tstar := Find ( T) y1star = 0.24 Temperatures in deg. y1 := 0.96 ⎞ T + 217.

33 water ⎝ ⎝ P2sat ( T) := exp ⎛ 16.548 Tstar = 79..35 Given Guess: y1 ( Tdew) = y10 Define the path of vapor mole fraction above and below the dew point.9 .15 Since 0. y10 . pressures in kPa. first liquid is pure species 2. P1sat ( T) := exp ⎛ 13. C.y1 := 0. No vapor exists below Tstar.26 ⎞ T + 216. and the mole fraction of the last vapor is y1*.34 Find temperature of initial condensation at y1=0. 576 .494 Ans.35: y10 := 0. P1sat ( Tdew) P In both cases the bubblepoint temperature is T*.70 ⎞ T + 230. y1 ( T) := 1 − P2sat ( T) P Tdew := Tstar Tdew := Find ( Tdew) Tdew = 88.3872 − ⎜ Find the three-phase equilibrium T and y: Guess: Given y1star := T := 50 P = P1sat ( T) + P2sat ( T) P1sat ( Tstar) P Tstar := Find ( T) y1star = 0. Tstar Path of mole fraction heptane in residual vapor as temperature is decreased. y1 ( T) ) T := 100 .432 ⎠ 3885.35<y1*.25 Temperatures in deg.170 ⎠ n-heptane P := 101. 14.7 Given Guess: y1 = Tdew := Tstar Tdew := Find ( Tdew) Tdew = 98. y1path ( T) := if ( T > Tdew .8622 − ⎜ 2910. 99.

45 0. y1star) ⎜ ⎝ y1star ⎠ Pstar = 160. P1sat := 75 P2sat := 110 A := 2.3 0.776 x1β := 1 − x1α Find the conditions for VLLE: Guess: Pstar := P1sat y1star := 0.55 y1path ( T ) 14.26 Pressures in kPa.224 x1α := 0.1 P := 50 577 . Guess: x1 := 0.100 95 90 T 85 80 75 Tstar Tdew 0.1 A⋅ ( 1 − 2⋅ x1α) = ln ⎜ ⎛ 1 − x1α ⎞ ⎝ x1α ⎠ x1α := Find ( x1α) x1β = 0.5 0.5 Given Pstar = x1β⋅ γ1 ( x1β) ⋅ P1sat + ( 1 − x1α) ⋅ γ2 ( x1α) ⋅ P2sat y1star⋅ Pstar = x1α⋅ γ1 ( x1α) ⋅ P1sat ⎛ Pstar ⎞ := Find ( Pstar . vapor an ideal gas. Modified Raoult's law.25 2 γ1 ( x1) := exp ⎡ A⋅ ( 1 − x1) ⎤ ⎣ ⎦ γ2 ( x1) := exp A⋅ x1 ( 2 ) Find the solubility limits: Guess: Given x1α = 0.4 0.699 y1star = 0.35 0.405 Calculate VLE in two-phase region.

0.1 0.368 0.15 0.2 0.2 x1 = 0 0.2 PL ( x1) = 110 133.05 0.214 0. Define liquid equilibrium line: PL ( x1) := if ( P ( x1) < Pstar . P ( x1) . Pstar) Define pressures for liquid phases above Pstar: Pliq := Pstar . Pstar) Define vapor equilibrium line: PV ( x1) := if ( P ( x1) < Pstar .397 578 .658 155...314 0.Given P = x1⋅ γ1 ( x1) ⋅ P1sat + ( 1 − x1) ⋅ γ2 ( x1) ⋅ P2sat y1 ( x1) := x1⋅ γ1 ( x1) ⋅ P1sat P ( x1) P ( x1) := Find ( P) Plot the phase diagram.523 159. 0.05 . 1 200 175 PL ( x1) 150 PV ( x1) Pliq Pliq 125 100 75 50 0 0.6 0.01 .4 0.598 y1 ( x1) = 0 0. x1β x1 := 0 . 0. Pstar + 10 x1 := 0 . x1α . y1 ( x1) .8 1 Pstar x1 . P ( x1) ..66 147.

x1 := 1 .444 0.504 0.95 .8 x1 = 1 0.907 158.602 x3α = 0.631 0.506 y1 ( x1) = 1 0. 0.8622 − ⎜ z1 := 0.30 n-Heptane: P := 101.432 ⎠ z3 := 1 − z1 − z2 n-Pentane: P2sat ( T) := exp ⎛ 13.096 150.014 ⎠ 2910.706 579 x2α = 0.33 (a) Calculate dew point T and liquid composition assuming the hydrocarbon layer forms first: Tdew1 := 100 x2α := z2 x3α := 1 − x2α Guess: Given P = x2α⋅ P2sat ( Tdew1) + x3α⋅ P3sat ( Tdew1) z3⋅ P = x3α⋅ P3sat ( Tdew1) x2α + x3α = 1 ⎛ x2α ⎞ ⎜ ⎜ x3α ⎟ := Find ( x2α .88 ⎞ T + 232.224 x1β = 0.414 x1α = 0.7667 − ⎜ P3sat ( T) := exp ⎛ 13.85 0.8 PL ( x1) = 75 113. 0.9 0.170 ⎠ 2451.776 y1star = 0. Water: P1sat ( T) := exp ⎛ 16.556 137.294 .27 Temperatures in deg. Tdew1) ⎜ Tdew1 ⎠ ⎝ Tdew1 = 66. x3α .95 0.45 z2 := 0.70 ⎞ T + 230.. pressures in kPa.405 14. C.26 ⎞ T + 216.3872 − ⎜ ⎝ ⎝ ⎝ 3885.

545 x3α = 0.288 Tdew3 = 68. y2 .8554 Calculate the bubble point given the total molar composition of the two phases x2α := z2 z2 + z3 x3α := z3 z2 + z3 Tbubble := Tdew3 x2α = 0.Calculate dew point temperature assuming the water layer forms first: x1β := 1 Given Guess: Tdew2 := 100 Tdew2 := Find ( Tdew2) Tdew2 = 79.388 x2α = 0. y3 . x3α) ⎜ Tdew3 ⎟ ⎜ ⎜ x2α ⎟ ⎜ ⎝ x3α ⎠ y1 = 0.1446 y3 = 0. x2α .324 x3α = 0. Tdew3 .455 580 .437 (c) y2 = 0. the water layer forms first (b) Calculate the temperature at which the second layer forms: Guess: Tdew3 := 100 y1 := z1 Given x2α := z2 y2 := z2 x3α := 1 − x2α y3 := z3 x1β⋅ P1sat ( Tdew2) = z1⋅ P P = P1sat ( Tdew3) + x2α⋅ P2sat ( Tdew3) + x3α⋅ P3sat ( Tdew3) y1⋅ P = P1sat ( Tdew3) y2 z2 = y3 z3 y1 + y2 + y3 = 1 x2α + x3α = 1 y2⋅ P = x2α⋅ P2sat ( Tdew3) ⎛ y1 ⎞ ⎜ ⎜ y2 ⎟ ⎜ y3 ⎟ ⎟ := Find ( y1 .021 Since Tdew2 > Tdew1.

111 y2 = 0.014 ⎠ 2910. x3α .Given P = P1sat ( Tbubble) + x2α⋅ P2sat ( Tbubble) + x3α⋅ P3sat ( Tbubble) Tbubble := Find ( Tbubble) P1sat ( Tbubble) P x2α⋅ P2sat ( Tbubble) y2 := P x3α⋅ P3sat ( Tbubble) y3 := P y1 := Tbubble = 48.122 x3α = 0.70 ⎞ T + 230. C.432 ⎠ z3 := 1 − z1 − z2 ⎝ ⎝ ⎝ n-Pentane: P2sat ( T) := exp ⎛ 13.45 n-Heptane: P := 101.113 y1 = 0.314 .8622 − ⎜ z1 := 0. Water: P1sat ( T) := exp ⎛ 16. Tdew1) ⎜ Tdew1 ⎠ ⎝ Tdew1 = 65. pressures in kPa.33 (a) Guess: Given Calculate dew point T and liquid composition assuming the hydrocarbon layer forms first: Tdew1 := 70 x2α := z2 x3α := 1 − x2α P = x2α⋅ P2sat ( Tdew1) + x3α⋅ P3sat ( Tdew1) z3⋅ P = x3α⋅ P3sat ( Tdew1) x2α + x3α = 1 ⎛ x2α ⎞ ⎜ ⎜ x3α ⎟ := Find ( x2α .686 581 x2α = 0.078 14.28 Temperatures in deg.7667 − ⎜ P3sat ( T) := exp ⎛ 13.88 ⎞ T + 232.3872 − ⎜ 3885.26 ⎞ T + 216.170 ⎠ 2451.81 y3 = 0.32 z2 := 0.

y3 .854 Since Tdew1>Tdew2.662 582 x3α = 0.24 Tdew3 = 64.7901 Calculate the bubble point given the total molar composition of the two phases x2α := z2 z2 + z3 x3α := z3 z2 + z3 Tbubble := Tdew3 x2α = 0.2099 y3 = 0. y2 . a hydrocarbon layer forms first (b) Calculate the temperature at which the second layer forms: Guess: Tdew3 := 100 y1 := z1 Given x2α := z2 y2 := z2 x3α := 1 − x2α y3 := z3 x1β⋅ P1sat ( Tdew2) = z1⋅ P P = P1sat ( Tdew3) + x2α⋅ P2sat ( Tdew3) + x3α⋅ P3sat ( Tdew3) y1⋅ P = P1sat ( Tdew3) y2 z2 = y3 z3 y1 + y2 + y3 = 1 x2α + x3α = 1 y2⋅ P = x2α⋅ P2sat ( Tdew3) ⎛ y1 ⎞ ⎜ ⎜ y2 ⎟ ⎜ y3 ⎟ ⎟ := Find ( y1 . x2α .503 x2α = 0.298 (c) y2 = 0.338 . Tdew3 . x3α) ⎜ Tdew3 ⎟ ⎜ ⎜ x2α ⎟ ⎜ ⎝ x3α ⎠ y1 = 0.257 x3α = 0.Calculate dew point temperature assuming the water layer forms first: x1β := 1 Given Guess: Tdew2 := 70 Tdew2 := Find ( Tdew2) Tdew2 = 70.

42748 ⎯ → T Tr := Tc ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ → α := ⎡ 1 + 0.176⋅ ω ⋅ 1 − Tr ⎣ 2 ( )( 0.83 ⎠ P := 10bar .224 ⎠ Tc := ⎜ ⎛ 748. (14.4 ⎞ K ⎝ 304.09 y2 = 0.33) ⎛ 1.51 ⎞ bar ⎝ 73.31) a := Pc ⎯⎯⎯ → Ω ⋅ R⋅ Tc b := Pc ⎛ 6.. (14.939 y1 = 0.5 ) ⎤2 ⎦ Eq.861 y3 = 0. (14.049 Tbubble := Find ( Tbubble) P1sat ( Tbubble) P x2α⋅ P2sat ( Tbubble) y2 := P x3α⋅ P3sat ( Tbubble) y3 := P y1 := 14. (14. p.480 + 1.968 × 10− 5 mol ⎝ ⎠ q2 := a2 b2⋅ R⋅ T Eq.574⋅ ω − 0. 300bar T := 353.32) ⎯⎯⎯⎯⎯ → 2 2 Ψ ⋅ α ⋅ R ⋅ Tc Eq.32 ω := ⎜ ⎛ 0.34) (guess) 583 .842 ⎞ kg m5 a=⎜ ⎝ 0. 98 of text: σ := 1 ε := 0 Ω := 0.08664 Ψ := 0.331 × 10− 4 ⎞ m3 b=⎜ ⎜ 2.302 ⎞ ⎝ 0.325 ⎠ s2 mol2 β 2 ( P) := z2 := 1 b2⋅ P R⋅ T Eq.2 ⎠ Pc := ⎜ ⎛ 40.1. 20bar .Given P = P1sat ( Tbubble) + x2α⋅ P2sat ( Tbubble) + x3α⋅ P3sat ( Tbubble) Tbubble = 43.15K Use SRK EOS From Table 3.

with φsat1 = 1 and (P .5 ⎡ ⎢⎢ ⎥⎥ b1 ⎤ ⎛ a1 ⎞ + −q2⋅ ⎢2⋅ ( 1 − l12) ⋅ ⎜ − ⎥ ⋅ I2 ( P) ⎥ ⎥ ⎢⎢ b2 ⎦ ⎣⎣ ⎣ ⎝ a2 ⎠ ⎦⎦ V1 := 124.36) ⎛ Z 2 ( P) + β 2 ( P) ⎞ ⎝ Z 2 ( P) ⎠ Eq. (14.10 1 .088 ⎡ ⎡ ⎡ b1 ⎤ ⎤⎤ ⋅ ( Z2 ( P) − 1) − ln ( Z2 ( P) − β 2 ( P) )⎥ .Given z2 = 1 + β 2 ( P) − q2⋅ β 2 ( P) ⋅ Z2 ( P) := Find ( z2) I2 ( P) := ln ⎜ ( z2 − β 2 ( P) z2 + ε ⋅ β 2 ( P) ⋅ z2 + σ ⋅ β 2 ( P) )( ) Eq.103): φ 1 ( P) := exp ⎢ ⎢ ⎢ l12 := 0..01 y1 ( P) 1 .99).98) and (14.1 0. (14.0102bar mol Eqs. (6.5 cm 3 Psat1 := 0. Eq. combine to give: y1 ( P) := Psat1 P ⋅ φ 1 ( P) ⋅ exp ⎜ ⎛ P⋅ V 1 ⎞ ⎝ R⋅ T ⎠ 0. let φ1 represent the infinite-dilution value of the fugacity coefficient of species 1 in solution.10 3 4 0 50 100 150 P bar 200 250 300 584 . ⎥ ⎥ ⎦ ⎥⎥ ⎢ ⎢ ⎣ b2 0. (14.Psat1) = P.65b) For simplicity..

585 .067 ⎠ s2 mol2 β 2 ( P) := z2 := 1 Given z2 = 1 + β 2 ( P) − q2⋅ β 2 ( P) ⋅ Z2 ( P) := Find ( z2) I2 ( P) := ln ⎜ b2⋅ P R⋅ T Eq. (14. (14. (6.480 + 1.51 ⎞ bar ⎝ 34.33 ω := ⎜ ⎛ 0.1.4 ⎞ K ⎝ 126. (14.298 ⎞ kg m5 a=⎜ ⎝ 0.36) ⎛ Z 2 ( P) + β 2 ( P) ⎞ ⎝ Z 2 ( P) ⎠ Eq.34) (guess) ( z2 − β 2 ( P) z2 + ε ⋅ β 2 ( P) ⋅ z2 + σ ⋅ β 2 ( P) )( ) Eq.331 × 10− 4 ⎞ m3 b=⎜ ⎜ 2.674 × 10− 5 mol ⎝ ⎠ q2 := a2 b2⋅ R⋅ T Eq. (14.176⋅ ω ⋅ 1 − Tr ⎣ ⎦ ( )( ) 2 ⎯⎯⎯⎯⎯ → 2 2 Ψ ⋅ α ⋅ R ⋅ Tc a := Pc Eq. let φ1 represent the infinite-dilution value of the fugacity coefficient of species 1 in solution.00 ⎠ P := 10bar . 98 of text: σ := 1 ε := 0 Ω := 0.31) ⎯⎯⎯ → Ω ⋅ R⋅ Tc b := Pc Eq..14.2 ⎠ Pc := ⎜ ⎛ 40.574⋅ ω − 0.038 ⎠ Tc := ⎜ ⎛ 748.32) ⎛ 7.302 ⎞ ⎝ 0.42748 ⎯ → T Tr := Tc ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ → 2 0. 300bar T := 308.33) ⎛ 1.65b) For simplicity. p.5 ⎤ α := ⎡ 1 + 0. (14. 20bar .08664 Ψ := 0.15K (K) Use SRK EOS From Table 3.

5 ⎡ ⎢⎢ ⎥⎥ b1 ⎤ ⎛ a1 ⎞ + −q2⋅ ⎢2⋅ ( 1 − l12) ⋅ ⎜ − ⎥ ⋅ I2 ( P) ⎥ ⎥ ⎢⎢ b2 ⎦ ⎣⎣ ⎣ ⎝ a2 ⎠ ⎦⎦ −4 Psat1 := 2.. ⎥ ⎥ ⎦ ⎥⎥ ⎢ ⎢ ⎣ b2 0. (14. (14. 586 .103): φ 1 ( P) := exp ⎢ ⎢ ⎢ ⎡ ⎡ ⎡ b1 ⎤ ⎤⎤ ⋅ ( Z2 ( P) − 1) − ln ( Z2 ( P) − β 2 ( P) )⎥ . combine to give: y1 ( P) := Psat1 P ⋅ φ 1 ( P) ⋅ exp ⎜ ⎛ P⋅ V 1 ⎞ ⎝ R⋅ T ⎠ 10 y1 ( P) ⋅ 10 5 1 0 50 100 150 P bar 200 250 300 Note: y axis is log scale.9⋅ 10 bar V1 := 125 cm 3 mol Eqs.99).98) and (14. with φsat1 = 1 and (P ..Psat1) = P.l12 := 0.0 Eq.

14.01 S nS xS3 = 1.001 xF2 := 0.5 A23 := −0.99 xF2 = 0. nF := 1 mol s xF1 := 0. 585 A12 := 1.0 Feed Mixer/ Settler Solvent R nR xα1 xα2 = 0.8 2 γα 2 ( x2) := exp ⎡ A12⋅ ( 1 − x2) ⎤ ⎣ ⎦ 2 γβ 2 ( x2) := exp ⎡ A23⋅ ( 1 − x2) ⎤ ⎣ ⎦ Material Balances nS + nF = nE + nR nS = xβ3⋅ nE xF1⋅ nF = xα1⋅ nR (Total) (Species 3) (Species 1) Substituting the species balances into the total balance yields xF1 1 nS + nF = ⋅ nS + ⋅ nF xβ3 xα1 Solving for the ratio of solvent to feed (nS/nF) gives nS nF = ⎜ ⎛ xα1 − xF1 ⎞ ⎛ xβ3 ⎞ ⋅⎜ 1 − xβ3 ⎠ ⎝ xα1 ⎠ ⎝ 587 .45 A labeled diagram of the process is given below.001 E nE xβ2 xβ3 Define the values given in the problem statement. The feed stream is taken as the α phase and the solvent stream is taken as the β phase.01 xα1 := 1 − xα2 xS3 := 1 Apply mole balances around the process as well as an equilibrium relationship From p. F nF xF1 = 0. Assume as a basis a feed rate nF = 1 mol/s.99 xα2 := 0.

9902 From above.n-hexane 2 .00979 xβ3 := 1 − xβ2 xβ3 = 0. Ans. Here. "Bad chemistry" would be reflected in a positive GE23. 14. Eqns. Assume exiting streams are at equilibrium.5 ( ) ( ) xβ2 := Find xβ2 ( ) xβ2 = 0. xα1 := 520 10 6 xα2 := 1 − xα1 xβ2 := 2 10 6 xβ1 := 1 − xβ2 588 .4 on p. with values less than (essential) but perhaps near to GE12. a) nSnF = 0.We need xβ3. the equation for the ratio nS/nF is: nSnF := ⎜ ⎛ xα1 − xF1 ⎞ ⎛ xβ3 ⎞ ⋅⎜ 1 − xβ3 ⎠ ⎝ xα1 ⎠ ⎝ Ans. Then xα2⋅ γα 2 = xβ2⋅ γβ 2 Substituting for γα2 and γβ2 2 2 xα2⋅ exp ⎡ A12⋅ 1 − xα2 ⎤ = xβ2⋅ exp ⎡ A23⋅ 1 − xβ2 ⎤ ⎣ ⎦ ⎣ ⎦ ( ) ( ) Solve for xβ2 using Mathcad Solve Block Guess: Given 2 2 xα2⋅ exp ⎡ A12⋅ 1 − xα2 ⎤ = xβ2⋅ exp ⎡ A23⋅ 1 − xβ2 ⎤ ⎣ ⎦ ⎣ ⎦ xβ2 := 0.9112 b) xβ2 = 0. (C) and (D) from Example 14. 584 can be used to find γ1α and γ2β.water Since this is a dilute system in both phases. the only distributing species is 2.00979 c) "Good chemistry" here means that species 2 and 3 "like" each other.46 1 . as evidenced by the negative GE23.

5 Ans. i − δ j . 1 := −7993 T := 318.081 ⎞ ⎝ 1. 2 := −1247 cm mol B1 . (11. 2 y1 := 0.5) δ j .07287bar 2. 2 j := 1 .923 × 10 γβ 2 = 4. 2 mol B2 .997 × 10 3 Ans. 14.006 ⎠ term_C = ⎜ ⎛1 ⎞ ⎝1 ⎠ Ans.1813 y2 := 1 − y1 P := 0.108 ⎠ ⎛ 0..29871bar cm 3 V1 := 90 V2 := 92 3 cm 3 mol cm 3 mol cm 3 B1 . i := 2⋅ B j .20941bar k := 1 . term_Ai := Term B is calculated using Eqns..γα 1 := γβ 2 := xβ1 xα1 1 − xα1 1 − xβ1 γα 1 = 1.44) fsati := φsati⋅ Psati term_A = ⎜ ⎡ ⎡Vi⋅ ( P − Psati)⎤ ⎤ ⎦ fi := φsati⋅ Psati⋅ exp ⎢ ⎣ ⎥ R⋅ T ⎣ ⎦ term_B = ⎜ 589 term_Ci := fsati fi ⎛ 1. (14. 1 := B1 .benzene Psat2 := 0..4) and (14. .986 ⎞ ⎝ 1. 2 yi⋅ P xi⋅ Psati Term A is calculated using the given data.butanenitrile Psat1 := 0. k)⎤ ⎥ ⎤ ⎥ ⎥ ⎢ ⎥⎥ j ⎤⎤ ⎣ k ⎦⎦⎦⎦ ⎛ Bi . j − Bi . i φhati := exp ⎡ ⎢ P ⎡ 1 ⋅ ⎢ Bi . i⋅ Psati ⎞ ⎝ R⋅ T ⎠ term_Bi := φhati φsati Term C is calculated using Eqn.4819 x2 := 1 − x1 mol B2 .50 1 . i + ⋅ ⎡ 2 ⎢ ⎢ R⋅ T ⎢ ⎣ φsati := exp ⎜ ⎣ ⎣ ⎣ ⎦⎤⎥ ∑ ⎡ ∑ ⎡y j⋅yk⋅( 2 δ j . 2 := −2089 x1 := 0.15K i := 1 . i − B j .

7 1 1 A ( T) − 2 + ⋅ 2 2 A ( T) xl := 0.51 a) Equivalent to d2(∆G/RT)/dx12 = 0.5. From Fig.14. the equations for the spinodal curves are: xspr1 ( T) := xr := 0.15: A ( T) := From above. Create functions to represent the left and right halves of the curves. x1 = 1/3 (consolute point) A>2: Two real roots. Substituting for x2: x1-x12 = 1/(2A) or x12-x1+1/(2A) = 0. x1 > 0 and x1 <1 b) Plot the spinodal curve along with the solubility curve −540K T⎞ + 21. -2A = -1/x1x2 or 2Ax1x2 = 1. use d2(GE/RT)/dx12 = -1/x1x2 For GE/RT = Ax1x2 = A(x1-x12) d(GE/RT)/dx1 = A(1-2x1) d2(GE/RT)/dx12 = -2A Thus. 1+ The solution to this equation yields two roots: x1 = 1− and The two roots are symmetrical around x1 = 1/2 Note that for: A<2: No real roots A = 2: One root.3 xspl1 ( T) := 1 1 A ( T) − 2 − ⋅ 2 2 A ( T) x1 = 1− 2 1− 2 2 A 2 A From Eq. (E) in Example 14. the solubility curves are solved using a Solve Block: 590 .1 − 3 ln ⎛ ⎜ T ⎝K⎠ Both curves are symmetrical around x1 = 1/2. 14.

5 0.0572 Psat1 ( T) := exp ⎢ A1 − Tc1 := 556.23 Pc1 := 45.4K B1 := 2914. The solutions for the other systems follow in the same manner.1 0.7 0..54 The solution is presented for one of the systems given.Carbon tetrachloride ω 1 := 0.4 0.15⎞ + C ⎥ ⎜ 1 ⎝K ⎠ ⎦ B1 591 .5 xr1 ( T) := Find ( xr) Given 1 − xl ⎞ ⎝ xl ⎠ xl < 0. T := 300K Given A ( T) = 2 Tu := Find ( T) Tu = 345.Given A ( T) ⋅ ( 1 − 2xr) = ln ⎛ ⎜ A ( T) ⋅ ( 1 − 2xl) = ln ⎛ ⎜ 1 − xr ⎞ ⎝ xr ⎠ xr > 0.5 xl1 ( T) := Find ( xl) Find the temperature of the upper consolute point.60bar C1 := 232.998 K T := 250K .2 xl1 xr1 xspl1 xpr1 0.193 A1 := 14.148 ⎡ ⎢ ⎣ ⎤ ⎥ kPa ⎛ T − 273.6 0.3 0. f) 1. 346K 360 340 320 300 280 260 240 0.8 14.

2 .15)K Tr1 := Tr2 := T Tc1 T Tc2 Tr1 = 0.2K B2 := 2910. ⎦ ⎢ ⎣ Λ 12 Λ 21 ⎤ ⎡ ⎢+ 1 − x ⋅ ( 1) ⎢ x + 1 − x ⋅ Λ − 1 − x + x ⋅ Λ ⎥ ⎢ ( 1) 1 21 ⎦ 1) 12 ⎣ ⎣ 1 ( γ 2 ( x1) := exp ⎡ −ln ⎡( 1 − x1) + x1⋅ Λ 21⎤ ..8622 Psat2 ( T) := exp ⎢ A2 − Tc2 := 540. x 1. Define the pressure and vapor mole fraction y1 as functions of the liquid mole fraction.039 Using Wilson's equation Λ 12 := 1.n-heptane ω 2 := 0.691 Psat1r := Psat2r := Psat1 ( T) Pc1 Psat2 ( T) Pc2 Psat1r = 0.5) 592 .. ⎦ ⎢ ⎣ Λ 12 Λ 21 ⎤ ⎡ ⎢ + −x ⋅ ( 1) ⎢ x + 1 − x ⋅ Λ − 1 − x + x ⋅ Λ ⎥ ⎢ ( 1) 1 21 ⎦ 1) 12 ⎣ ⎣ 1 ( ⎤ ⎥ ⎥ ⎥ ⎦ ⎤ ⎥ ⎥ ⎥ ⎦ For part i. use the modified Raoult's Law.26 Pc2 := 27.043 Psat2r = 0.. Pi ( x1) := x1⋅ γ 1 ( x1) ⋅ Psat1 ( T) + ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2 ( T) yi1 ( x1) := x1⋅ γ 1 ( x1) ⋅ Psat1 ( T) Pi ( x1) Modified Raoult's Law: Eqn.5410 Λ 21 := 0.5197 γ 1 ( x1) := exp ⎡ −ln ⎡ x1 + ( 1 − x1) ⋅ Λ 12 ⎤ .350 A2 := 13. (10.432 ⎡ ⎢ ⎣ ⎤ ⎥ kPa ⎛ T − 273.40bar C2 := 216.671 Tr2 = 0.15⎞ + C ⎥ ⎜ 2 ⎝K ⎠ ⎦ B2 T := ( 100 + 273..

φsat1 := PHIB Tr1 .1) for y1 and P given x1. . Psat2r .5 P := 1bar ( 1 − y1) ⋅ φ2 (P)⋅ P = ( 1 − x1) ⋅ γ 2 ( x1) ⋅ Psat2 (T) fii ( x1) := Find ( P . ω 2 φsat2 = 0. Psat1r . ω1 ⎜ P ⎝ c1 φsat2 := PHIB Tr2 . Guess: Given y1⋅ φ 1 ( P) ⋅ P = x1⋅ γ 1 ( x1) ⋅ Psat1 ( T) Eqn. y1 as functions of the liquid mole fraction. y1) fii is a vector containing the values of P and y 1..95 φ 2 ( P) := φhat2 ( P) φsat2 P ⎞ φhat2 ( P) := PHIB ⎛ Tr2 . Pii ( x1) := fii ( x1) 0 yii1 ( x1) := fii ( x1) 1 Plot the results in Mathcad x1 := 0 .68) and the PHIB function to calculate φhat and φsat. (11. ω2 ⎜ P ⎝ c2 ⎠ Solve Eqn.0 593 . (14.946 φ 1 ( P) := φhat1 ( P) φsat1 P ⎞ φhat1 ( P) := PHIB ⎛ Tr1 . Use Eqn.1 . ω 1 ( ( ) ) ⎠ φsat1 = 0. 1. Extract the pressure. assume the vapor phase is an ideal solution. (14.1) y1 := 0. .For part ii. 0. P and vapor mole fraction.

8 Pi ( x1 ) bar Pi ( x1 ) bar Pii ( x1 ) bar Pii ( x1 ) bar 1.6 0.6 1.2 1. x1 .4 1. yi1 ( x1 ) .2 1.4 0.9 1.5 1.2 P-x Raoult's P-y Raoult's P-x Gamma/Phi P-y Gamma/Phi x1 .7 0 0.3 1.8 594 . yii1 ( x1 ) 0.1 1 1.

05 BTU lbm S1 0. liquid at 70 degF. Data for Points A.1 Initial state: Liquid water at 70 degF. Point D: Mix of sat. 595 . H2 T (a) ( 0.3 491. & sat. Data for Point B from Fig. vapor at 32 degF.Section A . liq.2. G.3) BTU lbm S2 0. P = 85.0 143.3) Final state: Ice at 32 degF.Chapter 15 .02 ( 70 143.1. & D from Table 9. Point C: sat. Point B: Superheated vapor at 85.67 BTU lbm rankine 459.79(psia). H1 38.79(psia) and the entropy of Point A. C.Mathcad Solutions 15. vapor at 32 degF with the enthalpy of Point C.0745 BTU lbm rankine (Table F.67)rankine Point A: sat.

& minimum temp.79(psia) and S = 0. TC 491. by interpolation in the table: HA 107.2223: HB 114 BTU lbm 596 . with heat rejection to the surroundings at 70 degF.889 Ans.018 Wdot t mdot Work Wdot t 14.Wideal H2 H1 T S2 S1 Wideal 12.58 BTU lbm HD HC For superheated vapor at 85. For sat.79 kW Ans.37 BTU lbm Work QC TC 14. infinite flow rate of cooling water. heat equal to the enthalpy change of the water is extracted from a cold reservoir at 32 degF.60 BTU lbm SA 0.67 rankine TH TH TC T QC H2 Work H1 QC BTU lbm 181. Wdotideal Wdot 0.2223 BTU lbm rankine For sat. The only irreversibility is the transfer of heat from the water as it cools from 70 to 32 degF to the cold reservoir of the Carnot heat pump at 70 degF. difference for heat transfer = 0.466 BTU lbm mdot 1 lbm sec Wdotideal mdot Wideal Wdotideal 13.15 kW Ans. (b) For the Carnot heat pump. (c) Conventional refrigeration cycle under ideal conditions of operation: Isentropic compression. liquid and vapor at 32 degF. liquid at 70 degF: HC 34.

and sat.0433 Svap 0. Point C: Sat.75(psia). at pinch. liquid and vapor at 24 degF: Hliq 19. HA mdot HB Wdotideal HD HA Wdot t Wdot t 16. vapor at 24 degF with H of point C. (Note that minimum temp. (d) Practical cycle. See sketch. where there are finite temperature differences.48 BTU lbm BTU lbm rankine HA Hvap Sliq 0. diff. diff. 0. Ans. Point D: Mix of sat.75 Point A: Sat. liq.58 BTU lbm BTU lbm rankine Hvap 106. Point B: Superheated vapor at 134.2229 SA Svap 597 .77 kW 0.Refrigerent circulation rate: H2 mdot H1 1 lbm sec mdot 2.) For sat.784 Wdot The irreversibilities are in the throttling process and in heat transfer in both the condenser and evaporator. vapor at 24 degF. Liquid at 98 degF. is not at end of condenser.484 lbm sec Ans. but it is not practical to base design on 8-degF temp.

279 ( 70 Ans. P=134. G.228 Hliq Hliq xD 0.24 BTU lbm SC 0.2229 at P=134.75(psia).284 SD Sliq SD BTU lbm rankine Refrigerent circulation rate: lbm sec mdot 2.0902 BTU lbm rankine For isentropic compression. the entropy of Point B is 0.compressor Qdotcondenser mdot T SB HB SC 598 mdot HC mdot T Wdotlost. H'B 118 BTU lbm BTU lbm BTU lbm rankine xD Svap Sliq HB HA H'B HA HB 121.75(psia): HC 44.2 at P=134.75(psia) HD HC xD HD Hvap 0. G. From Fig.For sat.2. H2 mdot H1 1 HA mdot HB Wdotideal HD HA Wdot Wdot 47.094 SB 0.67)rankine THERMODYNAMIC ANALYSIS Wdotlost. 459.condenser SB Qdotcondenser . liquid at 98 degF.84 The entropy at this H is read from Fig.914 lbm sec Ans.22 kW t Wdot T SA t 0.

throttle Wdotlost. to which the quantities sum.condenser Wdotlost.968 kW The percent values above express each quantity as a percentage of the actual work.4 H298 S298 282984 J H298 G298 G298 S298 257190 J J K 298.305 kW 14.compressor Wdotlost.52% Wdotideal Wdotlost.513 BASIS: 1 mol CO and 1/2 mol O2 entering with accompanying N2=(1/2)(79/21)=1.2 Assume ideal gases.85% 17.evaporator T mdot SA SD lbm S 2 S1 1 sec 27. 15.02% 14.621 kW 4.152 kW 8. Data from Table C.59% 30.881 mol nCO 1 mol nair 2.381 mol nCO2 1 mol nN2 1.881 mol 599 .evaporator 13.Wdotlost.throttle mdot T SD SC Wdotlost.02% 10.178 kW 6.15 K 86.

223 J K Ans. the overall enthalpy change for the process is H y1 H298 nN2 nair For unmixing the air.35) with no minus sign: Sunmixing Sunmixing nair R y1 ln y1 10. define y1 0.15 K: Since the enthalpy change of mixing for ideal gases is zero.(a) Isothermal process at 298. (12. define y1 nCO2 nN2 nCO2 nCO2 y1 0.465 J K Smixing nN2 R y1 ln y1 Smixing S T Sunmixing 300 K S298 Wideal Smixing H 600 S S Wideal 81.174 J K y2 ln y2 For mixing the products of reaction.347 y2 y2 ln y2 1 y1 15.79 y2 1 y1 By Eq. T 259 kJ .

1: A nCO2 5.082 10 5 For the products.040 10 5 D 1.15 K The integral is given by Eq.280 A 3 11.7).160 10 K 2 3 . HP = R T0 CP R dT T0 298. by an energy balance.16 10 nN2 0.796 1 B 2 T0 2 T 601 1 T D T0 1 T0 2622.082 10 K 5 2 H298 = R mol A T0 Find 8.045 mol D nCO2 1. D 1.627 B 2.457 mol B nCO2 1. (4. Moreover.627 3 nN2 0.593 10 B 2.157 mol T nN2 3.(b) Adiabatic combustion: Heat-capacity data for the product gases from Table C. H298 Guess Given HP = 0 2 A 11.603 K .

0 1.7 kJ kg S1 6.83 10 J 5 S R mol ICPS H T S S Wideal.2244 kJ kg K For the sat.082 10 5 = 29.cooling S Q T S 246.701 246.160 10 ICPS H H t 3 0.934 J K 29. Wideal.6 298. 15. Table F. steam at 275 kPa. the entropy change is calculated by ICPS 2622. Ans. Table F.15 K.8078 The surroundings increase in entropy in the amount: Q H298 Wideal.15 11.cooling Wideal 0.0201 602 kJ kg K . Ans.cooling t 208904 J Ans.For the cooling process from this temperature to the final temperature of 298.2: H1 2801.2: H2 2720. steam at 2700 kPa.93 J K The irreversibility is in the combustion reaction.7 kJ kg S2 7.cooling Wideal.701 H298 2.3 For the sat.627 2.

Then by Eqs.5828 (a) Assume no heat losses. a quantity requirement.For sat.2 6. no shaft work.2: Hliq Hvap 762.03K 2776. and relation between H3 and S3 which assumes wet steam at point 3. Table F.1 H1 2 kg s mdot2 S3 mdot1 Sliq mdot3 H3 Hliq mdot1 mdot2 H2 Tsat H1 mdot1 S1 mdot1 H2 mdot2 = 0 S2 mdot2 = 0 H3 kJ s kJ sK Hliq mdot3 = 300 kJ s mdot3 = mdot1 S3 = Sliq mdot1 mdot2 mdot3 H3 S3 mdot2 Hliq H3 Tsat Find mdot1 mdot2 mdot3 H3 S3 603 . (2. The five equations (in 5 unknowns) are as follows: Guesses: mdot1 H3 Given H3 mdot3 S3 mdot3 0.1382 kJ kg K kJ kg K Tsat 453. and negligible changes in kinetic and potential energy.6 kJ kg kJ kg Sliq Svap 2. liquid and vapor at 1000 kPa.30) and (5.22) for a completely reversible process: H fs ( mdot)= 0 S fs ( mdot)= 0 We can also write a material balance.

94 Hliq Hliq Sturb Sturb Sliq 6. Interpolation in Table F.2 yields H'comp 2993.919 0.614 H1 2. 0.mdot1 H3 0.316 xturb Svap kJ kg K Sliq Compressor: Constant-S compression of steam from Point 2 to 1000 kPa results in superheated steam.15 kg s 2.4 kJ kg By interpolation: Scomp 7.655 x'turb Hvap 10 3 kJ Hliq kg H1 turb H'turb 10 3 kJ kg xturb xturb Hturb Hvap 0.064 kg s mdot3 Ans.767 10 kg 6.75 Hcomp H2 H'comp comp H2 Hcomp kJ kg K 3084. (b) Turbine: Constant-S expansion of steam from Point 1 to 1000 kPa results in wet steam of quality x'turb x'turb turb S1 Svap 0.1803 604 .086 kg s 3 kJ mdot2 S3 0.5 kJ kg comp 0.563 kJ kg K Steam at Point 3 is indeed wet.78 Sliq Sliq H'turb H'turb Hturb Hturb Hliq 2.

In addition.25).04274 kg s Ans.77844 3 kJ 10 kg Steam at Point 3 is slightly superheated. The work output of the turbine equals the work input of the compressor.14882 2.5876 kJ kg K 300K (assumed) THERMODYNAMIC ANALYSIS T By Eq.064 s s mdot3 Given Hcomp H3 mdot3 0. mass balance. and quantity requirement equations of Part (a) are still valid. with the enthalpy term equal to zero: Wdotideal T mdot3 S3 mdot1 S1 605 mdot2 S2 . S3 6. By interpolation. Thus we have 4 equations (in 4 unknowns): kg kg Guesses: mdot1 0.10608 mdot2 H3 0.086 mdot2 0. 0. kJ kg H2 mdot2 = H1 mdot1 mdot2 Hturb H1 mdot1 kJ s Hliq mdot3 = 300 kJ s H2 mdot2 = 0 H3 mdot3 = mdot1 mdot1 mdot2 mdot3 H3 kg s kg s Find mdot1 mdot2 mdot3 H3 mdot1 mdot3 0. (5.15 kg s H3 2770.The energy balance.

285 Svap H1 S1 S1 606 H4 Sliq 0.comp T mdot2 Scomp Wdotlost.22525 Sliq 0.015 BTU lbm Svap 0.2815% 34.1 are given in Example 9.1.9034 kW 2. 9.turb Wdotlost.mixing Wdotlost.mixing T mdot3 S3 mdot1 Sturb mdot2 Scomp 2. to which the quantities sum.Wdotideal Wdotlost. G. 15.07892 BTU lbm rankine H2 x1 x1 Hvap H1 Hvap 0.2.02744 BTU lbm rankine For sat. For sat. liquid at the condenser outlet temperature of 80 degF: H4 37.5620% The percent values above express each quantity as a percentage of the absolute value of the ideal work.1565% 17.054 kW 1. Others come from Table 9.014 kW T mdot1 Sturb S1 S2 Wdotlost.4 Some property values with reference to Fig.0561 kW 48.1 or Fig.090 BTU lbm BTU lbm rankine Hvap 103.084 x1 Svap BTU lbm rankine Sliq .978 BTU lbm S2 Hliq Hliq S4 0.turb 6.comp Wdotlost. liquid and vapor at the evaporator temperature of 0 degF: Hliq 12.

it is heat transfer to the SURROUNDINGS.225 hr The purpose of the condenser is to transfer heat to the surroundings.533 10 hr T mdot S3 H3 mdot T mdot S4 T mdot S1 1..5 BTU lbm From Fig.e.1 Wdot mdot H Wdot 3.67)rankine 120000 BTU hr TH TC TH TC T ( 10 459.2 at H3 and P = 101.231 BTU lbm rankine lbm hr 10 4 BTU mdot 1845.throttle S3 S4 607 Qdot .37(psia): S3 0. The ideal work of the process is that of a Carnot engine operating between the temperature of the refrigerated space and the temperature of the surroundings.1(b) for the compression step: H 17. T QdotC ( 70 459. Thus the heat transferred in the condenser is Q in the sense of Chapter 15. The heat transferred in the evaporator comes from a space maintained at 10 degF.67)rankine 4 BTU Wdotideal Wdotlost. G. which is part of the system.cond Wdotlost. Internal heat transfer (within the system) is not Q.523 10 5 BTU hr Wdotlost.48 BTU lbm H3 H2 H H3 120. i.From Example 9. taken here to be at a temperature of 70 degF.comp Qdot H4 QdotC TC Wdotideal S2 Qdot 1. and is treated as an internal heat reservoir.

evap 15329.2 14.comp Wdotlost.T mdot S2 S1 H1 H2 mdot T TC The final term accounts for the entropy change of the refrigerated space (an internal heat reservoir).6 9.67) rankine TH T The following vectors refer to Parts (a)-(e): 40 30 tC 20 10 0 608 600 500 QdotC 400 300 200 BTU sec .42% 3625.53% 5619.cond Wdotlost.5 The discussion at the top of the second page of the solution to the preceding problem applies equally here.4 BTU hr BTU hr BTU hr BTU hr 17.14% The percent values above express each quantity as a percentage of the actual work. T ( 70 459.2 11.67% 2947.3 BTU hr 15.throttle Wdotlost. In each case. to which they sum: Wdot 32252.evap Wdotlost.24% 4730. Wdotideal Wdotlost.9 BTU hr 47.

9: 609 .187 12.22325 0.22244 0.02073 BTU Svap lbm rankine BTU lbm 107.015 101.026 0. liquid and vapor at the evaporator temperature.471 103.22418 0. The flow rates come from Problem 9.TC tC 459.9.04065 Sliq 0.4 BTU lbm From these values we must find the corresponding entropies from Fig.9 H3 120.03408 0.1 121.7 123. They are read at the vapor pressure for 80 degF of 101.486 18.320 105.22525 0. 9. we find: 117.2.090 9.7 118.07892 BTU lbm rankine H1 H4 x1 H1 Hvap Hliq Hliq S1 Sliq x1 Svap Sliq From the results of Pb.67 rankine Wdotideal QdotC TH TC TC For sat.907 Hvap 104.978 BTU lbm S4 0.02744 0.1: 21.22647 BTU lbm rankine S2 Svap For sat.318 Hliq 15. Table 9.04715 0. liquid at the condenser temperature: H4 37.37 kPa. G.542 BTU lbm H2 Hvap 0.

229 S3 0.457 610 .234 0.cond Wdotlost.379 17.695 sec 38.evap T mdot S4 T mdot S1 T mdot S2 T H1 H2 TC The final term accounts for the entropy change of the refrigerated space (an internal heat reservoir).0.419 Wdotlost.016 4.227 0.613 3.361 mdot 6. Wdot mdot H3 36.732 21.844 H2 20.547 BTU sec Wdotideal BTU 41.comp 21.231 0.9 22.146 T mdot S3 H4 H3 mdot S3 S4 S1 mdot Qdot lbm sec Wdotlost.237 BTU lbm rankine 8.throttle Wdotlost.325 30.comp Qdot S2 Wdotlost.024 40.653 7.

991 11.375 BTU sec For sat.589 Wdotlost.04065 BTU lbm rankine BTU lbm rankine Hvap H2 105. 15.194 68.cond 9.818 95. and each term may be expressed as a percentage of the actual work.4 applies equally here.322 BTU sec 89.318 BTU lbm BTU lbm Sliq 0.149 10.1: Hliq 18. liquid and vapor at the evaporator temperature.throttle 11.evap 9.754 10.826 10.024 86.406 7.268 Wdotlost.22325 Svap 611 .67)rankine 459.907 Hvap Svap S2 0.744 11.6 The discussion at the top of the second page of the solution to Problem 15.52 Wdotlost.322 12.11.369 5.444 7.67)rankine TH TC TH QdotC T 2000 BTU sec Wdotideal QdotC TC Wdotideal 163. Table 9.641 Wdot 94.122 BTU sec BTU sec 8.765 BTU sec In each case the ideal work and the lost work terms sum to give the actual work. T TC ( 70 ( 30 459.292 5.

07892 BTU lbm rankine From Problem 9.885 BTU lbm Sliq Sliq 0.12.2435 BTU lbm rankine H3 H2A 14.05986 BTU lbm rankine lbm sec From Problem 9.11(psia): S3 0.For sat.67 BTU lbm From Fig.12: mdot 25. G.109 H2A Hliq Hliq H2 H1 S1 S1 27.2 at this enthalpy and 33.061 x1 Svap BTU lbm rankine Upstream from the throttle (Point 4A) the state is subcooled liquid with the enthalpy: H4A H1 The entropy at this point is essentially that of sat. by interpolation in Table 9.2475 BTU lbm rankine Energy balance on heat exchanger: H1 x1 x1 H4 H1 Hvap 0.634 612 .667 H3 130. liquid at the condenser temperature: H4 37. liquid with this enthalpy.1: S4A 0. BTU lbm BTU lbm S2A 0. H2A 116.978 BTU lbm S4 0.

45% 54.evap Wdotlost. to which the terms sum.31 BTU sec BTU sec 14.07 11.38 BTU sec S2 S4A S4 43.16% 9.16 4.97 The figures on the right are percentages of the actual work. Wdotlost.Wdotlost.comp Wdotlost.exchanger BTU sec T mdot S2A H2A 163.99% 16.throttle Wdotlost.exchanger Wdot mdot H3 Wdotideal Wdotlost.cond Wdotlost. 613 .comp Qdot H4 T mdot S3 H3 mdot T mdot S4 T mdot S1 S2A Wdotlost.throttle S3 S4A Qdot Wdotlost.30% Wdot 375.65% 45.evap T mdot S2 S1 H1 H2 T mdot TC The final term accounts for the entropy change of the refrigerated space (an internal heat reservoir).08 23.45% 87.cond Wdotlost.98 BTU sec BTU sec BTU sec 2.

3554 (sat.4 kJ kg 614 . liquid) 2676.15.75 419.3 kJ kg comp By more double interpolation in Table F.7 Compression to a pressure at which condensation in coils occurs at 110 degC. pressure as 143.4048 kJ kg K By an energy balance.2: H'3 2737. we find by double interpolation in Table F.1 gives this sat.1 kJ kg kJ kg H1 H2 S1 S2 1.0 7.27 kPa. Table F. assuming the slurry passes through unchanged. H4 H1 H3 H2 H4 500.2 at 143.27 kPa comp 0. S3 7.27 kPa.0 kJ kg H3 H2 H'3 H2 H3 2757.3069 kJ kg K kJ kg K (sat. vapor) For isentropic compression to 143.

667 kW The figures on the right are percentages of the actual work.evap Wdotlost.22% 40.41 kW 21.comp Wdot 8. the heat source may be considered a heat reservoir at some higher temperature.This enthalpy is a bit larger than that of sat. find quality and then the entropy: Hliq Slv 461.018 kg sec S4 T Sliq x4 Slv S4 1.0 H4 kJ kg Sliq x4 1.4185 kJ kg K 5. to which the terms sum.comp Wdot mdot H3 Wdotideal Wdotlost.606 kW 24.evap mdot H4 mdot T mdot T H2 H1 S4 S3 T S3 S2 S4 S2 S1 S1 Wdotlost.651 kW 7.5206 kJ kg K mdot 0. Since steam leaves the boiler at 900 degF.5 300 K Wdotideal Wdotlost. and in this case we must therefore specify the source of the heat transferred to the boiler. 615 . 15. The assumption of a different temperature would provide a variation in the solution.62% 18.16% 60. liquid at 110 degC.8203 Hliq Hlv 0. We assume in the following that this temperature is 950 degF.8 A thermodynamic analysis requires an exact definition of the overall process considered.3 kJ kg kJ kg K Hlv x4 2230.

4112 BTU lbm rankine H1 1 lbm QH 1 TC TH For purposes of thermodynamic analysis.8.boiler. The amount of heat is Q 1 lbm H5 1 lbm m H4 m H7 Q 829.7.The ideal work of the process in this case is given by a Carnot engine operating between this temperature and that of the surroundings. 8. here specified to be 80 degF.8 69.2 1047.6671 1. we consider the following 4 parts of the process: The boiler/heat reservoir combination The turbine The condenser and throttle valve The pump and feedwater heater Wlost.reservoir m 0. 8.8) Wlost.6 1461.67 80)rankine T TC Subscripts below correspond to points on figure of Pb.turbine T m S3 S2 1 lbm m S4 S2 The purpose of the condenser is to transfer heat to the surroundings.7 250.3970 1. H1 H2 H3 H4 H5 H7 QH H2 257.7431 1. Required property values come from Pb.8748 0. TH ( 459.67 950)rankine TC ( 459.2 BTU lbm S1 S2 S3 S4 S5 S7 Wideal 0.045 BTU 616 . We take as a basis 1 lbm of H2O passing through the boiler. 8.18688 lbm T S2 S1 1 lbm QH TH (From Pb.2 1242.1326 0.

reservoir Wlost.value = 374.43% 30.8: Wabs.0 kJ kg kJ kg S4 S5 S7 S9 S10 9.36 BTU (absolute value) The numbers on the right are percentages of the absolute value of the ideal work.13% 224. 9.heater T 1 lbm S1 S5 m S7 S3 The absolute value of the actual work comes from Pb.359 kJ kg K kJ kg K kJ kg K kJ kg K kJ kg K 1009.521 617 .boiler.30% 4.90% 1.3 plus additional values from the reference cited on page 331 at conditions given in Ex.7.82 BTU 50.44 BTU 8.cond.61 BTU Wlost.heater Wideal 742. page 330 The analysis presented here is for the liquefaction section to the right of the dashed line.928 796.24% 13.pump.8 kJ kg kJ kg kJ kg 7.Wlost.544 285. 9.9 Refer to Figure 9.81 BTU 36.3.9 9. Enthalpy and entropy values are those given in Ex. 8. 15.valve T 1 lbm S5 1 lbm m S4 m S7 Q Wlost.turbine Wlost.66 BTU 98.894 719.valve Wlost. Property values: H4 H5 H7 H9 H10 1140.4 4. to which they sum.cond.pump.7 8.

1 kJ kg S14 11. (5.001 z) H9 z kJ kg H4 T S15 ( 1 z) S9 z S4 Wout H12 H11 x Wout kJ kg (a) Heat Exchanger I: SG.26) for Ideal Work.a Wlost.113 x ( m) H fs 0. Eq.9 kJ kg S15 11. (5.33) for Entropy Generation. 9.and Eq.a SG.015 kJ kg K H15 1188.b T SG. (5.044 kJ kg K S5 S4 S15 S14 ( 1 z) kJ kg Wlost. All work quantities are in kJ.a 0.021 (b) Heat Exchanger II: SG.313 kJ kg K S7 S6 ( 1 x) Wlost.b S14 S13 ( 1 kJ kg z) Wlost.H14 1042. Results given in Ex.589 kJ kg K H6 H5 S6 S5 H11 H5 S11 S5 H12 H10 S12 S10 H13 H10 S13 S10 T 295K The basis for all calculations is 1 kg of methane entering at point 4.25 T ( m) SG = S fs Wideal = Q Wlost = T SG T ______________________________________________________________ ( m) S fs Wideal Wideal H15 ( 1 489.3 on this basis are: Fraction of entering methane that is liquefied: Fraction of entering methane passing through the expander: On this basis also Eq.b 92.a T SG.b 0.34) for Lost Work can be written: z 0.a 13.b SG.24 618 .

c 46.88% Wout Wlost.00% Work analysis.157 kJ kg K Wlost.d 284.14% 489.d S10 ( 1 T SG.c 0.20 13.313 21.22% 100. Eq.24 18.d z x) S7 ( 1 Wlost.964 1.02 2.d x) 284.18% S_Gc 0.(c) Expander: SG.62% S_Gd 0.98% S_Gb 0.964 SG.00% 619 .a 53.46% Wlost.30 58.d kJ kg K S9 z Wlost.157 10.044 2.c T SG. (15.66% Wlost.c S12 S11 x SG.c Wlost.3): kJ/kg Percent of 10.00 Note that: = Wideal 100.478 65.241 kJ kg (d) Throttle: SG.86% Wlost.b 92.d 0.304 kJ kg Entropy-generation analysis: kJ/kg-K Percent of S_Ga 0.c 46.24 9.

023 10 mol 23 1 P 1bar T 298.626 10 34 Js (Boltzmann's constant) 23 J k 1.05 J mol K 131.68 620 . NIST value: 169.025 m 3 mol 39.08 J mol K Ans.15K V RT P V 0.381 10 K (Avagodro's number) NA 6.800 b) For Krypton: M gm mol NIST value: 154. NIST value: 164.84 J mol K J mol K Ans.948 a) For Argon: gm mol M NA 3 2 Sig R ln 2 MkT h 2 Ve NA 5 2 Sig 154. 83.10(Planck's constant) h 6.Chapter 16 .84 NA 3 Sig R ln 2 MkT h 2 2 Ve NA 5 2 Sig 164.Mathcad Solutions 16.08 J mol K J mol K Ans.30 c) For Xenon M gm mol NA 3 Sig R ln 2 MkT h 2 2 Ve NA 5 2 Sig 164.Section A .

061 The given equation for log10 P sat /torr is: log10 P sat /torr = a − b t/∞ C + c Combining these last two equations with Eq.15 .3026 a − 2. (B) and (A).3 The following are general: ln x = ln 10 × log10 x P sat /kPa = P sat /torr × 100 kPa 750.Chapter 1 . Electric potential [=] kg·m2 electric potential [=] 3 current A2 ·s (e) Since electric potential is electric charge divided by electric capacitance.3026 b 621 C = c − 273.Non-Numerical Solutions 1.061 = 2.Section B .15 By Eqs. then kg·m2 power [=] current A·s3 (d) Since (by Ohm’s Law) current is electric potential divided by resistance. kg·m2 N·m energy [=] [=] s3 s time (b) Electric current is by deﬁnition the time rate of transfer of electrical charge.0150 Comparing this equation with the given equation for ln P sat /kPa shows that: A = 2. Thus. electrical included. Resistance [=] A2 ·s charge [=] Capacitance [=] electric potential kg·m2 4 1.1 This system of units is the English-system equivalent of SI. Thus Power [=] Charge [=] (electric current)(time) [=] A·s (c) Since power is given by the product of current and electric potential. gc = 1(lbm )(ft)(poundal)−1 (s)−2 1.0150 B = 2.15 + c + ln 100 750. ln P sat /kPa = ln 10 × log10 P sat /torr + ln 100 750.2 (a) Power is power.061 torr (A) (B) (C) t/∞ C = T /K − 273.15 + c − 2. Thus. (C) gives: ln P sat /kPa = ln 10 a − b T /K − 273.3026 a − b T /K − 273.

with no sites of stress concentration.600 Seconds Whence.21 One procedure here. (c) The surface area that must be insulated against heat transfer by solar radiation is minimized. p.1. 678.7) has units of mass·length·acceleration. 651 of text) • 1(mile) ≈ 1.6 km = 5280/3280.031797 Sc 1 Minute [=] 60 Second [=] 0.5 cm = 2.54 cm exactly. • 1(atm) ≈ 1 bar = 1/0. of text.0254)(36) = 0.20 See Table A. 1. by deﬁnition (see p. Its fundamental units are therefore: E K [=] kg·m2 ·s−2 [=] N·m [=] J Potential energy as given by Eq. which gives results that are internally consistent. is to assume: 1 Year [=] 1 Yr [=] 364 Days This makes 1 Year equivalent to exactly 52 7-Day Weeks.28084)(1/3600) = 0. though not exact. (1.5 m s−1 = (5280/3. 3 1 Year [=] 1 Yr [=] 364 Days [=] (364)(24)(3600) = 31.96 Second • 1 Dy [=] 31449.9 Reasons result from the fact that a spherical container has the minimum surface area for a given interior volume.172 × 4) = 0.947831 = 1.44704 m s−1 1.14469 Hr 1 Day [=] (24)(3600) Second [=] 2. by deﬁnition (see p.5 kg = 0.60934 km • 1(quart) ≈ 1 liter = 1000/(264.449. (1.92308 Wk 1 Month [=] (4 1 )(7)(24)(3600) Second[=] 0. (b) The tensile stress within the tank wall is everywhere uniform. Therefore: (a) A minimum quantity of metal is required for tank construction. 651 of text) • 1(lbm ) ≈ 0.94635 liter (1 liter ≡ 1000 cm3 ) • 1(yard) ≈ 1 m = (0.74725 Dy 1 Week [=] (7)(24)(3600) Second [=] 1.9144 m exactly.75 kW = 1/1.05504 kJ • 1(hp) ≈ 0.34102 = 0.745701 kW • 1(in) ≈ 2.496 Second • 1 Hr [=] 3144. the maximum stress within the tank wall is kept to a minimum.6 Second • 1 Wk [=] 314496. Then the average Month contains 30 1 Days 3 and 4 1 Weeks. • 1 Sc [=] 31.5) has units of mass·velocity2 . Second • 1 Mo [=] 3144960 Second 1 Second [=] 0.83333 Mo 3 The ﬁnal item is obviously also the ratio 10/12.1. by deﬁnition of the (in) and the (yard) An additional item could be: • 1(mile)(hr)−1 ≈ 0.01325 bar • 1(Btu) ≈ 1 kJ = 1/0. With this understanding. 622 .4496 Second • 1 Mn [=] 314.17 Kinetic energy as given by Eq. Moreover. Its fundamental units are therefore: E P [=] kg·m·m·s−2 [=] N·m [=] J 1.986923 = 1.45359237 kg exactly.84 = 1.19078 Mn 1 Hour [=] 3600 Second [=] 1.

the temperature of the kitchen. However.7)]. W = 0. Speciﬁcation of T and P ﬁxes the intensive state.10) then shows that ∂U = 0 for the compression process. usually located behind the unit or in its walls). A detailed examination of the process indicates that the kinetic energy of the egg just before it strikes the surface appears instantly as internal energy of the egg. (e) The given equation.Section B . Thus. This is not possible. (2. Since the liquid phase is pure species 1. 2. 623 .Non-Numerical Solutions 2. With only T and P ﬁxed. thus raising its temperature. (d) Assuming the egg does not get scrambled. some of species 1 must evaporate from the liquid phase. one degree of freedom remains. depending on the relative amounts of the two phases. The overall composition. (c) The egg is at rest both in its initial and ﬁnal states. its internal energy does not change. of the system. shows that sign(Q) is (−).Chapter 2 . the ethanol distributes itself between the phases so as to form new equilibrium phase compostions and altered amounts of the vapor and liquid phases.8 The phase rule [Eq. such additions or removals do alter the overall composition of the system. (b) Since the elevation of the egg decreases. we presume that no heat is transferred. Heat transfer to the surroundings then returns the internal energy of the egg to its initial value. sign(∂E P ) is (−).2) is here written: ∂U t + ∂E P + ∂E K = Q + W (a) In this equation W does not include work done by the force of gravity on the system.6 If the refrigerator is entirely contained within the kitchen. Since the cylinder is insulated. except for the unusual case where the two phase compositions are the same. 2. If ethanol is added in a quantity that allows T and P to be restored to their initial values. thus ∂U t = 0.3 Equation (2. whence ∂E K = 0. If the composition of the vapor phase is to be unchanged. (b) Adding or removing liquid having the composition of the liquid phase or adding or removing vapor having the composition of the vapor phase does not change the phase compositions. According to the laboratory report a pure material (N = 1) is in 4-phase (κ = 4) equilibrium. and does not alter the intensive state of the system.7)] yields: F = 2 − κ + N = 2 − 2 + 3 = 3. addition of species 2 to the system increases its amount in the vapor phase.7)] yields: F = 2 − κ + N = 2 − 2 + 2 = 2. then the electrical energy entering the refrigerator must inevitably appear in the kitchen. Nothing remains the same except T and P. with ∂U t = ∂E K = W = 0. can range from the composition of the liquid phase to that of the vapor phase. rather than lowers. and thus the phase compositions. F = 2 − κ + N . (2. If this is true. then F = 2 − 4 + 1 = −1. The only way to make the refrigerator double as an air conditioner is to place the condenser of the refrigerator outside the kitchen (outdoors). ﬁxing T and P leaves a single additional phase-rule variable to be chosen.14 If the ﬂuid density is constant. This raises. then the compression becomes a constant-V process for which the work is zero.9 The phase rule [Eq. The only mechanism is by heat transfer (from the condenser of the refrigerator. 2. thus decreasing the moles of liquid present.10 (a) Since F = 3. the claim is invalid.7 According to the phase rule [Eq. Equation (2. 2. 2. Thus changes in the phase compositions are possible for the given T and P. 2. This is accounted for by the ∂E K term. (2.

then: t C t (T − T0 ) = −Cw (Tw − Tw0 ) or Tw = Tw0 − Ct (T − T0 ) t Cw (A) This equation relates instantaneous values of Tw and T . 2.16 Electrical and mechanical irreversibilities cause an increase in the internal energy of the motor. (A) this becomes: Ct Ct dT = K Tw0 − t (T − T0 ) − T Cw dτ or dT =K dτ T − T0 Tw0 − T − t t Cw C = −T K 1 1 + t t Cw C +K T0 Tw0 + t t Cw C Deﬁne: β≡K 1 1 + t Cw Ct α≡K T0 Tw0 + t Cw Ct where both α and β are constants. The motor temperature could rise to a level high enough to cause damage. U t = − Uw . Heat transfer from the solid to the water is manifested by changes in internal energy.] It may also be written: Ct dT = K (Tw − T ) dτ (C) In combination with Eq. Insulating the motor does nothing to decrease the irreversibilities in the motor and merely causes the temperature of the motor to rise until heat-transfer equilibrium is reestablished with the surroundings. If total heat capacity of the solid is C t (= mC) and total heat capacity of t the water is Cw (= m w Cw ).19 Let symbols without subscripts refer to the solid and symbols with subscript w refer to the water. Since energy is t conserved.2. [This equation implies that the solid is the system. The preceding equation may now be written: dT = α − βT dτ Rearrangement yields: 1 d(α − βT ) dT = dτ =− β α − βT α − βT Integration from T0 to T and from 0 to τ gives: − α − βT 1 ln α − βT0 β =τ 624 . The temperature of the motor rises until a dynamic equilibrium is established such that heat transfer from the motor to the srroundings exactly compensates for the irreversibilities. manifested by an elevated temperature of the motor. It can be written in the alternative form: t t T C t − T0 C t = Tw0 Cw − Tw Cw or t t Tw0 Cw + T0 C t = Tw Cw + T C t (B) ˙ The heat-transfer rate from the solid to the water is given as Q = K (Tw − T ).

Another form of the equation for α/β is found when the numerator on the right is replaced by Eq. this becomes: T = α α + T0 − β β exp(−βτ ) where by the deﬁnitions of α and β.and kinetic-energy changes.20 The general equation applicable here is Eq.which may be written: α − βT = exp(−βτ ) α − βT0 When solved for T and rearranged.30): ˙ H + 1 u 2 + zg m 2 fs ˙ ˙ = Q + Ws (a) Write this equation for the single stream ﬂowing within the pipe. However. (2. The equation then reduces to: H + 1 u2 = 0 2 2 625 . (e) For a properly designed turbine the result is the same as in Part (c). One usually assumes adiabatic operation with negligible potential.and kineticenergy changes. (B): t Tw Cw + T C t α = t Cw + C t β By inspection. Since there is no work. the preceding equation reduces to T = T0 . the equation is: H =0 (g) The sole purpose of the nozzle is to produce a stream of high velocity.and kineticenergy changes is reasonable. Thus. This yields: ˙ ( H )m = Q ˙ (b) The equation is here written for the two streams (I and II) ﬂowing in the two pipes. ˙ between the two streams. (f ) The purpose of a throttle is to reduce the pressure on a ﬂowing stream. ˙ ( H )m = W ˙ (d) For a properly designed gas compressor the result is the same as in Part (c). There is no work. and no work: ˙ H + 1 u2 m = 0 2 The usual case is for a negligible inlet velocity. Tw C t + T0 C t α = 0 tw Cw + C t β When τ = 0.and kinetic-energy changes. neglect potential. When τ = ∞ . making Q = 0. Whence. ( H )I m I + ( H )II m II = 0 ˙ ˙ (c) For a pump operating on a single liquid stream. as is the assumption of negligible heat transfer to the surroundings. the assumption of negligible potential. and the the heat transfer is internal. for a single stream. again neglecting any potential. as it should. The kinetic-energy change must therefore be taken into account. and set the work term equal to zero. 2. the expected result. one usually assumes negligible potential-energy change. it reduces to T = α/β. adiabatic operation. T = α/β when Tw = T . Then.

29) become: dm +m =0 ˙ dt and d(mU ) ˙ +Hm =0 dt Expanding the derivative in the second equation. (2.24 With the tank as control volume.4). an increase in D results in a decrease in Re. (2. W =− P dV = − V2 V1 RT d(V − b) V −b Whence. U = H − P V With d W = −P d V Whence. Q= H− V dP 626 . Eqs.2. d(P V ) = P d V + V d P d W = V d P − d(P V ) and and d W = −P d V W = V dP − (P V ) By Eq. an increase in m results in an increase in Re. Re ≡ ˙ 4 m ˙ 4 m ρD uρ D = = 2ρ µ π Dµ πD µ (a) Clearly. (1. and eliminating m by the ﬁrst equation yields: ˙ m dm dm dU =0 −H +U dt dt dt Multiply by dt and rearrange: dm dU = m H −U Substitution of H for H requires the assumption of uniform (though not constant) conditions throughout the tank. d Q = dU − d W and dU = d H − P d V − V d P the preceding equation becomes d Q = d H − V d P By Eq. 2.35 Recall: Whence.32 From the given equation: P= RT V −b V2 V1 By Eq.11).21 We reformulate the deﬁnition of Reynolds number. (2. with mass ﬂowrate m replacing velocity u: ˙ m = u Aρ = u ˙ π 2 D ρ 4 Solution for u gives: u= ˙ 4 m π D2ρ Whence.3).25) and (2. This requires the absence of any pressure or temperature gradients in the gas in the tank. 2. ˙ (b) Clearly. W = RT ln V1 − b V2 − b 2.

2. dU dn +n Q = −(H − U ) dt dt or . . (2. simply change the quantities of the phases. q is also constant.32a): By Eq. A. At the very least.44 (a) By Eq. m = 2ρ(P1 − P2 ) 4 4 4 D1 D2 4 4 D1 − D2 . and ρ all constant.43 Let n represent the moles of air leaving the home. . 627 . . In other words. With q = u A. because M may change. (2. dU dn +n Q = −P V dt dt 2. Once T and P are speciﬁed. (2. Provided the two phases are still present. . But n = M/m may change. m2 ρ2 1 1 − 4 4 D1 D2 and given H2 − H1 = 1 (P2 − P1 ) ρ 1 1 (P2 − P1 ) + 2 ρ 4 π 2 . By an energy balance. +U =n H +n Q=nH+ dt dt dt But a material balance yields Then dn . Hence u and q can both change. (b) Because mass is conserved. the system has 6 degrees of freedom.40 In accord with the phase rule. the effect is to decrease the mass ﬂowrate. Once T and P are speciﬁed. (b) Proceed as in part (a) with an extra term.24a).24a): H2 − H1 + 1 (u 2 − u 2 ) = 0 1 2 2 . dn dU d(nU ) .38 (a) By Eq.41 In accord with the phase rule. n =− dt . . Here solution for m yields: . the system has 2 degrees of freedom. the intensive state of the system is ﬁxed. . . their compositions cannot change. . 2.. ρ depends on T and P. m = 2 ρ(P1 − P2 ) − ρ 2 C(T2 − T1 ) π 4 2 4 4 D1 D2 4 4 D1 − D2 1/2 Because the quantity in the smaller square brackets is smaller than the leading term of the preceding result. One can add liquid with the liquid-phase composition or vapor with the vapor-phase composition or both. Solve for m: π . m must be constant. m = u Aρ With m. 2. 4 m m = u= π ρ D2 Aρ Then u2 2 − u2 1 = 4 π 2 . m2 ρ2 2 4 4 D1 − D2 4 4 D1 D2 =0 1/2 . u must also be constant. 2. 4 remain.

V ) for constant gives: ln V = − (P − P1 ) V1 Whence.Non-Numerical Solutions 3. followed by substitution for V0 /V by the Tait equation leads to: AB = (B + P)[B + (1 − A)P] 3. One could of course start with Eq. it must be valid for the initial state.Section B . (3. (3. W =− = V2 V1 d V = − A(T ) exp(− P)d P P2 P1 P d V = A(T ) P exp(− P)d P A(T ) [( P1 + 1) exp(− P1 ) − ( P2 + 1) exp(− P2 )] 628 . (3.3). Application of Eq. A(T ) = V1 exp( P1 ). but this topic is not covered until Chapter 6.Chapter 3 . (3.3). V1 ) to an intermediate state (P.4) becomes: dV = − dP V Integration from the initial state (P1 . then.2 Differentiate Eq. and B are constants. 3. V = V1 exp[− (P − P1 )] = V1 exp(− P) exp( P1 ) If the given equation applies to the process.3 The Tait equation is given as: V = V0 1 − AP B+P where V0 . Eq. A. requires the derivative of this equation: πV πP T = V0 − AV0 AP A = + 2 B+P (B + P) B+P −1 + P B+P Multiplication by −1/V in accord with Eq. (3.3) with respect to T : πξ πP =− T 1 V2 πV πP T πV πT + P 1 V π2V π Pπ T =ξ + π2V π Pπ T π πT = P 1 V2 πV πT P πV πP − T 1 V π2V πT π P = −ξ − π2V π Pπ T Addition of these two equations leads immediately to the given equation. (3.2) with respect to P and Eq. and V = A(T ) exp(− P) (b) Differentiate the preceding equation: Therefore.4) and apply the condition for an exact differential. the deﬁnition of .7 (a) For constant T .

12 Example 2.35c) with respect to T : T 1−δ δ P [(1−δ)/δ]−1 dT dP =T + P (1−δ)/δ dz dz 1−δ δ dT P (1−δ)/δ d P =0 + P (1−δ)/δ dz dz P Algebraic reduction and substitution for d P/dz by the given equation yields: T P dT 1−δ =0 (−Mρg) + dz δ For an ideal gas Tρ/P = 1/R. a result strongly conditioned by the assumption of no heat transfer between gas and tank.36) and (3. this reduces to: T2 = γ T This result indicates that the ﬁnal temperature is independent of the amount of gas admitted to the tank. (3. U2 − U = C V (T2 − T ) and and U2 − U = RT C V (T2 − T ) = RT C P − CV R T2 − T = = CV CV T When C P /C V is set equal to γ . Here.37) in the alternative but equivalent forms: W = RT1 δ−1 T2 −1 T1 and Q= (δ − γ )RT1 (δ − 1)(γ − 1) T2 −1 T1 from which we ﬁnd immediately for δ = 0 that: W = −R(T2 − T1 ) and Q= γR (T2 − T1 ) = C P (T2 − T1 ) γ −1 629 .13 shows that U2 = H . this becomes: W = 1 [(κ P1 + 1)V1 − (κ P2 + 1)V2 ] κ or W = P1 V1 − P2 V2 + V1 − V2 κ 3.With V1 = A(T ) exp(−κ P1 ) and V2 = A(T ) exp(−κ P2 ).13 Isobaric case (δ = 0). The easiest resolution is to write Eq. If the gas is ideal. H = U + P V = U + RT For constant C V . Whence.37) reduce to: W = −RT1 (1∞ − 1) and Q= γ RT1 ∞ (1 − 1) γ −1 Both are indeterminate. This substitution reduces the preceding equation to: Mg dT =− R dz δ−1 δ 3. Eqs. (3.11 Differentiate Eq. 3. (3.36) and (3.

Application of l’Hˆ pital’s rule yields the appropriate results: o W = RT1 ln P2 P1 and Q = −RT1 ln P2 P1 Note that if y≡ P2 P1 (δ−1)/δ then 1 dy = 2 δ dδ P2 P1 (δ−1)/δ ln P2 P1 Adiabatic case (δ = γ ). Equations (3. which here becomes: n = (A) d(nU )tank ˙ −n H = Q ˙ dt where the prime ( ) identiﬁes the entrance stream of constant properties. (2. Here.15 K T = 318.36) and (3.Isothermal case (δ = 1).15 K P1 = 101.33 kPa P2 = 1500 kPa 630 . this becomes: n 2 (H2 − H − RT ) − n 1 (U1 − H − RT ) = Q or n 2 [C P (T − T ) − RT ] − n 1 [C P (T − T ) − RT ] = Q Because n = n 2 − n 1 .29). 000 cm3 T = 298. this reduces to: Q = n [C P (T − T ) − RT ] Given: V t = 100. simple substitution yields: W =0 and Q= RT1 γ −1 RT1 P2 −1 = γ −1 P1 T2 − 1 = C V (T2 − T1 ) T1 3. n1 = P1 V t RT and n2 = P2 V t RT The quantity of air admitted to the tank is therefore: V t (P2 − P1 ) RT The appropriate energy balance is given by Eq. In this case simple substitution yields: W = RT1 γ −1 P2 P1 (γ −1)/γ −1 and Q=0 Isochoric case (δ = ∞). Multiplying by dt and integrating over the time of the process yields: n 2 U2 − n 1 U1 − n H = Q With n = n 2 − n 1 . n 2 (U2 − H ) − n 1 (U1 − H ) = Q Because U2 = H2 − RT and U1 = H1 − RT .37) are both indeterminate of form 0/0. For an ideal gas in a tank of total volume V t at temperature T .14 What is needed here is an equation relating the heat transfer to the quantity of air admitted to the tank and to its temperature change.

314 J mol−1 K−1 and C P = (7/2)R. the energy equation gives: Q = (56.15) − 298.15) With R = 8.15 = −172. with γ = 1.33) = 56.29).425 mol (8. Apply the result of Part (d).314) 7 (298.425)(8. T2 = γ T (e) 1. and U2 − H = C V T2 − C V T − C P T + C V T = C V T2 − C P T U1 − H = C V T1 − C P T n 2 (C V T2 − C P T ) − n 1 (C V T1 − C P T ) = Q Note also: n2 = P2 Vtank RT2 n1 = P1 Vtank RT1 (c) If n 1 = 0.15) = 417. here written: d(nU )tank ˙ −n H = Q ˙ dt where the prime ( ) identiﬁes the entrance stream of constant properties.71 kJ 3. 000)(1500 − 101.15 (a) The appropriate energy balance is given by Eq. C V T2 = C P T and T2 = CP CV T Whence. (A) with R = 8. (2. n = (100. 314)(298. H = U + P V = U + RT Whence for an ideal gas with constant heat capacities.By Eq. rearrangement gives: n 2 (U2 − H ) − n 1 (U1 − H ) = Q (b) If the gas is ideal.15 − 318.41 K 631 .15 K: T2 = (1.4 and T = 298. Multiplying by dt and integrating over the time of the process yields: n 2 U2 − n 1 U1 − n H = Q Since n = n 2 − n 1 . n 2 (C V T2 − C P T ) = Q (d) If in addition Q = 0.4)(298. U2 − H = U2 − U − RT = C V (T2 − T ) − RT Substitute R = C P − C V : Similarly.6 J 2 or Q = −172. 314 cm3 kPa mol−1 K−1 . 705.

314 (3)(4 × 106 ) = −(400)(460)(T2 − 298.16 The assumption made in solving this problem is that the gas is ideal with constant heat capacities.15)] 2 (83.Then. (2. The equation of Part (c) now becomes: n 2 (C V T2 − C P T ) = −m tank C(T2 − T ) Moreover n2 = P2 Vtank RT2 These two equations combine to give: P2 Vtank (C V T2 − C P T ) = −m tank C(T2 − T ) RT2 With C P = (7/2)R and C V = C P − R = (7/2)R − R = (5/2)R.15 K P2 = 3 bar Appropriate values for R are therefore: Vtank = 4 × 106 cm3 R(denominator) = 83.45 mol = (83. The result is T2 = 304. R in the numerator has energy units.217 K. Then. or by the solve routine of a software package. R(numerator) = 8.14)(304. Given values in the appropriate units are: m tank = 400 kg C = 460 J mol−1 kg−1 T = 298. this equation becomes: R P2 Vtank (5T2 − 7T ) = −m tank C(T2 − T ) 2 RT2 Note: R in the denominator has the units of P V .8 mol = (83.14 bar cm3 mol−1 K−1 : n2 = (3)(4 × 106 ) P2 Vtank = 345. n2 = (3)(4 × 106 ) P2 Vtank = 474. here written: d(nU )tank ˙ +Hn =Q ˙ dt Multiplied by dt it becomes: d(nU ) + H dn = d Q 632 . with R = 83.314 J mol−1 K−1 8.14)(417. Heat transfer between gas and tank is: Q = −m tank C(T2 − T ) where C is the speciﬁc heat of the tank.29).14)(T2 ) Solution for T2 is by trial.14 bar cm3 mol−1 K−1 Numerically.217) RT2 3. by an iteration scheme. The appropriate energy balance is given by Eq.15) [(5)(T2 ) − (7)(298.41) RT2 2.

then we recover the isentropic expansion formulas. where H is the enthalpy of the contents of the tank. Thus. By material balance.where n and U refer to the contents of the tank. If mC = 0.27 For an ideal gas. If mC >>> nC V .27) 3. (3. Whence. dn ≡ = −dn. W = RT ln P2 P1 Compared with Eq. n1 = P1 Vtank RT1 and n2 = P2 Vtank RT2 These equations may be solved for T2 and n 2 . n dU + U dn − H dn = Q Also. or dU = C V dT or n dU − (H − U )dn = d Q d Q = −mC dT H − U = P V = RT nC V dT − RT dn = −mC dT where m is the mass of the tank. and H ≡ and n ≡ refer to the exit stream. H ≡ = H . R d(nC V + mC) R d(nC V ) R dT = dn = = C V nC V + mC C V nC V + mC nC V + mC T Integration yields: ln T2 T1 = n 2 C V + mC R ln n 1 C V + mC CV or T2 = T1 n 2 C V + mC n 1 C V + mC R/C V In addition. Thus. 3. then T2 = T1 .29 Solve the given equation of state for V : V = θ RT +b− RT P 633 . and C is its speciﬁc heat. Since the stream bled from the tank is merely throttled.28 Since Z = P V /RT the given equation can be written: V = RT + B ≡ RT P Differentiate at constant T : dV = − RT dP P2 V2 The isothermal work is then: W =− V1 P d V = RT P2 P1 1 dP P Whence. U = CV T U= P V = RT CV R (P V ) = R T (P V ) But 1 CV CV = = γ −1 C P − CV R Therefore : U= 1 (P V ) γ −1 3.

42) becomes: Z= a(T )V /RT V a(T )V /RT V − 2 = − V − b V + ( + σ )bV + σ b2 V − b (V + b)(V + σ b) Substitute V = 1/ρ: Z= 1 a(T )ρ 1 − RT 1 + ( + σ )bρ + σ (bρ)2 1 − bρ Expressed in series form. after reduction: Z =1+ b− ( + σ )a(T )b 2 a(T ) ρ + ··· ρ + b2 + RT RT Equation (3.12) may be written: Comparison shows: Z = 1 + Bρ + Cρ 2 + · · · B =b− a(T ) RT and C = b2 + ( + σ )ba(T ) RT 634 . the ﬁrst term on the right becomes: 1 = 1 + bρ + (bρ)2 + · · · 1 − bρ The ﬁnal fraction of the second term becomes: 1 = 1 − ( + σ )bρ + [( + σ )2 − σ ](bρ)2 + · · · 1 + ( + σ )bρ + σ (bρ)2 Combining the last three equations gives.Whence. substitution leads to: ∂P ∂T V P + = T P RT 2 dθ θ − dT T 3.31 When multiplied by V /RT .3)]: κ≡ −1 V ∂V ∂P T Substitution for both V and the derivative yields: κ= P2 RT θ RT +b− RT P Solve the given equation of state for P: P= RT V −b+ Differentiate: ∂P ∂T = V R θ V −b+ RT + θ RT dθ θ − dT T V −b+ θ RT 2 By the equation of state. ∂V ∂P =− T RT P2 By deﬁnition [Eq. Eq. (3. (3. the quantity in parentheses is RT /P.

(B).11): ∂Z ∂P = B + 2C P + 3D P 2 + · · · T Whence. ∂Z ∂P =B T.36 Differentiate Eq. with numerical values from Table 3. (A). the second equation becomes: C = b2 + a(T ) ba(T ) =b b+ RT RT Values for a(T ) and b are found from Eqs. the scope of which must be decided by the instructor.P=0 Equation (3.For the Redlich/Kwong equation.1: b= 0.39). (3. ∂Z ∂ρ =B T.2%.42748RTc a(T ) = Tr1.56 The compressibility factor is related to the measured quantities by: Z= M PV t PV t = m RT n RT (A) By Eq. a ±1% maximum error in Z requires errors in the variables of <0.45) and (3.12) with V = 1/ρ: Differentiate: Z = 1 + Bρ + Cρ 2 + Dρ 3 + · · · ∂Z ∂ρ = B + 2Cρ + 3Dρ 2 + · · · T Whence. (C). B = (Z − 1)V = (Z − 1)M V t m (B) (a) By Eq. Z dB = Z −1 B dT dP − T P + 2Z − 1 Z −1 dm dM dV t − + t m M V Therefore 635 . (b) By Eq. 3.08664RTc Pc 0.ρ=0 3.46).5 Pc RT The numerical comparison is an open-ended problem. (3. (3. dT dm dV t dP dM dZ − + t − + = T m V P M Z (C) Thus Max |% δ Z | ≈ |% δ M| + |% δ P| + |% δV t | + |% δm| + |% δT | Assuming approximately equal error in the ﬁve variables. dm dM dV t Z dZ dB − + t + = m M V Z −1 Z B By Eq.

(3. then B = 0.083 − 1. If B = 0. (D) becomes: P→0 lim ∂Z ∂P = T b − a/RT 3/2 RT For P → ∞. the error in B approaches inﬁnity.422 B 0 = 0. In the limit as Z → 1. (3.65).11) gives: ∂Z ∂P = B + 2C P + 3D P 2 + · T whence P→0 lim ∂Z ∂P =B T If the limiting value of the derivative is zero. (3. V → b.60 (a) Differentiation of Eq. 3. and Eq.02%. and Eqs. This is because the divisor Z − 1 ≈ 0. where a and b are constants: Z= a V − 3/2 (V + b) RT V −b P= a RT − 1/2 V − b T V (V + b) From these by differentiation. 0. ω = 0.57 The Redlich/Kwong equation has the following equivalent forms.52) and (3. V → ∞.Max |% δ B| ≈ Z Z −1 |% δ P| + |% δT | + 2Z − 1 Z −1 |% δV t | + |% δ M| + |% δm| For Z ≈ 0. ∂Z ∂V = T a(V − b)2 − b RT 3/2 (V + b)2 RT 3/2 (V − b)2 (V + b)2 (A) ∂P ∂V = T a(2V + b)(V − b)2 − RT 3/2 V 2 (V + b)2 T 1/2 V 2 (V − b)2 (V + b)2 (B) In addition. and Eq.1.53) combine to give B 0 = B Pc /RTc . then by Eq. (D) becomes: P→∞ lim ∂Z ∂P = T b RT 3.9 and for approximately equal error in the ﬁve variables. a ±1% maximum error in B requires errors in the variables of less than about 0. we have the mathematical relation: ∂Z ∂P = T (∂ Z /∂ V )T (∂ P/∂ V )T (C) Combining these three equations gives ∂Z ∂P = T aV 2 (V − b)2 − b RT 3/2 V 2 (V + b)2 a RT (2V + b)(V − b)2 − R 2 T 5/2 V 2 (V + b)2 (D) For P → 0.6 = 0 Tr 636 . and B = B RT = 0 (b) For simple ﬂuids.

(f ) Rackett equation: Saturated liquids. Subtract 1 from each side of the equation and divide by ρ.4) applied to a constant-V process: γP γT R V γP γT = V γP γT = = V β κ (b) For an ideal gas P V = RT . and σ are ﬁxed. See Fig. 3. © 2005 The McGraw-Hill Companies.46)]: ≡ b Pc RTc and ≡ ac Pc R 2 Tc2 For a given EOS. 3. (g) Constant β. 3.68 Follow the procedure laid out on p. (b) Two-term virial equation: Low to modest P. (c) Cubic EOS: Gases at (in principle) any conditions.63 Linear isochores require that (γ P/γ T )V = Constant. (a) By Eq. (3. .15 for quantitative guidance. 3. For absolute values of V . or low ρ. and V (c) Because a and b are constants. (h) Lydersen correlation for liquids: a corresponding-states method applicable to liquids at extreme conditions. a reference volume is required. Limited distribution permitted only to teachers and educators for course preparation. Inc. (3.and Tr = 0. Note that corresponding states correlations are strictly valid for non-polar ﬂuids. Inappropriate where changes in V are required. κ liquids: Useful where changes in V are required. or large V and/or high T . you are using it without permission. . .12) with 1/ρ substituted everywhere for V .083 (1/1. 637 PROPRIETARY MATERIAL. and so therefore is the derivative. but often more accurate. 93 with respect to the van der Waals equation to obtain from Eq. Take the limit as ρ → 0. (3. (e) Incompressible liquids: Liquids at normal T s and Ps. and Z c .422 0.763 3. unrelated to experimental values of Z c . (3. a corresponding states application.42) the following three more-general equations: 1 + (1 − − σ ) σ 2 = 3Z c 2 = 3Z c − ( + σ) ( σ 2 + 1) + ( + 1) + 3 = Zc where by deﬁnition [see Eqs.45) and (3.64 (a) Ideal gas: Low P. 3. differentiation of Eq. See Fig.66 Write Eq. and the above set represents 3 equations in 3 unknowns.42) yields: R V −b In each case the quantities on the right are constant. (d) Lee/Kesler correlation: Same as (c).14 for guidance. Thus. (3. for a given EOS the value of Z c is preordained. If you are a student using this Manual.6) = 2.

= 1 + B · · Z 2 Tr2 Z Tr R Tc Z Tr RTc Z Tr Rearrange: (Z − 1)Z Tr ˆ ˆ Pr + . (c) If attractive and repulsive interactions are both present. and V > V ig . .427480 √ √ (c) For the Peng/Robinson equation. they tend to cancel each other. . = 1 − 2 and σ = 1 + 2.30740 3. Z R T Z RT Z =1+ 2 P2 C P2 B Pc Pr ˆ ˆ Pr + C · Pr + . .69 Equation (3. and for a given T and P occupy a volume V ig . b) For the Redlich/Kwong and Soave/Redlich/Kwong equations. Substitution of these values into the 3-equation set allows their solution to yield: Zc = 1 3 = 0. In this case Z < 1. . . = 0 and σ = 1. Z =1+ C P2 BP + 2 2 2 + .12): Eliminate ρ: = 0. If in balance. As for the Soave and SRK equations the 3-equation set can be solved (with considerably greater difﬁculty) to yield: Z c = 0. . .75 van der Waals EOS: P= a RT − 2 V −b V Z= Set V = 1/ρ: Z= aρ bρ aρ 1 − =1+ − RT 1 − bρ RT 1 − bρ a V − V − b V RT whence Z rep = bρ 1 − bρ Z attr = aρ RT 638 . (a) For 1 mole of a gas with molecules having kinetic energy and purely attractive interactions at the same T and P. the molecules have kinetic energy only. then the average separation is the same as for an ideal gas. In this case Z > 1. In this case Z = 1. + 2 c2 · 2 r 2 + . the intermolecular separations are larger. . the intermolecular separations are smaller. and V < V ig ..457236 ρ = P/Z RT Z = 1 + Bρ + Cρ 2 + .077796 where = 0. (b) For 1 mole of a gas with molecules having kinetic energy and purely repulsive interactions at the same T and P. = B +C · Z Tr Pr ˆ B = lim (Z − 1)Z Tr /Pr Pr →0 3.086640 = 0. and V = V ig . 3.(a.74 In a cylinder ﬁlled with 1 mole of an ideal gas..

dU = C V dT whence dT dU = CV dt dt . a 2-term virial EOS in ρ.76 Write each modiﬁcation in “Z -form. Such an equation is quite inappropriate at higher densities. i.e. Also for an ideal gas. the equation makes Z linear in ρ.78 By Eq. (3.43. 2.0035)2 = 250 × 10−6 (40 − 10) − 45 × 10−6 (P2 − 6) Solution for P2 yields: P2 = 17. where the general equation was developed. V →∞ 3. PV t Q = −RT − RT 2 P V t dT dT PV t dT = CP CV + RT dt dt RT dt t2 t1 Integration yields: ln R T2 = CP PV t T1 .4 bar 639 .4).. dV = β dT − κ d P V where β and κ are average values Integrate: ln D2 Vt V2 = ln 2t = ln 2 = ln 2 V1 V1 D1 D1 + δ D D1 2 = ln 1 + δD D1 2 = β(T2 − T1 ) − κ(P2 − P1 ) ln(1. dU dn +n Q = −P V dt dt For an ideal gas. Q dt 3.77 Refer to Pb.” (a) Z= The required behavior is: (b) Z= a V − RT V −b V →∞ lim Z = 1 − a RT V →∞ lim Z = 1 The required behavior is: (c) Z= a V − 2 RT (V − b) V →∞ lim Z = − a RT V →∞ lim Z = 1 The required behavior is: (d) Z =1− a 1 − V − b V RT V →∞ lim Z = 0 lim Z = 1 aρ a =1− RT V RT V →∞ Although lim Z = 1 as required. n= PV t RT and dn =− dt PV t RT 2 dT dt Note that P V t /R = const.3. .

6 For consistency with the problem statement.5 For consistency with the problem statement.Section B . Then: 2 C Pam = A + BTam + C Tam where Tam ≡ T1 (ν + 1) T1 ν + T1 T2 + T1 = = 2 2 2 and 2 Tam = T12 2 (ν + 2ν + 1) 4 Whence. Then: D C Pam = A + BTam + 2 Tam As in the preceding problem. we rewrite Eq. C B T1 (ν + 1) + T12 (ν 2 + 2ν + 1) 4 2 Deﬁne ε as the difference between the two heat capacities: C Pam = A + ε ≡ C P − C Pam = C T12 ν 2 + ν + 1 ν 2 + 2ν + 1 − 4 3 This readily reduces to: C T12 (ν − 1)2 12 Making the substitution ν = T2 /T1 yields the required answer. 640 . we rewrite Eq.Chapter 4 . (4. (4. Deﬁne C Pam as the value of C P evaluated at the arithmetic mean temperature Tam .8) as CP = A + D B T1 (ν + 1) + 2 ν T12 where ν ≡ T2 /T1 . ε= 4.8) as: CP = A + C B T1 (ν + 1) + T12 (ν 2 + ν + 1) 3 2 where ν ≡ T2 /T1 . Deﬁne C Pam as the value of C P evaluated at the arithmetic mean temperature Tam . C Pam = A + 4D B T1 (ν + 1) + 2 2 2 T1 (ν + 2ν + 1) Deﬁne ε as the difference between the two heat capacities: ε ≡ C P − C Pam = D T12 4 1 − 2 ν + 2ν + 1 ν This readily reduces to: ε= D T12 ν ν −1 ν +1 2 Making the substitution ν = T2 /T1 yields the required answer. Tam = T1 (ν + 1) 2 and 2 Tam = T12 2 (ν + 2ν + 1) 4 Whence.Non-Numerical Solutions 4.

Therefore.520 J (HHV) 4.388 ◦ H298 = (11)(−44.625 ◦ H298 = (2)(−44. C P increases with increasing T . However. available. higher pressures allow higher temperature levels.818) ◦ H298 = 249.649 J (HHV) (c) Combustion of n-decane(l) with H2 O(g) as product (LHV): 10 C(s) + 10 O2 (g) → 10 CO2 (g) 11 H2 (g) + 5 1 O2 (g) → 11 H2 O(g) 2 ◦ H298 = (10)(−393. (b) Combustion of methane(g) with H2 O(g) as product (LHV): C(s) + O2 (g) → CO2 (g) 2H2 (g) + O2 (g) → 2H2 O(g) CH4 (g) → C(s) + 2H2 (g) ◦ H298 = −393.520 CH4 (g) + 2O2 (g) → CO2 (g) + 2H2 O(g) ◦ H298 = −802. non-toxic. the resulting latent-heat release adds to the heat given off as a result of the combustion reaction.1)].8 Except for the noble gases [Fig. thus yielding a higher heating value than the lower heating value obtained when the water is not condensed.509) ◦ H298 = (11)(−241.012) CH4 (g) + 2O2 (g) → CO2 (g) + 2H2 O(l) ◦ H298 = −890.4. (4.700 C10 H22 (l) → 10 C(s) + 11 H2 (g) C10 H22 (l) + 15 1 O2 (g) → 10 CO2 (g) + 11 H2 O(g) 2 ◦ H298 = −6.012) 11 H2 O(g) → 11 H2 O(l) C10 H22 (l) + 15 1 O2 (g) → 10 CO2 (g) + 11 H2 O(l) 2 ◦ H298 = −6.345.345. Water because it is cheap. H lv . 641 . the estimate is likely to be low. and hence P.625 J (LHV) Combustion of methane(g) with H2 O(l) as product (HHV): CH4 (g) + 2O2 (g) → CO2 (g) + 2H2 O(g) 2H2 O(g) → 2H2 O(l) ◦ H298 = −802.49 Saturated because the large H lv overwhelms the sensible heat associated with superheat. 4.829.818) ◦ H298 = 74.27 (a) When the water formed as the result of combustion is condensed to a liquid product.509 ◦ H298 = (2)(−241.388 J (LHV) Combustion of n-decane(l) with H2 O(l) as product (HHV): C10 H22 (l) + 15 1 O2 (g) → 10 CO2 (g) + 11 H2 O(g) 2 ◦ H298 = −6. and has a large The lower energy content is a result of the decrease in H lv with increasing T .

5. is negative.14) can be rewritten as: P2 T2 − R ln πS = C P ln P1 T1 (a) If P2 = P1 . So too is its change in kinetic energy. The net result is therefore a complete conversion of heat taken in by a cyclic process into work.5 The energy balance for the over-all process is written: Assuming the egg is not scrambled in the process. The practical way to increase is to increase TH . Eq. πStotal is positive. the efﬁciency changes more rapidly with TC than with TH . Q = πU t + πE K + πE P 5.8) the thermal efﬁciency of a Carnot engine is: T = 1 − TC H Differentiate: TC TH =− 1 TH and TH TC = TC 1 TC = 2 TH TH TH Since TC /TH is less unity. and therefore by the ﬁrst law. however.Chapter 5 .11 For an ideal gas with constant heat capacities. there are limits to this too. A cycle is formed by an isothermal line from 3 ∞ 1. (5. assumed to intersect at point 2.6 By Eq. indicating that heat is absorbed by the system. T2 P2 = T1 P1 Whence. πS P = C P ln T2 T1 If V2 = V1 . The potential-energy change. For the cycle πU = 0. and is not subject to control. and the process is irreversible. t πStotal = πSsurr = −Q Q surr = Tξ Tξ Since Q is negative. TC is ﬁxed by the environment. The assumption of intersecting adiabatic lines is therefore false. in violation of Statement 1a of the second law (Pg. Q + W = 0. In practice. Thus heat is transferred to the surroundings. and by the preceding equation. Q must be positive. 5. πSV = C P ln T2 T1 − R ln T2 T1 = C V ln T2 T1 642 .Section B . The total entropy change of the process is: t πStotal = πS t + πSsurr Just as πU t for the egg is zero. so is πS t . so is Q. however. Therefore. Since W is negative. An engine traversing this cycle would produce work. (5.1 Shown to the right is a P V diagram with two adiabatic lines 1 ∞ 2 and 2 ∞ 3. its internal-energy change after it returns to its initial temperature is zero. Of course. So in theory it is more effective to decrease TC . and for the changes T1 ∞ T2 and P1 ∞ P2 .Non-Numerical Solutions 5. 160).

P2 T2 = P1 T1 Whence.Since C P > C V . this demonstrates that (b) If T2 = T1 . 5.13 As indicated in the problem statement the basic differential equations are: d W − d Q H − d QC = 0 (A) TH d QH =− TC d QC (B) where Q C and Q H refer to the reservoirs. (5. dT dV dP = + T V P ig or ig dV dT dP − = V T P Whence. Return to the original equation and substitute dT /T = d P/P + d V /V : C dV C dP dP C dV C dP dS + P = V − + P = P R V R P P R V R P R ig ig ig ig Integration yields: V C C P S + P ln = V ln V0 R P0 R R ig ig 5. valid for constant heat capacities. 643 .12 Start with the equation just preceding Eq. one could ask for the following proof. this reduces to: C dT dS + d ln V = V R T R ig Integration yields: S = R T T0 V C V dT + ln V0 R T ig ********************** As an additional part of the problem. and ln P + ln V = ln R + ln T . If V2 = V1 . ST = −R ln P2 P1 SP > SV . 170: ig dP C dT C dT dS − − d ln P = P = P P R T R T R ig For an ideal gas P V = RT .14) on p. ig dV dT C dT dS = + − = P V T R T R ig dT CP + d ln V −1 T R Because (C P /R) − 1 = C V /R. Therefore. SV = C P ln P2 P1 − R ln P2 P1 = C V ln P2 P1 This demonstrates that the signs for ST and SV are opposite.

TH = TC ≡ T . Eq. d ln TC = − d ln TH where ≡ t CH t CC Integration from TH0 and TC0 to TH and TC yields: TC = TC0 TH TH0 − or TC = TC0 TH TH0 − t t (b) With d Q H = C H dTH and d Q C = CC dTC . and the boxed equation of Part (a) becomes: T = TC0 T TH0 +1 − = TC0 TH0 T From which: T = (TC0 )1/( +1) T (TH0 ) /( +1) = TC0 (TH0 ) and T = (TC0 )1/( TH0 +1) (TH0 ) /( +1)−1 Because /( + 1) − 1 = −1/( T = TH0 + 1). (A) becomes: t t d W = C H dTH + CC dTC Integration yields: t t W = C H (TH − TH0 ) + CC (TC − TC0 ) Eliminate TC by the boxed equation of Part (a) and rearrange slightly: W = t C H TH0 TH t − 1 + CC TC0 TH0 TH TH0 − −1 (c) For inﬁnite time. then: TC0 TH0 1/( +1) and T TH0 − = TC0 TH0 − /( +1) Because TH = T .14 As indicated in the problem statement the basic differential equations are: d W − d Q H − d QC = 0 (A) TH d QH =− TC d QC (B) where Q C and Q H refer to the reservoirs.t t (a) With d Q H = C H dTH and d Q C = CC dTC . (B) becomes: t TH C H dTH =− t TC CC dTC or C t dTH dTC =− H t C C TH TC Whence. Eq. 644 . substitution of these quantities in the boxed equation of Part (b) yields: W = t C H TH0 TC0 TH0 1/( +1) −1 + t CC TC0 TC0 TH0 − /( +1) −1 5.

|W | 1 −3 |W | dA = + = k(TH )4 (1 − r )r 4 (1 − r )2r 3 k(TH )4 dr 4r − 3 (1 − r )2r 4 Equating this equation to zero.8) and (5.20 Because W = 0. =1− 1−r TH |W | + | Q C | . |W | k(TH )4 1 (1 − r )r 3 Differentiate. |W | TC |W | = |W | + | Q| = 1−r or . (B) becomes: TH d QH =− t TC CC dTC or t d Q H = −CC TH dTC TC Substitute for d Q H and d Q C in Eq. . TC = TH . 645 T = (T1 + T2 )/2 .75 5. r 1 − 1 = |W | 1−r 1−r = k Ar 4 (TH )4 or A= . this becomes: m 1 C P (T − T1 ) + m 2 C P (T − T2 ) = 0 whence T = (1) If m 1 = m 2 . . . 5.3) here becomes: Q= U t = mC V T A necessary condition for T to be zero when Q is non-zero is that m = ∞ .1) in rate form and combine to eliminate | Q H |: . With | Q C | = k A(TC )4 = k A(r TH )4 . with T as the ﬁnal temperature. 5. this becomes: where r≡ TC TH . This is the reason that natural bodies (air and water) that serve as heat reservoirs must be massive (oceans) or continually renewed (rivers). Eq. and the boxed equation above becomes: t W = CC TH ln TC0 + TH − TC0 TH . . leads immediately to: 4r = 3 or r = 0. noting that the quantity in square brackets is constant: . (5.t (a) With d Q C = CC dTC . Eq. (A): t d W = −CC TH Integrate from TC0 to TC : t W = −CC TH ln dTC t + CC dTC TC TC t + CC (TC − TC0 ) TC0 or t W = CC TH ln TC0 + TC − TC0 TC (b) For inﬁnite time.15 Write Eqs. (2. |W | . .22 An appropriate energy balance here is: Q= Ht = 0 m 1 T1 + m 2 T2 m1 + m2 Applied to the process described.

one sees that for both T > T0 and T0 > T the numerators and denominators of the above fractions have the same sign. but neither reversible nor adiabatic. 5. and hence isentropic. More generally. a heat source. heat may be transferred between system amd surroundings. But the same change of state may be irreversible with heat transfer to the surroundings. and the fractions are indeterminate. C P dT T0 − T T − T0 By inspection. The process is then necessarily isentropic. for both cases C P H is positive. for both cases C P S is positive. An isentropic process must be either reversible and adiabatic or irreversible and non-adiabatic. For processes that are internally irreversible. When T = T0 . one sees that for both T > T0 and T0 > T the numerators and denominators of the above fractions have the same sign. causing the entropy to increase. The term isentropic denotes a process for which the system does not change in entropy. S t = m 1 C P ln (2) S t = mC P ln T2 T1 T2 or S t = 2mC P ln √ T T1 T2 Because T = (T1 + T2 )/2 > √ T1 T2 . The process is still isentropic. CP H = T T0 C P dT = T0 T Similarly. It may be reversible and adiabatic. causing the entropy of the system to increase or decrease. There are two causes for entropy changes in a system: The process may be internally irreversible. Such a process is isentropic. it is possible for heat to be transferred out of the system in an amount such that the entropy changes from the two causes exactly compensate each other. Expansion of gas in a piston/cylinder arrangement is a case in point. 5. S t is positive.31 The process involves three heat reservoirs: the house. One can imagine irreversible processes for which the state of the system is the same at the end as at the beginning of the process.The total entropy change as a result of temperature changes of the two masses of water: T T + m 2 C P ln T2 T1 Equations (1) and (2) represent the general case. but not necessarily reversible. the system conditions may change in such a way that entropy changes resulting from temperature and pressure changes compensate each other.24 By deﬁnition. a heat source.23 Isentropic processes are not necessarily reversible and adiabatic. Thus. the furnace. Thus. but neither reversible nor adiabatic. Notation is as follows: |Q| |Q F | |Q σ | Heat transfer to the house at temperature T Heat transfer from the furnace at TF Heat transfer from the surroundings at Tσ The ﬁrst and second laws provide the two equations: |Q| = |Q F | + |Q σ | and |Q σ | |Q| |Q F | =0 − − Tσ TF T 646 . If m 1 = m 2 = m. a heat sink. CP S dT dT T0 T CP T T = = ln(T0 /T ) ln(T /T0 ) T T0 CP By inspection. o 5. and the surroundings. Application of l’Hˆ pital’s rule leads to the result: C P H = C P S = C P . both the numerators and denominators of the above fractions become zero.

a heat source. a heat sink. and solve for |Q F |: |Q F | = |Q| T − Tσ TF − Tσ TF T With T = 295 K TF = 810 K Tσ = 265 K and |Q| = 1000 kJ The result is: |Q F | = 151. the tank. Notation is as follows: 647 . and the surroundings. The work produced by the engine drives a Carnot refrigerator (reverse Carnot engine) which extracts heat from the surroundings and discharges heat to the house. A Carnot heat engine operates with the furnace as heat source and the house as heat sink. |Q 1 | T − Tσ TF − T = |Q 2 | T T or |Q 2 | = |Q 1 | Because the total heat transferred to the house is |Q| = |Q 1 | + |Q 2 |. 5.32 The process involves three heat reservoirs: the house.Combine these equations to eliminate |Q σ |. Thus the heat rejected by the Carnot engine (|Q 1 |) and by the Carnot refrigerator (|Q 2 |) together provide the heat |Q| for the house. |Q| = |Q 1 | + |Q 1 | TF − T T − Tσ But |Q 1 | = |Q F | T TF TF − T TF − T = |Q 1 | 1 + T − Tσ T − Tσ = |Q 1 | whence |Q| = |Q F | T TF TF − Tσ T − Tσ TF − Tσ T − Tσ Solution for |Q F | yields the same equation obtained more easily by direct application of the two laws of thermodynamics to the overall result of the process. a heat source. The energy balances for the engine and refrigerator are: |W |engine = |Q F | − |Q 1 | Equation (5.14 kJ Shown to the right is a scheme designed to accomplish this result.7) may be applied to both the engine and the refrigerator: |W |refrig = |Q 2 | − |Q σ | Tσ |Q σ | TF |Q F | = = T |Q 2 | T |Q 1 | Combine the two pairs of equations: |W |engine = |Q 1 | TF − T TF − 1 = |Q 1 | T T |W |refrig = |Q 2 | 1 − Tσ T = |Q 2 | T − Tσ T Since these two quantities are equal.

38 kJ Shown to the right is a scheme designed to accomplish this result. j dt j 648 .7) may be applied to both the engine and the refrigerator: |W |refrig = |Q σ2 | − |Q | Combine the two pairs of equations: |W |engine = |Q| 1 − Tσ T Tσ |Q σ1 | = T |Q| Tσ |Q σ2 | = T |Q | = |Q| T − Tσ T |W |refrig = |Q | Tσ T = |Q | Tσ − t T Since these two quantities are equal.36 For a closed system the ﬁrst term of Eq.|Q| |Q | |Q σ | Heat transfer from the tank at temperature T Heat transfer from the house at T Heat transfer to the surroundings at Tσ The ﬁrst and second laws provide the two equations: |Q| + |Q | = |Q σ | and |Q | |Q σ | |Q| =0 − − T T Tσ Combine these equations to eliminate |Q σ |. A Carnot heat engine operates with the tank as heat source and the surroundings as heat sink. |Q| Tσ − T T − Tσ = |Q | T T or |Q| = |Q | Tσ − T T − Tσ T T 5. Qj d(m S)cv = SG ≥ 0 + Tσ.15 K T = 297. The energy balances for the engine and refrigerator are: |W |engine = |Q| − |Q σ1 | Equation (5. The work produced by the engine drives a Carnot refrigerator (reverse Carnot engine) which extracts heat |Q | from the house and discharges heat to the surroundings.21) is zero.15 K and |Q | = 1500 kJ The result is: |Q| = 143. and solve for |Q|: |Q| = |Q | Tσ − T T − Tσ T T With T = 448. .15 K Tσ = 306. and it becomes: . (5.

. d(m S)cv d Ssurr = SG ≥ 0 − dt dt or T t . .40 The ﬁgure on the left below indicates the direct. d Scv d Ssurr = SG ≥ 0 − dt dt Multiplication by dt and integration over ﬁnite time yields: t Scv + t Ssurr ≥ 0 or Stotal ≥ 0 5. 649 . = SG ≥ 0 ( S)m − Tσ (b) The equation is here written for two streams (I and II) ﬂowing in two pipes. between the two streams. Heat transfer is . this becomes: . Q . (g) For an adiabatic nozzle the result is the same as for Part (c). . . where Q j is here redeﬁned to refer to the system rather than to the surroundings. ( S)m = SG ≥ 0 (d) For an adiabatic gas compressor the result is the same as for Part (c). (5.. j (a) For a single stream ﬂowing within the pipe and with a single heat source in the surroundings. internal. (e) For an adiabatic turbine the result is the same as for Part (c). . and can be written simply as d Ssurr /dt: t . the sect ond term accounts for the entropy changes of the surroundings.22): . irreversible transfer of heat |Q| from a reservoir at T1 to a reservoir at T2 . Thus. Nevertheless. making Q = 0. ( S)I m I + ( S)II m II = SG ≥ 0 (c) For a pump operatiing on a single stream and with the assumption of negligible heat transfer to the surroundings: . 5. (f ) For an adiabatic throttle valve the result is the same as for Part (c).37 The general equation applicable here is Eq. (S m)fs − j . . Qj = SG ≥ 0 Tσ. The ﬁgure on the right depicts a completely reversible process to accomplish the same changes in the heat reservoirs at T1 and T2 .

45 Equation (5. because the heat it transfers to the reservoir at T2 is not Q. in the direct. Therefore. Wlost . irreversible transfer of heat |Q|.The entropy generation for the direct heat-transfer process is: SG = |Q| 1 1 − T1 T2 = |Q| T1 − T2 T1 T2 For the completely reversible process the net work produced is Wideal : |W1 | = |Q| T1 − Tσ T1 and |W2 | = |Q| T2 − Tσ T2 Wideal = |W1 | − |W2 | = Tσ |Q| T1 − T2 T1 T2 This is the work that is lost. with Srev = 0: Sirrev = CP dT T Since Sirrev must be greater than zero.14) can be written for both the reversible and irreversible processes: Sirrev = Tirrev T0 CP ig P dT − ln ◦ P T Srev = Tirrev Trev ig Trev T0 CP ig P dT − ln ◦ P T By difference. 5. 650 . Tirrev must be greater than Trev . Wlost = Tσ |Q| T1 − T2 = Tσ SG T1 T2 Note that a Carnot engine operating between T1 and T2 would not give the correct Wideal or Wlost .

12) to Eq.Chapter 6 .34): νV νT = εV P and νP νT = V ε ρ Combine with the boxed equation: C P − C V = εT V ε ρ 6. (6. 6.Non-Numerical Solutions 6.21) and (6.Section B .2 (a) Application of Eq.2) and (6. (6.33) are both general expressions for d S. νC P νP = −T T ν2V νT 2 P For an ideal gas: νV νT = P R P and ν2V νT 2 =0 P (b) Equations (6.3 By the deﬁnition of H . Differentiate: νU νT = P νH νT −P P νV νT or P νU νT = CP − P P νV νT P 651 . νH νS =T P and isobars have positive slope Differentiate the preceding equation: ν2 H ν S2 = P νT νS P Combine with Eq. U = H − P V .20) yields: νC P νP = T ν{V − T (ν V /ν T ) P } νT P or νC P νP = T νV νT −T P ν2V νT 2 − P νV νT P Whence.17): ν2 H ν S2 = P T CP and isobars have positive curvature.8). (6.1 By Eq. (6. and for a given change of state both must give the same value of d S. (3. They may therefore be equated to yield: (C P − C V ) dT = T νP νT dV + V νV νT dP P Restrict to constant P: C P = CV + T νP νT V νV νT P By Eqs.

Given that C V is constant. C V dT = −P d V = − d(V − b) RT d V = −RT V −b V −b or R dT d ln(V − b) =− CV T But from part (b). d H = dU + d(P V ) d(P V ) = R dT + b d P Combining these two equations and the deﬁnition of part (a) gives: d H = C V dT + R dT + b d P = (C V + R)dT + b d P Then. indicating that U = f (T ) only. substitution gives: ∂U ∂T = CV + P β (βT − κ P)V κ 6. this derivative is C P . Therefore C P = C V + R. (6. The immediate result is: ∂U ∂T = CV + T P ∂P ∂T −P V ∂V ∂T P Solve for the two derivatives by Eqs.34) and (3.4 (a) In general. (c) For a mechanically reversible adiabatic process. Substitution for T by the equation of state gives P(V − b)(V − b)γ −1 = const. P= RT V −b whence ∂P ∂T = V P R = T V −b Substituting this derivative into Eq.2). dU = d W .32) by dT and restrict to constant P. 652 . R/C V = (C P − C V )/C V = γ − 1. then so is C P and so is γ ≡ C P /C V . by the equation of state. the deﬁnition of β: ∂U ∂T = CP − β PV P Divide Eq.2).Substitute for the ﬁnal derivative by Eq.32) yields dU = C V dT . (b) From the deﬁnition of H . (6. R or P(V − b)γ = const. From the equation of state.32) By the equation of state. Whence. ∂H ∂T = CV + R P By deﬁnition. (6. (3. Then d ln T = −(γ − 1)d ln(V − b) From which: or d ln T + d ln(V − b)γ −1 = 0 T (V − b)γ −1 = const. dU = C V dT + T ∂P ∂T − P dV V (6.

The equation for S shows its relation to P to be that of an ideal gas. we can apply the equations: H = G +TS These become: H = (T ) − T d (T ) dT and U = H − P V = H − RT and U = (T ) − T d (T ) − RT dT By Eqs.10) that: V = ∂G ∂P and T S=− ∂G ∂T P Differentation of the given equation of state yields: V = RT P and S=− d (T ) − R ln P dT Once V and S (as well as G) are known. these become: C P = −T d2 dT 2 and C V = −T d2 − R = CP − R dT 2 The equation for V gives the ideal-gas value.16) and (2. (6.20).6 It follows immediately from Eq. C P = C V + R. (2.20). (6. (2. The equations for C P and C V show these properties to be functions of T only. 6. which conforms to ideal-gas behavior. we can apply the equations: H = G +TS These become: H = F(T ) + K P − T d F(T ) dT and U = H − PV = H − PK and U = F(T ) − T d F(T ) dT By Eqs.5 It follows immediately from Eq.10) that: V = ∂G ∂P and T S=− ∂G ∂T P Differentation of the given equation of state yields: V =K and S=− d F(T ) dT Once V and S (as well as G) are known. CP = ∂H ∂T and P CV = ∂U ∂T V Because is a function of temperature only.16) and (2.6. We conclude that the given equation of state is consistent with the model of ideal-gas behavior. which conforms to ideal-gas behavior. The equations for H and U show these properties to be functions of T only. CP = ∂H ∂T and P CV = ∂U ∂T V 653 . as does the result.

whereas U . it is shown that I = ∂/Z .13 This equation does not fall within the compass of the generic cubic. H R .59) may be rewritten as: 654 . (6. 6.58) and (6. At the bottom of page 215. (3. C P . these two equations may be solved iteratively for Z and ξ .2.Because F is a function of temperature only. 6.42). S. Z= 1 exp(−qbρ) 1 − bρ With the deﬁnition. All of this is consistent with the model of an incompressible ﬂuid. multiply the given equation of state by V /RT : −a V PV exp = V RT V −b RT Substitute: Z≡ PV RT V = 1 ρ a ≡q b RT Then. First. (6. (3. and C V are functions of T only. these become: C P = −T d2 F dT 2 and C V = −T d2 F = CP dT 2 The equation for V shows it to be constant. and S R respectively. Eq. Equation (6.1. this becomes: Z= 1 exp(−qξ ) 1−ξ (A) Because ρ = P/Z RT . Eqs.67) and (6.66b) therefore becomes: q∂ GR = Z − 1 − ln(Z − ∂) − Z RT For given T and P. H is seen to be a function of both T and P. ξ ≡ bρ. (6. Z is found by solution of Eq. independent of both T and P. We also have the result that C P = C V . (3. (6.12 Parameter values for the van der Waals equation are given by the ﬁrst line of Table 3. Eqs. as discussed in Ex.62) and (6. 6.53) and (3.11 Results for this problem are given in the text on page 217 by Eqs.52) for a vapor phase or Eq. so we start anew.61).54) for the van der Waals equation are: ∂= Pr 8Tr and q= 27 8Tr With appropriate substitutions.56) for a liquid phase with σ = δ = 0. Because b is a constant. ξ= bP Z RT Given T and P.68) become: q∂ HR = Z −1− Z RT and SR = ln(Z − ∂) R 6.63) for G R . This is the deﬁnition of an incompressible ﬂuid. Equations (3. page 98.

18 Assume the validity for purposes of interpolation of Eq.75). (A). are: ξ 0 (Z − 1) dξ = exp(−q){E[−q(1 − ξ )] − E(−q)} − E(qξ ) − ln(qξ ) − γ ξ where γ is Euler’s constant. . a special function whose values are tabulated in handbooks and are also found from such software packages as MAPLE R . Z is given by Eq.19 Write Eq. and T1 : ln P2sat = A − B T2 (A) ln P sat = A − B T (B) ln P1sat = A − B T1 (C) Subtract (C) from (A): ln P2sat =B P1sat 1 1 − T2 T1 =B (T2 − T1 ) T1 T2 Subtract (C) from (B): ln P sat =B P1sat 1 1 − T T1 =B (T − T1 ) T1 T The ratio of these two equations. (B) and (C) must be evaluated through the exponential integral.75) in log10 form: log P sat = A − B T (A) Apply at the critical point: log Pc = A − B Tc (B) 655 . 6. from which is also obtained: ln Z = − ln(1 − ξ ) − qξ and ∂Z ∂T = ξ qξ exp(−qξ ) T (1 − ξ ) The integrals in Eqs. . yields the required result. (6.GR = RT ξ 0 (Z − 1) ξ 0 dξ + Z − 1 − ln Z ξ (B) HR = RT ∂Z ∂T ξ dξ + Z −1 ξ (C) In these equations.57721566. T . as found from MAPLE R . The necessary equations. ξ and −T 0 ∂Z ∂T ξ sξ = q exp(−q){E[−q(1 − ξ )] − E(−q)} ξ Once values for G R /RT and H R /RT are known. 6. The difﬁculties of integration here are one reason that cubic equations have found greater favor. and write it for T2 .47). E(x). (6. . equal to 0. (6. upon rearrangement. values for S R /R come from Eq.

then application of (A) at the normal boiling point yields: log 1 = A − B Tn or A= B Tn With θ ≡ Tn /Tc .83 The slopes of isobars and isochores on a T S diagram are given by Eqs. (3.0 − log(Pr sat )Tr =0. (6.8) by d S and restriction to constant T yields: ∂H ∂S =T +V T ∂P ∂S By Eq. Whence.30): ∂T ∂S = P T CP and ∂T ∂S = V T CV Both slopes are necessarily positive. With C P > C V .7 = − 3 7 θ 1−θ log Pc By Eq. ∂C P ∂T =b P and 1− T CP ∂C P ∂T =1− P a bT = a + bT a + bT Because this quantity is positive. (6.7 ω= 3 7 θ 1−θ log Pc − 1 6. log Pr sat = B 1 1 − T Tc =B Tr − 1 T (C) If P sat is in (atm). An expression for the curvature of isobars results from differentiation of the ﬁrst equation above: ∂2T ∂ S2 = P 1 CP ∂T ∂S − P T C2 P ∂C P ∂S = P T T − 2 2 CP CP ∂C P ∂T P ∂T ∂S = P T T 1− 2 CP CP ∂C P ∂T P With C P = a + bT .25).48). (6. so then is the curvature of an isobar. B= Equation (C) then becomes: log Pr sat = Tn 1−θ Tn 1−θ log Pc Tr − 1 log Pc = T θ 1−θ Tr − 1 log Pc Tr Apply at Tr = 0.84 Division of Eq. 6. ω = −1. T ∂P ∂S = T −1 βV Therefore.By difference. Eq. isochores are steeper. ∂H ∂S =T− T 1 1 = (βT − 1) β β 656 .17) and (6. (B) can now be written: log Pc = B 1 1 − Tc Tn =B Tc − Tn Tn Tc =B 1−θ Tn Whence.7: log(Pr sat )Tr =0.

∂β ∂P =− T R β RT R (βT − 1) = + 2 2 V P2 V P VP Clearly. H R = G R + T S R .2) and (3. (3. By Eqs. By Eqs. the signs of quantity (βT − 1) and the derivative on the left are the same.56). and V R is (−). ∂V ∂T = P dB R + dT P and β= 1 V dB R + dT P Differentiation of the second preceding equation yields: ∂β ∂P =− T R − V P2 dB R + dT P 1 V2 ∂V ∂P =− T 1 R − (βV ) 2 V V P2 ∂V ∂P T From the equation of state. d 2 B/dT 2 is (−).7 is well above ”normal” temperatures for most gases. (6. and the second derivative in the second boxed equation negative.85 Since a reduced temperature of Tr = 2. 6. ∂2 H ∂ S2 =− T 1 β3V ∂β ∂P T By Eqs. From the deﬁnition of G R .) 657 . This makes the derivative in the ﬁrst boxed equation positive. Because RT /P is greater than |B|. C P ∂HR ∂T is (+). ∂2 H ∂ S2 = T 1 β2 ∂β ∂S = T 1 β2 ∂β ∂P T ∂P ∂S = T 1 β2 ∂β ∂P T −1 βV Whence. and H R : HR = P B − T dB dT Whence. both G R and S R are (−).38): β= 1 V ∂V ∂T and P V = RT +B P Whence. the quantity βT − 1 is positive.54) and (6. and S R = −P(d B/dT ) Whence. Combine the equations above for G R . we expect on the basis of Fig.38) and (6. 6.5. 3. The sign is determined from the relation of β and V to B and d B/dT : T V βT − 1 = dB R + dT P dB dB RT −B T +T dT − 1 = dT −1= P RT RT +B +B P P In this equation d B/dT is positive and B is negative. and H R is (−). GR = BP V R = B. P (See Fig.Also.10 that B is (−) and that d B/dT is (+). ∂HR ∂T =P P dB d2 B dB − −T 2 dT dT dT = −P T d2 B dT 2 R Therefore. S R . (3.40). Moreover. ∂V ∂P =− T RT P2 Whence.

5). ∂T ∂P V ∂ H ig ∂P = S ∂ H ig ∂P + T ∂ H ig ∂T P ∂T ∂P S = CP ig ∂T ∂P S 658 . (A). 6.5) at constant T : −P = V 1 − P1 ln κ V1 (A) (a) Work d W = −P d V = 1 1 V 1 − P1 d V = ln V d V − P1 + ln V1 d V ln κ κ κ V1 V2 V1 W = 1 κ ln V d V − P1 + 1 ln V1 (V2 − V1 ) κ W = 1 1 [(V2 ln V2 − V2 ) − (V1 ln V1 − V1 )] − P1 (V2 − V1 ) − (V2 ln V1 − V1 ln V1 ) κ κ = V2 1 + V1 − V2 − P1 (V2 − V1 ) V2 ln V1 κ By Eq.90 The given equation will be true if and only if dP = 0 T The two circumstances for which this condition holds are when (∂ M/∂ P)T = 0 or when d P = 0.89 By Eq. calculations give: W = 4. (3.036348 kJ kg−1 K−1 ∂M ∂P H = 134.6. The former is a property feature and the latter is a process feature. (6.28). d H = (1 − βT )V d P d H = −(1 − βT )V · 1 − βT 1 dV d ln V = − κ κ H= 1 − βT (V1 − V2 ) κ These equations are so simple that little is gained through use of an average V . 6. (3.91 Neither C P ig ∂T ∂ H ig ∂ H ig ∂ H ig ig = CP + = ∂T P ∂ P V ∂P T ∂P V nor (∂ T /∂ P)V is in general zero for an ideal gas. −P = d S = −βV d P ln V1 ln V − P1 − κ κ and −d P = 1 d ln V κ dS = β βV d ln V = d V κ κ and S= β (V2 − V1 ) κ (c) Enthalpy Substitute for d P: By Eq.55 kJ kg−1 6.9.855 kJ kg−1 S = −0. (6. By Eq. ln V2 = −κ(P2 − P1 ) V1 whence W = P1 V1 − P2 V2 − V2 − V1 κ (b) Entropy By Eq.29). For the conditions given in Pb.

92 For S = S(P. this becomes: dS = CV T ∂T ∂P dP + V CP T ∂T ∂V dV P 6. 6. P= a RT − 2 V −b V and ∂P ∂T = V R V −b Therefore RT a RT − − 2 = V −b V −b V ∂U ∂V and T ∂U ∂V = T a V2 (c) Similarly.30) and (6. (6. dS = ∂S ∂T V ∂T ∂P dP + V ∂S ∂T P ∂T ∂V dV P With Eqs.31). V ): dS = ∂S ∂P dP + V ∂S ∂V dV P By the chain rule for partial derivatives.∂T ∂P =− S ∂T ∂ S ig P ∂ S ig ∂P = T T CP T ig ∂ S ig ∂P T ∂ H ig ∂P ig =T S ∂ S ig ∂P Neither T nor (∂ S /∂ P)T is in general zero for an ideal gas.94 (a) The derivatives of G with respect to T and P follow from Eq. (6. P=T ∂P ∂T − V ∂U ∂V T (a) For an ideal gas.17). for a Redlich/Kwong ﬂuid ﬁnd: ∂U ∂V = T T 1/2 V (V (3/2)A + b) where A = a(Tc ) · Tc 1 2 6. The difﬁculty here is that the expression independent of pressure is imprecise. P= RT V and ∂P ∂T = V R V Therefore RT RT − = V V ∂U ∂V and T ∂U ∂V =0 T (b) For a van der Waals gas.93 By Eq. (6.10): −S = ∂G ∂T and P V = ∂G ∂P T Combining the deﬁnition of Z with the second of these gives: Z≡ P PV = RT RT ∂G ∂P T 659 .

(2. H lv and 660 .74) is exact: H lv d ln P sat =− R Z lv d(1/T ) The right side is approximately constant owing to the qualitatively similar behaviior of Z lv . 6.63) and solving for U gives U = G + T S − P V . Both decrease monotonically as T increases. (6. Replacing S and V by their derivatives gives: U =G−T ∂G ∂T −P P ∂G ∂P T Developing an equation for C V is much less direct. but starting with the derivatives inherent in Eq. becoming zero at the critical point.9).97 Equation (6.11) and (3.Combining Eqs. First differentiate the above equation for U with respect to T and then with respect to P: The two resulting equations are: ∂U ∂T = −T P ∂2G ∂T 2 2 −P P ∂2G ∂T ∂ P ∂U ∂P = −T T ∂ G ∂T ∂ P −P ∂2G ∂ P2 T From the deﬁnition of C V and an equation relating partial derivatives: CV ∂U ∂T = V ∂U ∂T + P ∂U ∂P T ∂P ∂T V Combining the three equations yields: C V = −T ∂2G ∂T 2 −P P ∂2G ∂T ∂ P − T ∂2G ∂T ∂ P +P ∂2G ∂ P2 T ∂P ∂T V Evaluate (∂ P/∂ T )V through use of the chain rule: ∂P ∂T =− V ∂P ∂V T ∂V ∂T = P −(∂ V /∂ T ) P (∂ V /∂ P)T The two derivatives of the ﬁnal term come from differentiation of V = (∂G/∂ P)T : ∂V ∂T = P ∂2G ∂ P∂ T and ∂V ∂P = T ∂2G ∂ P2 T Then ∂P ∂T = V −(∂ 2 G/∂ T ) P (∂ 2 G/∂ P 2 )T and C V = −T ∂2G ∂T 2 −P P ∂2G ∂T ∂ P + T ∂2G ∂T ∂ P +P ∂2G ∂ P2 T (∂ 2 G/∂ P∂ T ) (∂ 2 G/∂ P 2 )T Some algebra transforms this equation into a more compact form: C V = −T ∂2G ∂T 2 +T P (∂ 2 G/∂ T ∂ P)2 (∂ 2 G/∂ P 2 )T (b) The solution here is analogous to that of part (a).

8239 + 4. αc (L/K) = 5.102 Convert αc to reduced conditions: αc ≡ d ln P sat d ln T = T =Tc d ln Prsat d ln Tr = Tr Tr =1 d ln Prsat dTr = Tr =1 d ln Prsat dTr Tr =1 From the Lee/Kesler equation. and increases with increasing molecular complexity as quantiﬁed by ω.72): H lv d P sat = T V lv dT But V lv = RT P sat Z lv whence H lv d ln P sat = RT 2 Z lv dT lv (6. then so is the left side of the preceding equation.73) H 1 H lv Tc H lv d ln Pr sat = · 2 = = 2 Z lv lv 2 Z lv Tr RTc Tr Z RT dTr 6. (6.6.8300 ω Tr =1 Thus. ﬁnd that d ln Prsat dTr = 5.98 By the Clapeyron equation: If the ratio S sl to H sl S sl d P sat = = T V sl V sl dT sl V is assumed approximately constant. then P sat = A + BT If the ratio H sl to V sl is assumed approximately constant.82 for ω = 0.99 By Eq.73) and its analog for sv equilibrium: sat d Psv dT = t Pt Htsv Pt Htsv ≈ RTt2 RTt2 Z tsv sat d Plv dT = t Pt Htlv Pt Htlv ≈ RTt2 RTt2 Z tlv sat d Psv dT − t sat d Plv dT ≈ t Pt RTt2 Htsv − Htlv Because Htsv − Htlv = Htsl is positive. 661 . 6.100 By Eq. then P sat = A + B ln T 6. (6.

(6. this derivative is positive. It applies to reversible adiabatic expansions and compressions in turbines and compressors.30) shows that the ﬁrst product in square brackets on the far right is the ratio C P /C V . it implicitly requires that V represent speciﬁc volume. Reference again to the equation of the footnote on page 266 shows that the second product in square brackets on the far right is −(∂ P/∂ V )T . thus. this may be positive or negative. As written.16). ∂T ∂P = S T CP ∂V ∂T P For gases. Note that it is zero for an ideal gas. (3.31). ∂T ∂V = U 1 CV P−T ∂P ∂T V For gases.2 (a) Apply the general equation given in the footnote on page 266 to the particular derivative of interest here: ∂S ∂T ∂T =− ∂S P ∂P T ∂P S The two partial derivatives on the right are found from Eqs. (2. ∂P ∂V = S CP CV ∂P ∂V = T CP CV −1 κV 662 . (6.17) by Eq. thus. It applies directly to the Joule expansion. depending on conditions. 7. (b) Application of the same general relation (page 266) yields: ∂T ∂V =− U ∂T ∂U V ∂U ∂V T The two partial derivatives on the right are found from Eqs. If V is to be molar volume.16) and (6. then the right side must be divided by molar mass: c2 = − V2 M ∂P ∂V (A) S Applying the equation given in the footnote on page 266 to the derivative yields: ∂P ∂V =− S ∂P ∂S V ∂S ∂V P This can also be written: ∂P ∂V =− S ∂P ∂T V ∂T ∂S V ∂S ∂T P ∂T ∂V =− P ∂T ∂S V ∂S ∂T P ∂P ∂T V ∂T ∂V P Division of Eq. Therefore.17) and (6.Non-Numerical Solutions 7. an adiabatic expansion of gas conﬁned in a portion of a container to ﬁll the entire container. which is given by Eq. This is easily conﬁrmed by a dimensional analysis.3).Section B .Chapter 7 . (6.3 The equation giving the thermodynamic sound speed appears in the middle of page 257.

and κ = 0.11). (A): c2 = V CP MC V κ or c= V CP MC V κ (a) For an ideal gas. 663 . Moreover. (7. Therefore. P1 V1 = RT1 /M. cig = RT C P M CV (b) For an incompressible liquid.7 The mass-ﬂow rate m is of course constant throughout the nozzle from entrance to exit. RT1 /M has units of J·kg−1 or m2 ·s−2 . note that P1 V1 has the units of energy per unit mass. 7. with u 1 = 0 gives: u2 throat = 2 2γ P1 V1 1− γ +1 γ −1 = γ P1 V1 2 γ +1 where V1 is speciﬁc volume in m3 ·kg−1 and P1 is in Pa. Because 1 N · m = 1 J. leading to the result: c = ∞ . ˙ The velocity u rises monotonically from nozzle entrance (P/P1 = 1) to nozzle exit as P and P/P1 decrease. both u 2 and m steadily increase until the critical˙ pressure ratio is reached. and further reduction in P2 does not affect u 2 or m. equivalent units are J·kg−1 . The area ratio decreases from A/A1 = 1 at the nozzle entrance to a minimum value at the throat and thereafter increases to the nozzle exit. At this value of P2 . V = RT /P and κ = 1/P.8 Substitution of Eq. whence Pa · m3 · kg−1 = u2 throat = γ RT1 M 2 γ +1 With R in units of J·(kg mol)−1 ·K−1 .12) into (7. V is constant. 7.Substitute into Eq. This of course leads to the conclusion that the sound speed in liquids is much greater than in gases.6 As P2 decreases from an initial value of P2 = P1 . u 2 equals the speed of sound in the gas. ˙ 7. The units of u 2 throat are then: N · m3 · kg−1 = N · m · kg−1 = kg · m · s−2 · m · kg−1 = m2 · s−2 m2 With respect to the ﬁnal term in the preceding equation.

V = 1/ρ. We apply the following general equation of differential calculus: ∂x ∂y = z ∂x ∂y + w ∂x ∂w y ∂w ∂y z ∂Z ∂T = P ∂Z ∂T + ρ ∂Z ∂ρ T ∂ρ ∂T P Whence. deﬁne ξ ≡ bρ.54) with α (Tr ) = 1 for the van der Waals equation.51). Then.42) with van der Waals parameters becomes: P= a RT − 2 V −b V Multiply through by V /RT . deﬁne q ≡ a/b RT . ρ= P Z RT and ∂ρ ∂T = P P R −1 Z +T (Z T )2 ∂Z ∂T P Setting (∂ Z /∂ T ) P = 0 in each of the two preceding equations reduces them to: ∂Z ∂T =− ρ ∂Z ∂ρ T ∂ρ ∂T and P ∂ρ ∂T =− P ρ P =− 2 T Z RT Combining these two equations yields: T ∂Z ∂T =ρ ρ ∂Z ∂ρ T (a) Equation (3.7. 7. ∂Z ∂T = (−ξ ) − ρ q T = qξ T In addition. Z= 1 − qξ 1−ξ (A) Differentiate: ∂Z ∂T = ρ ∂Z ∂T = −ξ ξ dq dT By Eq. −1 Tr2 dTr =− dT 1 Tr2 Tc =− q 1 =− T T Tr Then. (3. In addition. ∂Z ∂T = ρ ∂Z ∂T − P ∂Z ∂ρ T ∂ρ ∂T P Because P = ρ Z RT . Whence. substitute Z = P V /RT . and rearrange: Z= aρ 1 − RT 1 − bρ In accord with Eq.16 It is shown at the end of Ex.5 that the Joule/Thomson inversion curve is the locus of states for which (∂ Z /∂ T ) P = 0. q = dq = dT / Tr . (3. ∂Z ∂ρ =b T ∂Z ∂ξ = T b − qb (1 − ξ )2 664 .

(A) gives Z . if saturated liquid at 5 bar expands isentropically to 1 bar. Division of the second equation by the ﬁrst gives Pr = ZρbT / Tc .3027 S2 − S2 . For a given value of Tr . As before.54) with α(Tr ) = Tr−0. (B) for ξ . for a given Tr . 7. (B): q= 1+ξ 1−ξ As in Part (a).8604 − 1. and with a single inlet stream.46). (A) then gives Z . P = Zρ RT . and solve Eq. 1 2. (2. (b) Less than. with exactly the same deﬁnitions. (e) Equal to. with the tank as control volume. (3. Pc = RTc /b. This leads to a new Eq. Pr inversion curve as in Fig. q = qξ 1 − 1+ξ 1−ξ (A) / Tr1. Since the process is adiabatic and the only work is shaft work. with n replacing m. A turbine properly designed for expansion of liquids cannot handle the much larger volumes resulting from the formation of vapor. calculate q.29) to this non-steady-state process.17 (a) Equal to. For example. (C) gives Pr .5 ξ (B) 7.5 + 1. by trial or a by a computer routine.2. Eq.28 When a saturated liquid is expanded in a turbine some of the liquid vaporizes. and Eq. (d) Equal to. calculate q.0921 = l v 7. 7. Moreover. Equation (B) then gives ξ . This leads to: 1.Substitute for the two partial derivatives in the boxed equation: T bρ qξ − qbρ = (1 − ξ )2 T or qξ = Whence. and Eq.5 for the Redlich/Kwong equation.5 qξ T (1 + ξ ) Moreover. ∂Z ∂ρ T = bq b − 2 (1 + ξ )2 (1 − ξ ) 2 Substitution of the two derivatives into the boxed equation leads to a new Eq. (C) of Part (a) gives Pr . Whence Pr = Z ξ Tr (C) These equations allow construction of a Tr vs. 1 ξ =1− √ 2q ξ − qξ (1 − ξ )2 (B) By Eq. this equation may be multiplied by dt to give: d(nU )tank − H dn = d Ws 665 l 1.33 Apply Eq. (A): Z= By Eq. (b) Proceed exactly as in Part (a). Eq. the fraction of liquid vaporized would be even greater. 7.3027 S1 − S2 = 0. (3. (c) Less than.5 q dq =− T dT and ∂Z ∂T ρ = 1.5 .3598 − 1. the fraction of the original liquid that vaporizes is found as follows: l v v l S2 = S2 + x2 (S2 − S2 ) = S1 or v x2 = Were the expansion irreversible.

17): ˙ ˙ Ws = n H =n ˙ ( H )S η By Eq. with R = 8.47 K.22) is the usual equation for isentropic compression of an ideal gas with constant heat capacities. integration from beginning to end of the process yields: Ws = n 2 U 2 − n 1 U 1 − n H where the subscripted quantities refer to the contents of the tank and n and H refer to the inlet stream.47) Substitution of numerical values into the boxed equation. can be approximated by V1 = ( H )S = RT1 P1 P and RT1 ˙ Ws = n ˙ η P1 P Equation (7. Substitute n = n 2 − n 1 and H = U + P V = U + RT : Ws = n 2U2 − n 1U1 − (n 2 − n 1 )(U + RT ) = n 2 (U2 − U − RT ) − n 1 (U1 − U − RT ) With U = C V T for an ideal gas with constant heat capacities. the quantity in square brackets becomes: P2 P1 R/C P −1= 1+ P P1 −1 1+ R P C P P1 −1 The boxed equation is immediately recovered from this result. 633 kJ 7. n1 = (101.30b). T = T1 .314 kJ kmol−1 K−1 .314)(298.Because the inlet stream has constant properties.314)(573.1948 kmol (8. T2 = 573. For irreversible compression it can be rewritten: nC P T1 ˙ ˙ Ws = η P2 P1 R/C P R/C P −1 For P sufﬁciently small. Then ( H )S = V dP = V P P is small enough that V . Assume now that RT1 /P1 . this becomes: Ws = n 2 [C V (T2 − T ) − RT ] − n 1 [C V (T1 − T ) − RT ] However. Then.4.8176 kmol (8. T2 = P2 P1 (γ −1)/γ ) Moreover. (7. an average value. n1 = P1 Vtank RT1 and n2 = P2 Vtank RT2 With γ = 1. with R = 8.15) and n2 = (1000)(20) = 4.8). (6.40 Combine Eqs. and therefore: Ws = n 2 [C V (T2 − T1 ) − RT1 ] + n 1 RT1 By Eq. 666 . (3. gives: Ws = 15.314 m3 kPa kmol−1 K−1 .33)(20) = 0.13) and (7.

45 The appropriate energy balance can be written: W = H − Q. η+π −1 CP SG ln = ηπ R R 7. the same H . the derivative is negative (try some values).23) becomes: π −1 T1 π − T1 = T1 1 + T2 = T1 + η η The entropy generation SG is simply S for the compression process. because compressor efﬁciency η and ﬂowrate n are ﬁxed. Since Q is negative (heat transfer is out of the system). Thus.46 There is in fact no cause for concern. the work of compression decreases as C P increases and as the molecular complexity of the gas increases.. 667 . the irreversibilities of operation would have to be quite different for the two cases.7.e. Note that in order to have the same change in state of the air. differentiation yields: dπ d Ws = T1 (π − 1) + C P dC P dC P From the deﬁnition of π. (7. (5. (7. (7. for π > 1. the derivative is zero.22) page 276 gives T2 = T1 π . Isentropic compression work on a mole basis is given by Eq. as adiabatic compression sends the steam further into the superheat region. i. Eq. ln π = P2 R ln P1 CP whence P2 R 1 dπ d ln π ln =− = 2 P1 π dC P dC P CP Then. the work of non-adiabatic compression is greater than for adiabatic compression. With all ˙ other variables constant.22). 7. for which Eq. With this substitution.14) may be rewritten: P2 R/C P C P T2 C P P2 C P T2 S ln − ln = − ln ln = P1 R T1 R P1 T1 R R Combine the two preceding equations: π −1 CP S ln 1 + = η R R CP ln − ln π = R 1+ π −1 η π Whence. which can be written: Ws = C P T1 (π − 1) where π≡ P2 P1 R/C P This equation is a proper basis. P2 πR dπ ln =− 2 P1 dC P CP and π R P2 d Ws ln = T1 π − 1 − P1 CP dC P = T1 (π − 1 − π ln π ) When π = 1. 7.43 The relevant fact here is that C P increases with increasing molecular complexity.41 The equation immediately preceding Eq.

= (d) ∂T P ∂V P ∂V P (e) Rearrange the given equation: ∂V (∂ P/∂ T )V V =− =− ∂P (∂ P/∂ V )T T T ∂P ∂T = V ∂V ∂T P For the ﬁnal equality see footnote on p. and with equal turbine efﬁciencies. (6.52 By Eq. (6. . ∂T ∂Z ∂Z but by (a).19) on page 267 of the text. 77): (T2 ) S = T1 Combine the last two equations. This result is the equation of (c). (b) This result follows immediately from the middle equation on page 267 of the text. H = η( H ) S For C P = constant.7.51 (a) On the basis of Eq. and solve for T2 : T2 = T1 1 + η P2 P1 R/C P −1 668 . W H = . (7. P. 266.50 From the result of Pb. (c) This result follows immediately from Eq.8). 7. this is zero.3: c = V CP 1 · · M CV κ where κ=− 1 V ∂V ∂P T With V = RT +B P then ∂V ∂P =− T RT P2 Also.49 (a) This result follows immediately from the last equation on page 267 of the text. ig = Z H ig W 7. T2 − T1 = η[(T2 ) S − T1 ] P2 P1 R/C P For an ideal gas with constant C P . write: HS = ig V ig d P = RT dP P (const S) HS = V dP = Z RT dP P (const S) HS HS ig = Z RT d P (const S) P ≡ Z RT d P (const S) P By extension. 7.16). let γ = CP CV Then c = PV BP γ γ = 1+ = (RT + B P) RT MRT MRT γ RT M c= B γ RT + RT M γ RT ·P M A value for B at temperature T may be extracted from a linear ﬁt of c vs. 7. (T2 ) S is related to T1 by (see p.

805. 7. Data from Tables F. 7.2 lead to the following: Benzene/4. i. 7. o-Xylene/9 bar 669 . For T2 = 348 K. n-Decane/17 bar.123. η = 0. η = 1.2 and B. The reason is that pumping a liquid is much less expensive than vapor compression. Only T2 = 398 K is possible. For T2 = 398 K.55 The proposal of Pb..53.56 What is required here is the lowest saturated steam temperature that satisﬁes the T constraint. Ethylene glycol/33 bar. η = 1.From which η= T2 −1 T1 P2 P1 R/C P Note that η < 1 −1 Results: For T2 = 318 K.e. pumping of liquid followed by vaporization.5 bar.004.

4 − 1 1.7) for the efﬁciency ηDiesel includes the expansion ratio.4 ηOtto = 0. Whence. x a = 1 + a · (x − 1) + 1 a · (a − 1) · [1 + θ (x − 1)]a−2 · (x − 1)2 2 Note that the ﬁnal term is R. then by Eq.Non-Numerical Solutions 8. taken to the 1st derivative.12 (a) Because Eq.Section B .4904 • rc = 3 ηDesiel = 1 − 1 8 0. r ≡ VC /VD . we relate this quantity to the compression ratio. Since VC = VB . re = VC /V A . R > 0.4 and r = 8.6): ηOtto = 1 − 1 8 0.4 31. R≡ g [1 + θ (x − 1)] · (x − 1)2 2! (0 < θ < 1) Then. VA VC /VD r = rc = = VD VC /V A re or rc 1 = r re Equation (8.4(3 − 1) and ηDiesel = 0. and the Diesel cutoff ratio. re ≡ VB /V A . (8. (8.4317 670 . is written: g = g(1) + g (1) · (x − 1) + R where.7) can therefore be written: ηDiesel 1 =1− γ (rc /r )γ − (1/r )γ rc /r − 1/r 1 (1/r )γ =1− γ 1/r γ −1 rc − 1 rc − 1 γ or ηDiesel = 1 − 1 r rc − 1 γ (rc − 1) γ (b) We wish to show that: rc − 1 >1 γ (rc − 1) γ or more simply xa − 1 >1 a(x − 1) Taylor’s theorem with remainder.Chapter 8 . Therefore: x a > 1 + a · (x − 1) γ x a − 1 > a · (x − 1) and rc − 1 >1 γ (rc − 1) (c) If γ = 1.5647 • rc = 2 ηDesiel = 1 − 1 8 21.4(2 − 1) and ηDiesel = 0.4 and 0.4 − 1 1. rc ≡ V A /VD . For a > 1 and x > 1.

η= TB − T A TA − TB + TC − TD =1− TC − TD TC − TD By Eq. η =1− PB PA (γ −1)/γ −1 TC 1 − PA PB (γ −1)/γ Multiplication of numerator and denominator by (PB /PA )(γ −1)/γ gives: η =1− TA TC PB PA (γ −1)/γ 671 .30b).8. (3. while the air temperature decreases in step D → D ∗ .15 See the ﬁgure below. Heat addition (replacing combustion) is in step B ∗ → C. W AB = (H B − H A ) = C P (TB − TA ) WC D = (H D − HC ) = C P (TD − TC ) Q B ∗ C = C P (TC − TB ∗ ) = C P (TC − TD ) Whence. η≡ −W AB − WC D Q B∗C where. TB = T A PB PA (γ −1)/γ and TD = TC PD PC (γ −1)/γ = TC PA PB (γ −1)/γ TA Then. the air temperature is raised in step B → B ∗ . In the regenerative heat exchanger. By deﬁnition.

Mark T.e. 78. (A) and (B) become: γ P dP = γ −1T dT P γ d2 P = (γ − 1)2 T 2 dT 2 We note here that γ /(γ − 1) and γ /(γ − 1)2 are both > 1.. P = K T δ/(δ−1) . δ=γ δ=1 P δ=∞ δ=0 0 0 T The required sketches appear on the following page.21 We give ﬁrst a general treatment of paths on a P T diagram for an ideal gas with constant heat capacities undergoing reversible polytropic processes. p.. Moreover. this requires δ = ∞ . (A). + For a constant-V process. Equation (3.) 672 . + δ = 0 −→ d P/dT = 0 δ = 1 −→ d P/dT = ∞ Constant P Constant T Special cases By Eq. State University of New York at Buffalo. Lines characteristic of the various processes are shown on the following diagram. i. Thus in relation to a constant-V process the isentropic process is represented by a line of greater slope and greater curvature for the same T and P. (Courtesy of Prof. δ d2 P = 2 δ−1 dT P 1 dP − 2 T T dT = δ 1 δ−1T P δ P − T δ−1T P δ d2 P = (δ − 1)2 T 2 dT 2 (B) Sign of d 2 P/dT 2 is that of δ.e. For a reversible adiabatic process (an isentropic process). Thus a constant-V process is represented on a P T diagram as part of a straight line passing through the origin. d P/dT = K and d 2 P/dT 2 = 0. P varies with T in accord with the ideal-gas law: P = RT /V or P = K T With respect to the initial equation. δ = γ . Swihart. i.8. The slope K is determined by the initial P T coordinates. In this case Eqs.35c). may be rewritten as P = K T δ/(δ−1) ln P = ln K + δ ln T δ−1 δ dT dP = δ−1 T P δ P dP = δ−1T dT (A) Sign of d P/dT is that of δ − 1.

23 This is a challenging and open-ended problem for which we offer no solution.P P 0 0 T Figure 1: The Carnot cycle 0 0 T Figure 2: The Otto cycle P P 0 0 T Figure 3: The Diesel cycle 0 0 T Figure 4: The Brayton cycle 8. 673 .21 may offer some insight. Problem 8.

then: What you get = |Q H | What you pay for = |W | Whence ν |Q H | |W | For a Carnot heat pump.3) yields: ερ ε TC = TH TH TC 1 = + 2 (TH − TC )2 (TH − TC ) TH − TC and ερ ε TH =− TC TC (TH − TC )2 Because TH > TC . TH is ﬁxed by environmental conditions. the ﬁrst of Carnot’s equations becomes: dTC d Q H = −C t TH TC Combine this equation with the second of Carnot’s equations: d W = −C t TH dTC + C t dTC TC Integration from TC = TH to TC = TC yields: W = −C t TH ln TC + C t (TC − TH ) TH or W = C t TH ln TC TH −1 + TH TC 9.3 Because the temperature of the ﬁnite cold reservoir (contents of the refrigerator) is a variable. a comparison shows that ρ < ρσ and therefore that ρ is the more conservative value.5 Differentiation of Eq. (9.Chapter 9 . (9. use differential forms of Carnot’s equations. ν= TH |Q H | = TH − TC |Q H | − |Q C | 9.8): TH d QH =− TC d QC and dW = 1 − TC TH d QH In these equations Q C and Q H refer to the reservoirs. 674 .3). 9.6 For a Carnot refrigerator.7) and (5. and not subject to control. With d Q H = C t dTC . the more effective procedure is to increase TC . because for all practical purposes.1 Since the object of doing work |W | on a heat pump is to transfer heat |Q H | to a heat sink. ρ is given by Eq. Write this equation for the two cases: ρ= TC TH − TC and ρσ = TσC Tσ H − TσC Because the directions of heat transfer require that TH > Tσ H and TC < TσC . (5.Section B . Eqs.Non-Numerical Solutions 9. increasing TC is hardly an option if refrigeration is required at a particular value of TC . Decreasing TH is no more realistic. For a real refrigeration system.

21 = 0. 675 . the coefﬁcient of performance will increase. at least in temperate climates. 9. then TC < 187.6 Carnot = 0.9.6. but beneﬁcial in the summer. then TC < TH /1.6 TC TH − TC If < 1. For TH = 300 K. which is most unlikely.20 On average.5 K. The proposed arrangement would result in cooling of the kitchen. thus providing savings on electric casts. as the refrigerator would act as an air conditioner. installation casts would be higher. This would be detrimental in the winter. On the other hand.

10. Solve for m i : Mi pi V t mi = RT Applied to moist air. the mole fraction of species i in the mixture: yi P V t = n i RT or pi V t = mi RT Mi where m i is the mass of species i. and are in fact only slightly soluble in one another at 300 K. and the preceding equation becomes: h sat = PHsat MH2 O 2O Mair P − PHsat 2O 676 . (d) Because isooctane and n-octane are chemically similar and at a temperature (373. considered a binary mixture of air and water vapor. then the partial pressure of water vapor in the air equals the vapor pressure of the water. h≡ m H2 O m air or h= MH2 O pH2 O Mair pair Since the partial pressures must sum to the total pressure. because no value of P sat for hydrogen is known. pair = P − pH2 O . 10.6 (a) Because benzene and toluene are chemically similar and the pressure is only 1(atm). P V t = n RT . a pressure of 25 bar is too high for modeling this system by Raoult’s law. deﬁned as pi ≡ yi P.Non-Numerical Solutions 10. this system can be modeled by Raoult’s law to a good approximation. this system can be modeled by Raoult’s law to a good approximation.2) shows that P is linear in x1 . (e) Water and n-decane are much too dissimilar to be modeled by Raoult’s law. hydrogen is supercritical.15 K) close to their normal boiling points. (b) Although n-hexane and n-heptane are chemically similar. h= p H2 O MH2 O Mair P − pH2 O (b) If air is in equilibrium with liquid water.Section B . and pi is its partial pressure. Thus no maximum or minimum can exist in this relation.12 For a total volume V t of an ideal gas. Since such an extremum is required for the existence of an azeotrope. no azeotrope is possible.Chapter 10 .5 For a binary system. Mi is its molar mass. this gives: m H2 O = M H 2 O p H2 O V t RT and m air = Mair pair V t RT (a) By deﬁnition. the next equation following Eq. Multiply both sides by yi . (10. whence. (c) At 200 K. and modeling the hydrogen/propane system at this temperature by Raoult’s law is out of the question.

Moreover.(c) Percentage humidity and relative humidity are deﬁned as follows: h pc pH2 O P − PHsat h 2O (100) ≡ sat = sat PH2 O P − pH2 O h and h rel ≡ p H2 O (100) PHsat 2O Combining these two deﬁnitions to eliminate pH2 O gives: h pc = h rel P − PHsat (h rel /100) 2O P − PHsat 2O 10.5) and the given equations for ln γ1 and ln γ2 .1 indicate that were air used rather than CO2 . P is then proportional to Hi . (10. y1 = K 1 x1 and y2 = K 2 x2 . 10. 10. 10. very little of this gas dissolves in the blood streams of divers at approximately atmospheric pressure.21 By Eq. y1 + y2 = 1.24 By the deﬁnition of a K -value. 2 y1 P = x1 exp(Ax2 )P1sat and 2 y2 P = x2 exp(Ax1 )P2sat These equations sum to give: 2 2 P = x1 exp(Ax2 )P1sat + x2 exp(Ax1 )P2sat Dividing the equation for y1 P by the preceding equation yields: y1 = 2 x1 exp(Ax2 )P1sat 2 2 x1 exp(Ax2 )P1sat + x2 exp(Ax1 )P2sat For x1 = x2 this equation obviously reduces to: P= P1sat P1sat + P2sat 10.23 A little reﬂection should convince anyone that there is no other way that BOTH the liquid-phase and vapor-phase mole fractions can sum to unity. These equations combine to yield: K 1 x1 + K 2 x2 = 1 Solve for x1 : or K 1 x1 + K 2 (1 − x1 ) = 1 x1 = 1 − K2 K1 − K2 Substitute for x1 in the equation y1 = K 1 x1 : y1 = K 1 (1 − K 2 ) K1 − K2 677 . Eq.15 Because Henry’s constant for helium is very high. (10. P would be about 44 times greater.14 Because the vapor space above the liquid phase is nearly pure gas.4) becomes P = xi Hi . For the same mole fraction of gas dissolved in the liquid phase. Values given in Table 10. much too high a pressure to be practical.

1. 10. Ms = 18. 678 .35 Molality ≡ Mi = xi ni = x s Ms ms where subscript s denotes the solvent and Ms is the molar mass of the solvent. x1 L + y1 V = z 1 or x1 (1 − V) + y1 V = z 1 Substitute for both x1 and y1 by the equations derived above: K 1 (1 − K 2 ) 1 − K2 V = z1 (1 − V) + K1 − K2 K1 − K2 Solve this equation for V: V= z 1 (K 1 − K 2 ) − (1 − K 2 ) (K 1 − 1)(1 − K 2 ) Note that the relative amounts of liquid and vapor phases do depend on z 1 .018015 kg mol−1 .Note that when two phases exist both x1 and y1 are independent of z 1 . or 0.4) shows that Hi = 1 x s Ms k i or for xi → 0 Hi = 1 Ms k i For water. The given equation may therefore be written: xi = ki yi P x s Ms or xi 1 x s Ms k i = yi P Comparison with Eq. (10.015 g mol−1 Thus.034) This is in comparison with the value of 1670 bar in Table 10. Hi = 1 = 1633 bar (0. By a material balance on the basis of 1 mole of feed.018015)(0.

Then m= νm νn i ε nk Mk = ni Mi + ε n j M j k j ( j = i) and = T.m j If Mi is the molar mass of species i.P.P.16).n j ν(n i Mi ) νn i = Mi T.P.P. m i = Mi ¯ ˜ (b) Deﬁne a partial speciﬁc property as: Mi νM t νm i = T.m j νM t νn i T. ni = mi Mi and νn i νm i = T.Chapter 11 .Non-Numerical Solutions 11. the initial equation may be written: ¯ Mi ˜ Mi = Mi 11.7): ¯ Ti ν(nT ) νn i =T P. dV ¯ V1 = V + x2 d x1 and dV ¯ V2 = V − x1 d x1 Because V = ρ −1 then −1 dρ dV = 2 ρ d x1 d x1 whence 1 x2 dρ 1 ¯ = V1 = − 2 ρ ρ d x1 ρ 1− x2 dρ ρ d x1 = dρ 1 ρ − x2 2 d x1 ρ 1 x1 dρ 1 ¯ = V2 = + 2 ρ ρ d x1 ρ 1+ x1 dρ ρ d x1 = dρ 1 ρ + x1 2 d x1 ρ With 2 ρ = a0 + a1 x 1 + a2 x 1 and dρ = a1 + 2a2 x1 d x1 these become: 1 2 ¯ V1 = 2 [a0 − a1 + 2(a1 − a2 )x1 + 3a2 x1 ] ρ and 1 2 ¯ V2 = 2 (a0 + 2a1 x1 + 3a2 x1 ) ρ 679 . (11.P. and deﬁne the partial molar mass by: m i ¯ νm νn i T.P.8 By Eqs.7 (a) Let m be the mass of the solution.m j νn i νm i T.n j Let Mk be the molar mass of species k.T.P.n j Whence. (10.n j νn νn i =P T.6 Apply Eq.n j νn νn i =T T.Section B .15) and (10.P.n j ¯ Pi ν(n P) νn i =P P.n j 11.m j 1 Mi Because constant m j implies constant n j .T.P.

∂n ∂n 1 =1 T. These two equations combine to give Z = 11.10 With the given equation and the Dalton’s-law requirement that P = P= RT V i pi . or MiE as functions of composition.9 For application of Eq. n1 n2n3 ¯ C M1 = M1 + 2 1 − 2 n n and ¯ M1 = M1 + x2 x3 [1 − 2x1 ]C Similarly. MiR .n 2 .n 2 .4 by n (= n 1 + n 2 ) and eliminate x1 by x1 = n 1 /(n 1 + n 2 ): n H = 600(n 1 + n 2 ) − 180 n 1 − 20 n3 1 (n 1 + n 2 )2 Form the partial derivative of n H with respect to n 1 at constant n 2 : ¯ H1 = 600 − 180 − 20 n3 n2 2n 3 3n 2 1 1 1 1 + 40 = 420 − 60 − (n 1 + n 2 )3 (n 1 + n 2 )2 (n 1 + n 2 )2 (n 1 + n 2 )3 3 2 ¯ H1 = 420 − 60 x1 + 40 x1 Whence.n 3 Because n = n 1 + n 2 + n 3 . (11. then: yi Z i i i For the mixture. P = Z RT /V .P. (11. 11. k = i) Here x j and xk are mole fractions on an i-free basis.11 The general principle is simple enough: yi Z i . (A) of Ex. ∂(n M) ∂n 1 T.n 3 Whence.P.7) all mole fractions must be eliminated from the given equation by the relation xi = n i /n: n1n2n3 C n M = n 1 M1 + n 2 M2 + n 3 M3 + n2 ¯ For M1 . ¯ M2 = M2 + x1 x3 [1 − 2x2 ]C and ¯ M3 = M3 + x1 x2 [1 − 2x3 ]C One can readily show that application of Eq. one may combine them by the summability relation to yield a mixture property.n 2 . The inﬁnite dilution values are given by: ¯ Mi∞ = Mi + x j xk C ( j.11.n 3 = M1 + n 2 n 3 C 2n 1 1 − 3 2 n n ∂n ∂n 1 T.11) regenerates the original equation for M.12 (a) Multiply Eq. 11.P. 11. Form the partial derivative of n H with respect to n 2 at constant n 1 : ¯ H2 = 600 + 20 2 n3 1 (n 1 + n 2 )3 or 3 ¯ H2 = 600 + 40 x1 680 . ¯ ¯ ¯ Given equations that represent partial properties Mi . Application of the deﬁning (or equivalent) equations for partial properties then regenerates the given equations if and only if the given equations obey the Gibbs/Duhen equation.

(11. dV 2 = 58 − 2 x1 − 21 x1 d x1 Then.(b) In accord with Eq. 2 3 3 H = x1 (420 − 60 x1 + 40 x1 ) + (1 − x2 )(600 + 40 x1 ) Whence.16) to ﬁnd expressions for V1 and V2 . The results are: ¯ d H1 d x1 = x1 =1 ¯ d H2 d x1 =0 x1 =0 (e) 11.11). (11. First.13 (a) Substitute x2 = 1 − x1 in the given equation for V and reduce: 3 2 V = 70 + 58 x1 − x1 − 7 x1 ¯ ¯ Apply Eqs. 3 2 ¯ V1 = 128 − 2 x1 − 20 x1 + 14 x1 and 3 2 ¯ V2 = 70 + x1 + 14 x1 681 .14) for a binary system and divide by d x1 : x1 ¯ ¯ d H2 d H1 =0 + x2 d x1 d x1 Differentiate the the boxed equations of part (a): ¯ d H1 2 = −120 x1 + 120 x1 = −120 x1 x2 d x1 and ¯ d H2 2 = 120 x1 d x1 Multiply each derivative by the appropriate mole fraction and add: 2 2 −120 x1 x2 + 120x1 x2 = 0 (d) Substitute x1 = 1 and x2 = 0 in the ﬁrst derivative expression of part (c) and substitute x1 = 0 in the second derivative expression of part (c).15) and (11. (11. 3 H = 600 − 180 x1 − 20 x1 (c) Write Eq.

2 3 2 3 V = x1 (128 − 2 x1 − 20 x1 + 14 x1 ) + (1 − x1 )(70 + x1 + 14 x1 ) Whence.14 By Eqs. The results are: ¯ d V1 d x1 = x1 =1 ¯ d V2 d x1 =0 x1 =0 (e) 11.11). 3 2 V = 70 + 58 x1 − x1 − 7 x1 which is the ﬁrst equation developed in part (a). (d) Substitute x1 = 1 in the ﬁrst derivative expression of part (c) and substitute x1 = 0 in the second derivative expression of part (c).15) and (11. (11.(b) In accord with Eq. (11. (11. (c) Write Eq.16): dH ¯ H1 = H + x2 d x1 and dH ¯ H2 = H − x1 d x1 682 .14) for a binary system and divide by d x1 : x1 ¯ ¯ d V2 d V1 =0 + x2 d x1 d x1 Differentiate the the boxed equations of part (a): ¯ d V1 2 = −2 − 40 x1 + 42 x1 d x1 and ¯ d V2 2 = 2 x1 + 42 x1 d x1 Multiply each derivative by the appropriate mole fraction and add: 2 2 x1 (−2 − 40 x1 + 42 x1 ) + (1 − x1 )(2 x1 + 42 x1 ) = 0 The validity of this equation is readily conﬁrmed.

P.Given that: Then. further evidence that they cannot be valid. Thus ln φi = ¯ G i /RT . written: x1 ¯ ¯ d H2 d H1 =0 + x2 d x1 d x1 The suggested expresions do not obey this equation.n j or n ∂V ∂n i ¯ = Vi − V T.n j Therefore.14).20 Equation (11.57) and (11.P.x ¯ HiR RT 2 The summability and Gibbs/Duhem equations take on the following forms: GR = RT ˆ xi ln φi i and i ˆ xi d ln φi = 0 (const T.P.n ∂V ∂n i T. ∂M ¯ ˜ Mi = Mi + n ∂V T.n j Whence. H = x1 (a1 + b1 x1 ) + x2 (a2 + b2 x2 ) dH = a1 + 2b1 x1 − (a2 + 2b2 x2 ) d x1 Combining these equations gives after reduction: ¯ H1 = a1 + b1 x1 + x2 (x1 b1 − x2 b2 ) and ¯ H2 = a2 + b2 x2 − x1 (x1 b1 − x2 b2 ) These clearly are not the same as the suggested expressions. Eq. ∂M ˜ ¯ ¯ Mi = Mi + (V − Vi ) ∂V T.V. The partial-property analogs of Eqs.x ¯ Vi R RT and ˆ ∂ ln φi ∂T =− P. P) 683 .58) are: ˆ ∂ ln φi ∂P = T.15 Apply the following general equation of differential calculus: ∂x ∂y = z ∂x ∂y + w ∂x ∂w y ∂w ∂y z ∂(n M) ∂n i = T.n j ∂V ∂n i +V T.n j By deﬁnition. (11.n ∂V ∂n i T. which are therefore not correct.P. Note further that differentiation of these same expressions yields results that satisfy the Gibbs/Duhem equation.n j ∂(n M) ∂n i + T. Note that application of the summability equation to the derived partial-property expressions reproduces the original equation for H . after simpliﬁcation.P.n j ∂(n M) ∂V T. ∂(nV ) ¯ Vi ≡ ∂n i =n T. 11.P.59) demonstrates that ln φi is a partial property with respect to G R /RT .x ˆ ˆ 11.P. (11.n ∂V ∂n i or T.n j ∂M ˜ ¯ Mi = Mi − n ∂V T.

28 (a) Because Eq.8 + 2 x1 + 2.16) may be written for M ≡ G E/RT : ln γ1 = d(G E/RT ) GE + x2 d x1 RT ln γ2 = d(G E/RT ) GE − x1 d x1 RT Substitute x2 = 1 − x1 in the given equaiton for G E/RT and reduce: GE 2 3 = −1.8 x1 + x1 + 0. (11. The results are: d ln γ1 d x1 = x1 =1 d ln γ2 d x1 =0 x1 =0 684 . (11.8 x1 d x1 and d ln γ2 2 = −2 x1 − 4.8 x1 ) = 0 The validity of this equation is readily conﬁrmed.8 x1 ) + (1 − x1 )(−2 x1 − 4. (3. GE 3 2 = −1.6 x1 ) + (1 − x1 )(−x1 − 1.8 x1 RT which is the ﬁrst equation developed in part (a).8 x1 d x1 Multiply each derivative by the appropriate mole fraction and add: 2 2 x1 (2 + 2.14) for a binary system with Mi = ln γi and divide by d x1 : x1 d ln γ2 d ln γ1 =0 + x2 d x1 d x1 Differentiate the the boxed equations of part (a): d ln γ1 2 = 2 + 2.11. (d) Substitute x1 = 1 in the ﬁrst derivative expression of part (c) and substitute x1 = 0 in the second derivative expression of part (c).36): Z =1+ BP RT and ln φ = BP RT then: ln φ ≈ Z − 1 11.8 x1 − 4.4 x1 d x1 Then. ¯ (c) Write Eq.6 x1 and 3 2 ln γ2 = −x1 − 1.8 x1 − 4.4 x1 − 1.8 x1 + x1 + 0. 3 2 ln γ1 = −1. (11.11).8 + 2 x1 + 1.96) shows that ln γi is a partial property with respect to G E/RT .6 x1 ) RT Whence.15) and (11.8 + 2 x1 + 1.26 For a pressure low enough that Z and ln φ are given approximately by Eqs. GE 2 3 2 3 = x1 ln γ1 + x2 ln γ2 = x1 (−1. Eqs. (11.38) and (11.6 x1 (b) In accord with Eq.8 x1 RT whence d(G E/RT ) 2 = −1.4 x1 − 1.

368 −1920 1595 984 −208 605 −416 1465 −491.857 2.4 1044.817 −2.15 and given in the following table: T = 30.3 −2.4 1039.935 −2.9 352.5 849.30 For C P = const.15. E II.857 2.614 −1. the following equations are readily developed from those given in the last column of Table 11.817 −3.354 1..0 11.9 716.0 685 .0 −3.54).9 699.817 −3.677 1. T = 313.8 683.5 1513.x E = CP T T Working equations are then: E S1 = E H1E − G 1 T1 and E E E S2 = S1 + C P T T E H2E = H1E + C P T and E E G 2 = H2E − T2 S2 For T1 = 298.602 −1794 1694 903 482 935 −86 1225 −497. results for all parts of the problem are I. E 11.5 −4.764 −2.0 −8. For C P = 0 E G1 H1E E S1 E CP E S2 H2E E G2 E S2 H2E E G2 (a) (b) (c) (d) (e) (f) (g) −622 1095 407 632 1445 734 759 −1920 1595 984 −208 605 −416 1465 −4.7 348.2 3.7 833. (14.677 1.(e) 11.1 (page 415): E H E = CP T and SE = − ∂G E ∂T P.0 11.7 688.951 1.677 −0.5 1529.368 4.354 1.15.817 −2.7 23.29 Combine deﬁnitions of the activity coefﬁcient and the fugacity coefﬁcients: γi ≡ fˆi /xi P f i /P or γi = ˆ φi φi Note: See Eq.993 1.803 1.935 −2. T2 = 328.

(11. written with M ≡ G and with x replaced by y: G E = B P − y1 B11 P − y2 B22 P or GE = GR − Equations (11.33) and (11.x Because δ12 is a function of T only: SE = − dδ12 P y1 y2 dT By the deﬁnition of G E . and convert remaining mole fractions to ratios of mole numbers: n2n3 n1n3 n1n2 nG E + A23 + A13 = A12 n n n RT Differentiation with respect to n 1 in accord with Eq. 402: G E = δ12 P y1 y2 From the last column of Table 11. (11.31 (a) Multiply the given equation by n (= n 1 + n 2 ).87). Multiplying each of these terms by the appropriate xi and adding gives: 2 2 A12 (x1 x2 − x1 x2 + x2 x1 − x2 x1 − x1 x2 x3 ) = A12 x1 x2 (1 − x1 + 1 − x2 − x3 ) = A12 x1 x2 [2 − (x1 + x2 + x3 )] = A12 x1 x2 An analogous result is obtained for the second and third terms on the right. whence.11.36) together give G iR = Bii P. and the terms are summed. For pure species 1. For inﬁnite dilution of species 3. H E = G E + T S E . Then for a binary mixture: G E = P(B − y1 B11 − y2 B22 ) i yi G iR Combine this equation with the last equation on Pg. and adding them yields the given equation for G E/RT . Consider the ﬁrst terms on the right of each expression for ln γi .x This equation and the preceding one lead directly to: E C P = −T d 2 δ12 P y1 y2 dT 2 686 . x1 = 0: x1 = 1: x2 = 0: x3 = 0: ln γ1 (x1 = 0) = A12 x2 + A13 x3 − A23 x2 x3 ln γ1 (x1 = 1) = 0 2 ln γ1 (x2 = 0) = A13 x3 2 ln γ1 (x3 = 0) = A12 x2 11. (c) For inﬁnite dilution of species 1.96) yields [(∂n/∂n 1 )n 2 .1: C P = ∂HE ∂T P. For inﬁnite dilution of species 2.n 3 = 1]: ln γ1 = A12 n 2 1 n1 − n n2 + A13 n 3 1 n1 − n n2 − A23 n2n3 n2 = A12 x2 (1 − x1 ) + A13 x3 (1 − x1 ) − A23 x2 x3 Similarly. ln γ2 = A12 x1 (1 − x2 ) − A13 x1 x3 + A23 x3 (1 − x2 ) ln γ3 = −A12 x1 x2 + A13 x1 (1 − x3 ) + A23 x2 (1 − x3 ) (b) Each ln γi is multiplied by xi .35 By Eq. H E = δ12 − T dδ12 dT P y1 y2 E Again from the last column of Table 11.1 (page 415): S E = − ∂G E ∂T P.

which is unusual. 11. x1 2 2 M E = Ax1 x2 11. as required. which is unusual behavior.14). which is unusual: For x1 = 0 and x1 = 1 ¯E d M1 =0 d x1 and ¯E d M2 =0 d x1 PLOTS OF THE FUNCTIONS ARE SHOWN ON THE FOLLOWING PAGE. they also change sign.01082 = 2 3132 Tmean The data are evidently thermodynamically consistent.41 From Eq.95): ∂(G E /RT ) ∂T = P −H E RT 2 or ∂(G E /T ) ∂T = P −H E T2 To an excellent approximation. as required.11.45 (a) For ﬁnd 2 ¯E M1 = Ax1 x2 (2 − 3x1 ) and 2 ¯E M2 = Ax1 x2 (2 − 3x2 ) Note that at both x1 = 0 (x2 = 1) and x1 = 1 (x2 = 0). the Gibbs/Duhem equation. write: ∂(G E /T ) ∂T ≈ P −H E (G E /T ) ≈ 2 Tmean T From the given data: −0. x1 ¯ ¯ d M2 d M1 =0 + x2 d x1 d x1 Given that ¯ M1 = M1 + Ax2 and ¯ M2 = M2 + Ax1 then ¯ d M1 = −A d x1 and ¯ d M2 =A d x1 Then ¯ ¯ d M2 d M1 = −x1 A + x2 A = A(x2 − x1 ) = 0 + x2 d x1 d x1 The given expressions cannot be correct.01084 = = 25 323 − 298 T and −1060 −H E = −0. In particular. Find also that ¯E ¯E d M2 d M1 = −2Ax1 (1 − 6x1 x2 ) = 2Ax2 (1 − 6x1 x2 ) and d x1 d x1 The two slopes are thus of opposite sign. (11.42 By Eq. ¯E ¯E d M2 d M1 =0 = 2A and For x1 = 0 d x1 d x1 For x1 = 1 ¯E d M1 =0 d x1 and ¯E d M2 = −2A d x1 (b) For M E = A sin(π x1 ) ﬁnd: ¯E M1 = A sin(π x1 ) + Aπ x2 cos(π x1 ) and ¯E M2 = A sin(π x1 ) − Aπ x1 cos(π x1 ) ¯E ¯E d M2 d M1 = Aπ 2 x1 sin(π x1 ) = −Aπ 2 x2 sin(π x1 ) and d x1 d x1 The two slopes are thus of opposite sign. 687 . ¯E ¯E ( M1 )∞ = ( M2 )∞ = 0 ¯E ¯E M1 = M2 = 0 ¯E ¯E Although M E has the same sign over the whole composition range. both M1 and M2 change sign. But note the following.271 785/323 − 805/298 (G E /T ) = −0. (11.

. 11. 1 .x .01 . xi MEbar2i 2 1. cos . i xi 2 xi 2 xi .x i i MEbar1i MEbar2i 40 30 MEi A . 1 xi .5 MEbar2i 0 0. 100 1 xi MEbar1i 3.2 0.x i p (pi prints as bf p) .4 xi 0.p . 0 .5 0 0.8 1 687A .Pb. cos p p .45 (a) A MEi 10 A .45 (b) MEi A .4 xi 0. p . sin A.5 MEi 1 A . 1 MEbar1 i 0. 11.x i p A . sin p . xi . 1 xi 2 3 .8 1 Pb. sin A . xi . 2 A .6 0. xi i 2.6 0.x i 20 MEbar1 i 10 0 10 MEbar2i 0 0. xi . xi .2 0.00001 .

n j k ∂M ∂ xk T.x j = 1 n ∂M ∂ xi − T.P. 688 .x j ∂ xk ∂n i nj With nk xk = n ∂ xk ∂n i = nj  n − k   n2 (k = i) ∂M ∂n i =− T.46 By Eq.P. dM = k ∂M ∂ xk d xk T.P.n j ∂M ∂n i T.P.P.P.11. x2 ).x j For species 1 of a binary mixture (all derivatives at constant T and P): ¯ M1 = M + ∂M ∂ x1 x2 − x1 ∂M ∂ x1 x2 − x2 ∂M ∂ x2 x1 = M + x2 ∂M ∂ x1 − x2 ∂M ∂ x2 x1 Because x1 + x2 = 1.P. the partial derivatives in this equation are physically unrealistic. however. they do have mathematical signiﬁcance.n j 1 n xk k=i ∂M ∂ xk 1  − ni  n n2 (k = i) T. Because M = M(x1 .n j At constant T and P.x j 1 n xk k ∂M ∂ xk T.P.x j k xk ∂M ∂ xk T.P. we can quite properly write: dM = ∂M ∂ x1 x2 d x1 + ∂M ∂ x2 x1 d x2 Division by d x1 yields: dM = d x1 ∂M ∂ x1 + x2 ∂M ∂ x2 x1 d x2 = d x1 ∂M ∂ x1 − x2 ∂M ∂ x2 x1 wherein the physical constraint on the mole fractions is recognized.P.7).x j ∂M 1 + (1 − xi ) ∂ xi n T. Therefore dM ¯ M1 = M + x 2 d x1 ¯ The expression for M2 is found similarly. (11.P.x j Divide by dn i with restriction to constant n j ( j = i): ∂M ∂n i = T. ∂(n M) ¯ Mi = ∂n i = M +n T.P.x j ¯ Mi = M + ∂M ∂ xi − T.

written for excess properties.48 By Eqs.7) to species 1: ∂(n M E ) ¯E M1 = ∂n 1 n2 Multiply the given equation by n and eliminate the mole fractions in favor of mole numbers: n M E = An 1 n 2 1 1 + n 1 + Bn 2 n 2 + Bn 1 ¯E M1 = An 2 1 1 + n 1 + Bn 2 n 2 + Bn 1 + n1 B −1 − (n 1 + Bn 2 )2 (n 2 + Bn 1 )2 Conversion back to mole fractions yields: ¯E M1 = Ax2 1 1 + x2 + Bx1 x1 + Bx2 − x1 B 1 + 2 (x2 + Bx1 )2 (x1 + Bx2 ) The ﬁrst term in the ﬁrst parentheses is combined with the ﬁrst term in the second parentheses and the second terms are similarly combined: ¯E M1 = Ax2 x1 1 1− x1 + Bx2 x1 + Bx2 + Bx1 1 1− x2 + Bx1 x2 + Bx1 Reduction yields: 2 ¯E M1 = Ax2 1 B + (x1 + Bx2 )2 (x2 + Bx1 )2 Similarly. its value and derivative with respect to xi become zero at xi = 1. when written for excess properties in a binary system at constant T and P: x1 ¯E ¯E d M2 d M1 =0 + x2 d x1 d x1 If the answers to part (a) are mathematically correct. 689 . (11. (11. (11. d M1 /d x1 = 0. because they were derived ¯ from a proper expression for M E .14). d M2 /d x1 = 0. for each partial property MiE .47 (a) Apply Eq. Furthermore. and by continuity can only increase or decrease for x1 < 1. this is inevitable. Similarly.15) and (11. at x1 = 0. Therefore the 2 E ¯ 1 /d x1 is the same as the sign of d 2 M E /d x1 . ﬁnd: ¯E d2 M E d M1 = x2 2 d x1 d x1 ¯E d2 M E d M2 = −x1 2 d x1 d x1 ¯E At x1 = 1. 2 ¯E M2 = Ax1 B 1 + 2 (x2 + Bx1 )2 (x1 + Bx2 ) (b) The excess partial properties should obey the Gibbs/Duhem equation.11. and by ¯E sign of d M 2 E 2 E ¯ the same argument the sign of d M2 /d x1 is of opposite sign as the sign of d M /d x1 . 1 1 ¯E ¯E +1 ( M 2 )∞ = A 1 + (c) ( M 1 )∞ = A B B 11. Eq.16).

11. β≡ 1 V ∂V ∂T V id = P i xi Vi β id = i 1 xi Vi xi i ∂ Vi ∂T = P 1 i xi Vi xi Vi βi i The claim is valid only if all the Vi are equal. 690 .49 The claim is not in general valid.

Differentiate at constant T : dπ2 dπ1 dP − π2 + π1 + P2sat x2 = P1sat x1 d x1 d x1 d x1 Apply this equation to the limiting conditions: For x1 = 0 : x2 = 1 π1 = π1∞ π2 = 1 dπ2 =0 d x1 dπ1 =0 d x1 For x1 = 1 : x2 = 0 π1 = 1 π2 = π2∞ Then. (12. (12.15).2 Equation (12. At this value of x1 . ln 2 ln π1 = Ax2 and 2 ln π2 = Ax1 π1 2 2 = A(x2 − x1 ) = A(x2 − x1 ) = A(1 − 2x1 ) π2 By Eq.Chapter 12 . 2 gives: P = x1 π1 P1sat + x2 π2 P2sat . ln(ξ12 r ) = A(1 − 2x1 ) az x1 If an azeotrope exists. An azeotrope exhists whenever |A| | ln r |. Thus the difference ln π1 − ln π2 is also an extremum. ξ12 = 1 at 0 1.1) may be written: yi P = xi πi Pi sat . NO azeotrope can exist when |A| < | ln r |.1).8) becomes useful: d(G E/RT π1 = ln π1 − ln π2 = ln d x1 π2 Thus. and Eq.Section B . we locate an extremum through: d ln(π1 /π2 ) d 2 (G E/RT ) =0 = 2 d x1 d x1 691 .5 Perhaps the easiest way to proceed here is to note that an extremum in ln π1 is accompanied by the opposite extremum in ln π2 . and there are two possible relationships.Non-Numerical Solutions 12. az ln r = A(1 − 2x1 ) The quantity A(1 − 2x1 ) is linear in x1 .4 By Eqs. dP d x1 x1 =0 = P1sat π1∞ − P2sat or dP d x1 x1 =0 + P2sat = P1sat π1∞ dP d x1 x1 =1 = P1sat − P2sat π2∞ or dP d x1 x1 =1 − P1sat = −P2sat π2∞ Since both Pi sat and πi∞ are always positive deﬁnite. it follows that: dP d x1 x1 =0 −P2sat and dP d x1 x1 =1 P1sat 12. y1 x2 P2sat π1 = = y2 x1 P1sat π2 y1 /x1 y2 /x2 P2sat P1sat = ξ12 r Whence. depending on the sign of A. (12. 12. given an expression for G E/RT = g(x1 ). Summing for i = 1. Therefore.

For the van Laar equation. substitution for A and d A/d x1 reduces the expression to A12 = 0 or A21 = 0. dA = A12 − A21 d x1 and d 2A =0 2 d x1 Then. The Margules equation is given by Eq. this makes G E/RT everywhere zero.16). here written: GE = Ax1 x2 RT where A = A21 x1 + A12 x2 dA = A21 − A12 d x1 d 2A =0 2 d x1 Then. d(G E/RT ) = A12 A21 d x1 x1 x2 d A x2 − x1 − 2 A d x1 A x2 − x1 2x1 x2 d A dA x1 x2 d 2A x2 − x1 d A 2 d 2 (G E/RT ) + − − − 2 = A12 A21 − − 2 2 3 dx 2 A2 A d x1 A d x1 d x1 A A d x1 1 = A12 A21 − 2x1 x2 2(x2 − x1 ) d A 2 + − 2 A3 d x1 A A dA d x1 2 = dA dA 2A12 A21 + x1 x2 −A2 − (x2 − x1 )A 3 d x1 d x1 A 2 = 2A12 A21 A3 A + x2 dA d x1 x1 dA −A d x1 This equation has a zero value if either A12 or A21 is zero. Then: (x2 − x1 ) dA − A = (x2 − x1 )(A21 − A12 ) − A21 x1 − A12 x2 = A21 x2 + A12 x1 − 2(A21 x1 + A12 x2 ) = 0 d x1 Substituting x2 = 1 − x1 and solving for x1 yields: x1 = A21 − 2A12 3(A21 − A12 ) or x1 = (r − 2) 3(r − 1) r≡ A21 A12 692 . write Eq. dA d(G E/RT ) = A(x2 − x1 ) + x1 x2 d x1 d x1 d 2A dA dA d 2 (G E/RT ) + x1 x2 2 + (x2 − x1 ) = −2A + (x2 − x1 ) 2 d x1 d x1 d x1 d x1 = −2A + 2(x2 − x1 ) dA dA −A = 2 (x1 − x2 ) d x1 d x1 This equation has a zero value when the quantity in square brackets is zero. again making G E/RT everywhere zero. and no extremum is possible. We conclude that no values of the parameters exist that provide for an extremum in ln(γ1 /γ2 ). omitting the primes ( ): x1 x2 GE = A12 A21 A RT where A ≡ A12 x1 + A21 x2 Moreover. (12. (12. However. If either quantity in parentheses is zero.9b).

(12. No extrema exist for values of r between 1/2 and 2. reaching a limiting value for r = ∞ at x1 = 1/3.When r = 2. x1 = 0. and the extrema in ln γ1 and ln γ2 occur at the right edge of a diagram such as those of Fig. x1 = 1. and the extrema in ln γ1 and ln γ2 occur at the left edge of a diagram such as those of Fig.15) and (11. in all of these cases A21 < A12 . For positive values of the parameters.9. and the intercepts of the ln γ1 curves at x1 = 0 are larger than the intercepts of the ln γ2 curves at x1 = 1. the extrema shift to the left. in all of these cases A21 > A12 . 12. and the intercepts of the ln γ2 curves at x1 = 1 are larger than the intercepts of the ln γ1 curves at x1 = 0. For values of r < 1/2. and write Eq. For values of r > 2. (12.7 Equations (11. the extrema shift to the right. x1 x2 x2 − x1 d(G E/RT ) − 2 (A12 − A21 ) = A12 A21 D D d x1 and ln γ1 = A12 A21 x1 x2 + x2 D x1 x2 x2 − x1 − 2 (A12 − A21 ) D D = 2 x1 x2 A12 A21 2 (A12 − A21 ) x1 x2 + x2 − x1 x2 − D D = 2 2 A12 A21 x2 A12 A21 x2 (A21 x2 + A21 x1 ) (D − A12 x1 + A21 x1 ) = D2 D2 = 2 A12 A2 x2 21 = A12 D2 A21 x2 D 2 = A12 D A21 x2 −2 = A12 A12 x1 + A21 x2 A21 x2 −2 ln γ1 = A12 1 + A12 x1 A21 x2 −2 The equation for ln γ2 is derived in analogous fashion. (b) With the understanding that T and P are constant. For positive values of the parameters. (12.17).16) as: x1 x2 GE = A12 A21 D RT where D ≡ A12 x1 + A21 x2 Then.16) and (12. 12.16) here become: ln γ1 = d(G E/RT ) GE + x2 d x1 RT and ln γ2 = d(G E/RT ) GE − x1 d x1 RT (a) For simplicity of notation. reaching a limiting value for r = 0 at x1 = 2/3. ln γ1 = ∂(nG E/RT ) ∂n 1 n2 and Eq.9. omit the primes that appear on the parameters in Eqs. When r = 1/2. 12.16) may be written: A12 A21 n 1 n 2 nG E = nD RT where 693 n D = A12 n 1 + A21 n 2 .

(11.273 x1 x2 RT (b) The preceding equation is of the form from which Eqs.096 x1 ) + x2 x1 (0. 12.6): GE = x1 ln γ1 + x2 ln γ2 RT 2 2 = x1 x2 (0. See Problem 11.273)(x1 + x2 ) GE = 0. just below Eq.10 This behavior requires positive deviations from Raoult’s law over part of the composition range and negative deviations over the remainder. x1 starts and ends with G E = 0 at x1 = 0 and x1 = 1 and shows positive values over part of the composition range and negative values over the remainder.25 Write Eq.096 x1 x2 + 0.273 x1 − 0.273 x1 (c) The equations of part (b) are not the reported expressions.273 − 0. (12.096 x2 ) = x1 x2 (0.273 + 0. and divide through by d x1 : x1 d ln γ2 d ln γ1 =0 + x2 d x1 d x1 whence x1 d ln γ1 x1 d ln γ1 d ln γ2 = =− x2 d x2 x2 d x1 d x1 694 . the vapor pressures P1sat and P2sat must not be too different. which therefore cannot be correct.15) are derived.100) for a binary system.096 x1 x2 ) = x1 x2 (0.24 (a) By Eq. 2 ln γ1 = 0.Differentiation in accord with the ﬁrst equation gives: ln γ1 = A12 A21 n 2 n1 1 − n D (n D)2 ∂(n D) ∂n 1 n2 ln γ1 = A12 x1 A12 A21 x2 n1 A12 A21 n 2 1− A12 = 1− D D nD nD 2 A12 A2 x2 A12 A21 x2 A12 A21 x2 21 A21 x2 = (D − A12 x1 ) = D2 D2 D2 = The remainder of the derivation is the same as in Part (a). 12. otherwise the dewpoint and bubblepoint curves cannot exhibit extrema. Thus a plot of G E vs.11 Assume the Margules equation. (12. Because these deviations are usually quite small. Eq.273 x2 + 0.11.273 x2 and 2 ln γ2 = 0. 12. (12.9b). From these. with an intermediate crossing of the x1 axis. applies: GE = x1 x2 (A21 x1 + A12 x2 ) RT and 1 GE (equimolar) = (A12 + A21 ) 8 RT But [see page 438.10b)]: A12 = ln γ1∞ A21 = ln γ2∞ 1 GE (equimolar) = (ln γ1∞ + ln γ2∞ ) 8 RT or 1 GE (equimolar) = ln(γ1∞ γ2∞ ) 8 RT 12. (12.

x1 0 x1 d ln γ1 d x1 = x2 d x2 x1 0 x1 d ln γ1 d x1 x2 d x2 d ln γ1 = 2Ax2 d x2 Whence ln γ2 = 2A x1 0 x1 d x1 or 2 ln γ2 = Ax1 By Eq. recalling that ln γ2 = 1 for x1 = 0: ln γ2 = ln(1) + 2 (a) For ln γ1 = Ax2 .. (12. (12.g.6): 3B GE 2 2 − Bx1 ) = x1 x2 (A + Bx2 ) + x2 x1 (A + 2 RT Algebraic reduction can lead to various forms of this equation. GE = Ax1 x2 RT d ln γ1 2 2 = 2x2 (A + Bx2 ) + x2 B = 2Ax2 + 3Bx2 = 2Ax2 + 3Bx2 (1 − x1 ) d x2 Whence 2 ln γ2 = Ax1 + ln γ2 = 2A 3B 2 3 x − Bx1 2 1 x1 0 x1 d x1 + 3B x1 0 x1 d x1 − 3B x1 0 2 x1 d x1 or 2 ln γ2 = x1 A + B 3B 2 − Bx1 = x1 A + (1 + 2x2 ) 2 2 Apply Eq. 2 (b) For ln γ1 = x2 (A + Bx2 ).Integrate.6). B GE = x1 x2 A + (1 + x2 ) 2 RT 2 2 (c) For ln γ1 = x2 (A + Bx2 + C x2 ). d ln γ1 2 2 2 3 = 2x2 (A + Bx2 + C x2 ) + x2 (B + 2C x2 ) = 2Ax2 + 3Bx2 + 4C x2 d x2 = 2Ax2 + 3Bx2 (1 − x1 ) + 4C x2 (1 − x1 )2 Whence or ln γ2 = 2A x1 0 x1 d x1 + 3B x1 0 x1 0 x1 (1 − x1 )d x1 + 4C x1 0 x1 0 x1 (1 − x1 )2 d x1 x1 0 3 x1 d x1 ln γ2 = (2A + 3B + 4C) ln γ2 = x1 d x1 − (3B + 8C) 2 x1 − 2 x1 d x1 + 4C 2A + 3B + 4C 2 3B + 8C 3 3 4 x1 + C x1 2 ln γ2 = x1 A + 8C 3B + 2C − B + 3 2 2 x1 + C x1 695 . e.

6) reduces to equations of various forms.16) written with M ≡ H E . d H = dn ˜ H − x1 dHE d H = H E − x1 d x1 d x1 Comparison with Eq.g.or 2 ln γ2 = x1 A + C B 2 (1 + 2x2 ) + (1 + 2x2 + 3x2 ) 3 2 The result of application of Eq. d H = dn ˜ H−I n ˜ Combining this with the result of Part (a) gives: ¯ H2E = H−I n ˜ From which. (12.: C B GE 2 = x1 x2 A + (1 + x2 ) + (1 + x2 + x2 ) 3 2 RT 12. Substitute: H= I = H − n H2E ˜ ¯ HE H = x1 x1 and n= ˜ x2 x1 696 . x1 = 1 1+n ˜ and H= H x1 H= H (1 + n) ˜ Eliminating 1 + n gives: ˜ (A) Differentiation yields: H d x1 1 d H d H = − 2 = ˜ ˜ x1 d n dn ˜ x1 d n H 1 d H − 2 x1 d x1 x1 d x1 dn ˜ where −1 d x1 2 = −x1 = (1 + n)2 ˜ dn ˜ Whence. e.40 (a) As shown on page 458. with reference to the following ﬁgure. (11. dH ¯ H2E = H E − x1 d x1 E shows that d H ¯ = H2E dn ˜ (b) By geometry.

¯ I = H1E 12.Whence. it follows that: ˜ ˜ ˜ n→∞ ˜ lim H = A12 (c) Analogous to Eq. H H0 d( H ) = C P dt H= H0 + C P dt 697 . this reduces to A21 . H E − x2 H2E = x1 H1E Then.x i xi ∂ Hi ∂t P. (A) of the preceding problem: H = x2 (A21 x1 + A12 x2 ) With x2 = 1 − x1 and x1 = 1/(1 + n) (page 458): x2 = ˜ n ˜ 1+n ˜ The preceding equations combine to give: H= n ˜ 1+n ˜ ˜ A12 n A21 + ˜ 1+n 1+n ˜ (a) It follows immediately from the preceding equation that: n→0 ˜ lim H =0 (b) Because n/(1 + n) → 1 for n → ∞. (12. ˜ it follows that n→0 ˜ lim d H = A21 dn ˜ 12. P. I = ¯ H E − x2 H2E x2 ¯ HE − H2E = x1 x1 x1 ¯ ¯ However.x With ∂H ∂t ≡ CP. by the summability equation. (12.42 By Eq. Differentiate: ∂ H ∂t = P.x this becomes t t0 ∂ H ∂t = CP − P. From the result of Part (a) of the preceding problem. page 438.x ∂H ∂t − P.x i xi C Pi = t t0 CP Therefore. H=H− i xi Hi .29) with M ≡ H .10b). we write: Eliminate the mole fractions in favor of n: ˜ ¯ H2E = 1 1+n ˜ 2 2 ¯ H2E = x1 [A21 + 2(A12 − A21 )x2 ] A21 + 2(A12 − A21 ) n ˜ 1+n ˜ In the limit as n → 0.41 Combine the given equation with Eq.

Moreover. By assumption. 1.67 (a) Written for G E .e.16). deﬁne G ≡ GE . and for the mixed system of particles. For mixing. and one must have accurate vapor-pressure data over a temperature range.15) and (11. 12.15) & (11. (The effect of pressure on liquid-phase properties is assumed negligible.66 Isobaric data reduction is complicated by the fact that both composition and temperature vary from point to point. Thus. which are correlated. 12. . (b) The requested plots are found in Section A.42). the Pi sat values depend strongly on T . Eqs. it is quite impossible without additional information to separate the effect of composition from that of T .12. . whereas for isothermal data composition is the only signiﬁcant variable. 3. (11. for an unmixed species i. . . yields the required result. t t t S t = Smixed − Sunmixed = Smixed − i Sit where the total emtropies are given by Eq. (11. written for excess properties. i. (5.63 In this application the microscopic “state” of a particle is its species identity.61 (a) From the deﬁnition of M: Differentiate: M E = x1 x2 M (A) dM dME = M(x2 − x1 ) + x1 x2 d x1 d x1 (B) Substitution of Eqs.91) that ¯ G iE = ln γi RT Then ln γ1 = G + x2 dG d x1 and ln γ2 = G − x1 dG d x1 Given: GE = A1/k x! x2 RT with 698 A ≡ x 1 Ak + x 2 Ak 21 12 . (11. RT note by Eq.) Because the activity coefﬁcients are strong functions of both liquid composition and T . 2.16) become: dG ¯E G 1 = G E + x2 d x1 E and dG ¯E G 2 = G E − x1 d x1 E Divide through by RT . this label is the only thing distinguishing one particle from another. ( A) & (B) into Eqs. Sit = k ln i = k ln Ni ! =0 Ni ! t Smixed = k ln N! N1 ! N2 ! N3 ! · · · Combining the last three equations gives: S t = k ln N! N1 ! N2 ! N3 ! · · · From which: 1 N! 1 St St S = (ln N ! − ln = = = N N1 ! N2 ! N3 ! · · · N kN R(N /N A ) R ln Ni !) i ln N ! ≈ N ln N − N and ln Ni ! ≈ Ni ln Ni − Ni 1 S ≈ (N ln N − N − N R Ni ln Ni + i i Ni ) = 1 (N ln N − N xi N ln xi N ) i = 1 (N ln N − N xi N ln xi − i i xi N ln N ) = − i xi ln x1 12..

and rewrite the right member of Eq. −∞. Whence • For k → +∞. most easily resolved by working with the logarithm: 1 ln g = ln(x1 Ak + x2 Ak )1/k = ln x1 Ak + x2 Ak 21 12 21 12 k g = (x1 A−1 + x2 A−1 )−1 = 21 12 Apply l’Hˆ pital’s rule to the ﬁnal term: o d ln x1 Ak + x2 Ak x1 Ak ln A21 + x2 Ak ln A12 21 12 21 12 = k dk x1 A21 + x2 Ak 12 (A) Consider the limits of the quantity on the right as k approaches several limiting values. 2 ln γ1 = x2 A1/k (Ak − Ak )x1 21 12 +1 kA Similarly. 699 . 2 ln γ2 = x1 A1/k 1 − (Ak − Ak )x2 21 12 kA (b) Appropriate substitition in the preceding equations of x1 = 1 and x1 = 0 yields: ln γ1∞ = A1/k = (Ak )1/k = A12 12 (c) Let g≡ ln γ2∞ = A1/k = (Ak )1/k = A21 21 If k = 1. x1 x2 ln g → x1 ln A21 + x2 ln A12 = ln A21 + ln A12 and x1 x2 g = A21 A12 • For k → ± ∞.Whence: G = x1 x2 A1/k and d A1/k dG + A1/k (x2 − x1 ) = x1 x2 d x1 d x1 1 A1/k k dA 1 d A1/k (A21 −Ak ) = = A(1/k)−1 12 k A d x1 k d x1 and A1/k k dG (A21 −Ak )+A1/k (x2 −x1 ) = x1 x2 12 kA d x1 Finally. Assume A12 /A21 > 1. Whence k→−∞ lim (A12 /A21 )k → 0 g = A21 and k→−∞ lim ln g = ln A21 except at x1 = 0 where g = A12 and k→∞ k→∞ lim (A12 /A21 )k → ∞ g = A12 lim ln g = ln A12 except at x1 = 1 where g = A21 If A12 /A21 < 1 rewrite Eq. +∞. If k = −1. indeterminate forms appear. • For k → 0. (A) to display A21 /A12 . (A) as x1 ln A21 + x2 (A12 /A21 )k ln A12 x1 + x2 (A12 /A21 )k • For k → −∞. GE = A1/k = (x1 Ak + x2 Ak )1/k 12 21 x1 x2 RT g = x1 A21 + x2 A12 (Margules equation) A21 A12 (van Laar equation) x1 A12 + x2 A21 For k = 0.

and for small xe let γe ≈ γe∞ . we have assumed ideal gases.95).x G = −x1 ln(x1 + x2 RT 12 ) − x2 ln(x2 + x1 21 ) (12. For volume fraction ξe in the vapor. with xe small l ξe = xe Vel xe Vel xe Vel ≈ ≈ Vb xb Vb xe Vel + xb Vb b ≡ blood Then Vb l ∞ sat ξ γ P ≈ ξev P Ve e e e Ve P volume % EtOH in blood ≈ Vb γe∞ Pesat volume % EtOH in gas 12.70 By Eq. C P must always be positive. (11.12.68 Assume that Eq.18) κ(G E /RT ) κT E x d 21 d 12 x2 x1 dT dT − =− x2 + x1 21 x1 + x2 12 x1 x2 d 12 H  dT = x1 x2 T  x1 + x2 RT  ij 12 d 21 dT + x2 + x1  21 = −ai j Vj exp RT Vi   (i = j) (12. 700 .24) Vj d ij = Vi dT exp −ai j RT 12 a12 ai j = RT 2 ij ai j RT 2 H E = x1 x2 x1 + x2 + 12 21 a21 x2 + x1 21 E Because C P = d H E /dT . written as xe γe Pesat = xe γe∞ Pesat = ye P e ≡ EtOH Because P is low. the ideal-gas assumption provides ξev ≈ ye . differentiate the preceding expression and reduce to get: E x2 21 (a21 /RT )2 x1 12 (a12 /RT )2 CP + = x1 x2 (x2 + x1 21 )2 (x1 + x2 12 )2 R Because 12 and 21 E must always be positive numbers.1) is the appropriate equilibrium relation. HE = −T RT E κ(G E /RT ) κT P. and for the liquid phase. (12.

(13.1 (a) ν= i 4NH3 (g) + 5O2 (g) ∞ 4NO(g) + 6H2 O(g) νi = −4 − 5 + 4 + 6 = 1 n0 = i0 =2+5=7 By Eq. yC2 H4 = 2 − ε1 − ε2 5 − 1 ε1 2 yO2 = 3 − 1 ε1 − 3ε2 2 5− 1 ε 2 1 y (CH2 )2 O = ε1 5 − 1 ε1 2 yCO2 = 2ε2 5 − 1 ε1 2 yH2 O = 2ε2 5 − 1 ε1 2 701 . j are as follows: i= C2 H4 O2 (CH2 )2 O CO2 H2 O j νj 1 −1 −1 2 1 0 0 −1 2 2 −1 −3 0 2 2 0 n0 = i0 =2+3=5 By Eq.Non-Numerical Solutions 13.5).5).Chapter 13 .Section B . (13.7). yNO2 = 3 − 6ε 8 + 5ε yNH3 = 4 − 8ε 8 + 5ε yN2 = 1 + 7ε 8 + 5ε yH2 O = 12ε 8 + 5ε 13. yNH3 = 2 − 4ε 7+ε yO2 = 5 − 5ε 7+ε yNO = 4ε 7+ε yH2 O = 6ε 7+ε (b) ν= 2H2 S(g) + 3O2 (g) ∞ 2H2 O(g) + 2SO2 (g) νi = −2 − 3 + 2 + 2 = −1 i n0 = i0 =3+5=8 By Eq.5).2 C2 H4 (g) + 1 O2 (g) ∞ (CH2 )2 O(g) 2 (1) (2) C2 H4 (g) + 3O2 (g) ∞ 2CO2 (g) + 2H2 O(g) The stoichiometric numbers νi. (13. (13. yH2 S = 3 − 2ε 8−ε yO2 = 5 − 3ε 8−ε yH2 O = 2ε 8−ε ySO2 = 2ε 8−ε (c) ν= i 6NO2 (g) + 8NH3 (g) ∞ 7N2 (g) + 12H2 O(g) νi = −6 − 8 + 7 + 12 = 5 n0 = i0 =3+4+1=8 By Eq.

j are as follows: (1) (2) i= CO2 H2 CH3 OH CO H2 O j νj 1 2 −1 −1 −3 −1 1 0 0 1 1 1 −2 0 n0 = i0 =2+5+1=8 By Eq.919. C.28). B. The required values of G ◦ = G ◦ in J mol−1 are: 0 298 (a) −32.22. In each case the value of H0 = H298 is tabulated in the solution to Pb. which may be concisely written: Ky = P P◦ −ν K (a) Differentiate this equation with respect to T and combine with Eq.21. (13.365. (r) −39. (u) 166. the values of A. (4.7 The equation for G ◦ . (n) 173.19) and (13.7). and evaluates ◦ ◦ parameters. yCO2 = 2 − ε1 − ε2 8 − 2ε1 yH2 = 5 − 3ε1 − ε2 8 − 2ε1 yCH3 OH = ε1 8 − 2ε1 yCO = 1 + ε2 8 − 2ε1 yH2 O = ε 1 + ε2 8 − 2ε1 13.8 The relation of K y to P and K is given by Eq. (13. (f ) −2.18) is: ◦ H0 − G◦ = T ◦ ( H0 − T0 G ◦) + R 0 T T0 ◦ CP dT − RT R T T0 ◦ C P dT R T To calculate values of G ◦ .13.430.455. (13. 4. (y) 83.900.14): ∂ Ky ∂T = P P P◦ −ν Ky H◦ d ln K Ky d K dK = = Ky = RT 2 dT K dT dT Substitute into the given equation for (∂εe /∂ T ) P : ∂εe ∂T = P K y dεe RT 2 d K y H◦ (b) The derivative of K y with respect to P is: ∂ Ky ∂P = −ν T P P◦ −ν−1 1 K = −ν K P◦ P P◦ −ν P P◦ −1 −ν K y 1 ◦ = P P 702 .19). one combines this equation with Eqs. (t) 79.124. (x) 39.010 13. (i) 113.100. In addition. and D are given in the solutions to Pb.245. appearing just above Eq. 4.3 CO2 (g) + 3H2 (g) → CH3 OH(g) + H2 O(g) CO2 (g) + H2 (g) → CO(g) + H2 O(g) The stoichiometric numbers νi.630. (13.

28). 13. By Eq. Differentiation then yields: 1 d Ky = K y dεe i νi dyi yi dεe (A) Because yi = n i /n.9 1 N (g) 2 2 + 3 H2 (g) → NH3 (g) 2 For the given reaction. (13. ν = −1. yNH3 1/2 3/2 yN2 yH2 = [ 1 (1 2 P εe (2 − εe ) =K ◦ 3 P − εe )]1/2 [ 2 (1 − εe )]3/2 703 . (A) gives 1 d Ky K y dεe = i νi yi νi − yi ν n 0 + νεe m i=1 = 1 n 0 + νεe m i νi2 − νi ν yi = 1 n 0 + νεe νi2 − νi yi νk k=1 In this equation. One can proceed by induction to ﬁnd the general result. If m = 2.5). (13. It remains to show that the summation term is positive. this term becomes 2 (y2 ν1 − y1 ν2 )2 ν2 ν1 − ν1 (ν1 + ν2 ) + 2 − ν2 (ν1 + ν2 ) = y1 y2 y2 y1 where the expression on the right is obtained by straight-forward algebraic manipulation. yN2 = 1 (1 2 − εe ) 2 − εe yH2 = 3 (1 2 − εe ) 2 − εe yNH3 = εe 2 − εe By Eq. n i = n i0 + νi εe dn i = νi dεe and n = n 0 + νεe and dn =ν dεe Therefore. νi − yi ν dyi = n 0 + νεe dεe Substitution into Eq. ln K y = i νi ln yi .Substitute into the given equation for (∂εe /∂ P)T : ∂εe ∂P = T K y dεe (−ν) P d Ky (c) With K y i (yi )νi . both K y and n 0 + νεe (= n) are positive. 1 n i dn 1 dn i dyi = − 2 = n n dεe n dεe dεe dn dn i − yi dεe dεe But Whence. which is m i=1 νi2 − νi yi m m m k νk k=1 = i (yk νi − yi νk )2 yi yk (i < k) All quantities in the sum are of course positive. n 0 = 2. and for the given amounts of reactants.

11b) and (13.10 The reactions are written: Mary: 2NH3 + 3NO → 3H2 O + 5 N2 2 (A) (B) Paul: Peter: 4NH3 + 6NO → 6H2 O + 5N2 3H2 O + 5 N2 → 2NH3 + 3NO 2 (C) Each applied Eqs.25). εe = 1 − 1 + 1. here written: ln K = − G ◦ /RT For reaction (A).299K P P◦ The roots of the quadratic are: εe = 1 ± 1 = 1 ± r −1/2 r 1/2 Because εe < 1.299K P◦ P This may be written: where. (13. and: 2 K A = (P ) ◦ −1 2 fˆf3H 2O 5/2 fˆfN 2 fˆf2NH fˆf3NO 3 and ln K A = − G◦ A RT For Paul’s reaction ν = 1. and: 2 K C = (P ) ◦ 1 2 fˆf2NH fˆf3NO 3 fˆf3H 2O 5/2 fˆfN 2 and ln K C = G◦ A RT In each case the two equations are combined: Mary: (P ) ◦ −1 2 fˆf3H 2O 5/2 fˆfN 2 fˆf2NH fˆf3NO 3 = exp − G◦ A RT 704 . and K B = (P ) ◦ −1 fˆf6H 2O fˆf5N 2 fˆf4NH fˆf6NO 3 and ln K B = −2 G ◦ A RT For Peter’s reaction ν = − 1 . G ◦ = 3 G ◦fH A and K = (P ◦ )−ν i ( fˆi )νi 2O − 2 G ◦fNH − 3 G ◦fNO 3 For Mary’s reaction ν = 1 . r εe 2 − 2 r εe + (r − 1) = 0 r ≡ 1 + 1.Whence. εe = 1 − r −1/2 .299K P P◦ −1/2 13. εe (2 − εe ) = (1 − εe )2 1 2 1/2 3 2 3/2 K P P ◦ = 1.

36 For the isomerization reaction in the gas phase at low pressure. (3) with Eq.36).35 (a) Equation (13. Other equivalent sets of two reactions may be obtained by different combination procedures. assume ideal gases. yields: F =2+2−1−1=2 This result means in general for single-reaction equilibrium between two species A and B that two degrees of freedom exist. By the phase rule. and that pressure as well as temperature must be speciﬁed to ﬁx the equilibrium state of the system. and (6).Paul: (P ) ◦ −1 fˆf6H 2O fˆf5N 2 fˆf4NH fˆf6NO 3 − G◦ A = exp RT 2 Taking the square root yields Mary’s equation.28) here becomes: yB = yA P P◦ 0 K =K Whence. Eq. However. 13. yB = K (T ) 1 − yB (b) The preceding equation indicates that the equilibrium composition depends on temperature only. (5).24 Formation reactions: 1 N 2 2 + 3 H2 → NH3 2 (1) 1 N 2 2 + 1 O2 → NO 2 (2) 1 N 2 2 + O2 → NO2 (3) H 2 + 1 O2 → H 2 O 2 (4) Combine Eq. (13. application of the phase rule. 13. combine Eq. (1) and with Eq. F = 2−π + N −r −s = 2−1+5−2−0 F =4 13. (2) to eliminate N2 : NO2 + 3 H2 → NH3 + O2 2 (5) NO2 → 1 O2 + NO 2 (6) The set now comprises Eqs. However. here. the speciﬁcation that the gases are ideal removes ˆ the pressure dependence. Peter: (P ◦ ) 2 1 fˆf2NH fˆf3NO 3 fˆf3H 2O 5/2 fˆfN 2 = exp − G◦ A RT −1 Taking the reciprocal yields Mary’s equation. Equation (13.28) then becomes: yB = yA P P◦ 0 K =K whence 1 − yA = K (T ) yA 705 . (4) with Eq. (4). which in the general case appears through the φi s. (5) to eliminate H2 : (7) NO2 + 3 H2 O → NH3 + 1 3 O2 4 2 Equations (6) and (7) represent a set of independent reactions for which r = 2.

and therefore: yOX + K I yOX + K II yOX + K III yOX = yOX (1 + K I + K II + K III ) = 1 yOX = 1 1 + K I + K II + K III (4) (c) With the assumption that combine to give: ◦ C P = 0 and therefore that K 2 = 1. yMX = yOX P P◦ 0 KI = KI yPX = yOX P P◦ 0 K II = K II yEB = yOX P P◦ 0 K III = K III (b) These equation equations lead to the following set: yMX = K I yOX (1) yPX = K II yOX (2) yEB = K III yOX (3) The mole fractions must sum to unity.21). Eqs.040 10.36) yields: and (1 − xA )PBsat (T ) = (1 − yA )P F = 2−π + N −r = 2−2+2−1 = 1 (b) Given T . (13.  K = exp    298. the system is assumed to be a mixture of ideal gases. and (13. the reaction-equilibriuum equation allows solution for yA . (13. The two phase-equilibrium equations can then be solved for xA and P. (13.38 (a) For low pressure and a temperature of 500 K.28) is appropriate. Therefore. because of the low pressure and the similarity of the species: xA PAsat (T ) = yA P (a) Application of Eq. for which Eq.300 −1.2637 0.1778 706 .15) G◦ 298     The data provided lead to the following property changes of reaction and equilibrium constants at 500 K: Reaction ◦ H298 G◦ 298 K I II III −1.920 −3.8470 1.000 8.314)(298. 13. (13.22) K = K 0 K 1 = exp − G◦ 298 exp RT0 ◦ H298 1 − ◦ H298 T0 1− T RT0 Whence.Assume that vapor/liquid phase equilibrium can be represented by Raoult’s law.690 2.750 −1.20).15 − 500 (8. The equilibrium state therefore depends solely on T .

10).42 A compound with large positive G ◦f has a disposition to decompose into its constituent elements.(d) Substitution of numerical values into Eqs. Thus. 13.47 (a) For isomers at low pressure Raoult’s law should apply: P = x A PAsat + x B PBsat = PBsat + x A (PAsat − PBsat ) For the given reaction with an ideal solution in the liquid phase.1176 13. nA nB nC nD n with n A0 the limiting reactant without (II) = n A0 − εI − εII = n B0 − εI = εI − εII = εII = n 0 − εI − εII Use given values of YC and SC/D to ﬁnd εI and εII : YC = εI − εII n A0 and SC/D = εI − εII εII Solve for εI and εII : εI = SC/D + 1 n A0 YC = SC/D 2+1 2 × 10 × 0.1176 = 0.2390 yEB = 0. (1).12).2353 = 0.5295 = 0. if any decomposition product f is a gas. Moreover. high pressures can be generated in a closed system owing to temperature increases resulting from exothermic decomposition.0336 13. (3). (13. large positive G ◦f often implies large positive H ◦ . G◦ ≡ i νi G i◦ ∂ G◦ ∂P◦ and from Eq. ∂ G◦ ∂P◦ Vi◦ = RT /P . (2). (13. (∂G i◦ /∂ P)T = Vi◦ = T i νi ◦ ∂G i◦ ∂P◦ = T i νi Vi◦ For the ideal-gas standard state.5383 yPX = 0. Therefore = T i νi RT P◦ = ν RT P◦ and G ◦ (P2◦ ) − G ◦ (P1◦ ) = ν RT ln P2◦ P1◦ 13. n A0 = 10 and n B0 = 15. Eq.40 For the given ﬂowrates.44 By Eq.40 n A0 YC =2 = 2 SC/D nA nB nC nD n = 10 − 6 − 2 = 15 − 6 =6−2 =2 = 17 =2 =9 =4 =2 yA yB yC yD = 2/17 = 9/17 = 4/17 = 2/17 =1 = 0.33) becomes: Kl = 1 − xA xB = xA xA from which xA = 1 Kl + 1 707 . and (4) yields the following values for the mole fractions: yOX = 0.1891 yMX = 0. (6.40 = 6 εII = 10 × 0.

Therefore Kl Kl + 1 PBsat + 1 l +1 K PAsat = (K v + 1)PAsat PBsat K v PAsat + PBsat Some algebra reduces this to: P sat Kv = Bsat PA Kl (d) As mentioned already. P = 1− Kl 1 +1 PBsat + Kl 1 +1 PAsat P= Kl Kl + 1 PBsat + Kl 1 +1 PAsat (A) P = PBsat For K l = 0 (b) Given Raoult’s law: P = PAsat For K l = ∞ 1 = x A + x B = yA P P =P sat + y B PBsat PA yB yA sat + PBsat PA P= y A /PAsat PAsat PBsat PAsat PBsat 1 sat sat sat = sat = PA + y A (PBsat − PAsat ) y A PB + y B PA + y B /PB For the given reaction with ideal gases in the vapor phase. (e) F = N + 2 − π − r = 2 + 2 − 2 − 1 = 1 Thus ﬁxing T should sufﬁce. Eq.28) becomes: yB = Kv yA whence yA = Kv 1 +1 Elimination of y A from the preceding equation and reduction gives: P= (K v + 1)PAsat PBsat K v PAsat + PBsat (B) P = PBsat For K v = 0 P = PAsat For K v = ∞ (c) Equations (A) and (B) must yield the same P. the species (isomers) are chemically similar. 708 .The preceding equation now becomes. and the low pressure favors ideal-gas behavior. (13.

2 Start with the equation immediately following Eq.40).61) after multiplication by n can be written: ρ 2 3 ρ nG R − n ln Z + n 2 (nC) = 2n(n B) n 2 n RT Differentiate: 3 ρ ρ ε(nG R/RT ) ¯ (n B + n Bi ) + =2 2 n n εn i 2 ¯ (2n 2 C + n 2 Ci ) − n ε ln Z − ln Z εn i or ε ln Z 3 ε(nG R/RT ) ¯ ¯ − ln Z = 2ρ(B + Bi ) + ρ 2 (2C + Ci ) − n εn i 2 εn i By deﬁnition.49). n/ρ (or ρ/n).n j ¯ Ci ε(nC) εn i T. Equation (6. Eq. ¯ Bi ε(n B) εn i and T. and n j . (14.Section B . can be written: Z = 1 + Bρ + Cρ 2 or n Z = n + n(n B) 2 ρ ρ + n 2 (nC) n n 2 Differentiate: ρ ρ ε(n Z ) ¯ (n B + n Bi ) + =1+ n n εn i ¯ (2n 2 C + n 2 Ci ) or ε(n Z ) ¯ ¯ = 1 + ρ(B + Bi ) + ρ 2 (2C + Ci ) εn i When combined with the two underlined equations.Chapter 14 .Non-Numerical Solutions 14. which can be modiﬁed slightly to read: ˆ ln νi = ε ln Z ε(nG R/RT ) ε(n Z ) +1 +n − εn i εn i εn i where the partial derivatives written here and in the following development without subscripts are understood to be at constant T . (3.n j The equation of state. the initial equation reduces to: ¯ ¯ ˆ ln νi = 1 + ρ(B + Bi ) + 1 ρ 2 (2C + Ci ) 2 The two mixing rules are: 2 2 B = y1 B11 + 2y1 y2 B12 + y2 B22 3 2 2 3 C = y1 C111 + 3y1 y2 C112 + 3y1 y2 C122 + y2 C222 ¯ ¯ Application of the deﬁnitions of Bi and Ci to these mixing rules yields: 2 2 ¯ B1 = y1 (2 − y1 )B11 + 2y2 B12 − y2 B22 2 2 2 3 ¯ C1 = y1 (3 − 2y1 )C111 + 6y1 y2 C112 + 3y2 (1 − 2y1 )C122 − 2y2 C222 2 2 ¯ B2 = −y1 B11 + 2y1 B12 + y2 (2 − y2 )B22 3 2 2 2 ¯ C2 = −2y1 C111 + 3y1 (1 − 2y2 )C112 + 6y1 y2 C122 + 2y2 (3 − 2y2 )C222 709 .

11 For the case described.In combination with the mixing rules. This yields on the left the difference between the actual pressure and the pressure given by Raoult’s law: P − P(RL) = x1 B11 P1sat (P1sat − P) + x2 B22 P2sat (P2sat − P) RT Because deviations from Raoult’s law are presumably small. Eqs. P on the right side may be replaced by its Raoult’s-law value.1) and (14. these give: ¯ B + B1 = 2(y1 B11 + y2 B12 ) 2 2 ¯ 2C + C1 = 3(y1 C111 + 2y1 y2 C112 + y2 C122 ) ¯ B + B2 = 2(y2 B22 + y1 B12 ) 2 2 ¯ 2C + C2 = 3(y2 C222 + 2y1 y2 C122 + y1 C112 ) In combination with the boxed equation these expressions along with Eq. ln Bii (Pi sat − P) Bii P Bii Pi sat φisat = − = ln φisat − ln φi = RT RT RT φi For small values of the ﬁnal term. (3. For the two terms. and yi P = xi Pi sat φisat φi When Eq.38) is valid. and sum. yi P = xi Pi sat 1 + Bii (Pi sat − P) RT or yi P − xi Pi sat = xi Pi sat Bii (Pi sat − P) RT Write this equation for species 1 and 2 of a binary mixture. φi = φi . (11. (3. the fugacity coefﬁcient of pure species i is given by Eq. P1sat − P = P1sat − x1 P1sat − x2 P2sat = P1sat − (1 − x2 )P1sat − x2 P2sat = x2 (P1sat − P2sat ) P2sat − P = P2sat − x1 P1sat − x2 P2sat = P2sat − x1 P1sat − (1 − x1 )P2sat = x1 (P2sat − P1sat ) Combine the three preceding equations: P − P(RL) = x1 x2 B11 (P1sat − P2sat )P1sat − x1 x2 B22 (P1sat − P2sat )P2sat RT = x1 x2 (P1sat − P2sat ) (B11 P1sat − B22 P2sat ) RT 710 .2) combine to give: yi P = xi Pi sat φisat ˆ φi ˆ If the vapor phase is assumed an ideal solution. this becomes approximately: Bii (Pi sat − P) φisat =1+ RT φi Whence. (14.40) allow calculation of ˆ ˆ ln φ1 and ln φ2 .36): ln φi = Bii P RT and φisat = Bii Pi sat RT Therefore. 14.

However.Rearrangement yields the following: P − P(RL) = x1 x2 (P1sat − P2sat )2 RT B11 P1sat − B22 P2sat P1sat − P2sat = (B11 − B22 )P2sat x1 x2 (P1sat − P2sat )2 B11 + P1sat − P2sat RT = B22 x1 x2 (P1sat − P2sat )2 (B11 ) 1 + 1 − B11 RT P2sat P1sat − P2sat Clearly. taken here as the ”heavier” species (the one with the smaller vapor pressure) has the more negative second virial coefﬁcient. G E (max) = −RT i 1 1 = RT ln N N i 1 ln N = RT ln N N For the special case of a binary solution. When the virial coefﬁcients are not equal.71) yields: 1 d fˆi >0 fˆi d xi Because fˆi ≥ 0. Therefore. 14. and the pressure deviation from the Raoult’s-law value has the sign of B11 . P) By Eq. This has the effect of making the quantity in parentheses negative and the quantity in square brackets < 1.14 Stability requires that G < 0 (see Pg. the term in square brackets equals 1. (14. (11. Whence. 575). d fˆi >0 d xi (const T. in which For an equimolar solution xi = 1/N where N is the number of species. this is normally negative.46).30) becomes: G E = −RT xi ln xi i G = 0. ln γi = ln fˆi − ln xi − ln f i 1 1 d fˆi 1 d ln fˆi d ln γi − = − = ˆi d xi xi xi d xi d xi f Combination of this expression with Eq. if this latter quantity remains positive (the most likely case). (11.13 By Eq. RT d fˆi d ln fˆi dµi = = RT d xi d xi fˆi d xi Combination with Eq. and G E (max) = RT ln 2 711 . (12. the deﬁnition of γi . the deﬁnition of fˆi .72) yields: dµi >0 d xi (const T. the sign of B11 still determines the sign of the deviations. N = 2. (14. a reasonable assumption is that species 2.90). P) 14. The limiting case obtains when event Eq. when B22 = B11 .

for C sufﬁciently greater than unity. 14. described by: GE = Ax1 x2 RT It is shown in Example 14. 14. For instability. deﬁne g ≡ (G E/RT ). (Examples of gas/gas equilibria are known. thus violating the stability condition of Eq. To simplify. (11. the formation of two immiscible vapor phases requires: δ12 P/RT > 2. for the formation of two liquid phases.23 (a) Refer to the stability requirement of Eq. (14.35. phase-splitting obtains if: 1 1 G E > 2 · · · RT = 0.71) and implying the formation of two liquid phases. 11.5 that phase splitting occurs for such a mixture if A > 2.21 Comparison of the Wilson equation.5. the derivative on the right side of this equation is always positive.96). for a quadratic mixture. at x1 = x2 = 0. Eq.17 According to Pb. Addition and subtraction of ln x1 on the left side of this equation and of C ln x1 on the right side yields: ln(x1 γ1 )m − ln x1 = C ln(x1 γ1 ) − C ln x1 or Differentiate: ln(x1 γ1 )m = C ln(x1 γ1 ) − (C − 1) ln x1 d ln(x1 γ1 ) C − 1 d ln(x1 γ1 )m − =C x1 d x1 d x1 As shown in Example 14.19 Consider a quadratic mixture. Thus. then gm = Cg ngm = Cng ∂(ng) ∂(ngm ) =C ∂n 1 ∂n 1 ln(γ1 )m = C ln γ1 where the ﬁnal equality follows from Eq.5RT for equimolar composition. where subscript m distinguishes the modiﬁed Wilson equation from the original Wilson equation.14.. the value of A = 2 corresponds to a consolute point. However.5RT 2 2 This is a model-dependent result.6 that phase-splitting occurs for A > 2.e. Many liquid mixtures are known which are stable as single phases.70). Suppose T = 300 K and P = 5 bar. G E = δ12 P y1 y2 or δ12 P GE y1 y2 = RT RT This equation has the form: GE = Ax1 x2 RT for which it is shown in Examples 14. but at conditions outside the range of applicability of the two-term virial EOS. the contribution of the second term on the right can make d ln(x1 γ1 )M <0 d x1 over part of the composition range. Thus. (12. i.7.18) with the modiﬁed Wilson equation shows that (G E/RT )m = C(G E/RT ). 1 d 2 (G E /RT ) <− 2 x1 x2 d x1 712 . (14. Such large positive values for δ12 are unknown for real mixtures. even though G E > 0.) 14. The preceding condition then requires: δ12 > 9977 cm3 mol−1 for vapor-phase immiscibility.5 and 14.

2) α If phase β is pure species 1 and phase α is pure species 2.over part of the composition range. e. (b) Equation (14.92a) are valid. (10. then the Clausius/Clapeyron equation applies (see Ex. 11. We know of no examples of liquid/liquid phasesplitting in systems exhibiting negative deviations from ideal-solution behavior. although it does not in fact occur for the cases shown.5): Hilv d ln Pi sat = RT 2 dT Integration from the boiling temperature Tbi at pressure P (where Pi sat = P) to the actual temperature T (where Pi sat = Pi sat ) gives: T Hilv P sat dT ln i = 2 P Tbi RT Combination with Eq.g. Thus. Equation (14. let the solid be pure species 1 and the solvent be liquid species 2.1) yields: yi = xi exp T Tbi Hilv dT RT 2 which is an analog of the Case I SLE equations. 713 .92a) contains no information about species 2. see. Whence the cited result for solids. (b).4. (10. α x1 γ1α = x1 γ1 = 1 β β and α x2 γ2α = x2 γ2 = 1 β β The reasoning applies generally to (degenerate) N -phase equilibrium involving N mutually immiscible species. 14. one merely requires that the curvature be sufﬁciently negative over part of the composition range.30 Consider binary (two-species) equilibrium between two phases of the same kind. (14. the solid solubility x1 is independent of the identity of species 2. Then Eqs.29 The analogy is Raoult’s law. 6.92a) apply: x1 = ψ1 = exp sl H1 RTm 1 T − Tm 1 T (a) Differentiate: sl H1 d x1 = ψ1 · RT 2 dT Thus d x1 /dT is necessarily positive: the solid solubility x1 increases with increasing T . 10. then x1 = γ1 = 1 and x2 = γ2α = 1. β β Hence. applied at constant P (see Fig.93) and (14. and (f ) in Fig. x1 for systems (a). (14. However. Such systems are candidates for liquid/liquid phase splitting. For concreteness.1). the sketches of G E vs.93) and (14.74) applies: β β xiα γiα = xi γi (i = 1.31 The rules of thumb are based on Case II binary SLE behavior.. positive curvature is the norm for such mixtures. (b) Nothing in principle precludes phase-splitting in mixtures for which G E < 0. 14.12): yi P = xi Pi sat If the vapor phase in VLE is ideal and the liquid molar volumes are negligible (assumptions inherent in Raoult’s law). The second derivative of G E must be sufﬁciently negative so as to satisfy this condition for some range of x1 . Eq. Negative curvature is the norm for mixtures for which G E is positive. to the extent that Eqs. (e). 14. Rather large values of G E are usually required. (d).

the solubilities x A and x B are related by: xA = exp xB H sl (Tm B − Tm A ) RTm A Tm B sl HB ≡ where by assumption. Thus.99): F1 ≡ sat V s (P − P1sat ) φ1 exp 1 ˆ RT φ1 From this. sl HA = H sl Accordingly.98). in Notice that Tm > T (see Fig.34 The shape of the solubility curve is characterized in part by the behavior of the derivative dyi /d P (constant T ). y1 = P1sat P/F1 .(c) Denote the two solid phases by subscripts A and B. (14. Then x A and x B are related by: sl sl ( H B − H A )(Tm − T ) xA = exp RTm T xB where by assumption. where the enhancement factor F1 depends (at constant T ) on P and y1 . after some reduction: ∂ ln F1 ∂P =− y1 ˆ ∂ ln φ1 ∂P + y1 V1s RT and ∂ ln F1 ∂ y1 =− P ˆ ∂ ln φ1 ∂ y1 P Whence. An expression for F1 is given by Eq. Then. dy1 = dP y1 ∂ ln F1 ∂P − y1 1 P 1 − y1 ∂ ln F1 ∂ y1 (A) P This is a general result.92a). (A). 14. A general expression is found from Eq. by Eq.93) and (14. dy1 = dP ˆ ∂ ln φ1 y1 − ∂P  y1 1 + y1 ˆ ∂ ln φ1 ∂ y1  1 V1s − + P RT P (B) 714 . 14. (14. Then x A /x B > 1 if and only if accord with the rule of thumb. (14. x A /x B > 1 if and only if TA < TB . Tm A = Tm B ≡ Tm sl HA < sl H B . (d) Identify the solid species as in Part (c). P sat P sat dy1 = − 1 2 F1 + 1 P P dP ∂ F1 ∂P + y1 ∂ F1 ∂ y1 P dy1 dP =− y1 + y1 P ∂ ln F1 ∂P + y1 ∂ ln F1 ∂ y1 P dy1 dP Whence. by Eqs.21b). thus validating the rule of thumb.

and the solubility y1 exhibits a minimum with respect to pressure. Qualitatively. If the two-term virial equation in pressure applies.63a). For very high pressures. by Eq. (B). then dy1 /d P is zero for some intermediate pressure. 1/P is small. then ln φ1 is given by Eq.ˆ This too is a general result. Application of l’Hˆ pital’s rule gives: o n= s→0 lim n = lim m s→0 2 Pe−s Pes + c + Pe−s c + Pes = m 2 P P + c+P c+P or lims→0 n = mP c+P which is the Langmuir isotherm. However. the two-term virial equation is only valid for low to moderate pressures. (3. (A): m dn = 2s dP e−s es − c + Pe−s c + Pes Whence.35 (a) Rewrite the UNILAN equation: m ln(c + Pes ) − ln(c + Pe−s ) (A) 2s As s → 0. 14. P curve observed for high pressures for the naphthalene/CO2 system. the sign of dy1 /d P is determined by the sign of the group in parentheses. and dy1 /d P can be positive.38) is likely to be valid. k= m 2s e−s es − c c = m cs es − e−s 2 or k= m sinh s cs (c) All derivatives of n with respect to P are well-behaved in the zero-pressure limit: lim P→0 m dn sinh s = cs dP 715 . If this is the case.23. (b) Henry’s constant. these features are consistent with the behavior illustrated by Fig. For very low pressures the 1/P term dominates and dy1 /d P is negative. by deﬁnition: k ≡ lim dn dP P→0 Differentiate Eq. dy1 = dP y1 2 1 V1s − B11 − y2 δ12 − P RT 2y1 y2 δ12 P 1− RT The denominator of this equation is positive at any pressure level for which Eq. and is unable to mimic the change in curvature and “ﬂattening” of the y1 vs. 14. Hence. (11. this expression becomes indeterminate. from which: ˆ ∂ ln φ1 ∂P = y1 1 2 (B11 + y2 δ12 ) RT and ˆ ∂ ln φ1 ∂ y1 =− P 2y2 δ12 P RT Whence.

2 14. On the left side of Eq. (A). (14.46) and (11.107). this simpliﬁes to: a d = d ln P + d ln φ (const T ) (A) RT which is the real-gas analog of Eq. a polynomial curve ﬁt of ln(P/n) in n yields − ln k and 2B as the ﬁrst two coefﬁcients. (14. 14. Eq. On the right side of Eq.105) then becomes: a ˆ d + d ln P + xi d ln yi φi = 0 − RT i (const T ) For pure-gas adsorption. (11.35). make the substitution: (B) dP (C) P which follows from Eq.52) give: µi = At constant temperature. written as: ln(P/n) = − ln k + n 0 (z − 1) dn +z−1 n With z = 1 + Bn + Cn + · · ·. (14. Alternatively. 14. ( A). Combination of Eqs.8): dP dn n − dz + (Z − 1) d ln = (1 − z) P n P which yields on integration and rearrangement: d ln φ = (Z − 1) n = k P · exp P 0 (Z − 1) dP · exp P n 0 (1 − z) dn +1−z n This equation is the real-gas analog of Eq. (B). although providing excellent overall correlation of adsorption data at low-to-moderate surface coverage.36 Start with Eq.m d 2n = − 2 sinh 2s P→0 d P 2 c s 2m d 3n = 3 sinh 3s lim 3 P→0 d P c s lim Etc. Eqs. introduce the adsorbate compressibility factor z through z ≡ a/RT = A/n RT : dn a d = dz + z n RT where n is moles adsorbed. (14. (A). and (C) gives on rearrangement (see Sec. 716 . g g g i (T ) ˆ + RT ln yi φi P ˆ dµi = RT d ln yi φi P With dµi = dµi .37 For species i in a real-gas mixture.109). this becomes: 3 ln(P/n) = − ln k + 2Bn + Cn 2 + · · · 2 Thus a plot of ln(P/n) vs. Numerical studies show that the UNILAN equation. (11. n produces − ln k as the intercept and 2B as the limiting slope (for n → 0).109). tends to underestimate Henry’s constant.

since the true 717 . i x i = 1. by Eq. (A). With z = (1 − bm)−1 . The deviation in value must be unity. xi = yi P/Pi ◦ . Summation for given P yields: yi xi = P Pi ◦ i i (B) By general differentiation.39 & 14. yi −1 δ xi = P Pi ◦ i i xi is known. is an approximation that becomes increasingly accurate as the solution procedure converges.41 By Eq. (C) can now be written in the simple but approximate form: d i xi = dP P Equation (A) then becomes: dψ = n d i xi or δψ = n δ i xi i where we have replaced differentials by deviations.107) with a = A/n.109). by rearrangement of Eq. (14. exp − bn 1 − bn ≈1− bn 1 − bn Whence. the adsorption isotherm is: n = k P exp(−2βn) from which.128). (14. one obtains the isotherm: n = k P(1 − bn) exp − bn 1 − bn (A) For bn sufﬁciently small. (B). Eq. dψ = n dP P (A) By Eq. d i xi = P d i yi + Pi ◦ i yi dP Pi ◦ (C) The equation.14. Therefore. (14. the Raoult’s law analogy. for βn sufﬁciently small. With z = 1 + βn. n ≈ k P(1 − 2bn) or n≈ kP 1 + 2bk P which is the Langmuir isotherm.40 Start with Eq. Thus. dP Ad =n P RT The deﬁnition of ψ and its derivative are: ψ≡ A RT and dψ = Ad RT Whence. 14. yi = Pi ◦ i xi i P = 1 P With P ﬁxed. the Langmuir isotherm is again recovered.

2 = A12 Also ∞ ln γ1. (14.2 ∞ ln H1.42 Multiply the given equation for G E/RT by n and convert all mole fractions to mole numbers: n2n3 n1n3 n1n2 nG E + A23 + A13 = A12 n n n RT Apply Eq. For x1 → 0. and ∞ ln γ1.2 + x3 ln H1.24) on page 552 may be applied to the several inﬁnite-dilution cases: ln H1 = ln f 1 + ln γ1∞ Whence. n= i 1 (xi /n i◦ ) Combine the three preceding equations: P δψ = i ◦ i yi −1 Pi ◦ (xi /n i◦ ) When xi = yi P/Pi .2 − ln f 1 ) + x3 (ln H1.3 = ln f 1 + ln γ1.3 − A23 x2 x3 In logarithmic form the equation immediately following Eq. is substituted the required equation is reproduced: P δψ = i P i yi −1 Pi ◦ yi Pi ◦ n i◦ 14. ∞ ∞ ln γ1∞ = x2 ln γ1. x2 = 1.3 = A13 Whence. x3 = 0.3 ln H1 − ln f 1 = x2 (ln H1.132). or ∞ ln H1.96) for i = 1: ln γ1 = A12 n 2 n2n3 1 n1 1 n1 − A23 2 − + A13 n 3 − n n n2 n n2 = A12 x2 (1 − x1 ) + A13 x3 (1 − x1 ) − A23 x2 x3 Introduce solute-free mole fractions: x2 x2 = x2 ≡ 1 − x1 x2 + x3 and x3 = x3 1 − x1 Whence. the Raoult’s law analogy.3 − A23 x2 x3 718 .3 − ln f 1 ) − A23 x2 x3 ln H1 = x2 ln H1. ln γ1 = A12 x2 (1 − x1 )2 + A13 x3 (1 − x1 )2 − A23 x2 x3 (1 − x1 )2 ln γ1∞ = A12 x2 + A13 x3 − A23 x2 x3 Apply this equation to the special case of species 1 inﬁnitely dilute in pure solvent 2. In this case.2 = ln f 1 + ln γ1. (11.2 + x3 ln γ1. (14.By Eq.

¯ 14.48 (a) In accord with Eqs. the derivative must be negative.1) and (14.136) with V2 = V2 : V2 = − ln(x2 γ2 ) RT Represent ln γ2 by a Taylor series: ln γ2 = ln γ2 |x1 =0 + d ln γ2 d x1 x1 =0 x1 + 1 d 2 ln γ2 2 2 d x1 x1 =0 2 x1 + · · · But at x1 = 0 (x2 = 1).95) applies: E ∂(G E/RT ) ∂T =− P. Figure 14. ln(x2 γ2 ) = + ln x2 + ln γ2 = −x1 − 1 2 1− 1 2 d 2 ln γ2 2 d x1 x1 =0 2 x1 − · · · and 1 1 V2 1− =1+ 2 2 x1 RT d 2 ln γ2 2 d x1 x1 + · · · x1 =0 Comparison with the given equation shows that: B= 1 1 1− 2 2 d 2 ln γ2 2 d x1 x1 =0 14. ln x2 = ln(1 − x1 ) = −x1 − 2 x4 x3 x1 − 1 − 1 − ··· 4 3 2 Therefore.12 would have two regions like the one shown from α to β. probably one on either side of the minimum in curve II.47 Equation (11.43 For the situation described. 719 . Therefore. both ln γ2 and its ﬁrst derivative are zero.14. yi ˆ φi P = xi γi Pi sat φisat ⇒ Ki ≡ γi Pi sat φisat yi · = ˆ P xi φi α12 ≡ ˆ γ1 P1sat φ1sat φ2 K1 · sat · = ˆ γ2 P2sat φ1 φ2 K2 (b) α12 (x1 = 0) = γ ∞ P1sat φ1 (P sat ) γ1∞ P1sat φ1 (P1sat ) φ2 (P2sat ) = 1 sat · ∞ 1 sat · ∞ sat · sat ˆ ˆ P2 P2sat φ1 (P2 ) φ1 (P2 ) φ2 (P2 ) α12 (x1 = 1) = ˆ ˆ∞ φ ∞ (P sat ) P sat φ1 (P1sat ) φ2 (P1sat ) P1sat = ∞1 sat · 2 1 · · sat sat ∞ sat φ2 (P2sat ) γ2 P2 φ1 (P1 ) φ2 (P2 ) γ2 P2 The ﬁnal fractions represent corrections to modiﬁed Raoult’s law for vapor nonidealities. (14.44 By Eq. This requires that H E be positive. ln γ2 = 1 2 d 2 ln γ2 2 d x1 x1 =0 2 x1 + · · · Also. (14.” and if it is to decrease with increasing T .x HE RT 2 For the partially miscible system G /RT is necessarily ”large. 14.2).

415.1. which is probably the cheapest possible solvent. then φi = φi for all compositions.x HE =0 RT 2 ⇒ GE = FA (x) RT (c) For solutions exhibiting LLE. ﬁnd: ∂G E ∂T = −S E = 0 P.x ¯ HiE RT 2 ¯ Assume that H E and HiE are functions of composition only. Then integration from Tk to T gives: ln ¯ HE γi (x. Therefore FR (x) GE = RT RT (b) By Eq. making it a suitable solvent for temperature-sensitive materials. Tk ) T Tk ¯ HE dT = i R T2 1 1 − Tk T =− ¯ HiE RT T −1 Tk γi (x.53 Why? Because they are both nontoxic. (11. G E /RT is generally positive and large.98) applies: ∂ ln γi ∂T =− P.49 Equation (11. both Tc and Pc for water are high. A=2 consolute point. 14. Tk ) · exp − ¯ HiE RT T −1 Tk 14. increasing T makes G E /RT smaller. T ) = γi (x. Thus α and β are positive for LLE. A>2 LLE With respect to Eq. (A). For symmetrical behavior. which increases heating and pumping costs. the consolute point is an upper consolute point. and readily available.52 (a) From Table 11. 14. thus. 720 .x and G E is independent of T . p. relatively inexpensive. It is considereably more expensive than water.95). the magic number is A = 2: A<2 homogeneous. 14.ˆ (c) If the vapor phase is an ideal solution of gases. ∂(G E /RT ) ∂T =− P.15. T ) = i R γi (x. However. For CO2 . Its value follows from: α =2 RTU ⇒ TU = α 2R The shape of the solubility curve is as shown on Fig. its Tc is near room temperature.

2 The table is shown below.3) [for U (el)].Non-Numerical Solutions 16. 1 dB −(K 3 − 1)ξ e−ξ/kT + (l 3 − K 3 ) e = kT 2 dT /kT according to which d B/dT = 0 for T ∞ and also for an intermediate temperature Tm : Tm = k ln ξ +ξ K3 − 1 l3 − K 3 That Tm corresponds to a maximum is readily shown by examination of the second derivative d 2 B/dT 2 . and Eq. 2.1 The potential is displayed as follows. Combination of the potential with Eq. contributions to U (long range) are found from Eq. Eq.10) yields on piecewise integration the following expression for B: 2 B = π N A d 3 1 + (K 3 − 1) 1 − e−ξ/kT − (l 3 − K 3 ) e /kT − 1 3 From this expression. 3. Note that K is used in place of k as a parameter to avoid confusion with Boltzmann’s constant.Chapter 16 . (16. (16. Here. the greater the difference in polarity of the interacting species.5) [for U (disp)]. 16.Section B . the fractional contribution of induction forces can be substantial for unlike molecular pairs. is identically zero unless both species in a molecular pair have non-zero permanent dipole moments. (16. Note the following: 1. the magnitude of the dispersion interaction in all cases is substantial.2. 721 . hence f (el). U (el). (16. As seen for several of the examples. Roughly: f (ind) is larger. As also seen in Table 16.4) [for U (ind)].

186 0. (See Sec. H E .8 34. Hence.088 0.008 0.0 98.680 16. we expect either Region I or Region II behavior: G E ⊕ and H E ⊕. (16. |Bi j | < 1 |Bii + B j j | 2 722 .1 95.263 0. Bii + B j j At normal temperature levels.) If interactions between unlike molecular pairs are weaker than interactions between pairs of molecules of the same kind. Here.4-dioxane is a solvating NA/NA mixture. and ethanol is a very strong associator. H E . with S E ⊕ or .770 0. Similar reasoning shows that the combination G E . We therefore expect G E ⊕.3 Water (H2 O).3 270.6. HE . in all four cases. Hence.586 0. a highly polar hydrogen donor and acceptor.795 0. and S E . 16. (h) Ethanol/n-nonane is an AS/NP mixture. H E ⊕. δi j ≡ 2 Bi j − 1 2 E E E . Here.087 0. Here. G E ⊕. interactions between unlike molecular pairs are stronger than interactions between pairs of molecules of the same kind. In series B.1 106. (e) Benzene/n-hexane is NP/NP. and S E . intermolecular attractions prevail.904 0. hydrogen bonding occurs between the donor hydrogens of CH2 Cl2 and the electron-rich benzene molecule.25). and therefore H is negative. by Eq. and S E is inconsistent with Eq. we expect Region II behavior: G E ⊕.188 0. it experiences strong attractive interactions with the second species. H E ⊕. (See Secs. without question.7 By deﬁnition. one expects G E ⊕.9 119. and S E ⊕. [At 323 K (50◦ C).450 5. All other combinations are possible in principle. (16. 16.4 Of the eight potential combinations of signs.25). H E ⊕. G E must be negative: the sign combination G E ⊕.205 0.] (d) Benzene/carbon disulﬁde is an NP/NP system. a charge-transfer complex occurs between acetone and the aromatic benzene molecule. and S E ⊕.806 0 0.) 16.992 0. H ⊕.6 (a) Acetone/cyclohexane is an NA/NP system. G E (g) Chloroform/n-hexane is NA/NP.052 1. and S E ⊕ is outlawed. Hence.992 0.142 0 0 0 0 0 0 0 0.2 for a discussion of the connection between intermolecular forces and the second virial coefﬁcient.Molecular Pair C6 /10−78 J m6 f (el) f (ind) f (disp) f (el)/ f (disp) CH4 /C7 H16 CH4 /CHCl3 CH4 /(CH3 )2 CO CH4 /CH3 CN C7 H16 /CHCl3 C7 H16 /(CH3 )2 CO C7 H16 /CH3 CN CHCl3 /(CH3 )2 CO CHCl3 /CH3 CN (CH3 )2 CO/CH3 CN 49.3 24. H E ⊕. G ⊕. Hence. 16. (f ) Chloroform/1. Neither cyclohexane nor n-hexane offers the opportunity for these special solvation interactions.25).912 0. Suppose that H E is negative and S E is positive. and S E ⊕.008 0.5 and 16. Then. and the second virial coefﬁcients are negative. experiment shows that S E is ⊕ for this system. (See the discussion of signs for H E in Sec. (16.096 0. two are forbidden by Eq. 16.) 16. one will see G E . and S E . 16.7. Hence the mixtures containing benzene have more negative (smaller positive) values of H E than those containing cyclohexane and n-hexane.143 0.1 161.3 0 0 0 0 0 0 0 0. and S ⊕.812 0.000 0. (c) Aniline/cyclohexane is an AS/NP mixture. is the common species for all four systems.9 22.5 In Series A. (b) Acetone/dichloromethane is a solvating NA/NA mixture. H E ⊕.151 0.

the triple bond being the stronger acceptor.l = H R. Because the normal boiling point is a representative T for typical liquid behavior. S sl . 16.7 apply approximately to the signs of δ12 for binary gas mixtures. the values of Hi are in the observed order. 6.5 and E. H is highly negative.l C lP ≈ C v + P ∂ H R. and H sv . R. Fig. whereas δ12 is usually negative for NA/NA mixtures comprising solvating species.12 By deﬁnition. Bi j = Bii = B j j . 16. Consequently.v − H R. NA/NP.6 A = N 6.g.023 × 1023 mol−1 × 1 bar × 106 cm3 m−3 For argon..5 or Tables E.l H lv At 1(atm). For identical interactions of all molecular pairs. H R. Thus.v should be negligible relative to H lv . No hydrogen bonds form between ethane and water. molecular factors that inﬂuence solubility also inﬂuence Hi . and C lP > C v ..70). In the present case. P 16.6). 649 with respect to separations at which attractions become negligible.and hence (since each B is negative) δi j > 0.l molecular forces (see. and so therefore are H sl . H lv has the stated feature.l ∂T P For liquids. S lv . C P = (∂ H R. 16. for binary gas mixtures of the isomeric xylenes. and δi j = 0 The rationalizations of signs for H E of binary liquid mixtures presented in Sec.4)]. and because H R reﬂects intermolecular forces. the triple bond in acetylene and the double bond in ethylene act as proton acceptors for hydrogen-bond formation with the donor H in water. less structure or order means larger S. If unlike interactions are stronger than like interactions. See comments on p. |Bi j | > 1 |Bii + B j j | 2 Hence δi j < 0. Then H R.8 The magnitude of Henry’s constant Hi is reﬂected through Henry’s law in the solubility of solute i in a liquid solvent: The smaller Hi . One expects δ12 to be essentially zero for ideal solutions of real gases.l ≈ − H lv . H lv (H2 O) is much larger than H lv (CH4 ) because of the strong hydrogen bonding in liquid water.l Also by deﬁnition. owing to diminution of interR. and the average length available is about: RT 1/3 V t 1/3 = NA P N 83. becoming less so as T increases. P ig Thus. Thus C P is positive. e.13 The ideal-gas equation may be written: Vt = N RT n RT · = NA P P ⇒ RT Vt = NA P N The quantity V t /N is the average volume available to a particle. (6. 1/3 723 . write C lP = C P +C P . By assumption (modest pressure levels) C P ≈ C v .l /∂ T ) P . 16. ig R. (10.v − H lv ≡ H v − H l = (H v − H ig ) − (H l − H ig ) = H R. Because hydrogen-bond formation between unlike species promotes solubility through smaller values of G E and γi than would otherwise obtain. this is about 10 diameters.11 At the normal boiling point: Therefore H R. and AS/NP mixtures.l R. and S sv are all positive. e.9 By Eq. H α β = T S α β .6 × 10−10 m or 34.14 cm3 bar mol−1 K−1 × 300 K V t 1/3 ˚ = 34. H lv . the larger the solubility [see Eq. where C P is the residual heat capacity for the liquid phase.l 16.g. positive δ12 is the norm for NP/NP. R. For the same temperaature and pressure. Hence.