From the Last Class

Vapor Pressure Equations

 Cox chart & Duhring plots: log p* vs. T
 Antoine equation: (Table B.4) ☺☺
B
log10 P*  A 
TC

 Wagner equation
 “Properties of Gases and Liquids”
ln P*  (A  B1.5  C3  D6 ) / 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  2m
The number of phases

The number of chemical species

The number of degree of freedom

 Raoult’s Law for GLE:
Single Condensable Component ☺☺☺
 Water evaporation into dry air
A+B
 Saturation (GLE)
B
 Gibbs Phase Rule
GLE
F  2m  222  2
두 개의 변수가 결정되면 다른 값들은 결정될 수 있다.

 Raoult’s Law for GLE ☺☺☺

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

pi  yi P  pi* (T ) P&Ty
P&yP
T&yP
 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

증기압이 526mmHg인 온도를 찾음.

Antoine equation B
log10 p*  A  Table B-4
T C

B 1668.21
Tdp   C   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

0.1 H2O y H2O

0.9 BDA 1-y BDA

Q1 mol H2O BDA : Bone-Dry Air

Number of component = 2
Number of unknown = (Q1, Q2, y) = 3 D.O.F. = 1: cannot be solved
Should we stop?
 Basis : 100 mol feed gas

100 mol feed Q2 mol

0.1 H2O y H2 O
0.9 BDA 1-y 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 .
o
thus, y is a saturated condition at 80 C, 5260 mmHg pi  yi P  pi
*
(T )
yH 2O  pH* 2O (80o C ) / P  355 / 5260  0.0675
yBDA  1  yH 2O  0.9325

Number of component = 2 D.O.F. = 0

Number of unknown = (Q1, Q2) = 2

Material Balance
BDA Balance 100×0.9 = Q2×0.9325 Q2=96.5 mol
Total Balance 100=Q1+Q2 Q1=3.5 mol
% Condensed 3.5/(100×0.1) ×(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

0.1 H2O y H2O

0.9 BDA 1-y BDA

Q1 mol H2O BDA : Bone Dry Air

Number of component = 2
Number of unknown = (Q1, Q2, y) = 3 Cannot be solved !
 Basis : 100 mol feed gas

100 mol feed Q2 mol

0.1 H2O y H2 O
0.9 BDA 1-y 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 .
o
thus, y is a saturated condition at 100 C, 8500 mmHg pi  yi P  pi
*
(T )
yH 2O  pH* 2O (100o C ) / P  760 / 8500  0.0894
1  yH 2O  0.9106

Number of component = 2 D.O.F. = 0

Number of unknown = (Q1, Q2) = 2

Material Balance
BDA Balance 100×0.9=Q2×0.9106 Q2=98.8 mol
Total Balance 100=Q1+Q2 Q1=1.2 mol

% Condensed 1.2/(100×0.1) ×(100) = 12 %

Let’s Start!
 6.4 Multicomponent Vapor-Liquid Equilibria

 Gas-Liquid Processes
 Chemical reactions
 Distillation (증류)
 Gas  Liquid : Absorption (흡수)
 Liquid Gas : Stripping (탈기)

 VLE information
 From literature, databases
 Raoult’s Law & Henry’s Law ☺☺☺
 Rigorous calculation using model equations

 Distribution of components between vapor and liquid

phases
 Phase-Equilibrium Thermodynamics
 Raoult’s Law and Henry’s Law ☺☺☺
Vapor  Ideal gas
(P and yi)

 Raoult’s Law Liquid

(xi)
 Ideal Solution

pi  yi P  xi pi* (T ) pi* = vapor pressure

 Valid for almost pure liquid (xi 1)

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

 Henry’s Law
yi P  xi H i (T ) Hi = Henry’s law constant

 Valid for dilute solution (xi0)

 Example 6.4-2 ☺☺
Use either Raoult’s law or Henry’s 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, ….
Dilute solution Apply Henry’s Law

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

From Perry’s Handbook

yi P  xi H i (T )
0.01 20 6
xi  yi P / H i (T )   7.6  10
2.63 104
 Example 6.4-2 ☺☺
Use either Raoult’s law or Henry’s 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 Similar Substances Apply Raoult’s Law

pi  yi P  xi pi* (T ) Table B.4 pB* (30o C )  119 mmHg

P   pi Antoine Eq’n pT* (30o C )  36.7 mmHg
pB  xB pB*  0.5 119  59.5 mmHg P  59.5 mmHg  18.35 mmHg  77.9 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
 Phase diagrams for binary VLE ☺☺

 Txy diagram  Pxy diagram

(at a fixed P) (at a fixed T)

T vapor
P
liquid
Bubble P

V+L Dew T

Bubble T
V+L Dew P

liquid
vapor

x1 y1 x1 y1

x or y x or y
 Bubble and Dew Points

 Bubble Point Temperature : Constant P, T

 Bubble Point Pressure : Constant T, P
 Dew Point Temperature : Constant P, T
 Dew Point Pressure : Constant T, P

Bubble point Dew point

 Bubble P
Pressure

Liquid

Vapor

yi xi Composition

Given T,x  Calculate P,y

 Dew P
Pressure

Liquid

Vapor

yi xi Composition

Given T,y  Calculate P,x

 Bubble T
Temperature

Vapor

Liquid

xi yi Composition

Given P,x  Calculate T,y

 Dew T
Temperature

Vapor

Liquid

xi yi Pressure

Given T,x  Calculate P,y

 VLE Calculations

 Bubble Point Temperature Calculation

 Given P, x  Calculate T,y
xi pi* (Tbp )
yi 
P
P  xa pa* (Tbp )  xb pb* (Tbp )  ...

 Dew Point Temperature Calculation

 Given P,y  Calculate T,x
yi P
xi 
pi* (Tdp )
yi P
 xi  
i i pi* (Tdp )
1
 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

x
i
i 1
Given P,x

y
i
i 1
Assume T
OBJ   xi  yi  0
i i yi  xi pi* (T ) / P
Calculate OBJ OBJ   xi  yi
i i
Phase Equilibrium
Calculate new T,y Newton Raphson
Secant iteration
yi P  xi pi* (T ) …

Ki  yi / xi  pi* (T ) / P |DT| <e

End
 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 (용해도)
 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 Saturated Solution

Fiter
Crystallizer

Filter Cake + Solution

Evaporator Water

Filter Cake
Basis: 150 kg Feed

150 kg Q1 kg
Cooler
Fiter
Crystallizer
0.689 AgNO3
0.905 AgNO3
0.311 H2O
0.095 H2O Q2 kg filter cake Q3 kg solution

0.689 AgNO3
0.311 H2O

Q4 kg H2O
Evaporator

Q5 kg filter cake

952 g AgNO3 / 100 g H2O at 100 o C

Additional Information
x2 = 952 / (100+952) = 0.905
Q2 = 0.8 (Q2 + Q3)
1-x2 = 0.095
 Q2 = 4Q3
222 g AgNO3 / 100 g H2O at 20 o C

x1 = 222/(100+222) = 0.689
1-x1 = 0.311
 Unknown = 2

150 kg Q1 kg
Cooler
Fiter
Crystallizer
0.689 AgNO3
0.905 AgNO3
0.311 H2O
0.095 H2O 4Q3 kg filter cake Q3 kg solution

0.689 AgNO3
0.311 H2O

Q4 kg H2O
Evaporator

Q5 kg filter cake

Unknown = 3 Unknown = 3
150 kg Q1 kg
Cooler
Fiter
Crystallizer
0.689 AgNO3
0.905 AgNO3
0.311 H2O
0.095 H2O 4Q3 kg filter cake Q3 kg solution

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
Q1 = 20 kg
Total Balance Q2 = 104 kg
150 = Q1 + 4Q3 + Q3 Q3 = 26 kg
150 kg 20 kg
Cooler
Fiter
Crystallizer
0.689 AgNO3
0.905 AgNO3
0.311 H2O
0.095 H2O 104 kg filter cake 26 kg solution
0.689 AgNO3
0.311 H2O

Q4 kg H2O
Evaporator

Q5 kg filter cake

Water balance
26 * 0.311 = Q4
Q4 = 8 kg
Total Balance Q5 = 122 kg
104 + 26 = Q4 + Q5

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

 Hydrated Salts

 Several structures can be produced for water-

salt systems.

 Example ) Solid magnesium sulfate

MgSO4 anhydrous magnesium sulfate

MgSO4·H2O magnesium sulfate monohydrate
MgSO4·6H2O magnesium sulfate hexahydrate
MgSO4·7H2O magnesium sulfate heptahydrate
MgSO4·12H2O magnesium sulfate dodecahydrate
 Colligative Solution Properties

 Colligative solution properties (용액의 총괄성)

 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
ˆ
DH v

 Melting point depression

RTm20
DTm  x
ˆ
DH m
 6.6 Immiscible and Partially Miscible Liquids

 Terminology
 Immiscibility (불혼화성)
 Partial miscibility (부분혼화성)
 Liquid extraction (액체 추출)
 Distribution coefficient ( x) MIBK
K
( x)WATER

Water Phase Water-Rich Phase Distribution

of
Chloroform Phase MIBK-Rich Phase Acetone

immiscible 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 Feed
EG : 44 % EG : 30 %
Furfural : 46 % Furfural : 30 %
Water : 10 % Water : 40 %