CHAPTER 1

VAPOR LIQUID
EQUILIBRIUM PART 1
 The nature of equilibrium
 The phase rule: Duhem’s Theorem
 VLE: Qualitative behavior
 Simple models for vapor-liquid equilibrium
 VLE by modified Raoult’s law
 VLE from K-value correlations
COURSE LEARNING OUTCOMES

The student should be able to:

1. Describe the behaviour of VLE and how to simplify the VLE

problem.
2. Derive and simplify equations of VLE.
3. Apply simplified VLE equations to obtain data for P-XY, T-XY and
X-Y diagrams.
4. Apply Raoult’s law and Henry’s law to solve simple
thermodynamic problems.
5. Carry out bubble and dew point calculations for a given mixture
6. Carry out flash calculation in order to determine the vapor/liquid
fraction as well as the mixture composition of each phase at
specified conditions using available K-Values etc.

2
 The Nature of Equilibrium
 Equilibrium
is a static condition in
which no changes occurs in the
macroscopic properties of a system
with time.

 The temperature, pressure and

phase compositions reach final
values which thereafter remain
fixed.
3
Measures of Composition
 Most common measures of composition are mass
fraction, mole fraction and molar concentration

 Mass or mole fraction is defined as the ratio of

mass or number of moles of a particular chemical
species in a mixture or solution to the total mass
or number of moles of mixture or solution:
• •
mi mi ni ni
xi ≡ = • xi ≡ = •
m n n
m

4
 Molar concentration is defined as the ratio of mole
fraction of a particular chemical species in a mixture
or solution to molar volume of the mixture of solution
xi moles of i
Ci ≡ per unit
V volume
 For flow process, gives the expression as a ratio of
rates:
•
ni
Ci =
•
q
wheren is the molar flow rate of species i, and q is the volumetric flow
rate.

5
 The molar mass of a mixture or solution : mole
fraction-weighted sum of the molar masses of all
species
M ≡ ∑ xi M i
i

6
The Phase Rule: Duhem’s Theorem
 The no. of variables that may be independently fixed in a
system at equilibrium is the difference between total no. of
phase-rule variables that characterize the intensive state of
the system and the no. of independent phase equilibrium
equations.
 The intensive state of a PVT system containing N chemical
species and π phases in equilibrium is characterized by the
intensive variables, temperature T, pressure P, and N–1
mole fractions for each phase.
 No. of phase-rule variables : 2 + (N-1)(π)
- masses of the phases are not phase-rule variable (no influence on intensive state of system)
 No. of independent phase equilibrium equations : (π–1)(N)
 Degrees of freedom of the system, F
F = 2 + (N – 1)(π) – (π–1)(N)
 Upon reduction, the phase rule becomes
F = 2–π + N
7
Duhem’s theorem
 It applies to closed systems at equilibrium for which the
extensive state as well as intensive state of the system
is fixed.
• Intensive phase rule variables : 2 + (N-1)π
• Extensive phase rule variable (masses or mole no. of the phases) :
π
 Total number of variables : 2 + (N-1)π + π = 2 + Nπ
 If the system is closed and formed from specified
amounts of each species,
 No. of independent equations: (π–1)(N)+N = πN
 The difference between the no. of variables and the no.
of equations,
2 + Nπ–πN = 2

8
 Duhem’s Theorem:
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.
 The two independent variables subject to specification
may in general be either intensive or extensive.

 However, the number of independent intensive variables

is given by the phase rule.

 When F = 1, at least one of the two variables must be

extensive, and when F = 0, both must be extensive.

9
 VLE: Qualitative Behavior
 VLE is the state of coexistence of liquid and vapor
phases.

 Consider a system comprising of two chemical species

(N=2), the phase rule becomes
F = 2- π + N = 2- π + 2 =4 - π
 Because there must at least one phase (π = 1),
 maximum number of phase rule variables = 3
 P, T, and one mole (or mass) fraction.

 All equilibrium states of the system can be represented

in three-dimensional (3D) P-T-composition space.

 Within this space, the states of pairs of phases

coexisting at equilibrium (F = 4 - 2 = 2) define surfaces. 10
3D diagram: surfaces for VLE

11
 P-T-composition surfaces
contain the equi. states of sat.
vapor and sat. liquid for species
1 and 2 of a binary system.

 Species 1 is 'lighter' or more

volatile.

 Upper surface represents sat. liquid

states, i.e. P-T-x1 surface

 Under surface represents sat. vapor

states, i.e. P-T-y1 surface

 Surfaces intersect along the line

RKAC1 & UBHC2 : vapor P vs. T
curves for pure species 1 and 2 12
 Rounded surfaces between C1 and C2:
critical locus –points at which vapor
and liquid phases in equilibrium
become identical

 Critical point: highest T & P where a

pure chemical species is observed to
exist in VLE

 Subcooled-liquid region – above

upper surface
 Superheated vapor region – below
under surface

 Interior space between two surfaces:

region of coexistence of both liquid
and vapor phase 13
 If starts with liquid at F and reduce the P
at constant T and composition along FG
line
 First bubble of vapor appears at point L:
bubblepoint;
upper surface: bubblepoint surface
 The state of vapor bubble in equilibrium
with the liquid at L, is represented by a
point on the under surface at the T,P of
L : point V. Line LV is tie line.

 As the pressure is further reduced,

more liquid is vaporized until at W, the
process is complete.
 W : point where last drop of liquid
(dew) disappear: dewpoint;
Lower surface: dewpoint surface
 Continued reduction of P leads into
superheated region.
14
  Complexity of figure, the detailed characteristics of binary VLE
are usually depicted by 2D by cutting the 3D diagram.
 Vertical plane perpendicular to T axis –
AEDBLA
 The lines on this plane form P-x1-y1
phase diagram at constant T
• Ta ~ AEDBLA
• Horizontal lines ~ tie line connecting
the compositions of phases in
equilibrium
• Tb and Td lie between two pure
species critical temperatures, Tc
identified by C1 and C2.
 Horizontal plane perpendicular to P axis
– KJIHLK
 The lines on this plane form T-x1-y1
phase diagram at constant P
• Pa ~ KJIHLK
• Pb ~ lies between the critical
pressures, Pc of two pure species at
point C1 and C2
• Pd ~ above critical pressure, Pc of
two pure species
15
 Vertical & perpendicular to
composition axis – SLMN and Q
 UC2 and RC1: vapor-pressures
curves for the pure species

 At point A & B , sat. liquid and

sat. vapor lines intersect –
sat. liquid of one composition
and sat. vapor of another
composition have same T & P
and two phases are in
equilibrium.

 Tie line connecting A & B are

perpendicular to P-T plane same
as tie line LV.
16
 Critical point of a binary mixture
occurs where the nose of a loop is
tangent to the envelope curve, i.e.
critical locus

 Location of the critical point on the

nose of the loop varies becomes
varies with composition

 Under certain conditions, a

condensation process occurs as the
result of a reduction in pressure.

17
 Fig. 10.4 shows the enlarged nose
section of a single P-T loop
 Critical point at C
 Point of maximum pressure ~ Mp
 Point of maximum temperature~ MT

 Interior dashed curved ~ liquid

fraction in a two phase mixture

 Pressure reduction along line BD ~

vaporization of liquid from
bubblepoint to dewpoint

 Retrograde condensation: initial

point is at F (sat. vapor) reduction in
P causes liquefaction until max at G,
after that vaporization takes place
until dewpoint is reached at H
Retrograde condensation: Refer page 344 18
Fig. 10.5: P-T diagram for typical mixtures
of non-polar substances such as Fig. 10.6: yx diagram of ethane/n-
hydrocarbon. The P-T diagram for the heptane for several pressures
ethane/n-heptane system.

19
Fig. 10.7: P-T diagram a very different kind of system, methanol(1)/benzene(2).
The nature of the curves suggests the difficulties in predicting phase behavior for
species so dissimilar as methanol and benzene

20
Fig. 10.8 and Fig. 10.9: Display common types of P-x-y and t-x-y behavior at
condition well removed from the critical region Explanation: Refer page 345-347

21
Fig. 10.10: The y1-x1 diagrams at constant P four systems

22
Simple Models for Vapor/Liquid Equilibr
 Goal thermodynamics applied in VLE: To find the
temperatures, pressures and compositions of phases in
equilibrium.

 Therefore, we need models for the behavior of systems

in vapor/liquid equilibrium

 Two simplest:
 Raoult’s Law
 System at low to moderate pressures and only
for systems comprised of chemically similar
species.
 Henry’s Law
 For any species present at low concentration
and limited to systems at low to moderate 23
Raoult’s Law
 Assumptions:
 The vapor phase is an ideal gas
 It means can apply only for low to moderate
pressures.
 The liquid phase is an ideal solution
 It have approximate validity when the species that
comprise the system are chemically similar
 Mathematical expressions to Raoult’s Law:

yi P = xi Pi sat (i = 1,2,..., N ) Eq.10.1

where;
xi = liquid phase mole fraction

yi = vapor phase mole fraction

sat
Pi = vapor phase pressure of pure species i at the temp. of the system
24
ewpoint and Bubblepoint Calculations With Raoult’s La
 Because ∑iyi = 1, Eq. (10.1) may be summed over all
species to yield P =
∑ ii
x P sat

i
Eq. 10.2

 This equation applied in bubblepoint calculations, where

the vapor-phase composition is unknown.

 For a binary system with x2 = 1 – x1,

(
P = P2sat + P1sat − P2sat x1 )
sat sat
P = x1 P1 + x 2 P2
P vs. x1 at constant T  straight line
sat sat
P = x1 P1 + ( 1 − x1 )P2 connecting

P = P2
sat
(
+ P1
sat
− P2
sat
) x1
P2sat at x1=0 to P1sat at x1=1

25
 Equation (10.1) may also be solved for xi and summed
over all species. With ∑ixi = 1, this yield
1
P= Eq. 10.3
∑y
i
i Pi sat

 This equation applied in dewpoint calculations, where

the liquid-phase composition is unknown.

 Pisat, or the vapor pressure of component i, is commonly

represented by Antoine Equation (Appendix B, Table B.2,
SVNA 7th ed.):
Bi
ln Pi sat ( kPa) = A −
T ( K ) + Ci
26
Dew Point Pressure:
Given a vapor composition at a specified temperature,
find the composition of the liquid in equilibrium
Given T, y1, y2,... yn find P, x1, x2, ... xn
Dew Point Temperature:
Given a vapor composition at a specified pressure,
find the composition of the liquid in equilibrium
Given P, y1, y2,... yn find T, x1, x2, ... xn
Bubble Point Pressure:
Given a liquid composition at a specified temperature,
find the composition of the vapor in equilibrium
Given T, x1, x2, ... xn find P, y1, y2,... yn
Bubble Point Temperature:
Given a liquid composition at a specified pressure,
find the composition of the vapor in equilibrium
Given P, x1, x2, ... xn find T, y1, y2,... yn 27
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
ln P1sat = 14.2724 −
T − 49.15
2972.64
ln P2sat = 14.2043 −
T − 64.15

a) Prepare a graph showing P vs. x1 and P vs. y1 for

a temperature of 75oC (348.15K).

b) Prepare a graph showing t vs. x1 and t vs. y1 for a

pressure of 70kPa.

28
Solution (a)
BUBL P calculations

1) Calculate P1sat and P2sat using Antoine equations

At 384.15K (75oC), P1sat = 83.21kPa and P2sat = 41.98kPa
2) Calculate P using equation for binary system:
(
P = P2sat + P1sat − P2sat x1)
3) Lets x1 = 0.6,
P = 41.98 + (83.21 − 41.98)0.6 = 66.72kPa
4) Calculate value of y1 using Raoult’s Law expression:
x1 P1sat (0.6)(83.21)
y1 = = = 0.7483
P 66.72

It means that at 75°C and 66.72 kPa, a liquid mixture of 60 mol%

acetonitrile and 40 mol% nitromethane is in equilibrium with a
vapor mixture of 74.83 mol% acetonitrile and 25.17 mol%
29
The results of calculations for 75oC (348.15K) at a number of values of x1:

States in calculation:
Two phase region: sat.liq &
X1=0.6,P=66.72kPa, y1=0.7483
sat. vapor coexist in
equilibrium
Locus of bubblepoint

Bubblepoint x1 y1 P(kPa)
0.0 0.0000 41.98
0.1 0.1805 46.10
0.2 0.3313 50.23
States of sat. liquid
0.3 0.4593 54.35
0.4 0.5692 58.47
Dewpoint
0.5 0.6647 62.60
States of sat. vapor Locus of dewpoint 0.6 0.7483 66.72
0.7 0.8222 70.84
0.8 0.8880 74.96
0.9 0.9469 79.09
1.0 1.0000 83.21

30
DEW P calculations

1) Calculate P using Eq. 10.3:

1
P=
y1 P1sat + y2 P2sat

2) Lets y1 = 0.6 (at point c) and T = 75 deg C, calculate P :

1
P= = 59.74kPa
0.6 83.21 + 0.4 41.98
3) Calculate value of x1 using Raoult’s Law expression:
y1 P (0.6)(59.74)
x1 = sat
= = 0.4308 Liquid phase
composition at point c’
P1 83.21

31
Solution (b)
1) Calculate T1sat and T2sat at the given pressure using Antoine
equations Bi
Ti sat = − Ci
Ai − ln P
For P = 70kPa, T1sat/ t1sat = 342.99K/69.84°C and T2sat/ t2sat = 362.73K/89.58°C

2) Select T1sat<T<T2sat, calculate P1sat and P2sat for these

temperature. For example take T = 78oC (351.15K),
At 351.15K (78oC), P1sat = 91.76kPa and P2sat = 46.84kPa

3) Lets evaluate x1 using equation for binary system:

P − P2sat 70 − 46.84
x1 = sat = = 0.5156
P1 − P2 sat
91.76 − 46.84
4) Calculate value of y1 using Raoult’s Law expression:
x1 P1sat (0.5156)(91.76)
y1 = = = 0.6759
P 70
32
 The results of this and similar calculations for P = 70kPa are as follows:

x1 y1 t (°C)
1.0000 1.0000 69.84 Two phase region: sat.liq &
sat. vapor coexist in
0.8596 0.9247 72 States of sat. vapor equilibrium

0.7378 0.8484 74
0.6233 0.7656 76
0.5156 0.6759 78
Locus of dewpoint
0.4142 0.5789 80
States of sat. liquid
0.3184 0.4742 82 Dewpoint

0.2280 0.3614 84
0.1424 0.2401 86
Locus of bubblepoint
0.0613 0.1098 88
Bubblepoint
0.0000 0.0000 89.58

33
Bubl T calculations
For x1 = 0.6 and P = 70kPa, T is determine by iteration.
Equation (10.2) is written as
P
P2sat = where α = P1
sat
P2
sat
Eq. (B)
x1α + x2
Subtract ln P2sat from ln P1sat as given by Antoine equations yield
2945.47 2972.64
ln α = 0.0681 − + Eq. (C)
t + 224.00 t + 209.00
Iterate as follow:
 Assume a t (an arbitrary intermediate t)
Calculate α at the t assumed with Eq. (C)
 calculate P2sat with Eq. (B) 2972.64
 Calculate t from Antoine equation for species 2:t = − 209.00
14.2043 − ln P2sat

Compare the t calculated and the t assumed

 If t calculated ≠ t assumed, start a new iteration using the t calculated

The result is t = 76.42oC (349.57K), the temperature at point b and b’. From
Antoine equation, P1sat=87.17 kPa and by Eq. (10.1), y1 = 0.7472

34
Dew T calculations
With α ≡ P1sat/P2sat, Eq. (10.3) is written as
P1sat = P ( y1 + y2α )
The iteration steps are as before, but are based on P1sat, with
2945.47
t= − 224.00
14.2724 − ln P1sat
The result is t=79.58oC (352.73K). From Antoine equation, P1sat=
96.53kPa and from Eq. (10.1), x1 = 0.4351

35
EXERCISE
Assuming the validity of Raoult’s law, do the following
calculation for the benzene (1)/toluene (2) system.

a) Given x1=0.33 and T=100°C(373.15K), find y1 and P

b) Given y1=0.33 and T=100°C(373.15K), find x1 and P
c) Given x1=0.33 and P=120kPa, find y1 and T
d) Given y1=0.33 and P=120kPa, find x1 and T

36