Chemical Engineering Thermodynamics II (EquilibriumF)
Chemical Engineering Thermodynamics II (EquilibriumF)
Chemical Engineering Thermodynamics II (EquilibriumF)
Thermodynamics II
Course Code: CEE4205
(2 Credits)
Course Content
• where:
• xi= liquid-phase mole fraction; yi= vapor-phase mole fraction;
• =vapor pressure of pure species i at the temperature of the system.
• The product yiP on the left side is known as the partial pressure of species i.
Vapor-Liquid Equilibrium (VLE)
• Raoult’s law states that partial vapor pressure exerted by a
component in an ideal solution is the product of its mole
fraction and vapor pressure of a pure component.
• Thereby, total vapor pressure exerted by an ideal solution
with k components, P is given by
• … (3)
• Where Pi is the vapor pressure of the pure component and xi
is the respective mole fraction.
Vapor-Liquid Equilibrium (VLE)
• For instance, if in a brine solution (two-component mixture),
one component (common salt) has negligible vapor at the
specified temperature.
• The mixture’s vapor pressure is simply a product of the mole
fraction of water and vapor pressure of water at the
specified temperature.
Vapor-Liquid Equilibrium (VLE)
• Raoult’s law is only valid for ideal solutions, assuming no
intermolecular interaction between components.
• In most cases dealt with in industries, ideal solutions are
uncommon.
• Modified Raoult’s law is used for non-ideal solutions;
accordingly, the total pressure exerted, P is expressed as
• ... (4)
• ϒ is the activity coefficient for the ith component.
Vapor-Liquid Equilibrium Diagram
• Dew (liquid) Pressure (P): Calculate {xi} and P, given {yi} and T
• Dew (liquid) Temperature (T): Calculate {xi} and T, given {yi} and P
Example 1:
• Binary system acetonitrile (1)/nitromethane (2) conforms
closely to Raoult’s law. Vapor pressures for the pure species
are given by the following Antoine equations:
(a) Prepare a graph showing P vs. xi & P vs. yi for a temperature of 75oC.
(b) Prepare a graph showing t vs. xi & t vs. yi for a pressure of 75 kPa.
Solution
• At 75oC, but the Antoine equations: and are 83.21 and 41.98
kPa respectively.
• Let x1 be 0.6, from Eq. (E3);
• The corresponding value of y1 is ten found from Eq. (4) as
follows:
•
Solution
Table 1
x1 y1 P/kPa
0.0 0.0000 41.98
0.2 0.3313 50.23
0.4 0.5692 58.47
0.6 0.7483 66.72
0.8 0.8888 74.96
1.0 1.0000 83.21
Solution
• The P-x1 and P-y1 meet at the edges of the diagram, where
saturated liquid and saturated vapor of the pure species
coexist at the vapor pressures P1 and P2
Solution
• The results of this and similar calculations for P=70 kPa are as
follows:
Solution
Table 2
x1 y1 t/oC
0.0000 0.0000 89.58 ()
0.1424 0.2401 86
0.3184 0.4742 82
0.5156 0.6759 78
0.7378 0.8484 74
1.0 1.0000 69.84 ()
Solution