Dr.

Mohammad
Batiha
THERMODYNAMI
CS (2)
CHAPTE
Vapor-Liquid EquilibriumR 4
Dr. Mohammad Batiha
Department of Chemical
Engineering
Al-Hussein Bin Talal University
Email: mbatiha@[Link]

AHU
1/46
 1. THE NATURE OF EQUILIBRIUM
 Equilibrium is reached when all potentials for
Dr. change are in balance. It is a static condition in
Mohammad which no changes occur in the system’s
Batiha
macroscopic properties with time.
THERMODYNAMI

 At equilibrium, temperature, pressure, and

phase compositions reach final values which
thereafter remain fixed.
CS (2)

AHU
2/46
 2. PHASE RULE & DUHEM’S THEORY
2.1 The Phase Rule
 To fix equilibrium thermodynamic state of one-
Dr.
component, single-phase system, two state
Mohammad
Batiha variables must be specified (system has two
degrees of freedom).
THERMODYNAMI

 For multi-phase, non-reacting systems at

equilibrium, the number of independent variables
that must be fixed to establish its intensive state is
CS (2)

given by the Gibbs phase rule:

F=2–π+N
where F is the degrees of freedom, π is the number
of phase,
2.2N isDuhem’s Theory
the number of species.
 For any closed system formed initially from given
masses of prescribed chemical species, equilibrium
AHU state is completely determined when any two
3/46 independent variables are fixed.
 Example 1: How many degrees of freedom has these
systems?
Dr.
(a) Liquid water in equilibrium with its vapor.
Mohammad
Batiha
(b) Liquid water in equilibrium with a mixture of water
vapor and nitrogen.
THERMODYNAMI

(c) A liquid solution of alcohol in water in equilibrium

with its vapor.
CS (2)

Solution:
(a) F=2–π+N=2–2+1=1
(b) F=2–2+2=2
(c) F=2–2+2=2

AHU
4/46
 3. BINARY MIXTURE

 VLE data can be measured by placing two

Dr. components mixture in a vessel held at either
Mohammad constant-T or constant-P.
Batiha
 Equilibrium between liquid and vapor phases will be
THERMODYNAMI

approached slowly, but may be promoted by

agitating vessel or by circulating vapor phase so
that it bubbles through liquid.
CS (2)


 After
Figure equilibrium,
shows T and
a P are measured and
typical
samples are taken
equilibrium to determine
condition attained the vapor and liquid
compositions.
under certain T & P.
 The 2-components that made
up the mixture distribute
themselves unequally in both
vapor and liquid phases.
AHU
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.
Dr.
Mohammad  At a different T and/or P, 2-components will
Batiha
distribute differently. For example, Figure shows
equilibrium at P and T1. The mole fraction of A in the
THERMODYNAMI

vapor and liquid are yA1 and xA1 respectively.

 At another higher T (T2)
but at same P, another
CS (2)

equilibrium is attained,
with different mole
fractions than at
temperature T1.
 Mole fractions of A in
vapor and liquid are yA2
and xA2, respectively.
AHU
6/46
 4. DIAGRAMS FOR BINARY SYSTEM
 The types of diagrams for binary system:

Dr. 1. Pxy diagram: x and y as functions of P at

Mohammad
Batiha constant-T.
2. Txy diagram: x and y as functions of T at
THERMODYNAMI

constant-P.
 Since most applications require data at constant P,
3. xy diagram: x vs. y at constant-P.
Txy and xy diagrams are most commonly used.
CS (2)

AHU
7/46
 4. DIAGRAMS FOR BINARY SYSTEM
4.1 Pxy Diagram

Dr.
 In this diagram, compositions are given as mole
Mohammad
Batiha
fraction of light component:
 Upper curve gives liquid composition (x) vs. pressure
THERMODYNAMI

(P).
 Lower curve gives vapor composition (y) vs. pressure
(P).
PH= VP of pure heavy
CS (2)

component at T at Constant T
P L

which data were Pure light

collected (x = 0). Subcooled liquid
y
x
i on
PL= VP of pure light sr
e g

Pressure
se
pha
component at T at Tw
o-

which data were

PH Superheated Vapor
collected (x = 1). Pure heavy
AHU 0 x, y 1.0
Composition (mole fraction light component)
8/46
  Liquid and vapor compositions x1 and y1 are
obtained from intersection of phase envelope with
Dr. P1 constant pressure line.
Mohammad
Batiha

Constant T
THERMODYNAMI

x
Subcooled liquid
CS (2)

P1
y

Pressure

Superheated Vapor

0 x1 1.0
y1
x, y
AHU
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.

Dr.
 PDP is called dew point pressure, because first
Mohammad drops of liquid form as "dew."
Batiha
 Liquid droplets that
THERMODYNAMI

form will be much Constant T

Saturated liquid
line
leaner in light Subcooled liquid x
component.
CS (2)

y
 Composition of first
drop of liquid formed Saturated

Pressure
vapor line
at PDP is xDP. PDP

Superheated Vapor

AHU 0 xDP z 1.0

Composition (mole fraction light component)

10/46
  As P is increased further, more liquid forms.
 At P1 there is almost as much liquid of composition
Dr.
x1 as vapor of composition y1.
Mohammad
Batiha
THERMODYNAMI

Saturated liquid
Constant T line

Subcooled liquid x
CS (2)

P1 Saturated

Pressure
vapor line

Superheated Vapor

AHU 0 x1 yz1 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
Dr.
this P is known as bubble point pressure (PBP) of
Mohammad mixture with composition z at specified T.
Batiha
THERMODYNAMI

Saturated liquid
Constant T line

Subcooled liquid x
CS (2)

PBP y

Saturated

Pressure
vapor line

Superheated Vapor

AHU 0 z yBP 1.0

12/46 Composition (mole fraction light component)

 4. DIAGRAMS FOR BINARY SYSTEM
4.2 Txy Diagram

Dr.  Boiling point T of pure light component TL at P

Mohammad
Batiha specified in diagram is T at point x = y = 1.
 TH is the boiling T of
THERMODYNAMI

TH y
heavy component at Superheated Vapor

system P. x
Saturated vapor
 Mixture is all liquid
CS (2)

line

until it reaches bubble Saturated liquid

Temperature
line
point temperature TBP

TBP, where first

bubble of vapor forms
and has a TL
composition yBp. Subcooled liquid

0 z yBP 1.0
AHU 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
Dr.
x1 as vapor of composition y1.
Mohammad
Batiha
THERMODYNAMI

TH y
Superheated Vapor

x
Saturated vapor
line
CS (2)

T1

Temperature
Saturated liquid
line

TL
Subcooled liquid

0 x1 yz1 1.0
AHU Composition (mole fraction light component)
14/46
  Increasing T further to dew point temperature TDP
yields a mixture that is all vapor.

Dr.
 The last drops of liquid have a composition xDP.
Mohammad
Batiha
THERMODYNAMI

TH y
Superheated Vapor

x
TDP Saturated vapor
line
CS (2)

Temperature
Saturated liquid
line

TL
Subcooled liquid

0 xDP z 1.0
AHU Composition (mole fraction light component)
15/46
 Effect of pressure on Txy

diagram
If Txy diagrams for same system at different total
Dr. Ps, then:
Mohammad 1. P2 > P1.
Batiha
2. VLE Ts are higher at P2 than at P1
TH at P2
THERMODYNAMI

3. Phase equilibrium lines at higher

Ps are usually closer together.
y
CS (2)

TH at P1
T TL at P2
y

TL at P1
AHU
16/46 0 x and 1.0
 4. DIAGRAMS FOR BINARY SYSTEM
4.3 xy Diagram
 xy diagram for a binary system, relates
Dr.
Mohammad compositions of liquid and vapor phases in
Batiha
equilibrium
 These with each
diagrams can other.
xy diagram for binary
THERMODYNAMI

be generated from system rve

either constant-P or m
cu

Vapor composition y (mole fraction, light component)

ri u
constant-T data. qu
i l i b
E
y
CS (2)

 They are most

vapor

5
commonly drawn for x

e4
li n
constant-P, since

O
0.4 liquid
most applications
are essentially

yA
=1
isobaric.

xA

-xA
=
yA
AHU 0.2
17/46 Liquid composition x (mole fraction, light component)
 5. SIMPLE MODELS FOR VLE
5.1 Raoult’s Law

Dr.
Mohammad
yi P xi Pisat
Batiha
xi :Liquidphasemolefraction
THERMODYNAMI

yi : Vaporphasemolefraction
Pisat : Vaporpressureof purespeciesi
P : Totalpressure.
CS (2)

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).
AHU Limitations:
18/46  Applied only to species of known VP “subcritical”.
 Dewpoint and Bubblepoint Calculations
with Raoult’s Law
Dr.
Mohammad
Batiha
THERMODYNAMI

FIND GIVEN

BUBL P: Calculate yi and P given xi and

CS (2)

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
AHU 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.
Dr. Bubblepoint calculation Dewpoint calculation
Mohammad (T is given) (T is given)
Batiha

 x 1
i
THERMODYNAMI

i
 y 1
i
i
1
P
yi
CS (2)

P  xi Pisat i Psat
i
i
1
P P2sat  P1sat  P2satx1 P
y1 y2
sat
 sat
P1 P2
x1P1sat
y1 
P y1P
x1  sat
AHU P1
20/46
 Development of VLE diagrams for a mixture that
obeys Raoult's law

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

Dr.
Mohammad
and
Batiha n-heptane(7) is ideal, prepare VLE
diagram for this mixture at a constant 35200
THERMODYNAMI

26799 sat
sat
lnP5 [bar] 10.422
temperature lnP
of 50°C. Given [bar
7 that] 11
.431

RT RT
CS (2)

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

Solution: P5sat 1.564 bar and P7sat 0.188bar

At 323.15 K,

AHU
21/46
 Equilibrium P at each liquid pentane composition x5. We
use:
PT (x5) x5 P5sat  x7 P7sat x5 P5sat  (1 x5)P7sat
Dr.
Mohammad
Batiha
then calculate vapor sat phase composition
x5 P5
y5 
THERMODYNAMI

PT (x5)
CS (2)

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

AHU 1.5640 1.0 1.0000

22/46
 Example 3:

Binary system acetonitrile(1)/nitromethane(2)

Dr. conforms closely to Raoult’s law. VP for
Mohammad
Batiha
pure species are given by:
2945.47
lnP1sat[kPa] 14.2724
T [o C]  224
THERMODYNAMI

2972 .64
lnP2sat[kPa] 14.2043
T [o C]  209
CS (2)

(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.

AHU
23/46
 (a) BUBL P calculations are required.

P P2sat  P1sat  P2satx1

Dr.
At 750C, the saturated pressure is given by Antoine
Mohammad
Batiha equation: sat sat
P1 83.21 P2 41.98
THERMODYNAMI

Substitute both values to find P:

P 41.98 83.21 41.980.6
CS (2)

P 66.72kPa
x1 P [kPa] y1

The value of y1 is found as: 0.0 41.98 0.0000

x1 P1sat 0.683.21 0.2 50.23 0.3313
y1  
P 66.72 0.4 58.47 0.5692
y1 0.7483 0.6 66.72 0.748
3
AHU
24/46
0.8 74.96 0.8880
 Dr.
Mohammad Bubblepoint
Batiha

x1 P [kPa] y1
THERMODYNAMI

0.0 41.98 0.0000

0.2 50.23 0.3313
0.4 58.47 0.5692
CS (2)

0.6 66.72 0.748 dewpoint

3
0.8 74.96 0.8880
1.0 83.21 1.0000

AHU
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:
Dr. y1 P y2 P
Mohammad x1  x2 1  sat
 sat 1 
Batiha P1 P2
1
P
THERMODYNAMI

y1 y2

P1sat P2sat
CS (2)

For y1 = 0.6 and T = 750C

1
P 59.74kPa
0.6 0.4

83.21 41.98

And y P 0.659.74
1
x1  sat
 0.4308
P
1 83.21
AHU
This is the liquid-phase composition at point c’.
26/46
 (b) When P is fixed, T varies with x1 and y1 along T1sat and T2sat.

Steps to Draw Txy diag

T1sat and T2sat are calculated from Antoine equation.
For P = 70 kPa, T1sat = 69.84ºC, T2sat = 89.58ºC.
Dr.
Mohammad
Batiha T2sat = 89.58ºC > Select T > T1sat = 69.84ºC
THERMODYNAMI

Calculate P1sat and P2sat

Evaluate x1. For example:

CS (2)

P  P2sat 70 46.84

x1  sat sat x1  0.5156
P1  P2 91.76 46.84

Get y1. For example:

x1P1sat 0.5156
91.76
y1   0.6759
P 70
AHU
27/46
 T [˚C] x1 y1
Dr.
Mohammad 89.58 0.000 0.000
Batiha (T2sat) 0 0
86 0.142 0.240
THERMODYNAMI

4 1 dewpoint
82 0.318 0.474
4 2
CS (2)

78 0.515 0.675
6 9 Bubblepoint
74 0.737 0.848
8 4
69.84 1.000 1.000
(T1sat) 0 0

AHU
28/46
 For x1 = 0.6 and P = 70 kPa, T is determined by BUBL
T calculation, which requires iteration:

Dr. sat sat  P1sat

sat 
P x P  x P
1 1 2 2 P  x1 sat  x2 
2
 P2
Mohammad
Batiha 
THERMODYNAMI

sat P P1sat
P2  where: α  sat
x1α  x2 P2

Subtracting ln P2sat from ln P1sat as given by Antoine

CS (2)

equations: 2945.47 2972 .64

ln 0.0681 
T  224 T  209

Initial value for α is from arbitrary intermediate T.

AHU
29/46
 Iteration Procedure
Dr.
Mohammad Choose α to calculate sat P
Batiha P
2 
P2sat x1α  x2
THERMODYNAMI

Calculate T from Antoine 2972.64

T sat
 209
equation for species 2 14.2043 ln P2
CS (2)

2945.47 2972 .64

Find new α lnα 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.
AHU
30/46
 Hence, the composition at
b’ is: sat
Dr.
x1P1 0.687.17
Mohammad y1   0.7472
Batiha P 70
THERMODYNAMI

Vapor composition at c
is
yb' = 0.7472
y = 0.6.
CS (2)

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.

AHU
31/46
 From Antoine eq., P1sat =
Dr. 96.53 kPa and
Mohammad composition at c’ is:
Batiha
y1P 0.670
x1  sat  0.4351
P1 96.53
THERMODYNAMI

This shows that T rises

from 76.42ºC to 79.58ºC
CS (2)

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

Continued heating simply

superheats vapor to point
d.

AHU
32/46
 5. SIMPLE MODELS FOR VLE
5.2 Henry’s Law

Dr.
yi P xi Hi
Mohammad
Batiha

where:
THERMODYNAMI

xi :Liquidphasemolefraction
yi : Vaporphasemolefraction
Hi :Henry'sconstant
CS (2)

P : Totalpressure

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
AHU liquid phase.
33/46
 Example 4:

Assuming that carbonated water contains only CO2(1)

and H2O(2), determine compositions of
Dr.
Mohammad vapor and liquid phases in a sealed can of
Batiha
‘soda’ and pressure exerted on can at 100C.
Henry’s constant for CO2 in water at 100C is
THERMODYNAMI

about 990 bar and x1 = 0.01.

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

y1P x1H1 y2 P x2 P2sat P x1H1  x2 P2sat

and Hence

With H1 = 990 bar and P2sat = 0.01227 bar (from steam

tables at 10P00.01990 0.990.01227
C):  9.912bar

Then by Raoult’s law for species

x2P2sat 2, 
0.990.01227
y2   0.0012
P 9.912
AHU
34/46
 6. VLE BY MODIFIED RAOULT’S LAW
A modification of Raoult’s law that removes restriction
Dr. to chemically similar species is treated by introduction
Mohammad of activity coefficient (γ) into Raoult’s Law:
Batiha

yi P xi γi Pisat
THERMODYNAMI

Activity coefficients are function of T and liquid phase

composition (x). Since
CS (2)

 y 1 P  xi γiPisat For bubble point

i i
i

1 For dew point

P
 x 1
i i  i ii
y γ Psat

AHU
35/46
 Example 5:
For system methanol (1)/methyl acetate (2), the
following provide a correlation for activity
Dr.
coefficients: 2
Mohammad
Batiha
ln 1 (2.771  0.00523T ) x2 ln 2 (2.771  0.00523T ) x12
THERMODYNAMI

The Antoine equations provide vapor pressures:

sat 3643.31
ln P [kPa] 16.59158 
1
T [ K ]  33.424
2665.54
CS (2)

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
AHU (d) T and xi for P = 101.33 kPa and y1 = 0.40
36/46
 Bubble Point Pressu
re
(a) For T = 318.15, and x1 = 0.25
Dr.
P1sat 44.51
Mohammad
Find Pi sat
Batiha P2sat 65.64
THERMODYNAMI

1 1.864
Find i
2 1.072
CS (2)

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 :
sat
y1 0.282
xii Pi
yi  y2 0.718
P
AHU
37/46
 Find Pi sat
Dew Point Pressure
Find 1 & 2 . Initial guess its=1

(b) For T = 318.15 K and y1 = 0.60

Dr. Find P:
Mohammad Converges at: P 62.89 kPa P
1
y1 1 P1  y2 2 P2sat
sat
Batiha
1 1.0378
THERMODYNAMI

Find xi:
2 2.0935 xi  yi P i Pi sat

x1 0.8169 Evaluate from the given

equation
CS (2)

C onverge?
NO
Pj = Pj-1?

YES

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

AHU
38/46
 Find Ti sat

Bubble Point Temperat

ure Find initial T from mole-fraction weighted average
T  x1T1sat  x2T2sat

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

Dr. For current T, find A, 1 , 2 ,
Mohammad Converges at: T 331.20 K P1 sat , P2sat   P1sat P2sat
Batiha
1 1.0236
Find new value for P1sat :
THERMODYNAMI

P
2 2.1182 P1sat 
x11  x22  

y2 0.330
Find new T from Antoine equation for species 1
y1 0.670 T
B1
 C1
CS (2)

A1  ln P1sat

NO Converge?
Tj = Tj-1?

YES

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

Find vapor phase mole fraction

AHU y1  x11 P1sat P & y 2 1  y1

39/46
 Dew Point Temperatur Find Ti sat

e
Find initial T from mole-fraction weighted average

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

Dr.
Mohammad
and y1 = 0.40 For current T, find A, P1sat , P2sat
  P1sat P2sat
Batiha

Converges at:
THERMODYNAMI

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 :

CS (2)

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
x2 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

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 7. VLE FROM K-VALUE CORRELATIONS
 There can be VLE data for mixtures of multi-
Dr. components, but such a boiling-point diagram
Mohammad is hard to show in either tabular or graphical
Batiha
form.
THERMODYNAMI

 For such multi-component mixtures, as well as

binary mixtures, VLE data are represented in terms
yi
of K-values (equilibrium ratio) (Ki) :
Ki 
CS (2)

xi

 K-value for Raoult’s Law: Pisat

yi P xi Pisat Ki 
P

 K-value for modified Raoult’s Law: sat

γP
AHU yi P xi γi Pisat Ki  i i
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P
 For binary systems to solve for bubble point
calculation:
Dr.
Mohammad  y 1
i i
 K x 1
i i
iHence,
Batiha
THERMODYNAMI

For binary systems to solve for dew point calculation:

yi
 x 1
i i
Hence,
i Ki
1
CS (2)

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 Dr.
Mohammad
Batiha
THERMODYNAMI
CS (2)

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 Dr.
Mohammad
Batiha
THERMODYNAMI
CS (2)

AHU
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 Example 6:

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

Dr.
and 70 mol-% propane at 50°F, determine:
Mohammad (a) dewpoint P, (b) bubblepoint P.
Batiha

Solution:
THERMODYNAMI

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

liquid is present (the given mole fractions are yi).
CS (2)

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

yi
we find the value for which:
1 K
i 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
AHU 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
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 (b) At bubble point, system is almost completely
condensed (given mole fractions are xi). By trial we
Dr. find the value for which:
Mohammad
Batiha  K x 1
i
i i
THERMODYNAMI

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
CS (2)

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

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