CHE 305: SOLUTION THERMODYNAMICS

5.0 Applications of Solution Thermodynamics

Introduction to Phase Equilibria, Simplified Vapor-Liquid Equilibrium

Related Readings: Chapter 12, Chapter 13 (Sec. 13.1 to 13.3) (Smith et al., 8th edition)

Instructor:
Engr. Michael Allan G. Ramos
Chemical Engineering Department
Technological Institute of the Philippines

1
 The Phase Rule

Consider a non-reactive system under equilibrium, with π phases each containing N species:

Total number of Number of independent

Degrees of Freedom = systemic intensive -
equations relating all the
variables variables

Phase Rule Variables: Chemical potential equality relations

• Temperature
• Pressure
• Mole Fractions

𝑭=𝟐+𝑵−𝝅
1
 The Duhem’s Theorem
• Applies to the extensive state of a closed system at equilibrium
• To completely determine the state of the system (both intensive and extensive states)
Total number of Number of independent
Degrees of Freedom = - equations relating all the
systemic variables
variables
Phase Rule Variables:
• Temperature • Chemical potential equality relations
• Pressure • Material balance equations
• Mole Fractions
• Mass/moles
𝐹 = 2 + 𝑁 − 1 𝜋 + 𝝅 − [ 𝜋 − 1 𝑁 + 𝑵]
For any closed system formed from known amounts of prescribed
𝑭=𝟐 chemical species, the equilibrium state is completely determined
when any two independent variables are fixed.

2
Three-Dimensional Phase Diagram for a Binary System (P-T-xy)

• Binary mixture of species 1 (lighter or more volatile)

and species 2 (heavier or less volatile).
• Upper surface à Saturated liquid states / Bubble surface
• Lower surface à Saturated vapor states / Dew surface
• Above the upper surface à subcooled liquid region
• Below the lower surface à superheated vapor region
• Interior space à region of co-existence of liquid and vapor
• Rounded edge of surface between C1 and C2
à critical locus / contains the critical lines of the various
mixtures of the two species
à defined by the points at which vapor and liquid phases
in equilibrium become identical

3
Two-Dimensional Phase Diagrams (P-xy & T-xy)

• Solid line à Saturated liquid line /

Bubble line
• Broken line à Saturated vapor line
/ Dew line

• Vapor forms at high temperature

and low pressure

4
Isobaric Evaporation on a T-xy diagram

• Equimolar mixture of Benzene (lighter or more volatile)

and Toluene (heavier or less volatile) at 1 atm.

State 1
• T= 80oC
• Subcooled liquid
(x1 = 0.50; x2 = 0.50)

5
Isobaric Evaporation on a T-xy diagram (cont.)

• Equimolar mixture of Benzene (lighter or more volatile)

and Toluene (heavier or less volatile) at 1 atm.

State 2
• T= 92oC
• Saturated liquid

• Start of formation of the first

vapor bubble à Bubble point
(y1 = 0.73; y2=0.27)
• Decrease in the benzene content
of the liquid (and some toluene)

6
Isobaric Evaporation on a T-xy diagram (cont.)

• Equimolar mixture of Benzene (lighter or more volatile)

and Toluene (heavier or less volatile) at 1 atm.

State 3
• T= 97oC
• Mixture of liquid and vapor

• Vapor (y1 = 0.59; y2=0.41)

• Liquid (x1 = 0.34; x2 = 0.66)

7
Isobaric Evaporation on a T-xy diagram (cont.)

• Equimolar mixture of Benzene (lighter or more volatile)

and Toluene (heavier or less volatile) at 1 atm.

State 4
• T= 99oC
• Saturated vapor
(y1 = 0.50; y2=0.50)
• Upon infinitesimal cooling,
first liquid dew will form as
a result of condensation
à Dew Point

8
Isobaric Evaporation on a T-xy diagram (cont.)

• Equimolar mixture of Benzene (lighter or more volatile)

and Toluene (heavier or less volatile) at 1 atm.

State 4
• T= 99oC
• Saturated vapor
(y1 = 0.50; y2=0.50)
• Initial composition of the
subcooled liquid is
recovered but now in
vapor phase.

9
Isobaric Evaporation on a T-xy diagram (cont.)

• Equimolar mixture of Benzene (lighter or more volatile)

and Toluene (heavier or less volatile) at 1 atm.

State 5
• T= 105oC
• Superheated vapor
(y1 = 0.50; y2=0.50)

10
Isothermal Evaporation on a P-xy diagram

• Similarly, decreasing the pressure while

maintaining the temperature constant would
convert a subcooled liquid into a saturated
liquid, saturated vapor, and superheated vapor.

11
Minimum Pressure Azeotrope in P-xy Diagram

• At the azeotropic point: x1 = y1

• Boiling liquid of this composition
produces a vapor of exactly the
same composition

• No separation of such a constant-

boiling solution is possible by
distillation

• Minimum pressure azeotrope

results from large negative
tetrahydrofuran(1) + Chloroform (1) +
departures from linearity
carbon tetrachloride(2) tetrahydrofuran(2) (Raoult’s Law)
at 30°C at 30°C

12
Maximum Temperature Azeotrope in T-xy Diagram

• Maximum temperature
azeotrope results from large
positive departures from linearity
(Raoult’s Law)

tetrahydrofuran(1) + Chloroform (1) +

carbon tetrachloride(2) tetrahydrofuran(2)
at 101.3 kPa at 101.3 kPa

13
Maximum Pressure Azeotrope in P-xy Diagram

• Maximum pressure azeotrope

results from large positive
departures from linearity
(Raoult’s Law)

furan(1) + ethanol(1) +
carbon tetrachloride(2) toluene(2)
at 30°C at 65°C

14
Minimum Temperature Azeotrope in T-xy Diagram

• Minimum temperature azeotrope

results from large positive
departures from linearity
(Raoult’s Law)

furan(1) + ethanol(1) +
carbon tetrachloride(2) toluene(2)
at 101.3 kPa at 101.3 kPa

15
Fugacity of a species in a gas mixture

Subtracting:
𝜇! ≡ 𝐺̅! = Γ! 𝑇 + 𝑅𝑇 ln 𝑓.! 𝑓.!
!" !" 𝜇!# ≡ 𝐺̅!# = 𝑅𝑇 ln = 𝑅𝑇 ln 𝜙0 !
𝜇! ≡ 𝐺!̅ = Γ! 𝑇 + 𝑅𝑇 ln 𝑦! 𝑃 𝑦! 𝑃

𝑓.!
Clarifying symbols: 𝜙0 ! =
𝑦! 𝑃
𝑓/! = fugacity of species i in solution
𝑓! = fugacity of pure species i
#
𝑓/!" , 𝑓/! = fugacity of species i in multi-component phases 𝛼 and 𝛽, respectively.
#
𝑓!" , 𝑓! = fugacity of species i in pure component phases 𝛼 and 𝛽, respectively.
16
Fugacity of a species in a liquid mixture

Subtracting:
𝜇! ≡ 𝐺̅! = Γ! 𝑇 + 𝑅𝑇 ln 𝑓.! 𝑓 .!
𝜇!% ≡ 𝐺̅!% = 𝑅𝑇 ln !$ = 𝑅𝑇 ln 𝛾!
𝜇!!$ ≡ 𝐺̅!!$ = Γ! 𝑇 + 𝑅𝑇 ln 𝑓.!!$ 𝑓. !

#"!
𝛾! = !" (Activity coefficient)
Clarifying symbols: #"
!

𝑓/! = fugacity of species i in solution

𝑓! = fugacity of pure species i
#
𝑓/!" , 𝑓/! = fugacity of species i in multi-component phases 𝛼 and 𝛽, respectively.
#
𝑓!" , 𝑓! = fugacity of species i in pure component phases 𝛼 and 𝛽, respectively.
17
Fugacity applied in Vapor-Liquid Equilibrium

For vapor: 𝐺̅!# = 𝑅𝑇 ln 𝜙0 ! For liquid: 𝐺̅!% = 𝑅𝑇 ln 𝛾!

𝑓/! 𝑓/!
𝜙4 ! = 𝛾! = !$
𝑦! 𝑃 𝑓/!

Criterion for phase equilibrium: 𝑓.!& = 𝑓.!' i = 1, 2, 3 … N component

𝜙0 !( 𝑦! 𝑃 = 𝛾! 𝑓.!!$ 𝑓.!!$ = 𝑥! 𝑓!'

𝜙0 !( 𝑦! 𝑃 = 𝛾! 𝑥! 𝑓!'
,!" (./.!#$% )
𝜙0 !( 𝑦! 𝑃 = 𝛾! 𝑥! 𝑃!)*+ ∅!)*+ exp
#1

Φ𝑦! 𝑃 = 𝛾! 𝑥! 𝑃!)*+ Gamma/Phi Formulation for VLE

18
Raoult’s Law for VLE
Quantitative analysis of VLE can be performed by Raoult’s Law, which requires two
major assumptions:

1. The vapor phase behaves as an ideal gas

àClose or less to atmospheric pressure

2. The liquid phase behaves as an ideal solution

àSpecies involved are chemically similar (size, chemical nature)

Other forms:

where:
i = 1, 2, 3 … N component (for Binary System only)

19
VLE Calculations using Raoult’s Law

1. Bubble Point Temperature Calculation

àGiven: pressure, liquid phase composition
àUnknown: temperature, vapor phase composition

For binary systems:

Psat = f(TB)
TB should be between TB1 and TB2

• Assume TB
• Evaluate P1sat or P2sat at assumed TB
• Solve for P, if equal to given, proceed. Otherwise, assume another TB
• Solve for y1 and y2
20
VLE Calculations using Raoult’s Law (cont.)

2. Bubble Point Pressure Calculation

àGiven: temperature, liquid phase composition
àUnknown: pressure, vapor phase composition

For binary systems:

• Evaluate P1sat and P2sat at the given TB

• Solve for P
• Solve for y1 and y2
21
VLE Calculations using Raoult’s Law (cont.)

3. Dew Point Temperature Calculation

àGiven: pressure, vapor phase composition
àUnknown: temperature, liquid phase composition

For binary systems:

Psat = f(TD)
TD is greater than TB

• Assume TD
• Evaluate P1sat or P2sat at assumed TD
• Solve for P, if equal to given, proceed. Otherwise, assume another TD
• Solve for x1 and x2
22
VLE Calculations using Raoult’s Law (cont.)

4. Dew Point Pressure Calculation

àGiven: temperature, vapor phase composition
àUnknown: pressure, liquid phase composition

For binary systems:

• Evaluate P1sat and P2sat at the given TD

• Solve for P
• Solve for x1 and x2
23
Illustrative Problems

1. Determine the temperature and composition of the first bubble created from a
saturated liquid mixture of benzene and toluene containing 45 mole percent benzene at
200 kPa. Benzene and toluene mixtures may be considered as ideal.
2. Determine the pressure and composition of the first bubble created from a saturated
liquid mixture of benzene and toluene containing 45 mole percent benzene at 400 K.
Benzene and toluene mixtures may be considered as ideal.
3. Determine the temperature and composition of the first dew created from a saturated
vapor mixture of benzene and toluene containing 45 mole percent benzene at 200 kPa.
Benzene and toluene mixtures may be considered as ideal.
4. Determine the pressure and composition of the first dew created from a saturated
vapor mixture of benzene and toluene containing 45 mole percent benzene at 400 K.
Benzene and toluene mixtures may be considered as ideal.

24
Graphical Solution using T-xy Diagram

25
Use of K-values

Raoult’s Law Equilibrium Ratio

𝑃!" 𝑦! 𝑃
𝑦! = 𝑥 = 𝑥!
𝑃 ! 𝑃!"
𝑦!
𝑦! = 𝐾! 𝑥! = 𝑥!
𝐾!
𝑦!
) 𝑦! = ) 𝐾! 𝑥! ) = ) 𝑥!
𝐾!
𝑦!
1 = ) 𝐾! 𝑥! ) =1
𝐾!

(for Bubble Calculations) (for Dew Calculations)

26
Evaluation of K-values

Equilibrium Ratio

27
Evaluation of K-values

28
Illustrative Problem

Assuming the validity of the DePriester charts, make the following VLE calculations for
the methane(1)/ethylene (2)/ethane (3) system:

a. Bubble pressure, given x1 = 0.10, x2 = 0.50, and T = 222.15 K

b. Dew pressure, given y1 = 0.50, y2 = 0.25, and T = 222.15 K

c. Bubble temperature, given x1 =0.12, x2 = 0.40, and P = 17.24 bar

d. Dew point temperature, given y1 = 0.43, y2 = 0.36, and P = 17.24 bar

29
Illustrative Problem (cont.)

a. Bubble pressure, given x1 = 0.10, x2 = 0.50, and T = 222.15 K

Solution: 1 = ) 𝐾! 𝑥!

Trial 1: P = 200 psia

Component xi Ki xi*Ki
Methane 0.10 5.65 0.565
Ethylene 0.50 0.71 0.355
Ethane 0.40 0.455 0.182
1.102

30
P = 200 psia
(assumption)

T = -59.8 oF

31
Illustrative Problem (cont.)

a. Bubble pressure, given x1 = 0.10, x2 = 0.50, and T = 222.15 K

Solution: 1 = ) 𝐾! 𝑥!

Trial 1: P = 200 psia

Component xi Ki xi*Ki
Methane 0.10 5.65 0.565
Ethylene 0.50 0.71 0.355
Ethane 0.40 0.455 0.182
1.102

32
Illustrative Problem (cont.)

a. Bubble pressure, given x1 = 0.10, x2 = 0.50, and T = 222.15 K

Solution: 1 = ) 𝐾! 𝑥!

Trial 1: P = 200 psia Trial 2: P = 220 psia

Component xi Ki xi*Ki Component xi Ki xi*Ki
Methane 0.10 5.65 0.565 Methane 0.10 5.15 0.515
Ethylene 0.50 0.71 0.355 Ethylene 0.50 0.65 0.325
Ethane 0.40 0.455 0.182 Ethane 0.40 0.425 0.17
1.102 1.010

33
P = 220 psia
(assumption)
T = -59.8 oF

34
Illustrative Problem (cont.)

a. Bubble pressure, given x1 = 0.10, x2 = 0.50, and T = 222.15 K

Solution: 1 = ) 𝐾! 𝑥!

Trial 1: P = 200 psia Trial 2: P = 220 psia

Component xi Ki xi*Ki Component xi Ki xi*Ki
Methane 0.10 5.65 0.565 Methane 0.10 5.15 0.515
Ethylene 0.50 0.71 0.355 Ethylene 0.50 0.65 0.325
Ethane 0.40 0.455 0.182 Ethane 0.40 0.425 0.17
1.102 1.010

35
Illustrative Problem (cont.)

a. Bubble pressure, given x1 = 0.10, x2 = 0.50, and T = 222.15 K

Solution: 1 = ) 𝐾! 𝑥!

Trial 1: P = 200 psia Trial 2: P = 220 psia Trial 3: P = 222 psia

Component xi Ki xi*Ki Component xi Ki xi*Ki Component xi Ki xi*Ki
Methane 0.10 5.65 0.565 Methane 0.10 5.15 0.515 Methane 0.10 5.1 0.51
Ethylene 0.50 0.71 0.355 Ethylene 0.50 0.65 0.325 Ethylene 0.50 0.645 0.3225
Ethane 0.40 0.455 0.182 Ethane 0.40 0.425 0.17 Ethane 0.40 0.42 0.168
1.102 1.010 1.0005

36
P = 222 psia
(assumption)
T = -59.8 oF

37
Illustrative Problem (cont.)

a. Bubble pressure, given x1 = 0.10, x2 = 0.50, and T = 222.15 K

Solution: 1 = ) 𝐾! 𝑥!

Trial 1: P = 200 psia Trial 2: P = 220 psia Trial 3: P = 222 psia

Component xi Ki xi*Ki Component xi Ki xi*Ki Component xi Ki xi*Ki
Methane 0.10 5.65 0.565 Methane 0.10 5.15 0.515 Methane 0.10 5.1 0.51
Ethylene 0.50 0.71 0.355 Ethylene 0.50 0.65 0.325 Ethylene 0.50 0.645 0.3225
Ethane 0.40 0.455 0.182 Ethane 0.40 0.425 0.17 Ethane 0.40 0.42 0.168
1.102 1.010 1.0005

38
Illustrative Problem (cont.)

b. Dew pressure, given y1 = 0.50, y2 = 0.25, and T = 222.15 K

𝑦!
Solution: 1=)
𝐾!

Trial 1: P = 200 psia

Component yi Ki xi*Ki
Methane 0.50 5.65 0.0885
Ethylene 0.25 0.71 0.3521
Ethane 0.25 0.455 0.5495
0.9901

39
P = 200 psia
(assumption)
T = -59.8 oF

40
Illustrative Problem (cont.)

b. Dew pressure, given y1 = 0.50, y2 = 0.25, and T = 222.15 K

𝑦!
Solution: 1=)
𝐾!

Trial 1: P = 200 psia Trial 2: P = 205 psia

Component yi Ki xi*Ki Component yi Ki yi/Ki
Methane 0.50 5.65 0.0885 Methane 0.50 5.6 0.0892
Ethylene 0.25 0.71 0.3521 Ethylene 0.25 0.7 0.3571
Ethane 0.25 0.455 0.5495 Ethane 0.25 0.445 0.5618
0.9901 1.0081

41
P = 205 psia
(assumption)
T = -59.8 oF

42
Illustrative Problem (cont.)

b. Dew pressure, given y1 = 0.50, y2 = 0.25, and T = 222.15 K

𝑦!
Solution: 1=)
𝐾!

Trial 1: P = 200 psia Trial 2: P = 205 psia

Component yi Ki xi*Ki Component yi Ki yi/Ki
Methane 0.50 5.65 0.0885 Methane 0.50 5.6 0.0892
Ethylene 0.25 0.71 0.3521 Ethylene 0.25 0.7 0.3571
Ethane 0.25 0.455 0.5495 Ethane 0.25 0.445 0.5618
0.9901 1.0081

43
END.