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From the Last Class

Vapor Pressure Equations

Cox chart & Duhring plots: log p* vs. T Antoine equation: (Table B.4) ☺☺

log

10

P*

A

B

T

C

Wagner equation

“Properties of Gases and Liquids”

ln P*

(A

1.5

    

B

C

3

D

1

 

T

r

6

) / T

r

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.

F 2m 

F  2  m  No reaction The number of phases The number of chemical

No reaction

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

A+B

Saturation (GLE) Gibbs Phase Rule

 
 

B

  B
 

F 2m  222 2

  F  2  m  2  2  2  2 두 개의

두 개의 변수가 결정되면 다른 값들은 결정될 수 있다.

GLE

Raoult’s Law for GLE ☺☺☺

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

p

i

y P p T  * ( ) i i
y P p T
*
(
)
i
i

P

& T y

P

& y P

T

& y P

Example 6.3.-2 Material Balance Around a Condenser

☺☺☺

A stream of air at 100 o C contains 5260 mmHg contains 10% water by volume.

(a) Calculate the dew point and degrees of superheat of the air.

p H 2 O

y P p

H 2 O

*

(

T

H 2 O d p

)

p  H O 2
p
H O
2

0.1

5260

526 mmHg

증기압이 526mmHg인 온도를 찾음.

Antoine equation

log

10

*

p A

B

T C

Table B-4

T

d

p

B

A

log

10

p

*

C

1668.21

7.96681

log

10

526

228

90

o

C

degree of superheat = 100 -90 = 10 o C

Example 6.3.-2: A stream of air at 100 o C 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

80 o C at constant pressure.

Basis : 100 mol feed gas

to 80 o C at constant pressure. Basis : 100 mol feed gas 100 mol feed

100 mol feed

at constant pressure. Basis : 100 mol feed gas 100 mol feed 0.1 H 2 O

0.1 H 2 O 0.9 BDA

Q 2 mol

mol feed gas 100 mol feed 0.1 H 2 O 0.9 BDA Q 2 mol y

y H 2 O 1-y BDA

Q 1 mol H 2 O

BDA : Bone-Dry Air

Number of component = 2

Number of unknown

= (Q 1 , Q 2 , y) = 3

= 2 Number of unknown = ( Q 1 , Q 2 , y ) =

D.O.F. = 1: cannot be solved Should we stop?

Basis : 100 mol feed gas

Basis : 100 mol feed gas 100 mol feed Q 2 mol y H 2 O

100 mol feed

Basis : 100 mol feed gas 100 mol feed Q 2 mol y H 2 O

Q 2 mol

Basis : 100 mol feed gas 100 mol feed Q 2 mol y H 2 O

y H 2 O 1-y BDA

T = 80 o C, P = 5260 mmHg

0.1 H 2 O 0.9 BDA T = 100 o C, P = 5260 mmHg

Q 1 mol H 2 O

Use thermodynamic information:

mmHg Q 1 mol H 2 O Use thermodynamic information: A gas in equilibrium with liquid

A gas in equilibrium with liquid must be saturated with the liquid . thus, y is a saturated condition at 80 o C, 5260 mmHg

y

H O

2

y

BDA

p

*

H O

2

(80

o

 

1

y

2

H O

)/

C P

0.9325

355/5260

0.0675

p

i

y P p T

i

i

*

(

)

Number of component = 2

Number of unknown = (Q

1 , Q 2 ) = 2

Number of component = 2 Number of unknown = (Q 1 , Q 2 ) =

D.O.F. = 0

Material Balance

BDA Balance

Total Balance

% Condensed

100×0.9 = Q 2 ×0.9325

100=Q 1 +Q 2

Q 2 =96.5 mol

Q 1 =3.5 mol

3.5/(100×0.1) ×(100) = 35 %

Example 6.3.-2: A stream of air at 100 o C 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

isothermally to 8500 mmHg. Basis : 100 mol feed gas 100 mol feed 0.1 H 2

100 mol feed

to 8500 mmHg. Basis : 100 mol feed gas 100 mol feed 0.1 H 2 O

0.1 H 2 O 0.9 BDA

Q 2 mol

mol feed gas 100 mol feed 0.1 H 2 O 0.9 BDA Q 2 mol y

y H 2 O 1-y BDA

Q 1 mol H2O

BDA : Bone Dry Air

Number of component = 2

Number of unknown

= (Q 1 , Q 2 , y) = 3

Dry Air Number of component = 2 Number of unknown = ( Q 1 , Q

Cannot be solved !

Basis : 100 mol feed gas

Basis : 100 mol feed gas 100 mol feed Q 2 mol y H 2 O

100 mol feed

Basis : 100 mol feed gas 100 mol feed Q 2 mol y H 2 O

Q 2 mol

Basis : 100 mol feed gas 100 mol feed Q 2 mol y H 2 O

y H 2 O 1-y BDA

T = 100 o C, P = 8500 mmHg

0.1 H 2 O 0.9 BDA T = 100 o C, P = 5260 mmHg

Q 1 mol H2O

Use thermodynamic information :

= 5260 mmHg Q 1 mol H2O Use thermodynamic information : A gas in equilibrium with

A gas in equilibrium with liquid must be saturated with the liquid . thus, y is a saturated condition at 100 o C, 8500 mmHg

*

y

p

2

H O

(100

o

C P  )/
C P 
)/

760/8500

2

H O

H O

2

1

y

0.9106

Number of component = 2

Number of unknown = (Q

1 , Q 2 ) = 2

D.O.F. = 0

0.0894

Material Balance

BDA Balance

Total Balance

% Condensed

100×0.9=Q 2 ×0.9106

Q 2 =98.8 mol Q 1 =1.2 mol

100=Q 1 +Q 2

1.2/(100×0.1) ×(100) = 12 %

p

i

y P p T

i

i

*

(

)

Let’s Start!

6.4 Multicomponent Vapor-Liquid Equilibria

Gas-Liquid Processes

Chemical reactions

Distillation (증류)

Gas Liquid : Absorption (흡수)

LiquidGas : 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
Phase-Equilibrium Thermodynamics

Raoult’s Law and Henry’s Law ☺☺☺

Raoult’s Law

p

i

y P x p T

i

i

i

*

(

)

Vapor (P and y i )

Vapor (P and y i )

Liquid

Liquid

(x

i )

Ideal gasi * ( ) Vapor (P and y i ) Liquid (x i )  Ideal

Ideal Solution(P and y i ) Liquid (x i ) Ideal gas   p i *

p i * = vapor pressure

Valid for almost pure liquid (x i 1) Valid for mixture of similar substances (over entire range of compositions: 0 < x i < 1)

Henry’s Law

y

i

P

x H (T )

i

i

H i = Henry’s law constant

Valid for dilute solution (x i 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 20 o C and 20 atm. Estimate the mole fraction of dissolved ethane.

N 2 , O 2 , CO 2 , …. CH 4 , C 2
N 2 , O 2 , CO 2 , ….
CH 4 , C 2 H 6 , ….
Dilute solution
Apply Henry’s Law
H
(20
o
C 
)
4
C H
2
6
From Perry’s Handbook
y
P
2.63 10 atm/mole fraction
x H (T )
i
i
i
0.01
 20
x  y P H T 
 6
i
2.63 10

i

/

i

(

)

4

7.6

10

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 30 o C. What is the system pressure and the composition of the vapor?

Benzene + Toluene Similar Substances Apply Raoult’s Law * * o p  y P
Benzene + Toluene
Similar Substances
Apply Raoult’s Law
*
*
o
p
y P
x p (T )
Table B.4
p
(30
C 
)
119 mmHg
i
i
i
i
B
 p
p
*
(30
o
P 
C 
)
36.7 mmHg
Antoine Eq’n
i
T
P  59.5 mmHg 18.35 mmHg  77.9 mmHg
p
 x p
*
0.5
119
59.5 mmHg
B
B B
p
 x p
*
0.5
36.7
18.35 mmHg
T
T
T
y
 x p P
*
/
59.5/ 77.9
0.764
B
B B
y
 x p P
*
/
18.35/ 77.9
0.236
T
T
T

Phase diagrams for binary VLE ☺☺

T

Txy diagram (at a fixed P)

vapor Dew T V+L Bubble T liquid x1 y1
vapor
Dew T
V+L
Bubble T
liquid
x1
y1

x or y

P

Pxy diagram

(at a fixed T) liquid Bubble P V+L Dew P vapor x1 y1
(at a fixed T)
liquid
Bubble P
V+L
Dew P
vapor
x1
y1

x or y

Bubble and Dew Points

Bubble Point Temperature : Constant P, T

: Constant T, P

: Constant P, T : Constant T, P

Dew Point Temperature

Bubble Point Pressure

Dew Point Pressure

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

Bubble point

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

Dew point

Bubble P

Pressure

P

Liquid

Liquid Vapor

Vapor

y i

x i

Given T,x Calculate P,y

Bubble P Pressure P Liquid Vapor y i x i Given T,x  Calculate P,y Composition
Bubble P Pressure P Liquid Vapor y i x i Given T,x  Calculate P,y Composition
Bubble P Pressure P Liquid Vapor y i x i Given T,x  Calculate P,y Composition

Composition

Dew P

Pressure

P

Liquid

Liquid Vapor

Vapor

y

i

x

i

Given T,y Calculate P,x

Dew P Pressure P Liquid Vapor y i x i Given T,y  Calculate P,x Composition
Dew P Pressure P Liquid Vapor y i x i Given T,y  Calculate P,x Composition
Dew P Pressure P Liquid Vapor y i x i Given T,y  Calculate P,x Composition

Composition

Bubble T

Temperature

T

Vapor

Vapor Liquid

Liquid

x

i

y

i

Given P,x Calculate T,y

Bubble T Temperature T Vapor Liquid x i y i Given P,x  Calculate T,y Composition
Bubble T Temperature T Vapor Liquid x i y i Given P,x  Calculate T,y Composition
Bubble T Temperature T Vapor Liquid x i y i Given P,x  Calculate T,y Composition

Composition

Dew T

Temperature

T

Vapor

Vapor Liquid

Liquid

x

i

y i

Given T,x Calculate P,y

Dew T Temperature T Vapor Liquid x i y i Given T,x  Calculate P,y Pressure
Dew T Temperature T Vapor Liquid x i y i Given T,x  Calculate P,y Pressure
Dew T Temperature T Vapor Liquid x i y i Given T,x  Calculate P,y Pressure

Pressure

VLE Calculations

Bubble Point Temperature Calculation

Given P, x Calculate T,y

y

i

P

* x p T ( ) i i b p P * x p T
*
x p T
(
)
i
i
b p
P
*
x p T
(
)
a
a
b p

x p T

b

b

b p

*

(

)

Dew Point Temperature Calculation

Given P,y Calculate T,x

x

i

y P

i

p

*

i

(

T

d p

)

 

x

i

i

i

y P

i

p

*

i

(

T

d p

)

1

VLE Calculation

Iterative calculation required

Not explicit form

Iterative calculation techniques

Trial and error method

Newton-Raphson Method

Secant Method

OBJ ( X ) 0

 Newton-Raphson Method  Secant Method O B J ( X )  0 find X

find X that satisfies given relation

Algorithm for Bubble/Dew Point Calculations

Objective Function

OBJ

i

i

x i 1

y

i 1

 

x

i

i

i

y

i

0

Phase Equilibrium

y P x p T

i

i

i

*

(

)

K i

/

y x

i

i

p T P

i

*

(

)/

Example : Bubble T Calculation

Start

i i  p T P i * ( )/ Example : Bubble T Calculation Start

Given P,x

Assume T

Calculate OBJ Calculate new T,y |DT| <e
Calculate OBJ
Calculate new T,y
|DT| <e

End

y  x p T P * ( )/ i i i OBJ  
y  x p T P
*
(
)/
i
i
i
OBJ
 
x 
y
i
i i
Newton Raphson

i

Secant iteration

VLE Calculations for Nonideal Systems

Phase equilibrium relations

Ideal Gas + Ideal Solution

y P x p T

i

i

i

*

(

)

Nonideal Gas + Nonideal Solution

Fugacity coefficient : gas phase nonideality

Activity coefficient : liquid phase nonideality

 y P  x p T * ( ) i i i i i
y P

x p T
*
(
)
i
i
i
i
i
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?

100 o C

95

o C

steadily vaporized until the remaining liquid contains 25% benzene, what is the final temperature? 100 o

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?

102 o C

96 o C

x=0.2
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 AgNO 3 / 100 g H 2 O at 20 o C 952 g AgNO 3 / 100 g H 2 O at 100 o C

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 AgNO 3 at 100 o C is cooled to 20 o C, thereby forming AgNO 3 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 AgNO 3 in the feed stream eventually recovered as dry crystals and the amount of water that must be

removed in the drying stage.

Cooler

Crystallizer

Fiter

150 kg

in the drying stage. Cooler Crystallizer Fiter 150 kg Filter Cake + Solution Evaporator Filter Cake
in the drying stage. Cooler Crystallizer Fiter 150 kg Filter Cake + Solution Evaporator Filter Cake
in the drying stage. Cooler Crystallizer Fiter 150 kg Filter Cake + Solution Evaporator Filter Cake

Filter Cake + Solutionmust be removed in the drying stage. Cooler Crystallizer Fiter 150 kg Evaporator Filter Cake Saturated

Evaporator

drying stage. Cooler Crystallizer Fiter 150 kg Filter Cake + Solution Evaporator Filter Cake Saturated Solution

Filter Cakeremoved in the drying stage. Cooler Crystallizer Fiter 150 kg Filter Cake + Solution Evaporator Saturated

Saturated Solution

Water

Basis: 150 kg Feed

Q 1 kg 150 kg Cooler Fiter Crystallizer 0.689 AgNO3 0.905 AgNO3 0.311 H2O 0.095
Q 1 kg
150 kg
Cooler
Fiter
Crystallizer
0.689 AgNO3
0.905
AgNO3
0.311 H2O
0.095
H2O
Q 2 kg filter cake
Q 3 kg solution
0.689
AgNO3
0.311
H2O
Q 4 kg H2O
Evaporator
Q 5 kg filter cake

952 g AgNO 3 / 100 g H 2 O at 100 o C

x2 = 952 / (100+952) = 0.905 1-x2 = 0.095

222 g AgNO 3 / 100 g H 2 O at 20 o C

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

Additional Information

Q 2 = 0.8 (Q 2 + Q 3 )

Q 2 = 4Q 3

Unknown = 2 Q 1 kg 150 kg Cooler Fiter Crystallizer 0.689 AgNO3 0.905 AgNO3
Unknown = 2
Q 1 kg
150 kg
Cooler
Fiter
Crystallizer
0.689 AgNO3
0.905
AgNO3
0.311 H2O
0.095
H2O
4Q 3 kg filter cake
Q 3 kg solution
0.689
AgNO3
0.311
H2O
Q 4 kg H2O
Evaporator
Q 5 kg filter cake
Unknown = 3
Unknown = 3
Q 1 kg 150 kg Cooler Fiter Crystallizer 0.689 AgNO3 0.905 AgNO3 0.311 H2O 0.095
Q 1 kg
150 kg
Cooler
Fiter
Crystallizer
0.689 AgNO3
0.905
AgNO3
0.311 H2O
0.095
H2O
4Q 3 kg filter cake
Q 3 kg solution
0.689
AgNO3
0.311
H2O

Evaporator

Q 4 kg H2O

solution 0.689 AgNO3 0.311 H2O Evaporator Q 4 kg H2O Q 5 kg filter cake Water

Q 5 kg filter cake

Water balance 150 * 0.095 = Q1 * 0.689 + Q3 *0.311

Total Balance 150 = Q1 + 4Q3 + Q3

Water balance 150 * 0.095 = Q1 * 0.689 + Q3 *0.311 Total Balance 150 =

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

20 kg 150 kg Cooler Fiter Crystallizer 0.689 AgNO3 0.905 AgNO3 0.311 H2O 0.095 H2O
20 kg
150 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
Q 4 kg H2O
Evaporator
Q 5 kg filter cake

Water balance 26 * 0.311

= Q4

Total Balance 104 + 26 = Q4 + Q5

balance 26 * 0.311 = Q4 Total Balance 104 + 26 = Q4 + Q5 Q4

Q4 = 8 kg Q5 = 122 kg

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

Hydrated Salts

Several structures can be produced for water-

salt systems.

Example ) Solid magnesium sulfate

MgSO4

MgSO4·H2O

MgSO4·6H2O

MgSO4·7H2O

MgSO4·12H2O

anhydrous magnesium sulfate magnesium sulfate monohydrate magnesium sulfate hexahydrate magnesium sulfate heptahydrate 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

p T

(

D

s

(

*

p

s

p

*

x

)

)

e

p

(1

x p T

s

)

*

(

)

p

*

s

s

(1

*

s

(

p

)

e

x p T

s

)

*

(

xp

*

s

)

Boiling point elevation

D T

b

2

RT

b

0

ˆ

D H

v

x

Melting point depression

D T

m

2 0

RT

m

ˆ

D H

m

x

6.6 Immiscible and Partially Miscible Liquids

Terminology

Immiscibility (불혼화성)

Partial miscibility (부분혼화성)

Liquid extraction (액체 추출)

Distribution coefficient

Water Phase

Chloroform Phase

immiscible

Water-Rich Phase

MIBK-Rich Phase

partially miscible

Water-Rich Phase MIBK-Rich Phase partially miscible Acetone K  ( x ) MIBK ( x )
Water-Rich Phase MIBK-Rich Phase partially miscible Acetone K  ( x ) MIBK ( x )

Acetone

K

( x )

MIBK

( x )

WATER

Distribution

Distribution

of

Acetone

Phase Diagram for Partially Miscible

Ternary Systems

Equilateral ternary LLE phase diagram

Phase Diagram for Partially Miscible Ternary Systems  Equilateral ternary LLE phase diagram

Phase Diagram for LLE Systems

Phase Diagram for LLE Systems Single Phase Region Two liquids have identical compositions Two liquid Phase
Phase Diagram for LLE Systems Single Phase Region Two liquids have identical compositions Two liquid Phase
Phase Diagram for LLE Systems Single Phase Region Two liquids have identical compositions Two liquid Phase
Phase Diagram for LLE Systems Single Phase Region Two liquids have identical compositions Two liquid Phase

Single Phase

Region

Two liquids have identical compositions

Two liquid

Phase Region

Tie Lines

Miscibility limit for water-furfural

Phase Diagram for LLE Systems

Phase Diagram for LLE Systems Extract EG : 44 % Furfural : 46 % Water :

Extract EG : 44 % Furfural : 46 %

Water : 10 %

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

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

% Furfural : 46 % Water : 10 % Feed EG : 30 % Furfural :