Gavin Duffy
School of Electrical Engineering Systems
DIT Kevin Street
Learning Outcomes
After this lecture you should be able to .
Define an azeotrope
Derive a relationship for liquid and vapour phase mole
fractions using Daltons and Raoults laws
Develop vapour liquid equilibrium data from vapour
pressures or from relative volatility
Generate vapour pressures from the Antoine equation
Create an equilibrium curve for a binary mixture
1.0
EA and Eth
form an
Azeotrope at
55% EA
0.9
0.8
Ya (EA vapour)
0.7
0.6
0.5
0.4
0.3
0.2
0.1
Azeotrope
0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Xa (EA liquid)
0.7
0.8
0.9
1.0
The Azeotrope
An azeotrope is formed when the liquid and vapour
compositions are the same
Bubble
1.0
80
0.9
79
0.8
78
0.7
77
0.6
76
Temp C
Ya (EA vapour)
Dew
0.5
75
0.4
74
0.3
73
0.2
72
0.1
71
70
0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Xa (EA liquid)
0.7
0.8
0.9
1.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Xa, Ya (EA)
0.7
0.8
0.9
1.0
Bubble
Dew
1.0
0.9
109
108
0.7
107
0.6
106
0.5
105
Temp C
Ya (H2O vapour)
0.8
0.4
104
103
0.3
102
0.2
101
0.1
100
0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Xa (H2O liquid)
0.7
0.8
0.9
1.0
99
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Xa, Ya (H2O)
0.9
1.0
Activity - Azeotrope
Check the Ethanol Water T-x-y diagram from earlier.
Does it form an azeotrope?
If so, at what point?
What are the consequences?
What can we do?
Calculating them
PT Pbo
xa o
Pa Pbo
Pao xa
ya
PT
a ,b
Pa
o
Pb
ya
xa
1 xa 1
A
P
B
Temp
Antoine equation
The Antoine equation relates vapour pressure to
temperature
B
log10 P A
T C
Where P = pressure of the saturated vapour (mmHg)
T = Temperature (K)
A, B, C = Antoine coefficients
Perry and the CRC handbook have Antoine coefficients
Clausius-Clapeyron Equation
P2o
T1T2 ln
o
P1
o
ln P
B
T1 T2 T
See example 6.1-1 in Felder and Rousseau
0.000
0.389
0.470
0.545
0.583
0.656
0.684
100
95
Temp C
Ethanol Water
Temp
Xa
Ya
100.0
0.000
89.0
0.072
85.3
0.124
82.7
0.234
81.5
0.327
79.8
0.508
79.3
0.573
90
85
80
75
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Xa, Ya (Eth)
0.9
1.0