From the Last Class

Vapor Pressure Equations

Cox chart & Duhring plots: log p* vs. T
Antoine equation: (Table B.4)
B
log10 P* A
TC

Wagner equation
Properties of Gases and Liquids
ln P* (A B1.5 C3 D6 ) / Tr
1 Tr

Note : the vapor pressure equations should be used

within the specified temperature range !

6.2 Gibbs Phase Rule

Types of Process Variables
Extensive Variables
depend on the size of the system (mass and volume)

Intensive Variables
do not depend on the size of the system (T,P, density, and mass fraction)

Gibbs Phase Rule

Degree of freedom (F) is the number of intensive variables that can
be specified independently for a system at equilibrium.
No reaction

F 2m
The number of phases
The number of chemical species
The number of degree of freedom

Raoults Law for GLE:

Single Condensable Component
Water evaporation into dry air
Saturation (GLE)
Gibbs Phase Rule

A+B
B
GLE

F 2m 222 2
.

Raoults Law for GLE

Partial pressure of vapor in the gas
= Pure-component vapor pressure at the system temperature

pi yi P pi* (T )

P&Ty
P&yP
T&yP

Example 6.3.-2 Material Balance Around a Condenser

A stream of air at 100oC contains 5260 mmHg contains

10% water by volume.
(a) Calculate the dew point and degrees of superheat of the
air.
*
pH 2O yH 2O P pH 2O (Tdp )

pH 2O 0.1 5260 526 mmHg

526mmHg .
Antoine equation

Tdp

log10 p* A

B
T C

Table B-4

B
1668.21

228 90o C
*
A log10 p
7.96681 log10 526

degree of superheat = 100 -90 = 10 oC

Example 6.3.-2: A stream of air at 100oC contains 5260

mmHg contains 10% water by volume.

(b) Calculate the percent of vapor that condenses and the

final composition of the gas phase if the gas is cooled to
80oC at constant pressure.
Basis : 100 mol feed gas

100 mol feed

Q2 mol

y H2O
1-y BDA

0.1 H2O
0.9 BDA

Q1 mol H2O
Number of component = 2
Number of unknown = (Q1, Q2, y) = 3

BDA : Bone-Dry Air

D.O.F. = 1: cannot be solved

Should we stop?

Basis : 100 mol feed gas

100 mol feed

Q2 mol
y H2 O
1-y BDA

0.1 H2O
0.9 BDA
T = 100oC, P = 5260 mmHg

T = 80oC, P = 5260 mmHg

Q1 mol H2O

Use thermodynamic information:

A gas in equilibrium with liquid must be saturated with the liquid .
*
p

y
P

p
(T )
o
i
i
i
thus, y is a saturated condition at 80 C, 5260 mmHg

yH 2O pH* 2O (80o C ) / P 355 / 5260 0.0675

yBDA 1 yH 2O 0.9325
Number of component = 2
Number of unknown = (Q1, Q2) = 2

D.O.F. = 0

Material Balance
BDA Balance

1000.9 = Q20.9325

Q2=96.5 mol

Total Balance

100=Q1+Q2

Q1=3.5 mol

% Condensed

3.5/(1000.1) (100) = 35 %

Example 6.3.-2: A stream of air at 100oC contains 5260

mmHg contains 10% water by volume.

(c) Calculate the percentage condensation and the final

gas-phase composition if the gas is compressed
isothermally to 8500 mmHg.
Basis : 100 mol feed gas

100 mol feed

Q2 mol

y H2O
1-y BDA

0.1 H2O
0.9 BDA

Q1 mol H2O
Number of component = 2
Number of unknown = (Q1, Q2, y) = 3

BDA : Bone Dry Air

Cannot be solved !

Basis : 100 mol feed gas

100 mol feed

Q2 mol
y H2 O
1-y BDA

0.1 H2O
0.9 BDA
T = 100oC, P = 5260 mmHg

T = 100 oC, P = 8500 mmHg

Q1 mol H2O

Use thermodynamic information :

A gas in equilibrium with liquid must be saturated with the liquid .
*
p

y
P

p
(T )
o
i
i
i
thus, y is a saturated condition at 100 C, 8500 mmHg

yH 2O pH* 2O (100o C ) / P 760 / 8500 0.0894

1 yH 2O 0.9106

Number of component = 2
Number of unknown = (Q1, Q2) = 2

D.O.F. = 0

Material Balance
BDA Balance

1000.9=Q20.9106

Total Balance

100=Q1+Q2

% Condensed

1.2/(1000.1) (100) = 12 %

Q2=98.8 mol
Q1=1.2 mol

Lets Start!

6.4 Multicomponent Vapor-Liquid Equilibria

Gas-Liquid Processes

Chemical reactions
Distillation ()
Gas Liquid : Absorption ()
Liquid Gas : Stripping ()

VLE information
From literature, databases
Raoults Law & Henrys Law
Rigorous calculation using model equations

Distribution of components between vapor and liquid

phases
Phase-Equilibrium Thermodynamics

Raoults Law and Henrys Law

Vapor
(P and yi)

Raoults Law
pi yi P xi pi* (T )

Liquid
(xi)

Ideal gas
Ideal Solution

pi* = vapor pressure

Valid for almost pure liquid (xi 1)

Valid for mixture of similar substances
(over entire range of compositions: 0 < xi < 1)

Henrys Law
yi P xi H i (T )

Hi = Henrys law constant

Valid for dilute solution (xi0)

Example 6.4-2
Use either Raoults law or Henrys law to solve the following problems.
1. A gas containing 1 mole% ethane is in contact with water at 20oC
and 20 atm. Estimate the mole fraction of dissolved ethane.

N2, O2, CO2, .

CH4, C2H6, .

From Perrys Handbook

Dilute solution

Apply Henrys Law

H C 2 H 6 (20o C ) 2.63 104 atm/mole fraction

yi P xi H i (T )

xi yi P / H i (T )

0.01 20
6

7
.
6

10
2.63 104

Example 6.4-2
Use either Raoults law or Henrys law to solve the following problems.
2. An equimolar liquid mixture of benzene (B) and toluene (T) is in
equilibrium with its vapor at 30oC. What is the system pressure and
the composition of the vapor?
Benzene + Toluene

pi yi P xi pi* (T )

P pi

Similar Substances

Apply Raoults Law

Table B.4

pB* (30o C ) 119 mmHg

Antoine Eqn

pT* (30o C ) 36.7 mmHg

pB xB pB* 0.5 119 59.5 mmHg

pT xT pT* 0.5 36.7 18.35 mmHg
yB xB pB* / P 59.5 / 77.9 0.764
yT xT pT* / P 18.35 / 77.9 0.236

P 59.5 mmHg 18.35 mmHg 77.9 mmHg

Phase diagrams for binary VLE

Txy diagram
(at a fixed P)
T

Pxy diagram
(at a fixed T)
P

vapor

liquid

Bubble P

Dew T

V+L

Bubble T

V+L

Dew P

liquid
vapor

x1

x or y

y1

x1

y1

x or y

Bubble and Dew Points

Bubble Point Temperature

Bubble Point Pressure
Dew Point Temperature
Dew Point Pressure

Bubble point

: Constant P, T
: Constant T, P
: Constant P, T
: Constant T, P

Dew point

Bubble P
Pressure
Liquid

Vapor

yi

xi
Given T,x Calculate P,y

Composition

Dew P
Pressure
Liquid

Vapor

yi

xi
Given T,y Calculate P,x

Composition

Bubble T
Temperature

Vapor

Liquid

xi

yi
Given P,x Calculate T,y

Composition

Dew T
Temperature
Vapor

Liquid

xi

yi
Given T,x Calculate P,y

Pressure

VLE Calculations
Bubble Point Temperature Calculation
Given P, x Calculate T,y
yi

xi pi* (Tbp )

P
P xa pa* (Tbp ) xb pb* (Tbp ) ...

Dew Point Temperature Calculation

Given P,y Calculate T,x
xi

yi P
pi* (Tdp )

xi
i

yi P
1
pi* (Tdp )

VLE Calculation
Iterative calculation required
Not explicit form

Iterative calculation techniques

Trial and error method
Newton-Raphson Method
Secant Method
OBJ ( X ) 0

find X that satisfies given relation

Algorithm for Bubble/Dew Point Calculations

Example : Bubble T Calculation
Objective Function
Start

1
Given P,x

OBJ xi yi 0
i

Assume T

yi xi pi* (T ) / P

Calculate OBJ

Phase Equilibrium
Calculate new T,y

yi P xi pi* (T )
Ki yi / xi pi* (T ) / P

OBJ xi yi

|DT| <e

End

Newton Raphson
Secant iteration

VLE Calculations for Nonideal Systems

Phase equilibrium relations
Ideal Gas + Ideal Solution
yi P xi pi* (T )

Nonideal Gas + Nonideal Solution

Fugacity coefficient : gas phase nonideality
Activity coefficient : liquid phase nonideality
i yi P i xi pi* (T )

from activity models : WILSON, NRTL, UNIQUAC, ,.

from equation of state models : SRK, PR ,.

Example 6.4-4
Bubble- and Dew- point calculation using Txy diagrams
1. Using the Txy diagram, estimate the bubble-point temperature and
the equilibrium vapor composition associated with a 40 mol %
benzene-60 mol % toluene liquid mixture at 1 atm. If the mixture is
steadily vaporized until the remaining liquid contains 25% benzene,
what is the final temperature?

100oC
95oC

Example 6.4-4
Bubble- and Dew- point calculation using Txy diagrams
1. Using the Txy diagram, estimate the dew-point temperature and the
equilibrium liquid composition associated with a vapor mixture of
benzene abd toluene containing 40 mol % benzene at 1 atm. If
condensation proceeds until the remaining vapor contains 60 %
benzene, what is the final temperature?

102oC
96oC

x=0.2

6.5 Solutions of Solids in Liquid Solution

Solubility ()
Limits on the amount of solid that can be dissolved
Solubility strongly depends on T
Example)
222 g AgNO3 / 100 g H2O at 20 o C
952 g AgNO3 / 100 g H2O at 100 oC

Crystallization
Separation of solids and liquids
Driving force = solubility differences
A solute in equilibrium with a crystal must be
saturated

Example 6.5-1
150 kg of a saturated aqueous solution of AgNO3 at 100oC is cooled
to 20oC, thereby forming AgNO3 crystals, which are filtered from the
remaining solution.
The wet filter cake, which contains 80% solid crystals and 20%
saturated solution by mass, passes to a dryer in which the remaining
water is vaporized.
Calculate the fraction of the AgNO3 in the feed stream eventually
recovered as dry crystals and the amount of water that must be
removed in the drying stage.
150 kg

Cooler
Crystallizer

Saturated Solution

Fiter
Filter Cake + Solution

Evaporator

Filter Cake

Water

Basis: 150 kg Feed

150 kg
0.905 AgNO3
0.095 H2O

Q1 kg

Cooler
Crystallizer

Fiter
Q2 kg filter cake

Q3 kg solution

0.689 AgNO3
0.311 H2O

0.689 AgNO3
0.311 H2O
Q4 kg H2O
Evaporator

Q5 kg filter cake

952 g AgNO3 / 100 g H2O at 100

x2 = 952 / (100+952) = 0.905

1-x2 = 0.095
222 g AgNO3 / 100 g H2O at 20 o C
x1 = 222/(100+222) = 0.689
1-x1 = 0.311

Additional Information
Q2 = 0.8 (Q2 + Q3)
Q2 = 4Q3

Unknown = 2
150 kg

Q1 kg

Cooler
Crystallizer

0.905 AgNO3
0.095 H2O

Fiter
4Q3 kg filter cake

Q3 kg solution

0.689 AgNO3
0.311 H2O

0.689 AgNO3
0.311 H2O
Q4 kg H2O
Evaporator

Q5 kg filter cake
Unknown = 3

Unknown = 3

150 kg
0.905 AgNO3
0.095 H2O

Q1 kg

Cooler
Crystallizer

Fiter
4Q3 kg filter cake

Q3 kg solution

0.689 AgNO3
0.311 H2O

0.689 AgNO3
0.311 H2O
Q4 kg H2O
Evaporator

Q5 kg filter cake
Water balance
150 * 0.095 = Q1 * 0.689 + Q3 *0.311
Total Balance
150 = Q1 + 4Q3 + Q3

Q1 = 20 kg
Q2 = 104 kg
Q3 = 26 kg

150 kg

Cooler
Crystallizer

0.905 AgNO3
0.095 H2O

20 kg
Fiter
104 kg filter cake

26 kg solution

0.689 AgNO3
0.311 H2O

0.689 AgNO3
0.311 H2O
Q4 kg H2O
Evaporator

Q5 kg filter cake
Water balance
26 * 0.311 = Q4
Total Balance
104 + 26 = Q4 + Q5

Recovery % = 122 / (150*0.905) * 100 % = 89.9 %

Q4 = 8 kg
Q5 = 122 kg

Hydrated Salts
Several structures can be produced for watersalt systems.
Example ) Solid magnesium sulfate
MgSO4
MgSO4H2O
MgSO46H2O
MgSO47H2O
MgSO412H2O

anhydrous magnesium sulfate

magnesium sulfate monohydrate
magnesium sulfate hexahydrate
magnesium sulfate heptahydrate
magnesium sulfate dodecahydrate

Colligative Solution Properties

Colligative solution properties ( )

Property change of a solution
Vapor pressure lowering
Boiling point elevation
Melting point depression

Depends only on molar concentration

Not depends on solute and solution

Colligative Solution Properties

Vapor pressure lowering
ps (T ) (1 x) ps* (T )
( ps* ) e ps (1 x) ps* (T )
Dp*x ps* ( ps* ) e xp s*

Boiling point elevation

RTb20
DTb
x

DH v

Melting point depression

RTm20
DTm
x

DH m

6.6 Immiscible and Partially Miscible Liquids

Terminology

Immiscibility ()
Partial miscibility ()
Liquid extraction ( )
Distribution coefficient

Water Phase

Water-Rich Phase

Chloroform Phase

MIBK-Rich Phase

immiscible

( x) MIBK
K
( x)WATER

Distribution
of
Acetone

partially miscible
Acetone

Phase Diagram for Partially Miscible

Ternary Systems
Equilateral ternary LLE phase diagram

Phase Diagram for LLE Systems

Single Phase
Region
Two liquids have identical
compositions

Two liquid
Phase Region

Tie Lines

Miscibility limit for water-furfural

Phase Diagram for LLE Systems

Raffinate
EG : 12 %
Furfural : 8 %
Water : 80 %

Extract
EG : 44 %
Furfural : 46 %
Water : 10 %

Feed
EG : 30 %
Furfural : 30 %
Water : 40 %