ChE 101 Fundamentals of Chemical Engineering

Material Balances
in Multiphase Systems

Outline
Vapor-Liquid Equilibrium
Phase diagrams
Raoults Law

Gas-Liquid Equilibrium
Henrys Law
Psychrometric charts

Liquid-Liquid Equilibrium
Solid-Liquid Equilibrium

Recall: Separation Processes

How do we determine
these compositions?

Phase Diagrams

Phase Diagrams

Phase Diagrams

Phase Diagrams
Equations for vapour/saturation pressure
Clapeyron equation
Antoine equation
ln

=
+

Phase Diagrams
Graphs for vapour/saturation pressure (Cox chart)

Phase Diagrams

Phase Diagrams

10

Gibbs Phase Rule

Applicable to systems at equilibrium with no reaction
F: degrees of freedom, number of independent intensive variables
needed to fix all other intensive variables
P: number of phases
C: number of independent components
=2+

Ex. How many number of phases in:

A solution of salt in water
Saturated salt solution with salt crystals settling
A system of CaCO3 decomposing to CaO and CO2
Oil and water
11

Vapor-Liquid Equilibrium
Ex. Alcohol solution
NBP of water: 100oC
NBP of ethanol: 78.4oC
How many degrees of freedom?
Composition in vapour:
Composition in liquid:
Recall: partial pressure
=

12

Vapor-Liquid Equilibrium
Raoults Law:

=
13

Vapor-Liquid Equilibrium
Non-ideal solutions

14

Vapor-Liquid Equilibrium
P-xy Diagram
Tie line

Total
Total

Liquid region
Vapor region

15

Vapor-Liquid Equilibrium
T-xy diagram
Liquid region

Vapor region

16

Vapor-Liquid Equilibrium
Recall: ILAR

V
L

=+
= +

17

Vapor-Liquid Equilibrium
Ex. Based on the T-xy diagram for
toluene and benzene (x-axis is for
benzene),
Which is the more volatile
component?
What are the vapor pressures of
each component at 100oC?
What are the normal boiling points
of each component?
Equal amounts of toluene at 85oC
and benzene at 110oC are mixed at
atmospheric conditions
What it the final temperature?
What are the final compositions?

18

Vapor-Liquid Equilibrium
Ex. A 70% toluene mixture in a closed
isothermal piston cylinder at 100oC
and 1000 mmHg is depressurized to
600 mmHg
What is the initial state of the
system?
At what P will the first bubble
form? What is its composition?
At what P will the last drop of
liquid evaporate? What is its
composition?
What are the liquid and vapor
compositions at 750 mmHg? What
is the vapor-liquid ratio at this
point?

19

Vapor-Liquid Equilibrium

20

Vapor-Liquid Equilibrium
Bubble-P calculation
Given: T,

Dew-P calculation
Given: T,

1
=

21

Vapor-Liquid Equilibrium
Ex. A 70% toluene mixture in a closed isothermal piston cylinder at 100oC and 1000
mmHg is depressurized to 600 mmHg
What is the initial state of the system?
At what P will the first bubble form? What is its composition?
At what P will the last drop of liquid evaporate? What is its composition?
What are the liquid and vapor compositions at 750 mmHg? What is the vapor-liquid
ratio at this point?

22

Vapor-Liquid Equilibrium
Bubble-T calculation
Given: P,

= 0

For binary solutions,

= 1 1 + 2 2
Let =

1
2

1
+1

= exp 1 2

2 =
1 + 2
2
=
2
2 ln 2

2
+2

23

Vapor-Liquid Equilibrium
Bubble-T calculation
Given: P,

Guess T

Calc

Calc 2

Converge

Calc new
T
24

Vapor-Liquid Equilibrium
Dew-T calculation
Given: P,

1
=

For binary solutions,

1
1
2
= + 1 = 1 + 2
1
2
1
=
1
1 ln 1

25

Vapor-Liquid Equilibrium
Dew-T calculation
Given: P,

Guess T

Calc

Calc 1

Converge

Calc new
T
26