Vapor-Liquid Equilibrium

Dr. Mohammad Batiha

Department of Chemical Engineering
Al-Hussein Bin Talal University
Email: mbatiha@[Link]

1/46

1. THE NATURE OF EQUILIBRIUM

 Equilibrium is reached when all potentials for change are in

balance. It is a static condition in which no changes occur in
the system’s macroscopic properties with time.
 At equilibrium, temperature, pressure, and phase
compositions reach final values which thereafter remain
fixed.

2/46

١
 2. PHASE RULE & DUHEM’S THEORY
2.1 The Phase Rule
 To fix equilibrium thermodynamic state of one-component,
single-phase system, two state variables must be specified
(system has two degrees of freedom).
 For multi-phase, non-reacting systems at equilibrium, the
number of independent variables that must be fixed to
establish its intensive state is given by the Gibbs phase rule:
F=2–π+N
where F is the degrees of freedom, π is the number of phase,
N is the number of species.

2.2 Duhem’s Theory

 For any closed system formed initially from given masses of
prescribed chemical species, equilibrium state is completely
determined when any two independent variables are fixed.
3/46

Example 1: How many degrees of freedom has these systems?

(a) Liquid water in equilibrium with its vapor.
(b) Liquid water in equilibrium with a mixture of water vapor
and nitrogen.
(c) A liquid solution of alcohol in water in equilibrium with its
vapor.
Solution:
(a) F=2–π+N=2–2+1=1
(b) F=2–2+2=2
(c) F=2–2+2=2

4/46

٢
 3. BINARY MIXTURE

 VLE data can be measured by placing two components

mixture in a vessel held at either constant-T or constant-P.
 Equilibrium between liquid and vapor phases will be
approached slowly, but may be promoted by agitating vessel
or by circulating vapor phase so that it bubbles through liquid.
 After equilibrium, T and P are measured and samples are taken
to determine the vapor and liquid compositions.

 Figure shows a typical equilibrium

condition attained under certain T & P.
 The 2-components that made up the
mixture distribute themselves
unequally in both vapor and liquid
phases.

5/46

 The substance with lower boiling point is known as more

volatile component and correspondingly substance with
higher boiling point is known as less volatile component.
 At a different T and/or P, 2-components will distribute
differently. For example, Figure shows equilibrium at P and T1.
The mole fraction of A in the vapor and liquid are yA1 and xA1
respectively.

 At another higher T (T2) but

at same P, another
equilibrium is attained, with
different mole fractions than
at temperature T1.
 Mole fractions of A in vapor
and liquid are yA2 and xA2,
respectively.

6/46

٣
 4. DIAGRAMS FOR BINARY SYSTEM
 The types of diagrams for binary system:
1. Pxy diagram: x and y as functions of P at constant-T.
2. Txy diagram: x and y as functions of T at constant-P.
3. xy diagram: x vs. y at constant-P.

 Since most applications require data at constant P, Txy and xy

diagrams are most commonly used.

7/46

4. DIAGRAMS FOR BINARY SYSTEM

4.1 Pxy Diagram

 In this diagram, compositions are given as mole fraction of

light component:
 Upper curve gives liquid composition (x) vs. pressure (P).
 Lower curve gives vapor composition (y) vs. pressure (P).

PH= VP of pure heavy component

at T at which data were Constant T
PL
collected (x = 0).
Pure light
Subcooled liquid
PL= VP of pure light component x
y

at T at which data were

Pressure

collected (x = 1).
PH Superheated Vapor
Pure heavy
0 x, y 1.0
8/46 Composition (mole fraction light component)

٤
  Liquid and vapor compositions x1 and y1 are obtained from
intersection of phase envelope with P1 constant pressure line.

Constant T

x
Subcooled liquid

P1
y

Pressure
Superheated Vapor

0 x1 1.0
y1
x, y
Composition (mole fraction light component)
9/46

 For composition z. If P is increased at constant-T to PDP, liquid

phase will begin to form.
 PDP is called dew point pressure, because first drops of liquid
form as "dew."

 Liquid droplets that form

will be much leaner in light Constant T
Saturated liquid
line
component.
Subcooled liquid x
 Composition of first drop y
of liquid formed at PDP is
xDP. Saturated
Pressure

vapor line
PDP

Superheated Vapor

0 xDP z 1.0

10/46 Composition (mole fraction light component)

٥
  As P is increased further, more liquid forms.
 At P1 there is almost as much liquid of composition x1 as vapor
of composition y1.

Saturated liquid
Constant T line

Subcooled liquid x

P1 Saturated

Pressure
vapor line

Superheated Vapor

0 x1 z y1 1.0

11/46 Composition (mole fraction light component)

 As P is further increased, PBP is reached.

 Here, last bit of vapor phase exists as bubbles, so this P is
known as bubble point pressure (PBP) of mixture with
composition z at specified T.

Saturated liquid
Constant T line

Subcooled liquid x

PBP y

Saturated
Pressure

vapor line

Superheated Vapor

0 z yBP 1.0

12/46 Composition (mole fraction light component)

٦
 4. DIAGRAMS FOR BINARY SYSTEM
4.2 Txy Diagram

 Boiling point T of pure light component TL at P specified in

diagram is T at point x = y = 1.
 TH is the boiling T of heavy
TH y
component at system P. Superheated Vapor

 Mixture is all liquid until it x

Saturated vapor
reaches bubble point line
temperature TBP, where Saturated liquid

Temperature
first bubble of vapor TBP
line

forms and has a

composition yBp.
TL
Subcooled liquid

0 z yBP 1.0

Composition (mole fraction light component)

13/46

 As T is increased further, more vapor forms.

 At T1 there is almost as much liquid of composition x1 as
vapor of composition y1.

TH y
Superheated Vapor

x
Saturated vapor
line
T1
Temperature

Saturated liquid
line

TL
Subcooled liquid

0 x1 z y1 1.0

Composition (mole fraction light component)

14/46

٧
  Increasing T further to dew point temperature TDP yields a
mixture that is all vapor.
 The last drops of liquid have a composition xDP.

TH y
Superheated Vapor

x
TDP Saturated vapor
line

Temperature
Saturated liquid
line

TL
Subcooled liquid

0 xDP z 1.0

Composition (mole fraction light component)

15/46

Effect of pressure on Txy diagram

 If Txy diagrams for same system at different total Ps, then:

1. P2 > P1.
2. VLE Ts are higher at P2 than at P1
TH at P2
3. Phase equilibrium lines at higher Ps are
usually closer together.
y

TH at P1
T TL at P2
y

TL at P1

16/46 0 x and y 1.0

٨
 4. DIAGRAMS FOR BINARY SYSTEM
4.3 xy Diagram
 xy diagram for a binary system, relates compositions of liquid
and vapor phases in equilibrium with each other.
 These diagrams can be
xy diagram for binary system
generated from either
constant-P or constant-T

Vapor composition y (mole fraction, light component)

data.
y
 They are most commonly vapor
drawn for constant-P, x
since most applications 0.4 liquid
are essentially isobaric.

0.2
17/46 Liquid composition x (mole fraction, light component)

5. SIMPLE MODELS FOR VLE

5.1 Raoult’s Law

yi P  xi Pi sat
xi : Liquid phase mole fraction
y i : Vapor phase mole fraction
Pi sat : Vapor pressure of pure species i
P : Total pressure.

Assumptions:
 Vapor phase is an ideal gas, i.e. valid for low to moderate P.
 Liquid phase is an ideal solution, i.e. valid only if species are
chemically similar (size, same chemical nature).
Limitations:
 Applied only to species of known VP “subcritical”.
 Applied to species with mole fraction approaching unity.
18/46

٩
 Dewpoint and Bubblepoint Calculations
with Raoult’s Law

FIND GIVEN

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

19/46

For binary systems, Raoult’s law can be solved for xi and yi to solve
for dewpoint and bubblepoint calculation, respectively.

Bubblepoint calculation Dewpoint calculation

(T is given) (T is given)

x i 1
y
i
i 1
i
1
P
yi
P   xi Pi sat P
i
sat
i
i

P  P2sat  P1sat  P2sat x 1

1
P
y1 y2
sat
 sat
P1 P2
x 1 P1sat
y1 
P y1 P
x1 
P1sat
20/46

١٠
 Development of VLE diagrams for a mixture that obeys Raoult's law

Example 2: Assuming a mixture of n-pentane(5) and

n-heptane(7) is ideal, prepare VLE diagram for this
mixture at a constant temperature of 50°C. Given
that
26799 35200
ln P5sat [bar]  10.422  ln P7sat [bar]  11.431 
RT RT

for T in K, and R = 8.314 J/K mol.

Solution:

At 323.15 K, P5sat  1.564 bar and P7sat  0.188 bar

21/46

Equilibrium P at each liquid pentane composition x5. We use:

PT ( x5 )  x5 P5sat  x7 P7sat  x5 P5sat  (1  x5 )P7sat

then calculate vapor phase composition

x5 P5sat
y5 
PT ( x5 )

P x5 y5
0.1880 0.0 0.0000
Bubble point curve
0.4632 0.2 0.6753
0.7384 0.4 0.8472
1.0140 0.6 0.9254
1.2890 0.8 0.9705 Dew point curve

1.5640 1.0 1.0000

22/46

١١
 Example 3:

Binary system acetonitrile(1)/nitromethane(2) conforms closely

to Raoult’s law. VP for pure species are given by:

2945.47
ln P1sat [kPa]  14.2724 
T [o C]  224
2972.64
ln P2sat [kPa]  14.2043 
T [o C]  209

(a) Prepare a graph showing P vs. x1 and P vs. y1 at T = 75ºC.

(b) Prepare a graph showing T vs. x1 and T vs. y1 for a P = 70 kPa.

23/46

(a) BUBL P calculations are required.

P  P2sat  P1sat  P2sat x1

At 750C, the saturated pressure is given by Antoine equation:

P1sat  83.21 P2sat  41.98

Substitute both values to find P:

P  41.98  83.21  41.980.6
P  66.72 kPa
x1 P [kPa] y1
The value of y1 is found as: 0.0 41.98 0.0000
sat
x1 P 0.683.21 0.2 50.23 0.3313
y1  1

P 66.72 0.4 58.47 0.5692
y 1  0.7483 0.6 66.72 0.7483
0.8 74.96 0.8880
24/46 1.0 83.21 1.0000

١٢
 Bubblepoint
x1 P [kPa] y1
0.0 41.98 0.0000
0.2 50.23 0.3313
0.4 58.47 0.5692
0.6 66.72 0.7483 dewpoint
0.8 74.96 0.8880
1.0 83.21 1.0000

25/46

At point c, vapor composition is y1 = 0.6, but composition of liquid

at c’ and P must read from graph or calculated. This is DEW P:

y1 P y2 P
x1  x2  1   1 
P1sat P2sat
1
P
y1 y
 2
P1sat P2sat

For y1 = 0.6 and T = 750C

1
P  59 .74 kPa
0 .6 0 .4

83 .21 41 .98
And
y 1 P 0.659.74
x1    0.4308
P1sat 83.21
This is the liquid-phase composition at point c’.
26/46

١٣
 (b) When P is fixed, T varies with x1 and y1 along T1sat and T2sat.

T1sat and T2sat are calculated from Antoine equation.

Steps to Draw Txy diagram

For P = 70 kPa, T1sat = 69.84ºC, T2sat = 89.58ºC.

T2sat = 89.58ºC > Select T > T1sat = 69.84ºC

Calculate P1sat and P2sat

Evaluate x1. For example:

PP sat
70  46.84
x1  2
x1   0.5156
P1sat  P 2
sat
91.76  46.84

Get y1. For example:

x 1P1sat 0.515691.76
y1    0.6759
P 70

27/46

T [˚C] x1 y1
89.58 (T2 sat) 0.0000 0.0000
86 0.1424 0.2401
82 0.3184 0.4742 dewpoint
78 0.5156 0.6759
74 0.7378 0.8484
69.84 (T1 sat) 1.0000 1.0000
Bubblepoint

28/46

١٤
 For x1 = 0.6 and P = 70 kPa, T is determined by BUBL T calculation,
which requires iteration:

 P sat 
P  x 1P1sat  x 2P2sat  P2sat  x 1 1sat  x2 
 P2 

P P1sat
P2sat  where: α
x 1α  x2 P2sat

Subtracting ln P2sat from ln P1sat as given by Antoine equations:

2945.47 2972.64
ln  0.0681  
T  224 T  209

Initial value for α is from arbitrary intermediate T.

29/46

Iteration Procedure
Choose α to calculate P
P2sat 
P2sat x 1α  x2

Calculate T from Antoine 2972.64

T  209
equation for species 2 14.2043  ln P2sat

2945.47 2972.64
Find new α ln α  0.0681  
T  224 T  209

Return to initial step and iterate T = 76.420C and

until converge for final value of T P1sat = 87.17 kPa.

30/46

١٥
 Hence, the composition at b’ is:
x1P1sat 0.687.17
y1    0.7472
P 70
Vapor composition at c is
y = 0.6.
yb' = 0.7472

P is known (P = 70 kPa), a DEW

T calculation is possible. Steps
are same as BUBL T, but it is
based on P1sat, rather than P2sat.

The result is T = 79.580C.

31/46

From Antoine eq., P1sat = 96.53

kPa and composition at c’ is:

y 1P 0.670
x1    0.4351
P1sat 96.53

This shows that T rises from

76.42ºC to 79.58ºC during
vaporization step from point b P1sat=96.53kPa
to c.

Continued heating simply

superheats vapor to point d.

32/46

١٦
 5. SIMPLE MODELS FOR VLE
5.2 Henry’s Law
y i P  x i Hi

where:
xi : Liquid phase mole fraction
yi : Vapor phase mole fraction
Hi : Henry' s constant
P : Total pressure

Assumptions:

 Valid for low P. It is so low that it is assumed as ideal gas.

 Valid for species present as a very dilute solution in liquid phase.

33/46

Example 4:

Assuming that carbonated water contains only CO2(1) and H2O(2),

determine compositions of vapor and liquid phases in a sealed can
of ‘soda’ and pressure exerted on can at 100C. Henry’s constant
for CO2 in water at 100C is about 990 bar and x1 = 0.01.

Solution:
Henry’s law for species 1 and Raoult’s law for species 2 are:

y 1 P  x 1 H1 and y 2 P  x2 P2sat Hence P  x 1 H1  x2 P2sat

With H1 = 990 bar and P2sat = 0.01227 bar (from steam tables at
100C):
P  0.01990  0.990.01227   9.912 bar
Then by Raoult’s law for species 2,
x2P2sat 0.990.01227 
y2    0.0012
P 9.912
Whence y1 = 1 – y2 = 0.9988, and vapor phase is nearly pure CO2.
34/46

١٧
 6. VLE BY MODIFIED RAOULT’S LAW

A modification of Raoult’s law that removes restriction to

chemically similar species is treated by introduction of activity
coefficient (γ) into Raoult’s Law:

yi P  xi γi Pi sat
Activity coefficients are function of T and liquid phase
composition (x). Since

y 1 P   xi γi Pi sat For bubble point

i i
i

1
P
xi i
1
 yi γiPi sat
For dew point
i

35/46

Example 5:
For system methanol (1)/methyl acetate (2), the following provide
a correlation for activity coefficients:
ln  1  (2.771  0.00523T ) x22 ln  2  ( 2.771  0.00523T ) x12
The Antoine equations provide vapor pressures:
3643.31
ln P1sat [ kPa ]  16.59158 
T [ K ]  33.424
2665.54
ln P2sat [ kPa ]  14.25326 
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
36/46

١٨
 Bubble Point Pressure

(a) For T = 318.15, and x1 = 0.25

P1sat  44.51
Find Pi sat
P2sat  65.64

 1  1.864
Find  i
 2  1.072

Find P: P  (0.251.864 44.51)  (0.751.072 65.64)

P  x1 1P1sat  x2 2 P2sat P  73.5

Find yi :
y1  0.282
x  P sat
yi  i i i y 2  0.718
P

37/46

Dew Point Pressure Find Pi sat

Find 1 &  2 . Initial guess its=1

(b) For T = 318.15 K and y1 = 0.60
Converges at: P  62.89 kPa Find P:
1
P
y1  1P1sat  y2  2 P2sat
 1  1.0378
 2  2.0935 Find xi:
xi  yi P  i Pi sat
x1  0.8169
Evaluate from the given
equation

Converge?
NO
Pj = Pj-1?

YES

It is the P dew.
Find liquid phase mole fraction
yP
x1  1 sat & x2  1 x1
 1P1

38/46

١٩
 Find Ti sat
Bubble Point Temperature
Find initial T from mole-fraction weighted average
T  x1T1sat  x2T2sat

(c) For P = 101.33 kPa and x1 = 0.85

For current T, find A,  1 ,  2 ,
Converges at: T  331 .20 K P1 sat , P2sat   P1sat P2sat

 1  1.0236
Find new value for P1sat :

 2  2.1182
P
P1sat 
x1 1  x2 2  

y 2  0.330
Find new T from Antoine equation for species 1
y1  0.670 T 
B1
A1  ln P1sat
 C1

NO Converge?
Tj = Tj-1?

YES

It is the T bubble.
Find Pi sat , A and  1 &  2

Find vapor phase mole fraction

y1  x1 1 P1sat P & y 2  1  y1

39/46

Dew Point Temperature Find Ti sat

Find initial T from mole-fraction weighted average

(d) For P = 101.33 kPa T  y1T1sat  y 2T2sat

and y1 = 0.40 For current T, find A, P1sat , P2sat

  P1sat P2sat

Converges at: Find x1  y1 P  1 P1sat & x 2  1  x1

T  326 .70 K Calculate  1 &  2 from given correlation

 1  1.3629 Find new value for P1sat :

y y 
P1sat  P 1  2  
 2  1.2523  1  2 

x1  0.4602 Find new T from Antoine equation for species 1

B1
T  C1
A1  ln P1sat
x 2  0.5398

NO Converge?
Tj = Tj-1?
It is the T bubble.
Find Pi sat , A and  1 &  2

YES
Find vapor phase mole fraction
y1  x1 1 P1sat P & y 2  1  y1

40/46

٢٠
 7. VLE FROM K-VALUE CORRELATIONS

 There can be VLE data for mixtures of multi-components, but

such a boiling-point diagram is hard to show in either tabular
or graphical form.
 For such multi-component mixtures, as well as binary
mixtures, VLE data are represented in terms of K-values
(equilibrium ratio) (Ki) :
y
Ki  i
xi

 K-value for Raoult’s Law:

Pi sat
yi P  xi Pi sat Ki 
P
 K-value for modified Raoult’s Law:
γi Pi sat
y i P  xi γi Pi sat Ki 
41/46
P

For binary systems to solve for bubble point calculation:

y i i
1 Hence, K x
i
i i 1

For binary systems to solve for dew point calculation:

yi
x i i
1 Hence, K i
1
i

42/46

٢١
 43/46

44/46

٢٢
 Example 6:

For a mixture of 10 mol-% methane, 20 mol-% ethane, and 70 mol-%

propane at 50°F, determine: (a) dewpoint P, (b) bubblepoint P.

Solution:

(a) At its dewpoint, only an insignificant amount of liquid is

present (the given mole fractions are yi).

For given T, K-values depend on choice of P. By trial we find

the value for which:
yi
K
i
1
i

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
45/46

(b) At bubble point, system is almost completely condensed

(given mole fractions are xi). By trial we find the value for
which:
K x i
i i 1

P = 380 (psia) P = 400 (psia) P = 385 (psia)

Species xi Ki xi Ki Ki xi Ki Ki xi 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

46/46

٢٣