Vapor/Liquid Equilibrium:

Phase equilibrium
Application
Distillation, absorption, and 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 vs. Duhems theorem

(The number of variables that is independently fixed in a
system at equilibrium) = (the number of variables that
characterize the intensive state of the system) - (the
number of independent equations connecting the variable):
Phase rule: F 2 ( N 1)( ) ( 1)( N ) 2 N
Duhems rule: F 2 ( N 1)( ) ( 1)( 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.
Two ? When phase rule F = 1, at least one of the two variables
must be extensive, and when F = 0, both must be extensive.

VLE: qualitative behavior

When two chemical species:
phase rule: F 4
the maximum value of F = 3
( = 1), namely, P, T, and one
mole fraction. All equilibrium
states of the system can be
represented in threedimensional P-T-composition
space.

Fig 10.1

N 2

 Within this space, the states of pairs of phases coexisting at

equilibrium define surfaces.
The subcooled-liquid region lies above the upper surface; the
superheated-vapor region lies below the under surface.
UBHC1 and KAC2 represent the vapor pressure-vs.-T curves for
pure species 1 and 2.
C1 and C2 are the critical points of pure species 1 and 2.
L is a bubble point and the upper surface is the bubblepoint surface.
Line VL is an example of a tie line, which connects points
representing phases in equilibrium.
W is a dewpoint and the lower surface is the dewpoint surface.

Pxy diagram at constant T

Txy diagram at constant P
PT diagram at constant composition

 Fig 10.8 (a)(b), Negative departures from P-x1 linearity: strong liquidphase inter-molecular attractions between unlike than between like pairs
of molecules.
Fig 10.8 (c)(d), Positive departures from P-x1 linearity: strong liquidphase inter-molecular attractions between like than between unlike pairs
of molecules.
Fig 10.8 (b)(d), the azeotrope: the point where x1 = y1 the dewpoint
and bubblepoint curves are tangent to the same horizontal line. The
liquid does not change in composition as it evaporates. No separation of
such a constant-boiling solution is possible by distillation.

Fig 10.8

Fig 10.8

Fig 10.9

Fig 10.10

Simple models for VLE

The simplest are Raoults law and Henrys law.
Raoults law:
the vapor phase is an ideal gas (apply for low to
moderate pressure)
the liquid phase is an ideal solution (apply when the
species that are chemically similar)
yi P xi Pi sat (i 1, 2, ..., N )
although it provides a realistic description of actual behavior
for a small class of systems, it is valid for any species present
at a mole fraction approaching unity, provided that the vapor
phase is an ideal gas.

yi P xi Pi

sat

(i 1, 2, ..., N )

P xi Pi sat

(i 1, 2, ..., N )

Binary system

P P2sat ( P1sat P2sat ) x1

1
yi / Pi sat

(i 1, 2, ..., N )

For dewpoint calculation

For bubblepoint calculation

Binary system acetonitrile (1)/nitromethane(2) conforms closely to Raoults law.

Vapor pressures for the pure species are given by the following Antoine equations:
sat
1

ln P

2945 .47
2972 .64
sat
/ kPa 14.2724
ln P2 / 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 75C.
(b) Prepare a graph showing t vs. x1 and t vs. y1 for a pressure of 70 kPa.
sat
sat
sat
(a) BUBL P P P2 ( P1 P2 ) x1

At 75C

P1sat 83.21 P2sat 41.98

P 41.98 (83.21 41.98) x1

e.g. x1 = 0.6

P 66.72

x1 P1sat (0.6)(83.21)
y1

0.7483
P
66.72

At 75C, a liquid mixture of 60 mol-% (1) and 40 mol-% (2) is in equilibrium with
a vapor containing 74.83 mol-% (1) at pressure of 66.72 kPa.

Fig. 10.11

Fig. 10.11

(b) BUBL T, having P = 70 kPa

ln P1sat / kPa 14.2724

Select t

P1sat
P2sat

2945 .47
2972 .64
sat
ln
P
/
kPa

14
.
2043

2
t / C 224 .00
t / C 209 .00

P P2sat
x1 sat
P1 P2sat

t vs. x1
y1

sat
1 1

xP
P

t vs. y1

Fig. 10.12

Henrys 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 H i

Table 10.1

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 10C. Henrys constant for CO2 in
water at 10C is about 990 bar.
Henrys law for species 1:

y1 P x1 H 1

Raoults law for species 2:

y2 P x2 P2sat
P x1 H1 x2 P2sat
Assuming x1 = 0.01

P (0.01)(990) (0.99)(0.01227 ) 9.912

Justified the assumption x1 0.01

y2 P x2 P2sat
y2 0.0012
y1 0.9988 Justified the assumption

Positive deviation of solutions

from ideality
Non ideal behavior
Results when actual partial pressure is greater than that
obtained from Raoults Law
Intermolecular forces between like molecules is stronger
than unlike ones
Absorption of heat
As temperature increases, the solution tends to ideality
Eg. Oxygen-nitrogen, water-ethanol, benzene-cyclohexane

Negative deviation of solutions

from ideality
Non ideal behavior
Results when actual partial pressure is less
than that obtained from Raoults Law
Intermolecular forces between unlike
molecules is stronger than like ones
Evolution of heat
Eg. Chloroform-acetone, HCl-water

P-x-y diagrams at constant T

T-x-y diagrams at constant P

Minimum boiling azeotrope

The system shown in fig. d) exibits positive
departures from linearity sufficiently large
to cause a maximum in P-x1 curve
This state is a maximum pressure
azeotrope(minimum boiling azeotrope).

Eg. Ethanol-water

Maximum boiling azeotrope

The system shown in fig. b) exibits negtive
departures from linearity sufficiently large to
cause a minimum in P-x1 curve
This state is a minimum pressure
azeotrope(maximum boiling azeotrope).
The vapor and liquid phases in equilibrium
have identical compositions
Eg. HCl-water

Maximum boiling azeotrope

VLE modified Raoults law

Account is taken of deviation from solution
ideality in the liquid phase by a factor inserted into
Raoults law:
sat
yi P xi i Pi

(i 1, 2, 3, ...N )

The activity coefficient, f (T, xi)

P xi i Pi sat
i

1
P
sat
y
/

P
i ii
i

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
The Antoine equations provide vapor pressures:
ln P1sat / kPa 16.59158

3643 .31
T ( K ) 33.424

ln P2sat / kPa 14.25326

2665 .54
T ( K ) 53.424

Calculate
(a): P and {yi} for T = 318.15 K and x1 = 0.25
(b): P and {xi} for T = 318.15 K and y1 = 0.60
(c): T and {yi} for P = 101.33 kPa and x1 = 0.85
(d): T and {xi} for P = 101.33 kPa and y1 = 0.40
(e): the azeotropic pressure and the azeotropic composition for T = 318.15 K
(a) for T = 318.15, and x1 = 0.25
P1sat 44.51 P2sat 65.64 1 1.864 2 1.072

P xi i Pi sat (0.25)(1.864)( 44.51) (0.75)(1.072 )(65.64) 73.50

i

yi P xi i Pi sat

y1 0.282 y2 0.718

(b): for T = 318.15 K and y1 = 0.60

P1sat 44.51 P2sat 65.64

1
P
sat
y
/

P
i ii

An iterative process is applied, with 1 1 2 1

x1

y1 P
1 P1sat

x2 1 x1

Converges at: P 62.89 kPa 1 1.0378 2 2.0935 x1 0.8169

(c): for P = 101.33 kPa and x1 = 0.85
T1sat 337.71 T2sat 330.08

A iterative process is applied, with T (0.85)T1sat (0.15)T2sat 336.57

ln P1sat / kPa 16.59158

3643 .31
T ( K ) 33.424

1 ... 2 ...

P xi i Pi sat
i

P1sat ...

Converges at: T 331.20 K

1 1.0236 2 2.1182

y1 0.670

y2 0.330

(d): for P = 101.33 kPa and y1 = 0.40

T1sat 337.71 T2sat 330.08

A iterative process is applied, with T (0.40)T1sat (0.60)T2sat 333.13

1 1 2 1
ln Pi sat / kPa Ai

ln P1sat / kPa 16.59158

3643 .31
T ( K ) 33.424

P1sat ...

Bi
T ( K ) Ci

P2sat ...
P xi i Pi sat
i

x1 ...

x2 ...

1 ... 2 ...
P1sat ...

Converges at: T 326.70 K

1 1.3629 2 1.2523

P2sat ...
x1 0.4602 x2 0.5398

(e): the azeotropic pressure and the azeotropic composition for T = 318.15 K
y1

Define the relative volatility: 12

Azeotrope

12

x1 0

y2

y1 x1 y 2 x2

yi P xi i Pi sat

x1
x2

1 P1sat
12
2 P2sat

12 1

P1sat exp(2.771 0.00523T )

2.052 12
sat
P2

P1sat
0.224
x1 1
sat
P2 exp(2.771 0.00523T )

Since 12 is a continuous function of x1: from 2.052 to 0.224, 12 = 1 at some point

There exists the azeotrope!
1 P1sat
12
1
sat
2 P2

1az P2sat
sat 1.4747
az
2
P1

ln 1 (2.771 0.00523T ) x22

ln 2 (2.771 0.00523T ) x12

ln

1
(2.771 0.00523T )( x2 x1 ) (2.771 0.00523T )(1 2 x1 )
2

x 0.325 y
az
1

az
1

1az 1.657
P az 1az P1sat 73.76kPa

VLE from K-value correlations

A convenient measure, the K-value:
Ki

yi
xi

the lightness of a constituent species, i.e., of its

tendency to favor the vapor phase.
The Raoults law:
P sat
Ki

The modified Raoults law:

Ki

i Pi sat
P

Flash calculations
A liquid at a pressure equal to or greater than its
bubblepoint 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 nonreacting
chemical species:

L V 1

zi xi L yiV

The moles of vapor

The moles of liquid

zi xi (1 V ) yiV

The vapor mole fraction

The liquid mole fraction

yi

zi K i
1 V ( K i 1)

zi K i
1 V ( K 1) 1
i

The system acetone (1)/acetonitrile (2)/nitromethane(3) at 80C and 110 kPa has the
overall composition, z1 = 0.45, z2 = 0.35, z3 = 0.20, Assuming that Raoults law is
appropriate to this system, determine L, V, {xi}, and {yi}. The vapor pressures of the
pure species are given.
Do a BUBL P calculation, with {zi} = {xi} :
Pbubl x1P1sat 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} :

Pdew

1
101.52 kPa
sat
sat
sat
y1 / P1 y2 / P2 y3 / P3

L 1 V 0.2636 mol

Since Pdew < P = 110 kPa < Pbubl, the system is in the two-phase region,
Pi sat
Ki
P

zi K i
1 V ( K 1) 1
i

K1 1.7795 K 2 0.8895 K 3 0.4575

yi

x1 0.2859
x2 0.3810
x3 0.3331

Ki

yi
xi

V 0.7364 mol

zi K i
1 V ( K i 1)

y1 0.5087
y2 0.3389
y3 0.1524