Vapor/Liquid Equilibrium:

Introduction
Chemical Engineering
Thermodynamics II
Prepared by: Engr. Abhel Y. Ananoria, MSc.
In this lecture we will talk about...
• The nature of equilibrium
• Phase rule
• Qualitative analysis of VLE
• Simple models of VLE
• Raoult’s law and modified Raoult’s law
• Henry’s Law
• K-value correlation
• Flash VLE calculation
 Vapor-liquid equilibrium
 Application
– Distillation
– Absorption
– Extraction
 Bring phases of different composition into contact.

Both the extent of change and the rate of transfer

depend on the departure of the system from
equilibrium.

Quantitative treatment of mass transfer the

equilibrium T, P, and phase compositions must be
known.
The nature of equilibrium
 A static condition in which no changes occur in the macroscopic
properties of a system with time.

 At the microscopic level, conditions are not static.

- The average rate of passage of molecules is the same in both
directions, and no net interphase transfer of material occurs.

 An isolated system consisting of liquid and vapor phases in intimate

contact eventually reaches a final state wherein no tendency exists
for change to occur within the system.
- Fixed temperature, pressure, and phase composition
 Phase rule and Duhem’s theorem
The number of variables the number of variables number of independent
that is independently that characterize the equations connecting the
fixed in a system at intensive state of the variable
equilibrium system

 An intensive state of PVT system with N chemical species and π phases

in equilibrium:
variables : 2  ( N  1)( )
Independent quations : (  1)( N )
variables that can be fixed : F  2  ( N  1)( )  (  1)( N )

Phase rule: F  2   N
 Phase rule and Duhem’s theorem
 Duhem’s theorem: applies to closed system with fixed extensive and
intensive states.
 An intensive state of PVT system plus the extensive variables:
variables : 2  ( N  1)( )    2  N
Independent equations : (  1)( N )  N  N
variables that can be fixed : F  2  N  N  2

For any closed system formed initially from given masses of prescribed
chemical species, the equilibrium state is completely determined when any
two independent variables are fixed.

Example: When phase rule F = 1, at least one of the two variables must be
extensive, and when F = 0, both must be extensive.
Qualitative behavior of VLE
 P-T-composition diagram for a binary
system; species 1 is the more volatile
component.

 Lower surface: Saturated vapor state or

the P-T-y1 surface

 Upper surface: Saturated liquid state or

the P-T-x1 surface

 RKAC1 and UBHC2: intersection of the 2

phases: vapor pressure-vs-temperature
curves
Qualitative behavior of VLE
 C1 and C2: Critical points of pure species 1
and 2; rounded edge surface is the critical
points of various mixtures
 Above the upper surface: Subcooled
region.

 Below the lower surface: Superheated

region

 Surface in-between: 2-phase region

Qualitative behavior of VLE
Example analysis:

F → L →W → G: Pressure drop at constant

composition from F to G.

 Starting with supercooled liquid at F.

 First buble appears at L (bubble point).
 The composition of vapor phase at the
same pressure and temperature is given
by point V.
 LV is a tie line
 Last drop of liquid disappears at W
(dewpoint)
 Further reduction in pressure brings to
point G in the superheated region
Qualitative behavior of VLE
AEDBLA: Perpendicular plane to the T axis
 Lines on this plane form P-x1-y1 phase
diagrams at constant T.
Qualitative behavior of VLE
KJIHLK: Perpendicular plane to the P axis
 Lines on this plane form T-x1-y1 phase
diagrams at constant P.
Qualitative behavior of VLE
SLMNQ: Perpendicular plane to the x1-y1 axis
 Lines on this plane form P-T phase
diagrams at constant composition.

R
Qualitative behavior of VLE:
Retrograde Condensation
B → D : Reduction of pressure starting from
saturated liquid B results in vaporization to
the two phase and finally to a saturated
vapor D.

F → H : Reduction of pressure starting from

saturated vapor F results in condensation to
the two phase to a maximum at G before
vaporizing again to saturated vapor H.

 This phenomena is called retrograde

condensation

 Typically important in natural gas deep

wells where natural well formation may
start at conditions similar to F.
 Examples of VLE diagrams:
Ethane(1)/n-heptane(2) system

 Interection of a pressure curve with the diagonal are the minimum and
maximum concentration of the more volatile component obtainable.
 Point A is the concentration at the maximum pressure where vapor and
liquid co-exist; at about 77.1% ethane.
 Examples of VLE diagrams:
Tetrahydrofuran(1)/carbon tetrachloride(2) system

Pxy diagram at 30⁰C Txy diagram at 1 atm

 Negative departure from linear P-x1 model of Raoult’s law.

 Examples of VLE diagrams:
Chloroform(1)/Tetrahydrofuran (2) system

Pxy diagram at 30⁰C Txy diagram at 1 atm

 Large enough negative departure from linear P-x1 model of Raoult’s law
results in an azeotrope.
 Azeotrope: vapor and liquid phase have the same composition.
 Examples of VLE diagrams:
Furan(1)/carbon tetrachloride (2) system

Pxy diagram at 30⁰C Txy diagram at 1 atm

 Positive departure from linear P-x1 model of Raoult’s law.

 Examples of VLE diagrams:
Ethanol(1)/Toluene (2) system

Pxy diagram at 30⁰C Txy diagram at 1 atm

 Large enough positive departure from linear P-x1 model of Raoult’s law
results in an azeotrope.
 VLE Models: Raoult’s Law
Assumptions:
1. The vapor phase is an ideal gas (apply for low to moderate pressure)
2. The liquid phase is an ideal solution (apply when the species that are
chemically similar)

Raoult’s law: yi P  xi Pi sat (i  1, 2, ..., N )

Limitations:
1. Requires species to be in the subcritical region.
2. Only describes actual behavior of a small class of systems.
 VLE Models: Raoult’s Law
Types of VLE calculations:
BUBL P : Calculate {yi} and P , given {xi} and T
DEW P : Calculate {xi} and P , given {yi} and T
BUBL T : Calculate {yi} and T , given {xi} and P
DEW T : Calculate {xi} and T , given {yi} and P

Raoult’s law: yi P  xi Pi sat (i  1, 2, ..., N )

For bubble point calculation For dew point calculation

y i 1 x
i
i 1
i

P   xi Pi sat
1
(i  1, 2, ..., N ) P (i  1, 2, ..., N )
i  i i
y /
i
P sat

Binary system: Binary system:

1
PP sat
 (P sat
 P ) x1
sat P
2 1 2 y1 / P1sat  y2 / P2sat
Example 1
Binary system acetonitrile (1)/nitromethane(2) conforms closely to Raoult’s law.
Vapor pressures for the pure species are given by the following Antoine equations:
2945.47 2972.64
ln P1sat / kPa  14.2724  ln P2sat / kPa  14.2043 
t /  C  224.00 t /  C  209.00
(a) Prepare a graph showing P vs. x1 and P vs. y1 for a temperature of 75°C.
(b) Prepare a graph showing t vs. x1 and t vs. y1 for a pressure of 70 kPa.

(a) BUBL P P  P2sat  ( P1sat  P2sat ) x1

@ 75°C, using the Antoine Equations; P1sat  83.21 P2sat  41.98

P  41.98  (83.21  41.98) x1

 We set values of x1 from 0 to 1 and find the corresponding P and y1.

e.g. x1 = 0.6
x1 P1sat (0.6)(83.21)
P  41.98  (83.21  41.98)(0.6) y1  
P 66.72
P  66.72 y1  0.7483
Example 1
(a) BUBL P P  P2sat  ( P1sat  P2sat ) x1

Example analysis:

a → b →c → d: Constant T expansion

 Starting with supercooled liquid at a.

 First buble appears at b (bubble point):
The compositions:
whole system: 60% 1/40% 2
liquid phase: 60% 1/40% 2 (b)
vapor phase: 74.83% 1/ 25.17% 2 (b’)
 Further reduction produces a two-phase
system.
Example 1
(a) BUBL P P  P2sat  ( P1sat  P2sat ) x1

Example analysis:
a → b →c → d: Constant T expansion

 Last drop of liquid disappears at c

(dewpoint)
whole system: 60% 1/40% 2
vapor phase: 60% 1/40% 2 (c)
liquid phase: c’
@ y1 = 0.6, T= 75⁰C
1 1
P 
y1 / P1sat  y2 / P2sat 0.6 / 83.21  0.4 / 41.98
P  59.74kPa
P  59.74  41.98  (83.21  41.98)( x1 )
x1  0.4308
Example 1
Binary system acetonitrile (1)/nitromethane(2) conforms closely to Raoult’s law.
Vapor pressures for the pure species are given by the following Antoine equations:
2945.47 2972.64
ln P1sat / kPa  14.2724  ln P2sat / kPa  14.2043 
t /  C  224.00 t /  C  209.00
(a) Prepare a graph showing P vs. x1 and P vs. y1 for a temperature of 75°C.
(b) Prepare a graph showing t vs. x1 and t vs. y1 for a pressure of 70 kPa.

(b) BUBL T, having P = 70 kPa

Bi
Rearranging the Antoine Equations; tisat   Ci
Ai  ln P
Temperature boundaries: t1
sat
 69.84C t 2sat  89.58C
sat sat
 We set values of t from t1 to t 2 ; calculate P1sat and P2sat ; find x1 then y1.
e.g. t = 78⁰C: From Antoine Equations; P1sat  91.76 P2sat  46.84

70  46.84  (91.76  46.84) x1 x1 P1sat (0.5156)(91.76)

y1  
P 70
x1  0.5156 y1  0.6759
Example 1 xi yi T xi yi T
0.0000 0.0000 89.58 0.5156 0.6759 78
(a) BUBL P P  P2sat  ( P1sat  P2sat ) x1 0.1424 0.2401 86 0.7378 0.8484 74
0.3184 0.4742 82 1.0000 1.0000 69.84

Example analysis:

a → b →c → d: Constant P heating

 Starting with supercooled liquid at a.

 First buble appears at b (bubble point):
The compositions:
whole system: 60% 1/40% 2
liquid phase: 60% 1/40% 2 (b)
vapor phase: b’
Example 1 xi yi T xi yi T
0.0000 0.0000 89.58 0.5156 0.6759 78
(a) BUBL P P  P2sat  ( P1sat  P2sat ) x1 0.1424 0.2401 86 0.7378 0.8484 74
0.3184 0.4742 82 1.0000 1.0000 69.84

Finding y1 (b’); x1=0.6 :

1.) Assume T; Calc. 
B1 B2
ln   A1  A2  
T  C1 T  C2
where   P1sat / P2sat
P
2.) Calc. Psat P2sat 
x1  x2
B2
3.) Calc. new T T  C2
A2  ln P
4.) Repeat until T converges
Following the steps; T  76.42C
from Antoine eq. P1sat  87.17
x1 P1sat (0.60)(87.17)
y1   y1  0.7472
P 70
Example 1 xi yi T xi yi T
0.0000 0.0000 89.58 0.5156 0.6759 78
(a) BUBL P P  P2sat  ( P1sat  P2sat ) x1 0.1424 0.2401 86 0.7378 0.8484 74
0.3184 0.4742 82 1.0000 1.0000 69.84

Example analysis:

a → b →c → d: Constant P heating

 Further reduction produces a two-phase

system.
 Last drop of liquid disappears at c
(dewpoint)
vapor phase: 60% 1/40% 2 (c)
liquid phase: c’
 Another iterative process of the same
procedure as before to find x1 at c’.
T  79.58C P1sat  96.53
x1 P1sat x (96.53) x1  0.4351
y1   0.6  1
P 70
 VLE Models: Henry’s Law
 For a species present as a very dilute solute in the liquid phase, the partial
pressure of the species in the vapor phase is directly proportional to its liquid-
phase mole fraction:
yi P  xi  i

Henry’s Constants for Gases Dissolved in Water at 25⁰C

Example 2
Assuming that carbonated water contains only CO2 (species 1) and H2O (species
2) , determine the compositions of the vapor and liquid phases in a sealed can of
“soda” and the pressure exerted on the can at 10°C. Henry’s constant for CO2 in
water at 10°C is about 990 bar.
Henry’s law for species 1: y1P  x1H1
Raoult’s law for species 2: y2 P  x2 P2sat

P  x1H1  x2 P2sat
Assuming x1 = 0.01
P  (0.01)(990)  (0.99)(0.01227)  9.912
Check by assuming y1 = 1.0: y1P  x1H1 x1  0.01

For the vapor phase: y 2 P  x P

2 2
sat
y2  0.0012 y1  0.9988
 VLE Models: Modified Raoult’s Law
 Accounts for the departure from ideal solution assumption of the Raoult’s
law

yi P  xi i Pi sat (i  1, 2, 3, ...N )

 i  Activity coefficient
 A function of temperature and liquid composition
 Emperical values

For bubblepoint calculation: P   xi i Pi sat

i

1
For dewpoint calculation: P
 i ii
y
i
/  P sat
Example 3
For the system methanol (1)/methyl acetate (2), the following equations provide a
reasonable correlation for the activity coefficients:
ln  1  (2.771  0.00523T ) x22 ln  2  (2.771  0.00523T ) x12
3643.31 2665.54
ln P1sat / kPa  16.59158  ln P2sat / kPa  14.25326 
T ( K )  33.424 T ( K )  53.424
(a) P and {yi} for T = 318.15 K and x1 = 0.25
(a) for T = 318.15, and x1 = 0.25

@ 318.15K, using the Antoine Equations;

3643.31
ln P1sat  16.59158  P1sat  44.51
318.15  33.424
2665.54
ln P2sat / kPa  14.25326  P2sat  65.64
318.15  53.424
For the activity coefficients;

ln  1  (2.771  0.00523(318.15))(0.752 )  1  1.864

ln  2  (2.771  0.00523(318.15))(0.252 )  2  1.072

Example 3
For the system methanol (1)/methyl acetate (2), the following equations provide a
reasonable correlation for the activity coefficients:
ln  1  (2.771  0.00523T ) x22 ln  2  (2.771  0.00523T ) x12
3643.31 2665.54
ln P1sat / kPa  16.59158  ln P2sat / kPa  14.25326 
T ( K )  33.424 T ( K )  53.424
(a) P and {yi} for T = 318.15 K and x1 = 0.25
(a) for T = 318.15, and x1 = 0.25 P1sat  44.51  1  1.864

P2sat  65.64  2  1.072

P   xi i Pi sat
i
 (0.25)(1.864)(44.51)  (0.75)(1.072)(65.64)
P  73.50
y1  (0.25)(1.864)(44.51) y1  0.282
73.50
yi P  xi i Pi sat
y2  (0.75)(1.072)(65.64) y2  0.718
73.50
Example 3
For the system methanol (1)/methyl acetate (2), the following equations provide a
reasonable correlation for the activity coefficients:
ln  1  (2.771  0.00523T ) x22 ln  2  (2.771  0.00523T ) x12
3643.31 2665.54
ln P1sat / kPa  16.59158  ln P2sat / kPa  14.25326 
T ( K )  33.424 T ( K )  53.424
(b) P and {xi} for T = 318.15 K and y1 = 0.60
(b): for T = 318.15 K and y1 = 0.60 P1sat  44.51 A  (2.771  0.00523T )
P2sat  65.64 A  1.107

1
An iterative process is applied:
1  1  2  1 P
1.) Starting with:  1  1  2  1 , Calculate P  yi /  i Pi sat
ln  1  Ax22 ln  2  Ax12 i
2.) Calculate x1
3.) Calculate new  1 and  2 y1 P
x1 
4.) Repeat until P converges  1 P1sat
x2  1  x1
 Example 3
For the system methanol (1)/methyl acetate (2), the following equations provide a
reasonable correlation for the activity coefficients:
ln  1  (2.771  0.00523T ) x22 ln  2  (2.771  0.00523T ) x12
3643.31 2665.54
ln P1sat / kPa  16.59158  ln P2sat / kPa  14.25326 
T ( K )  33.424 T ( K )  53.424
(b) P and {xi} for T = 318.15 K and y1 = 0.60
(b): for T = 318.15 K and y1 = 0.60 P1sat  44.51 A  (2.771  0.00523T )
P2sat  65.64 A  1.107

1
P γ1 γ2 P x1 x2
1  1 2 1
 yi /  i Pi sat 1 1 51.0882 0.6886 0.3113
ln  2  Ax12
i 1.1132 1.6904 63.6397 0.7705 0.2294
ln  1  Ax22
1.0599 1.9296 62.9913 0.8010 0.1989
1.0447 2.0347 62.9041 0.8116 0.1883
y1 P
x1  1.0400 2.0734 62.8937 0.8151 0.1848
 1 P1sat 1.0385 2.0866 62.8926 0.8163 0.1836
1.0380 2.0911 62.8924 0.8167 0.1832
x2  1  x1
Example 3
For the system methanol (1)/methyl acetate (2), the following equations provide a
reasonable correlation for the activity coefficients:
ln  1  (2.771  0.00523T ) x22 ln  2  (2.771  0.00523T ) x12
3643.31 2665.54
ln P1sat / kPa  16.59158  ln P2sat / kPa  14.25326 
T ( K )  33.424 T ( K )  53.424
(c) T and {yi} for P = 101.33 kPa and x1 = 0.85
(c): for P = 101.33 kPa and x1 = 0.85
T1sat  337.71
Bi
Rearranging the Antoine Equations; tisat   Ci
Ai  ln P T2sat  330.08
Mole-fraction weighted average T: T  (0.85)(337.71)  (0.15)(330.08)  336.57
Start w/ mol - fr - weighted T
An iterative process is applied:
B1 ln  1  Ax22 ln  2  Ax12
1.) Starting with T = 336, calc T  C1
A1  ln P1sat B1 B2
A,  1 ,  2 , and   P1sat / P2sat ln   A1  A2  
T  C1 T  C2
sat sat
2.) Calculate new P1 (or P2 )
3.) Calculate new T from Antoine equation P1sat 
P
x1 1  x2 1 
4.) Repeat until T converges
 Example 3
For the system methanol (1)/methyl acetate (2), the following equations provide a
reasonable correlation for the activity coefficients:
ln  1  (2.771  0.00523T ) x22 ln  2  (2.771  0.00523T ) x12
3643.31 2665.54
ln P1sat / kPa  16.59158  ln P2sat / kPa  14.25326 
T ( K )  33.424 T ( K )  53.424
(c) T and {yi} for P = 101.33 kPa and x1 = 0.85
(c): for P = 101.33 kPa and x1 = 0.85 Mole-fraction weighted average T: T  336.57

T γ1 γ2 α P1
Start w/ mol - fr - weighted T
336.57 1.0230 2.0756 0.7664 79.4264
B1 ln  1  Ax 2
2 ln  2  Ax12 331.6465 1.0235 2.1145 0.7424 78.109
T  C1 331.2389 1.0236 2.1178 0.7404 77.998
A1  ln P1sat B1 B2
ln   A1  A2   331.2043 1.0236 2.1181 0.7402 77.989
T  C1 T  C2
331.2014 1.0236 2.1181 0.7402 77.988

x1 1 P1sat (0.85)(1.0236)(77.988)

P1sat 
P y1  
x1 1  x2 1  P 101.33
y1  0.670

y2  1  y1  1  0.670 y2  0.330
Example 3
For the system methanol (1)/methyl acetate (2), the following equations provide a
reasonable correlation for the activity coefficients:
ln  1  (2.771  0.00523T ) x22 ln  2  (2.771  0.00523T ) x12
3643.31 2665.54
ln P1sat / kPa  16.59158  ln P2sat / kPa  14.25326 
T ( K )  33.424 T ( K )  53.424
(d) T and {xi} for P = 101.33 kPa and y1 = 0.40
(d): for P = 101.33 kPa and y1 = 0.40 T1sat  337.71 T2sat  330.08

Mole-fraction weighted average T: T  (0.40)(337.71)  (0.60)(330.08)  333.13

An iterative process is applied: Start w/ mol - fr - weighted T

1.) Starting with T = 336,  1  1  2  1 1  1 2 1

P1sat , P2sat
calc A,  1 ,  2 , and   P1sat / P2sat
T
B1
 C1   P1sat P2sat
2.) Calculate x1 A1  ln P1sat

3.) Calculate new  1 and  2 y1 P

x1 
4.) Calculate new P1sat (or P2sat )  1 P1sat
5.) Calculate new T from Antoine equation P ln  2  Ax12 x2  1  x1
P1sat 
x1 1  x2 1 
6.) Repeat until T converges ln  1  Ax22
 Example 3
For the system methanol (1)/methyl acetate (2), the following equations provide a
reasonable correlation for the activity coefficients:
ln  1  (2.771  0.00523T ) x22 ln  2  (2.771  0.00523T ) x12
3643.31 2665.54
ln P1sat / kPa  16.59158  ln P2sat / kPa  14.25326 
T ( K )  33.424 T ( K )  53.424
(d) T and {xi} for P = 101.33 kPa and y1 = 0.40
(d): for P = 101.33 kPa and y1 = 0.40 Mole-fraction weighted average T: T  333.13
Start w/ mol - fr - weighted T
1  1 2 1
P1sat , P2sat
T
B1
 C1   P1sat P2sat
A1  ln P1sat

y1 P
x1 
 1 P1sat
Psat

P ln  2  Ax12 x2  1  x1
x1 1  x2 1 
1
ln  1  Ax22
Example 3
For the system methanol (1)/methyl acetate (2), the following equations provide a
reasonable correlation for the activity coefficients:
ln  1  (2.771  0.00523T ) x22 ln  2  (2.771  0.00523T ) x12
3643.31 2665.54
ln P1sat / kPa  16.59158  ln P2sat / kPa  14.25326 
T ( K )  33.424 T ( K )  53.424
(e) the azeotropic pressure and the azeotropic composition for T = 318.15 K
(e) First verify if an azeotrope exists P1sat  44.51 P2sat  65.64 A  1.107

y1 yi P  xi i Pi sat
x1
relative volatility: 12  y
 1 P1sat
12 
2
x2
 2 P2sat
Notice that when x1  0   2  1;  1  exp( A)
x1  1   1  1;  2  exp( A)
then Since α12 is a continuos function
sat
P exp( A) In the boundary of x1, the limits
(12 ) x1 0  1
(12 ) x1 0  2.052
P2sat suggest that α12 passed through a
P1sat value of 1, i.e y/x=1 (azeotrope)
(12 ) x1 1  sat (12 ) x1 1  0.224 hence an azeotrope exists.
P2 exp( A)
Example 3
For the system methanol (1)/methyl acetate (2), the following equations provide a
reasonable correlation for the activity coefficients:
ln  1  (2.771  0.00523T ) x22 ln  2  (2.771  0.00523T ) x12
3643.31 2665.54
ln P1sat / kPa  16.59158  ln P2sat / kPa  14.25326 
T ( K )  33.424 T ( K )  53.424
(e) the azeotropic pressure and the azeotropic composition for T = 318.15 K
(e) First verify if an azeotrope exists P1sat  44.51 P2sat  65.64 A  1.107

 1 P1sat  1az P2sat

At the azeotrope point, 12  1   1.4747
 2 P2sat  2az P1sat

Taking the difference of the activity coefficients,

1
ln  Ax22  Ax12  A( x2  x1 )( x2  x1 )  A(1  2 x1 ) ln 1.4747  1.107(1  2 x1az )
2
x1az  y1az  0.325
ln  1az  1.107(1  0.325) 2  1az  1.657

P1az   1az P1sat  1.657(44.51) P az  73.76

 VLE Models: K-value correlation
yi
Ki 
xi

 A measure of the tendency of a given chemical species to partition itself

preferrence between liquid and vapor phase
 the “lightness” of a constituent species, i.e., of its tendency to favor the
vapor phase.
Pi sat
– The Raoult’s law: Ki 
P

 i Pi sat
– The modified Raoult’s law: K i 
P
VLE Models: K-value correlation
VLE Models: K-value correlation
Example 4
For a mixture of 10 mol-% methane, 20 mol-% ethane, and 70 mol-% propane at
50°F, determine:
(a) the dewpoint pressure
(b) the bubblepoint pressure. The K-values are given by Fig. 10.13.

(a) at its dewpoint, only an insignificant amount of liquid is present:

P = 100 (psia) P = 150 (psia) P = 126 (psia)
Species yi Ki yi /Ki Ki yi /Ki Ki yi /Ki
Methane 0.10 20.0 0.005 13.2 0.008 16.0 0.006
Ethane 0.20 3.25 0.062 2.25 0.089 2.65 0.075
Propane 0.70 0.92 0.761 0.65 1.077 0.762 0.919
Σ(yi /Ki) = 0.828 Σ(yi /Ki) = 1.174 Σ(yi /Ki) = 1.000

(b) at bubblepoint, the system is almost completely condensed:

P = 380 (psia) P = 400 (psia) P = 385 (psia)
Species xi Ki x i Ki Ki x i Ki Ki x i Ki
Methane 0.10 5.60 0.560 5.25 0.525 5.49 0.549
Ethane 0.20 1.11 0.222 1.07 0.214 1.10 0.220
Propane 0.70 0.335 0.235 0.32 0.224 0.33 0.231
Σ (xi Ki) = 1.017 Σ (xi Ki) = 0.963 Σ (xi Ki) = 1.000
 Flash calculations
 A liquid at a pressure equal to or greater than its bubble point pressure
“flashes” or partially evaporates when the pressure is reduced, producing a
two-phase system of vapor and liquid in equilibrium.
 Consider a system containing one mole of non reacting chemical species:

L V  1 zi  xi L  yiV
L  mol of liquid
zi  overall mol fraction of component i
V  mol of vapor

zi  xi (1  V )  yiV
zi K i
yi 
1  V ( K i  1)

zi K i
 1  V ( K  1)  1
i
Example 5
The system acetone (1)/acetonitrile (2)/nitromethane(3) at 80°C and 110 kPa has
the overall composition, z1 = 0.45, z2 = 0.35, z3 = 0.20, Assuming that Raoult’s law
is appropriate to this system, determine L, V, {xi}, and {yi}. The vapor pressures of
the pure species are:
P1sat  195.75 P2sat  97.84 P3sat  50.32

Do a BUBL P calculation, with {zi} = {xi} :

Pbubl  x1 P1sat  x2 P2sat  x3 P3sat
 (0.45)(195.75)  (0.35)(97.84)  (0.20)(50.32)  132.40 kPa

Do a DEW P calculation, with {zi} = {yi} :

1
Pdew   101.52 kPa
y1 / P1  y2 / P2  y3 / P3
sat sat sat

Since Pdew < P = 110 kPa < Pbubl, the system is in the two-phase region,
Example 5
The system acetone (1)/acetonitrile (2)/nitromethane(3) at 80°C and 110 kPa has
the overall composition, z1 = 0.45, z2 = 0.35, z3 = 0.20, Assuming that Raoult’s law
is appropriate to this system, determine L, V, {xi}, and {yi}. The vapor pressures of
the pure species are:
P1sat  195.75 P2sat  97.84 P3sat  50.32

sat
The Raoult’s law: K  Pi K1  1.7795 K 2  0.8895 K3  0.4575
i
P

zi K i (0.45)(1.7795) (0.35)(0.8895) (0.20)(0.4575)

 1  V ( K  1) 1  0.7795V  1  0.1105V  1  0.5425V  1

i

V  0.7364 mol L  1V L  0.2636 mol

(0.45)(1.7795)
y1   0.5087 y2  0.3389 y3  0.1524
1  0.7795(0.7364)
yi x3  0.3331
Ki  x1  0.2859 x2  0.3810
xi