VAPOR/LIQUID

EQUILIBRIUM

Mata Kuliah : Termodinamika II

Lilik Suprianti, ST, MSc

TEKNIK KIMIA
UPN “VETERAN” JAWA TIMUR
Capaian Pembelajaran
➝ Mahasiswa mampu menjelaskan konsep
kesetimbangan uap-cair (VLE)
➝ Mahasiswa memahami dan dapat
mengaplikasikan konsep konsep
termodinamika yang berhubungan dengan
VLE pada sistem proses

2
OUTLINE
INTRODUCTION
 PHASE RULE : DUHEM’S THEORY
VLE : QUALITATIVE BEHAVIOR
SIMPLE MODEL FOR VAPOR /LIQUID
EQUILIBRIUM
RAULT LAW
HENRY’S LAW
 VLE BY MODIFIED RAOULT’ LAW
 VLE FROM K-VALUE CORRELATION
3
Nature Of Equibrium
➝ 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.

4
Measure of Composition

Mass or mole
fraction
Composition
Measure of

Molar
concentration

Molar mass of a
mixture or
solution
5
THE PHASE RULE:
DUHEM’S THEORY

6
Phase Rule
It describes the mathematical relationship for determining the stability
of phase present at equilibrium

Intensive and Extensive Variables

extensive variable: which depends on system size (ex: mass or volume)
intensive variable: which does not depend on system size (ex:
temperature, pressure, or density)

Phase and Number of species (component)

Remember phase (π)???
Number of component (N)???
7
 
Total Variables = Composition variable + Thermodynamic variables
Number of composistion variable is
Thermodynamic variables are (T and P)
So, the The number of variables given by phase rule =

The number of relation between variable/ fixed variables

suppose component i with π phase will have the equilibrium
equation
(i=1,2....N)
By knowing the chemichal potensial of one phase, then no need to
determine the chemical potential of other phases.
So, the equations of the independent phase equilibrium

8
8
Independent variable (degree of freedom) F is the difference between
the number of variables of phase rule and the number of equation /
relation between variable

Simplify 𝑭=[ ( 𝑵 −𝟏 )( 𝝅 ) +𝟐 ] − [ (𝝅 − 𝟏)( 𝑵 )   ]

 

Where :
F : Degrees of freedom
𝑭=𝟐 − 𝝅 + 𝑵
 
π : Number of phase
N : Number of species

9
 
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 :  𝑭=𝟐 − 𝝅 + 𝑵
Extensive phase rule variable (masses or mole no. of the phases): 
 Total number of variables :
 If the system is closed and formed from specified amounts of each
species, Number of independent phase equilibrium equations is

 The difference between the no. of variables and the no. of equations,

10
 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.
11
VLE : QUALITATIVE
BEHAVIOR

12
 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-  + N = 2-  + 2 =4 - 
 Because there must at least one phase ( = 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.

13
14
 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 the 'lighter' or more
volatile.
 Upper surfaces contains sat. liquid
states [P-T-x1]
 Under surfaces contains sat. vapor
states [P-T-y1]
 Surfaces intersect along the line
RKAC1 & UBHC2 : vapor P vs. T
curves for pure species 1 and 2

15
 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
16
 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.

17
 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-x 1-y1 phase diagram at
constant T
 T ~ AEDBLA
a
 Horizontal lines ~ tie line connecting the
compositions of phases in equilibrium
 T and T lie between two pure species critical
b d
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, P c of two pure species at point C1 and C2
• Pd ~ above critical pressure, Pc of two pure species
18
 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.

19
 Critical point of a binary mixture occurs
where nose of a loop tangent to the
envelope curve: 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.

20
 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 take place until dewpoint is
reached at H
21
Fig. 10.5: P-T diagram for typical mixtures Fig. 10.6: y1-x1 diagram of ethane/n-
of non-polar substances such as heptane for several pressure.
hydrocarbon. The P-T diagram for the
ethane/n-heptane system.

22
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

23
24
SIMPLE MODEL VLE

25
 Goal thermodynamics
“ applied in VLE:
To find the temperatures,
pressures and compositions
of phases in equilibrium.
.

26
 Simple Models For VLE :
Find T, P, composition

Raoult’s Law Henry’s Law:

System at low to moderate For any species present at
pressures and only for low concentration and
systems comprised of limited to systems at low to
chemically similar species. moderate pressures.

27
RAULT 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:

28
Because iyi = 1, Eq. (10.1) may be summed over all species to yield
 

This equation applied in bubble point calculations, where the vapor-phase

composition is unknown.
For a binary system with x2 = 1 – x1

P= P2sat +( P1sat − P2sat ) x 1

 

Equation (10.1) may also be solved for xi and summed over all species. With
ixi = 1, this yield
1 This equation applied in dew point
P Eq.10.3 calculations, where the liquid-phase
y
i
i Pi sat
composition is unknown.

29
Bubble Point Pressure (Bubble P)
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
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
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
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

30
For binary systems to solve for Bubblepoint Calculation (T
is given)
 i
yi  1

P   xi Pi sat
i

P  P2sat  P1sat  P2sat x1 
x1 P1 sat
y1 
P

31
Raoult’s law equation for xi to solve for Dewpoint
Calculation (T is given)
i xi 1

1
P
1 P
y1 / P1 sat  y2 / P2sat
 i i
y
i
P sat

y1 P
x1 
P1 sat
32
P sat,
or the vapor pressure of component i, is commonly
i
represented by Antoine Equation (Appendix B, Table B.2,
SVNA 7th ed.):

Bi
ln Pi sat
(kPa)  A 
T ( K )  Ci

 
𝑠𝑎𝑡 𝐵
𝑇 = −𝐶
𝐴 − ln 𝑃
33
EXAMPLE
Binary system acetonitrile(1)/nitromethane(2) conforms closely to
Raoult’s law. Vapor pressure 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.
34
a) BUBL P calculations
 Corresponding of yi from eq 10.1
Calculate P1 and P using
sat
2
sat

Antoine equations At 384.15K

(75oC),
 
𝑦 𝑖 𝑃=𝑥𝑖 𝑃𝑖𝑠𝑎𝑡
P1sat = 83.21kPa
P sat = 41.98kPa
 
𝑥1 𝑃1𝑠𝑎𝑡
2
𝑦 1=
Since it is a binary system, Eq. 10.2 𝑃
may be used.
  ...........(i)   ( 0.6 ) ( 83.21 )
¿ =0,7483
66.72
 Lets x1 = 0.6, subtitute to eq (i)

35
The results of calculations for 75oC (348.15K) at a number of values of x1:
States in calculation:
X1=0.6,P=66.72kPa, y1=0.7483
Two phase region: sat.liq & Locus of x1 y1 P(kPa)
sat. vapor coexist in bubblepoint
equilibrium 0.0 0.0000 41.98
Bubblepoint
0.1 0.1805 46.10
0.2 0.3313 50.23
0.3 0.4593 54.35
0.4 0.5692 58.47
0.5 0.6647 62.60
Dewpoint
0.6 0.7483 66.72
States of sat. vapor
States of sat. liquid Locus of dewpoint 0.7 0.8222 70.84
0.8 0.8880 74.96
0.9 0.9469 79.09
36
1.0 1.0000 83.21
At point c, the vapor composition is y1=0.6, but the composition of liquid at
c’ and the pressure must read from graph or calculated. This is DEW P, by
Eq. 10.3;
  1
𝑃=
𝑦1 𝑦1
𝑠𝑎𝑡
+ 𝑠𝑎𝑡
𝑃1 𝑃1
For y1=0.6 and t=750C
1
P  59.74kPa
0.6 83.21  0.4 41.98

And by Eq. 10.1,

y1 P  0.6  59.74 
x1  sat
  0.4308
P1 83.21
This is the liquid-phase composition at point c’
37
b) When P is fixed, the T varies along T1sat and T2sat, with x1 & y1. T1sat & T2sat are
calculated from Antoine equation;
Bi
tisat   Ci
Ai  ln P

For P=70kPa, T1sat=69.840C, T2sat=89.580C.

Select T between these two temperatures and calculate P1sat & P2sat for the
two temperatures and evaluate x1
For example, at T 78oC, P1sat and P2sat
P  P2sat 70  46.84
x1  sat
P1  P2sat
x1   0.5156
91.76  46.84

38
Get y1 from Eq. 10.1

x1 P1sat  0.5156  91.76 

y1    0.6759
P 70

x1 y1 T/oC

0.0000 0.0000 89.58 (t2sat)

0.1424 0.2401 86
0.3184 0.4742 82
0.5156 0.6759 78
0.7378 0.8484 74
1.0000 1.0000 69.84 (t1sat)
39
Bubl T calculations
For x1 = 0.6 and P = 70kPa, T is determine by iteration.
P sat sat
Equation (10.2) is written as P2sat  where   P1 P2 Eq. (B)
x1  x2

Subtract ln P2sat from ln P1sat as given by Antoine equations yield

2945.47 2972.64
ln   0.0681   Eq. (C)
t  224.00 t  209.00

Iterate as follow:
With the current value of  (found for an arbitrary intermediate T) calculate P2sat
by using Eq. (B)
Calculate t from Antoine equation for species 2:
2972.64
t  209.00
14.2043  ln P2sat

40
Find a new value of  by using Eq.(C)
Return to initial step and iterate to convergence for a final value of T
The result is t = 76.42oC (349.57K).
From Antoine equation,
P1sat = 87.17 kPa and
by Eq. (10.1), y1 = 0.7472

41
 HENRY LAW
Assumption
 For pressure low: It is so low that it can be assume as ideal gas
 For species present as a very dilute solution in liquid phase

yi P  xi H i  i  1,2,..., N 
xi : L  phase mole fraction
yi : V  phase mole fraction
H i : Henry' s constant
P : Total pressure
42
43
 Example 10.2

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

determine the compositions of the V & L phases in a sealed can of ‘soda’ &
the P exerted on the 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 & Raoult’s law for species 2 are written;

y1 P  x1 H 1 y2 P  x2 P2sat

P  x1 H1  x2 P 2
sat

44
With H1=990 bar & P2sat = 0.01227 bar (from steam tables at 100C)
 

Then by Raoult’s law, Eq. 10.1 written for species 2;

x2 P2sat  0.99  0.01227 

y2    0.0012
P 9.912

Whence y1=1-y2=0.9988, and the vapor phase is nearly pure CO2, as

expected.
45
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

46
VLE BY MODIFIED
RAULT LAW

47
  The 2ndassumption of Raoult’s Law is abandoned, taking into account
the deviation from solution ideality in L phase.
Thus, activity coefficient is introduced in Raoult’s Law

Activity coefficients are function of T & liquid phase

composition, x

yi P  xi  i Pi sat  i  1,2,..., N 

48
 i yi  1 Bubble P   xi i Pi sat
Point
i

1
P
i xi 1 Dew Point  i ii
y
i
 P sat

49
BUBL P
Find Pi sat

Find  i

Find P from equation 10.6

P  x1 1P1sat  x2 2 P2sat

Find yi from equation 10.5

yi  xi i Pi sat P
DEW P
Fin d Pi sat

Fin d  1 &  2 . Initia l g u e ss its=1

Fin d P u sin g e q ua tio n 10.7

1
P
y1  1 P1sat  y 2  2 P2sat

Fin d xi u sin g e q u a tio n 10.5

xi  yi P  i Pi sat

Eva lu a te fro m th e g ive n e q u a tio n

NO
C o n ve rg e ?

YES

It is th e P d e w .
y1 P
Fin d liq u id p h a se m o le fra c tio n x1  & x2  1  x1
 1 P1sat
 Find Ti sat

BUBL T Find initial T from mole-fraction weighted average

T  x1T1sat  x2T2sat

For current T, find A,  1 ,  2 ,

P1 sat , P2sat   P1sat P2sat

Find new value for P1sat from equation 10.6;

P
P1sat 
 x1 1  x2 2  

Find new T from Antoine equation for species 1

B1
T  C1
A1  ln P1sat

NO Converge?

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
 Find Ti sat

DEW T Find initial T from mole-fraction weighted average

T  y1T1sat  y 2 T2sat

For current T, find A, P1sat , P2sat

  P1sat P2sat

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

Calculate  1 &  2 from given correlation

Find new value for P1sat from equation 10.7;

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

Find new T from Antoine equation for species 1

B1
T  C1
A1  ln P1sat

NO
Converge?
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
AZEOTROP

When x1=y1, the dew point and

bubble point curves are tangent
to the same horizontal line
A boiling L of this composition
produce a vapor exactly the
same composition; L does not
change in composition as it
evaporates

54
55
 y1 x1   𝛾 1 𝑃1
12  (10.8) 𝛼 12 =
y 2 x2 𝛾 2 𝑃2

 Determine value of and

If one limit is >1 & the other limit is <1; azeotrope
exists.

Relative Volatility
56
Example 10.3
For system methanol (1)/methyl acetate (2), the following equation
provide a reasonable correlation for the activity coefficient:
  𝛾 =𝐴 𝑥 2   𝛾 =𝐴 𝑥 2
ln 1 2 ln 2 1 𝑤h𝑒𝑟𝑒
  , 𝐴 =2.771− 0.00523 𝑇
  𝑠𝑎𝑡 3643.31   2665.54
ln 𝑃1 =16.59158 − 𝑠𝑎𝑡
ln 𝑃2 =14.25326 −
𝑇 −33.424 𝑇 −53.424

T in Kelvi, P in kPa. Calculate:

a. P and yi, for T=318.15 K abd xi= 0.25
b. P and xi for T= 318,15 K and yi=0.6
c. T and yi, for P=101.33 kPa and xi=0.85
d. T and xi, for P=101.33 kPa and yi=0.4
e. The azeotropic pressure and azeotropic composition, for
T=318.15 K 57
VLE FROM K-VALUE K-value for Raoult’s Law
CORRELATTIONS
Pi sat
Ki 
The partition between liquid P
and vapor phases of a chemical
species is equilibrium ratio, Ki. K-value for modified Raoult’s Law

This quantity is called K-value

 i Pi sat
Ki 
  𝑦𝑖 P
𝐾𝑖 ≡
𝑥𝑖
58
 For binary systems to solve for bubble point calculation;

y i i 1 Hence,
Kx i i i 1

For binary systems to solve for dew point calculation;

yi
x i i 1  i
Ki
1

59
60
When given a mixture of composition at certain T or P;

Bubble point Dew point

• Insignificant L
• The given mole fraction is yi  System is almost condensed
• Need to satisfy equation 10.14  The given mole fraction is xi
• Composition of dew is  Need to satisfy equation 10.13
xi=yi/Ki  Composition of buble is
yi=Kixi

61
Example 10.4
For a mixture of 10 mol % methane, 20 mol % ethane, 70 mol%
propane, at 50oF
Determine:
a. Dew point pressure
b. Bubble point pressure
Solution

a. System ay dew point. Few number of liquid, the given mol

fractions are value of yi. Trial P

62
Flash Calculation
Originates from a fact that a liquid at a pressure equal to or greater
that its bubble point pressure ‘flashes’ or evaporates when the
pressure is reduced, producing a two-phase system of vapor and
liquid in equilibrium
Vapor, V • Liquid at P > Pbubble partially
V
evaporates when P is
Feed, F
reduced, producing 2-phase
system of V & L in
equilibrium
L Liquid, L
63
 yi
From K-value xi  yi
Ki Ki 
xi
Hence solving for yi, zi K i
yi   i  1,2,.....N 
1  V  K i  1

Because y i i 1

zi K i
Hence,  yi  1  V  K  1  1
i

64
 Find BUBL P with zi  xi ; Pbubble

Flowchart for flash

Find DEW P with zi  yi ; Pdew
pressure

Is the given P
between NO
Pbubble & Pdew ?

No need for flash

calculation
YES

Using equation 10.11, find K i

Substitute K i in equation 10.17. By trial & error,

solve for V. Then L=1-V

Solve equation 10.16 for each component - yi

Solve equation 10.10 for each component - xi

65
In a system with one mole chemical species with an overall
composition by set of mole fraction, zi.
Li would be the moles of liquid with mol fraction xi and V be the
moles of vapor with the mol fraction of yi:

L V  1

zi  xi L  yiV  i  1,2,.....N 
zi  xi 1  V   yiV  i  1,2,.....N 
66
Example 10.5
 Thesystem acetone (1)/ acetonitrile (2)/ nitromethane(3), at
80oC and 110 kPa has overall composition. Assuming that
Raoult’s law is appropriate to the system, determine The vapor
pressure of the pure species at 80oC are:

𝑃1𝑠𝑎𝑡 =195.75
   𝑃2𝑠𝑎𝑡 =97,84 𝑃3𝑠𝑎𝑡 =60.32
 

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Let’s review some concepts
Simple Model
Kesetimbangan Dew Point
VLE
Hukum Fase Bubble point
 Rault Law
Azeotrop
 Henry Law

Modiefied K Value Flash

Rault Law Calculation

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Thanks!
Any questions?

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