CENG 221 Homework 1 Solution

Q1:
Part I
Antoine Equation:
Let liquid() and vapour() be two phases of pure component at equilibrium.
Then dG = dG
dG = VdP SdT

V dP* S dT = V dP* S dT
dP* S S S
=
=
dT V V V

(1)

As G = 0 , therefore, H = T S
dP* S
H
=
=
dT V T V
For P =

(2)

RT
V

Then Eq.(2) can be changed as following:

dP* H P*
=
dT
RT 2
dP* H dT
=
P*
RT 2
d (ln P* ) =

H
1
d( )
R
T

if H is a constant at a small range of temperatures, Then

Let B=

H
R

ln( P* ) = A

B
T

(3)

For the temperature in Eq.3 is K, and H is depend on temperature.then Eq.3 is modified as,

ln( PA* ) = A

B
T ( C) + C
o

where A, B, and C are "Antoine coefficients" that vary from substance to substance.
Sublimations and vaporizations of the same substance have separate sets of Antoine
coefficients, as do components in mixtures. The Antoine equation is accurate to a few percent
for most volatile substances (with vapor pressures over 10 Torr).
Assumptions:
1. The vapour is an idea gas of negligible molecular size and there is no interaction between
gas molecules.
2. The solution is ideal solution, which is defined as a solution formed with no accompanying
energy change, when the intermolecular attractive forces between the molecules of the solvent
are the same as those between the molecules in the separate components.
3. The system is a close system and in equilibrium. The volume of liquid is negligible
compared to volume of vapour.

Part II

log P* = A

B
(P:mmHg, T oC)
T +C

P*
P
=
760 101.3
P* =
log

760* P
101.3

760
B
P = A
101.3
T +C

ln10*log

ln

B
760
P = [A
]*ln(10)
T +C
101.3

B
760
+ ln P = [ A
]*ln(10)
T +C
101.3

ln P = [ A *ln(10) ln

B *ln(10)
760
]
T +C
101.3

then new A= [ A *ln(10) ln

760
]
101.3

new B= B *ln(10)
new C=C

Table 1. The Antoine coefficients of different compounds

Compound

Reference

Cyclohexane

13.297

2802.08

224.53

Gaw and Swinton, 1968

1-Hexene.

13.794

2654.81

225.85

Forziati, Camin, et al., 1950

Methol

13.88

2921.56

216.95

Ambrose and Sprake, 1970

1-Heptene

13.881

2921.14

216.95

Bent, Cuthbertson, et al., 1936

Decane

13.996

3477.521

194.48

Williamham, Taylor, et al., 1945

Heptane

14.285

3641.17

239.65

Williamham, Taylor, et al., 1945

Acetone

14.793

2021.574

240.705

Ambrose, Sprake, et al., 1974

Toluene

15.069

3094.51

219.377

Williamham, Taylor, et al., 1945

Methane

13.36

928.18

267.67

Cutler and Morrison, 1965

Ethane

14.983

1828.943

279.57

Carruth and Kobayashi, 1973

Pentane

13.791

2465.187

232.696

Osborn and Douslin, 1974

Note: The attachment is Excel File which I got from Angela. There are thousand of the A,B and
C parameters.

Q2
Given:
Antoine equation
P

2.3 atm

A mixture of toluene and n-heptane

Find: calculate T, X,Y ,x, y, Kh,Kt and
Soln:
For pure compound:

Pt * = Ph* = PT = 2.3atm = 233.45kPa

ln Pt* = 14.0098 3103.01/(T + 219.79)
ln Ph* = 13.8587 2991.32 /(T + 216.64)
Ttb=142.854
Thb=139.23

T
Tmin

Tmax

Ph

Pt

Xh

Xt

Yh

Yt

xh

xt

yh

yt

Kh
0

Kt

alpha

139.227 233.45 214.16

139.727 236.22 216.75

0.8578

0.1422

0.8679

0.1321

0.8677

0.1323

0.8773

0.142 1.0119 0.9285 1.0898

140.227 239.01 219.36

0.7169

0.2831

0.7339

0.2661

0.7336

0.2664

0.75

0.2829 1.0238 0.9397 1.0896

140.727 241.83

222

0.5773

0.4227

0.598

0.402

0.5976

0.4024

0.618

0.4225 1.0359

141.227 244.68 224.66

0.439

0.561

0.4601

0.5399

0.4598

0.5402

0.481

0.5608 1.0481 0.9624 1.0891

141.727 247.55 227.35

0.302

0.698

0.3203

0.6797

0.32

0.68

0.3388

0.6979 1.0604 0.9739 1.0888

142.227 250.44 230.06

0.1663

0.8337

0.1784

0.8216

0.1782

0.8218

0.191

0.8337 1.0728 0.9855 1.0886

142.727 253.37

232.8

0.0318

0.9682

0.0345

0.9655

0.0344

0.9656

0.0374

0.9682 1.0853 0.9972 1.0884

142.845 254.06 233.45

0.951 1.0893

144
143

T(oC)

142
141
140
139
138
0

0.2

0.4

0.6

0.8

1.2

x, y

1.2
1

yh

0.8
0.6
0.4
0.2
0
0

0.2

0.4

0.6
xh

0.8

1.09
1.0898
1.0896
Alpha

1.0894
1.0892
1.089
1.0888
1.0886
1.0884
1.0882
139.5

140

140.5

141

141.5

T(oC)

142

142.5

143

Q3:
We wished to use a distillation system with a still pot to batch
distill a mixture of methanol and water. A total condenser is used. The
feed is 57 mole% methanol (use VLE data in Table 3-3) Please find the
Wfinal, D, and XD using 1 Kg as basis of your calculation. The final
concentration in the still is 15 mole% methanol.

Solution:
Given: F = 1kg;
Find: Xd, Wfinal, D
x

y
0
2
4
6
8
10
15
20
30
40
50
60
70
80
90
95
100

Xf = 0.57;

y-x
0
13.4
23
30.4
36.5
41.8
51.7
57.9
66.5
72.9
77.9
82.5
87
91.5
95.8
97.9
100

Xw,final = 0.15

1/(y-x)
11.4
19
24.4
28.5
31.8
36.7
37.9
36.5
32.9
27.9
22.5
17
11.5
5.8
2.9
0

8.77193
5.263158
4.098361
3.508772
3.144654
2.724796
2.638522
2.739726
3.039514
3.584229
4.444444
5.882353
8.695652
17.24138
34.48276

10
9
8
7
6
Series1

5
4
3
2
1
0
0

20

40

.57 *32
= .702kg = 21.94mol
.57 *32 + .43*18
Mass of water=1-.702=.298=16.56mol
F=21.94+16.56=38.5mol
Mass of methaol=

By Rayleigh Equation,
dX w
dW
=
W
Yd X w
W final
ln
F

By Simpsons Rule,

0.15
X W , final

dX w
dX w
=
= X f
0.57 X X
Xd Xw

d
w

60

80

100

Area =
W final
ln
F

( X f X w, final )[ F ( X w, final ) + 4 F ( X m ) + F ( X f )]
6

( X f X w, final )[ F ( X w, final ) + 4 F ( X m ) + F ( X f )]

=
6

(0.57 0.15)(2.725+4*2.9+4.18)
=
= 1.295
6

Wfinal = F * e1.295 = 11.84mol

By overall material balance,

F =W + D
FX f = WX w + DX d
Xd =

FX f WX w
F W

38.5 0.57 11.84 0.15

= 0.756
38.5 11.84

1/(y-x)

D=38.5-11.84=26.66mol

4.6
4.5
4.4
4.3
4.2
4.1
4
3.9
3.8
3.7
3.6
3.5
3.4
3.3
3.2
3.1
3
2.9
2.8
2.7
2.6
2.5
2.4
2.3
2.2
2.1
2

Series1

10

20

30

40
x

50

60

70