INSTITUTO POLITECNICO NACIONAL

ESCUELA SUPERIOR DE INGENIERIA QUIMICA E INDUSTRIAS

EXTRACTIVAS
TERMODINAMICA DE EQUILIBRIO DE FASES
Tarea: vapour-liquid equilibrium

ALUMNO: JOSE GERARDO RAMIREZ MARTINEZ

GRUPO: 2IV32
FECHA DE ENTREGA: 2 DE JUNIO DE 2015

Vapor-Liquid Equilibrium
Distillation is one of the most commonly used separation processes in the
chemical process industries. It is based on the differences in boiling points of
components in the mixture. A typical distillation column is shown in Fig. 9.1. The
feed enters the distillation column in any state (from subcooled liquid to
superheated vapour). The parts of the distillation column above and below the
feed point are called the rectifying and stripping sections, respectively. The vapour
stream from the top of the distillation column is sent to a condenser. Part of the
liquid is taken as the overhead product, while the rest is returned to the column as
reflux. The overhead product is rich in more volatile component(s). The ratio of
the reflux flow rate to the overhead product flow rate is called the reflux ratio. Part
of the liquid stream from the bottom of the distillation column is taken as the
bottoms product, which is rich less volatile component(s). The rest is vaporized in
reboiler and returned to the column.
The trays placed in the column are used to bring the vapour and liquid streams,
which flow in counter current direction, into contact with each other. The trays
may be of various types, i.e. sieve, bubble-cap, valve, etc. In sieve tray column, for
example, liquid flows across the tray through channels separated by baffles and
vapour flows from the bottom, up through holes in the tray. When the two streams
mix each other, if the component fugacities are not the same in the vapour and
liquid phases, the resulting driving force causes mass transfer to take place. While
the more volatile component transfers from the liquid to the vapour phase, the
less volatile component transfers from the vapour to the liquid phase. The system
reaches equilibrium, or, in other words, mass transfer between the phases stops,
when component fugacities in the vapour and liquid phases are equal to each
other. Once reaches equilibrium, the two phases leave the tray as two separated
streams. The combination of these stages, i.e. mixing, reaching equilibrium, and
separation, is called equilibrium stage. The purpose of this chapter is provide the
necessary tools to determine the compositions of the liquid and vapour streams
leaving each equilibrium stage.

9.1 Vapour- Liquid

Calculations

Equilibrium

When vapour is in
liquid, besides
pressure of the vapour
fugacities of each
vapour an liquid
equal to each other,

equilibrium with
temperature and
and liquid phases,
component in the
phases must be
i.e.

f^ Vi ( T , P , y i ) =f^ iL ( T , P , x i ) i=1,2, , k .(9.11)

There are mainly two approaches for the modelling of vapour-liquid equilibrium: in
the first approach, also known as the model, fugacity of the component i in
the vapour phase is expressed in terms of the fugacity coefficient, and the fugacity
of component i in the liquid phase is expressed in terms of the activity coefficient,
i.e.
y i PVi ( T , P , y i )=x i y i ( T . P x i ) f iL (T , P ) .(9.12)
The use of equation (5.4-8) to express the fugacity of pure component i in the
liquid phase reduces equation (9.1-2) to
V

vap V

vap

y i Pi ( T , P , y i )=x i y i ( T , P x i ) Pi i ( T , Pi

) exp

^ Li (PPivap)
V
(9.13)
RT

The fugacity coefficient of component i and the fugacity coefficient of pure i are
calculated from the equation of state. In the second approach, also known as the
model, fugacities of component i in the vapour and liquid phases are
expressed in terms of the fugacity so that equation (9.1-1) takes the form
L

T , P y i=x ii ( T , P , x i) (9.14)
V
y ii
In which fugacity coefficients are calculated either using by a single equation of
state for both vapour and liquid phases or by using different equations of state for
vapour and liquid phases. This chapter mainly focuses on the use of the first
approach, i.e. equation (9.1-3)

Note that the use of equation 9.1-3 requires the vapour pressures of pure
component to be known. The most commonly used vapour pressure equation is
that of Antoine, given by equation 5.6-18, i.e.
ln Pvap
i =A i

Bi
(9.15)
T +C i

Appendix C provides the parameters Ai, Bi and Ci for various substances. Once the
equilibrium data are obtained either experimentally or theoretically, the results are
presented either in tabular form or as a vapour-liquid equilibrium diagram (VLE).
Such equilibrium diagrams may be different forms as presented below.
Pressure-composition diagram: to construct a pressure-composition diagram,
compositions of the liquid and vapour phases are experimentally determined as a
function of pressure at a specified temperature. Liquid phase composition, xi,
versus pressure, P, and vapour composition, yi, versus pressure, P, curves are
called bubble point and dew point curves, respectively. For a binary system, a
typical pressure-composition diagram is shown in Fig. 9.2a.
The region between the bubble point and dew point curves represents the two
phase, i.e. vapour and liquid, region in which the number of degrees of freedom, F,
is two. When liquid and vapour phase are in equilibrium, their temperatures and
pressures must be equal to each other. Thus, any horizontal line in the region
between dew point and bubble point curves joins the vapour and liquid phases
that are in equilibrium. Such a line is called the tie line.
The region above the bubble point curve represents the subcooled liquid. The
region below the dew point curve represents the superheated vapour. In these two
regions F=3. At specific temperature, examination of figure 9.2a indicates that the
vapour pressures of pure components 1 and 2 are 17.82 kPa and 1.84 kPa
respectively.

Since P1vap > P2vap , pure component 1 boils at a lower temperature as compared to
component 2. In other words, component 1 is more volatile.
Suppose that a liquid mixture of x1=0.5 is initially at a pressure of 15kPa (point A)
as shown in Fig. 2b. Let us decrease pressure while keeping the temperature
constant. When the vertical line passing through the point A intersects the bubble
point curve (point B), the liquid mixture stars to boil whit the corresponding
pressure of 10kPa, known as the bubble point pressure. The dashed horizontal line
passing through the point B, i.e. the line intersects the dew point curve at point C.
Thus, the composition of the first bubble of vapor is y1=0.91. Since component 1
is more volatile, the vapor is rich in component 1. This in turn, increases the
amount pf component 2 (the less volatile component) liquid. As the boiling
continues, while the composition of the liquid moves along BD on the bubble point
curve, the composition of the vapor moves along CE on the dew point curve. The
tie line DE represents the equilibrium between the last liquid droplet (point D)
having a composition of x1=0.08 and vapor (point E). The pressure at point D (or
point E) is 3.1kPa. Further decrease of pressure leads to superheated vapor with
composition y=0.5. At given temperature, pure liquid boils at a single pressure, i.e.
when its vapor pressure equals the ambient pressure. On the other hand, for
multicomponent liquid at a specified temperature and initial composition, boiling

takes place over a range of pressure (10-3.1 kPa in the above example) due to the
varying composition of the liquid phase.
Now consider a vapor mixture at a pressure of 2kPa with a composition of y1=0.7

(Point A) as shown in Fig. 92c. Let us increase pressure while keeping the
temperature constant. When the vertical line passing through the point A
intersects the dew point curve (point B), the vapor mixture stars to condense with
the corresponding pressure of 5kPa, known as the dew point 2 pressure. The
dashed horizontal line passing through the point B,i.e tie line intersects the bubble
point curve at point C: Thus, the composition of the first liquid droplet is around
x1=0.2.
Since component 2 is less volatile, the liquid is rich in component 2. This in turn.
Increases the amount of component 1 (the move volatile component) in the vapor.
As the condensation continues, while the composition of the vapor moves along
BD on the dew point curve, the composition of the liquid moves along CE on the
bubble point curve. The tie line DE represents the equilibrium between the last
vapor molecule (point D) having a composition of y1=0.96 and liquid (point E).
The pressure at point D (or point E) is13.3 kPa. Further increase of pressure leads
to subcooled liquid with composition x1=0.7.
At a given temperature, pure vapor condenses at a single pressure. On the other
hand, for a multicomponent vapor at a specified temperature and initial
composition, condensation takes place over a range of pressure (5-13.3kPa in the
above example) due to the varying composition of the vapor phase.
Temperature-composition diagram: To construct a temperature-composition
diagram, compositions of the liquid and vapor phases are experimentally
determined as function of temperature at a specified pressure. Liquid phase
composition, xi, versus temperature, T, and vapor phase composition, yi, versus
temperature, T, curves are called bubble point and dew point curves, respectively.
For a binary system, a typical temperature composition diagram is shown in Fig.
9.3a.
The region between the bubble point and dew point curves represents the two
phase region. The horizontal line within the two-phase region joining the vapor and
liquid phases that are in equilibrium is called the tie line. The region below the
bubble point curve represents the sub-cooled liquid. The region above the dew
point curve represents the super-heated vapor.

At a specified pressure, examination of Fig. 9.3a indicates that the saturation (or
boiling point) temperatures of pure components 1 and 2 are 290K and 340K,
respectively. Since T1sat< T2sat , component 1 is more volatile. Suppose that a liquid
mixture of x1=0.4 is initially at a temperature of 280K (point A) as shown in Fig.
9.3b. Let us increase temperature while keeping the pressure constant. When the
vertical line passing through the point A intersects the bubble point curve (point
B), the liquid mixture starts to boil whit the corresponding temperature of 309K,
known as the bubble point temperature. The tie line passing through the intersects
the dew point curve at point C. Thus, the composition of the first bubble of vapor
is y1=0.8. Since component 1 is more volatile, the vapor is rich in it. This, in turn,
increases the amount of component 2 the less volatile component) in the liquid. As
the boiling continues, while the composition of the liquid moves along BD on the
bubble point curve, 3 the composition of the vapor moves along Ceon the dew
point curve. The tie line DE represents the equilibrium between the last liquid
droplet (point D) having a composition of x1=0.09 and vapor (point E). The
temperature at point D (or point E) is 330K. Further increase of temperature leads

to super-head vapor with composition y1=0.4. At a given pressure, pure liquid

boils at a single temperature. On the other hand, for a multi-component liquid at a
specified pressure and initial composition, boiling takes place over a range of
temperature (308-330K in the above example) due to the varying composition of
the liquid phase.
New consider a vapor mixture at a temperature of 330K whit a composition
y1=0.62 (point A) as shown in Fig. 9.3c. Let us decrease temperature while
keeping the pressure constant. When the vertical line passing through the point A
intersects the dew point curve (point B), the vapor mixture starts to condense with
the corresponding temperature of 320K, known as the dew point temperature.
The tie line passing through the point B intersects the bubble point curve at point
C. Thus, the composition of the first liquid is x1==.2. Since component 2 is less
volatile the liquid is rich in it. This, in turn, Increases the amount of component 1
(the more volatile component) in the vapor. As the condensation continues, while
the composition of the vapor moves along BD on the dew point curve, 4 the
composition of the liquid moves along CE on the bubble point curve. The tie line
DE represents the equilibrium between the last vapor molecule (point D) having a
composition of y1=0.91 and liquid (point E). The temperature at point D (or point
E) is 299 K. Further decrease of temperature leads to subcooled liquid whit
composition x1=0.62. At a given pressure, pure vapor condenses at a single
temperature. On the other hand, for a multicomponent vapor at a specific pressure
and initial composition, condensation takes place over a range of temperature
(320-295 K in the above example) due to the varying composition of the vapor
phase. x-y diagram: In this diagram, vapor phase composition, y, is plotted versus
the liquid phase composition, x, as shown in Fig. 9.4. Usually, a 45 line, i.e.
x=y, is included on the diagram for reference. These diagrams are typically made
at constant pressure, and so each point represents a different temperature.

9.1.1 Types of Vapor-Liquid Equilibrium Calculations

To solve a well-posed vapor-liquid equilibrium problem, of number of equations
must be equal to the number of unknowns. The number of degrees of freedom, F,
is:

F=

][

Total
of independent equations ( 9.16)
of independent
relating these variables
intensive variables

Figure 9.4: x-y diagram for a binary mixture of 1-propanol (1) and
1-butanol (2) (Mohsen-Nia and Memarzadeh, 2010).
For a K-component
system at equilibrium, if each component is present in each phase, the total
number of independent intensive variables is expressed as
varibales=T + P+ ( x 1 , x 2 , , x k1 ) + ( y 1 , y2 , , y k1 )=2+2 ( k 1 )=2 k .(9.17)
The equations relating xi to yi (or vice versa) are given by either Eqn (9.1-2) or
Eqn (9.1-4). Therefore, the total number of independent equations is k and Eqn
(9.1-6) becomes
F=2 kk=k (9.18)
which indicates that k variables must be specific so that equations at equilibrium,
i.e. Eqn (9.1-2), are used for determining the remaining unknown variables.
Vapor-liquid equilibrium calculations can be divided into five types depending on
the specified set of variables:

Bubble point pressure calculation: Calculate pressure and vapor phase

composition, given temperature and liquid phase composition.

Dew point pressure calculation: Calculate pressure and liquid phase

composition, given temperature and vapor phase composition.

Bubble point temperature calculation: Calculate temperature and vapor

phase composition, given pressure and liquid phase composition.

Dew point temperature calculation: Calculate temperature and liquid phase

composition, given pressure and vapor phase composition.

Flash calculation: Calculate amounts and compositions of liquid and vapor phases,
given overall composition and amount of feed stream besides temperature and
pressure within the flash chamber. Once temperature is specified, vapor pressures
of species making up the mixture can be easily determined. Thus, bubble point
and dew point pressure calculations are easiest to perform. On the other hand, if
pressure is specified, bubble point and dew point temperature calculations rely on
a trial-and-error procedure since vapor pressures of species cannot be determined
a priori.

9.2 Raoults Law

Let us simplify Eqn (9.1-3) with the following assumptions:

Assumption 1: Vapor is an ideal gas mixture

For an ideal gas mixture, fugacity of component i in the mixture is equal to

its partial pressure, i.e. =1. Thus,

Eqn (9.1-3) simplifies to

yiP=xii ( T , P , xi ) Pi

vap

i ( T , Pi

vap

vap
L
) exp V i (PP i ) (9.21)

RT

Assumption 2: Liquid is an ideal mixture.

Forces between like and unlike molecules do not differ and the Lewis-Randall rule
^
applies, i.e. f i=fixi and =1. Thus, Eqn (9.2-1) reduces to

yiP=xi Pi vap V i ( T , Pi vap ) exp

V i L ( PP i vap )
( 9.22)
RT

Assumption 3: The Poynting correction factor is equal to unity.

When pressure is not very high, Eqn (9.2-2) simplifies to

yiP=xiP i vapV i ( T , Pi vap ) (9.23)

Assumption 4: The saturated vapor of i at T and Pivap is ideal.This assumption

implies that fugacity of pure vapor is equal to the vapor pressure,

i. e .V i ( T , Pi vap )=1 , and Eqn (9.2-3) takes the final form of

Figure 9.5: Pressure-composition diagram of a system obeying Raoults law.

Which is known as Raoults law. 5 It simply states that the partial pressure of each
component in the vapor phase is equal to its mole fraction in the liquid phase
times its pure-component vapor pressure, v Summation of Eqn (9.2-4) over all
components present in the system yields

i=1

i=1

y 1 p= x i p

vap
1

i=!

i=1

p y 1= x i p 1

vap

Therefore, the total pressure (or bubble point pressure) is given by

P= x 1 p vap
1
i=1

For a binary system, Eqn reduce to

vap
vap
vap
vap
vap
P= x 1 p1 + x 2 p 2 = p2 + ( p1 p 2 ) x 1

which indicates that the equilibrium total pressure changes linearly with the liquid
phase mole fraction at constant temperature as shown in Fig. 9.5.
It is also possible to rearrange Eqn (9.2-4) as.
x i=

yi p
p vap
i

(9.28)

Therefore, the total pressure (or dew point pressure) is given by

P=

1
k

yi

i=1

( 9.2 10 )

p vap
For a binary system, Eqn (9.2-10) reduces to
P=

1
y1
vap

p1

y2

( 9.2 11 )

vap

p2

Figure 9.5 also shows the variation of system pressure as a function of the vapor
phase mole fraction at constant temperature. Note that Fig. 9.5 is nothing more
than the pressure-composition diagram for a system obeying Raoult's law.
The system pressure is calculated from Eqn (9.2-6) when the liquid phase
composition is known. On the other hand, the system pressure is calculated from
Eqn (9.2-10) if the vapor phase composition is known.
For a binary system obeying Raoult's law, the temperature-composition diagram
can be prepared as follows:

Specify pressure P.
sat
Calculate T 1
and

sat

T2

at the specified P from

T isat =

Bi
Ci
A i LnP

Pick temperature values between

Calculate

Calculate x1 from Enq (9.27)

T 1sat

and

T 2sat .

vap
Pvap
1 P 2

vap

PP
x 1= vap 2 vap
P1 P2
Calculate y1 from Eqn (9.28)
vap

x P
y 1= 1 1
P

Example 9.1 Prepare temperature-composition diagram for a binary mixture of nhexane (1) and n-heptane (.2) ata I .013 bar. Compare your results with the
following experimental data given by Jan et al (1994):
T(k)
X1
371.4 0
7
367.1 .0964
8
363.5 .1904
2
359.1 .3146
1
Solution

Y1
0
.1986
.36
.5258

T(k)
356.3
7
352.9
3
350.2
7
348.1
3

X1
.3953

Y1
.6236

.5123

.727

.6187

.8074

.7012

.8615

T(k)
345.5
5
343.7
4
341.8
1

From appendix C, the vapor pressures are give as

ln pvap
1 =9.2164

2697.55
T 48.78

ln Pvap
2 =9.2535

2911.32
T 56.51

At 1.013 bar, the saturation temperatures are

X1
.8160

Y1
.9240

.8991

.9637

T 1sat =

sat

T2 =

2697.55
+48.78=341.9 K
9.2164 ln1.013

2911.32
+ 56.51=371.6 K
9.2535 ln 1.013

By picking temperatura values between 341.9 K and 371.6 K, the calculet values
of x1 and y1 are tabulated as follows:
T(k)

P1

P2

343

1.04
9
1.11
6
1.18
6
1.26

345
347
349
351

vap

X1

Y1

T(k)

P1

vap

P2

.403

.944

.978

359

.433

.849

.936

361

1.68
3
1.78

.464

.76

.89

363

.497

.676

.841

365

vap

1.33 .531 .598 .789

7
353
1.41 .568 .524 .733
8
355
1.50 .607 .454 .673
3
357
1.59 .647 .388 .609
1
The plot of Txy diagram is shown in
experimental data given by Jan.

367
369
371

X1

Y1

.69

.325

.540

.735

.266

.467

1.88

.782

.21

.39

1.98
5
2.09
5
2.20
9
2.32
7

.832

.157

.307

.884

.106

.22

.939

.058

.127

.996

.013

.029

vap

the figure below. The points represent the

9.3 Calculations when Raoults Law is Applicable

Raoults lawis applicable formixtures composed of chemically similar components
at low pressure.

9.3.1 Bubble Point Pressure Calculation

At a given temperature, it is required to calculate the pressure at which a liquid of

known composition first begins to boil (see Fig. 9.6a). The bubble point pressure
calculation is straightforward and is given below:
1. Calculate vapor pressures of pure components from eqn.(9.1-5)
2. Calculate the bubble point pressure from eqn. (9.2-6)
3. Determine the composition of the vapor phase from eqn.(9.2-4),i.e.

vap

yi=

Example 9.2. Estimate

pressure of a liquid
butane (1), 25% nhexane(3), and 20% nAlso calculate the
bubble of vapor.

xiPi
PP

(9.3-1)

the bubble point

mixture of 20 mol% npentane(2), 35% nheptane (4) at 290 K.
composition of the first

Solution
From Appendix C, the vapor pressures are given in the form

ln P1 =9.0580

2154.90
T34.42

ln P1 vap=9.2131

2477.07
T 39.94

ln P1 vap=9.2164

2697.55
T 48.78

vap

vap

ln P1 =9.2535

2911.32
T56.51

At 290 K, the vapor pressures are calculated as

P1 vap=1.871 P 2vap=0.500 P 3vap =0.140 P 4vap =0.040
The use of eqn (9.2-6) gives the bubble point pressure as
Pbubble =x 1 P 1 vap+ x 2 P 2vap + x 3 P3 vap + x 4 P 4 vap
=(0.20)(1.871)+(0.25)(0.500)+(0.35)(0.140)+(0.20)(0.040)=0.556 bar
Composition of the first bubble of vapor can be calculates from Eqn.(9.3-1),i.e.

y 1=

(0.20)(1.871)
=0.673
0.556

y 2=

(0.25)(0.500)
=0.225
0.556

y 3=

(0.35)(0.140)
=0.088
0.556

y 4=

(0.20)(0.040)
=0.014
0.556

Note that

yi=1.0

sometimes, as a result of round off errors, the summation of

mole fractions may not be exactly equal to unity.

Comments:
When Raoults law is applicable
(P1 vap)least volatile < P bubble <( Pivap)most volatile
The vapor phase is rich in n-butane, the component with the highest vapor
pressure.
The problem can also be stated as follows: A vapor mixture of 20%mol % nbutane (1), 25% n-pentane(2), 35% n-hexane(3), and 20% n-heptane (4) at 290 K
is compressed isothermally. Estimate the minimum pressure at which the vapor
mixture is completely condensed

9.3.2 Dew Point Pressure Calculation

At given temperature, it is required to calculate the pressure at which a vapor of
know composition first begins to condense. The dewpoint pressure calculation is
also straightforward and is given below:

xi

Calculate vapor pressures of pure components from Eqn.(9.1-5)

Calculate the dew point pressure from eqn.(9.2-10)

Determine the composition of the liquid phase from Eqn.(9.2-4)

yiP
vap
Pi

Example 9.3 estimate the dew point pressure of a vapor mixture of % mol nbutane (1), 25% n-pentane (2), 35% n-hexane (3), and 20% n-heptane (4) at 290
K. also calculate the composition of the first drop of liquid.
Solution:
From example 9.2, the vapor pressures at 290K are
vap
vap
vap
vap
P1 =1.871 P2 =0.500 P3 =0.140 P4 =0.040

The use of eqn (9.2-10) gives the dew point pressure as:
Pdew =

1
=0.123
0.20 0.25 0.35 0.20
+
+
+
1.871 0.500 0.140 0.040

Composition of the first drop of liquid can be calculated from Eqn (9.3-2), i.e.
x 1=

( 0.20 )( 0.123 )
=0.013
1.871

x 2=

( 0.25 )( 0.123 )
=0.062
0.500

x 3=

( 0.35 )( 0.123 )
=0.308
0.140

x 4=

( 0.20 ) ( 0.123 )
=0.615
0.040

As result of round off errors

x 1=0.998 .

Comments:
o When Raoult law is applicable

( P1vap ) teast volatile< P dew< ( P1vap ) most volatile

o The liquid phase is rich in n-heptane, the component with the lowest vapor
pressure.
o The problem can also be stated in the following ways:
a) A vapor mixture of 20 mol % n-butane (1), 25% n-pentane (2), 35% nhexane (3), and 20% n-heptane (4) at 290K is compressed isothermally
until condensation occurs. Estimate the pressure at which condensation
starts and determine the composition of the first liquid droplet.
b) A liquid mixture of 20% mol n-pentane (2), 35% n-hexane (3), and 20% nheptane (4) is pressurized isothermally at 290K. what is the mximum
pressure for the complete evaporation of the mixture.
9.3.3 bubble point temperature calculation
At a given pressure, it is required to calculate the temperature at which a liquid of
known composition first begins to boil (see fig. 9.6c). Since temperature is an
unknown quantity, vapor pressures of pure liquids cannot be determined a priori
and the following trial-and-error procedure should be followed:
1.- Assume T and determine vapor pressures of pure components from Eqn (9.1-5).
When Raoult law is applicable,

(T isat ) min T bubble < (T isat ) max

2. Use Eqn (9.2-6) and the calculate

( Pcalc )

3. compare

( Pcalc )

with the specified P if

( Pcalc )> P , assumed T is too high; if IF

( Pcalc )< P , assumed T is too low. When the calculated pressure matches the
specified pressure, mole fractions in the vapor phase are calculate from:
y 1=

( x i) ( P ivap )
P

.. ( 9.33 )

9.3.4 dew point temperature calculation:

At a given pressure, it is required to calculate the temperature at which a vapour
of known composition first begins to condense (see fig. 9.6d). Since temperature is
an unknown quantity, we have to use the following trial-and-error procedure
should be followed:
1.- Assume T and determine vapor pressures of pure components from Eqn (9.1-5).
When Raoult law is applicable,

(T isat ) min T bubble < (T isat ) max

2. Use Eqn (9.2-10) and the calculate

3. compare

( Pcalc )

( Pcalc )

with the specified P if

( Pcalc )> P , assumed T is too high; if IF

( Pcalc )< P , assumed T is too low. When the calculated pressure matches the
specified pressure, mole fractions in the vapor phase are calculate from:
x 1=

( y i) ( P )
Pivap

.. ( 9.34 )

Example 9.4- Estimate the bubble point and dew point temperatures of a
mixture consisting of 50% n-pentane (1) 45% n-hexane (2), and 5% n-heptane (3)
at 0.8 bar.
Solution:
The boilindg point temperatures of pure components at 0.8 bar are:
T 1 sat =39.94+

2477.07
=302.4 K
9.2127ln ( 0.8 )

T 2 sat =48.78+

sat

T 3 =56.51+

2697.5
=334.6 K
9.2164ln ( 0.8 )
2911.32
=363.7 K
9.2535ln ( 0.8 )

Therefore, our initial estimates for the bubble and the dew point temperatures
should lie between 302.4K and 363.7K. le us choose the mole fraction weighted
average of the pure component boiling points as an initial estimate, i.e.
T =( 0.50 ) ( 302.4 ) + ( 0.45 ) ( 334.6 ) + ( 0.05 ) ( 334.6 )=320 K
Bubble point temperature: in this case we know the total pressure, 0.8 bar, and
the liquid phase composition x 1=0.50, x 2=0.45, x 3=0.05 . At the correct value of
temperatura, the pressure calculate from:
Pcalc =( x 1) ( P 1vap ) + ( x 2 ) ( P2vap ) + ( x 3 ) ( P 3vap )

Must be equal to 0.8. The results of the iterative procedure are shown in the table
below:
Trial #

T(K)

1
2
3

320.00
310.00
314.91

P1vap(bar
)
1.445
1.042
1.227

P2vap(bar
)
0.482
0.329
0.399

P3vap(bar
)
0.166
0.107
0.134

Pcalc(bar)
0.948
0.674
0.800

Therefore, the bubble point temperature is approximately 315K. Composition of

the first bubble of vapour can be calculated from:
y i=

xi Pvap
i
P

Substitution of the values gives the vapour phase mole fractions as:

y 1=

( 0.50 ) (1.227 )
=0.767
0.8

y 2=

( 0.45 ) ( 0.399 )
=0.229
0.8

y 3=

( 0.05 ) ( 0.134 )
=0.008
0.8

As a result of round off errors yi=0-999

Dew point temperature: in this case we know the total pressure, 0.8 bar and the
vapour phase composition, y1=0.50, y2=0.45 and y3=0.05. At the correct value of
temperature, the pressure calculated from:
Pcalc =

y1
P

vap
1

1
y2
P

vap
2

y3
vap

P3

Must be equal to 0.8. The results of the iterative procedure are shown in the table
below:

Trial #

T(K)

1
2
3

320.00
330.00
326.57

P1vap(bar
)
1.445
1.961
1.770

P2vap(bar
)
0.482
0.687
0.610

P3vap(bar
)
0.166
0.259
0.217

Pcalc(bar)
0.633
0.900
0.800

Therefore, the dew point temperature is approximately 327K. Composition of the

first drop of liquid can be calculated from:
x i=

yi P
Pivap

Substitution of the values gives the liquid phase mole fractions as:

x 1=

( 0.50 )( 0.8 )
=0.226
1.770

y 2=

( 0.45 ) ( 0.8 )
=0.590
0.610

y 3=

( 0.05 ) ( 0.8 )
=0.184
0.217

Note that xi=1.0. The dew point and bubble point temperatures differ by 327315= 12 K for this mixture.
Comment: problem 9.5 discusses the use of the Newton-Raphson method for the
calculation of bubble point and dew point temperatures.

Phase Equilibrium
General phase equilibrium relations
Phase equilibrium variables: T. P, moles of each component
Consider a closed system with no chemical reactions: The fundamental property
relation with T and P as independent variables involved the Gibbs free energy:
d Gt=V t dPSt dT
Gt
P

( )

V t=

S t=

G t
T

( )

Note that only the first and the second laws are involved in deriving this property
relation, plus the definition of G(G=H-TS)
If the system ca exchange mass with the surroundings (another phase),then it
becomes an open system, and the fundamental property relationship must be
modified:

dG =V dPS dT + i dni
t

i=1

i=

( ) ( )
G
ni

T , P, n

nG
ni

T , P ,n

This few defined property is called the chemical potential for component i in a
mixture.
At equilibrium, the temperature and pressure must be the same in all phases, for
thermal and mechanical equilibrium considerations (i.e. no driving forces to cause
fluxes of heat or fluid movement)
Consider a system containing two phases (vapour and liquid, V and L) at
temperature T and pressure P:

Each phase is an open system, because it can exchance energy and mass whit the
other phase. The entire system is considered to be isolated from the surroundings.
In the vapor an liquids phases we can write the following fundamental property
relations:
V

LV

d (Gt )V =(V t )V dP( St ) dT + Vi dnVi

d (Gt ) L=(V t )L dP( S t ) dT + Li dn Li

We can

add these to get the total change in Gibbs free energy for the entire system:
t

d G =V dPS dT + i dni + i dni

But, since this is a closed system, the last two terms must sum to zero. Also, any
mass leaving one phase must enter the order.

 Vi dn Vi + iL dniL=0
dnVi =dniL

( i iL) dnVi =0

Since the dn`s are arbitrary independent variables, we conclude that:

V

i = i i=1 , 2 ,3 , , N This can be expanded to any number of phases.

Thus, in addition to thermal and mechanical equilibrium, the chemical potential for
any given component must be the same in al phases at equilibrium.

This is phase equilibrium (i.e., no driving forces for diffusion).

At equilibrium in a system of phases and N components:
i =i==i i=1,2, 3, , N
Thus, we have derived the phases equilibriums relations without any new concepts
being introduced, in addition to the 1st and 2nd laws.
Fugacities
Our problem with chemical potentials is that we have no real feelings about how
they behave.
Thus, it is traditional to throw them away, in favor of another defined property,
fugacity.
ii0 =RTLn

f^i
f^ oi

f^i Py i as P 0
That over the symbol for fugacity means for a component (i) in a muxire.
Thus, for a ideal gas mixture, fugacity is equal to partial pressure. This is at least

some progress.
In terms of fugacities, the phase equilibrium relations do not change:
f^ i =f^ i == f^ i i=1,2,3, , N

Thermodynamic propieties of mixtures.

Ideal gas mixtures:
P= Py i

H= y i H i

S= yi SiR y i ln y i

G= y i GiRT y i ln y i

Ideal solutions:
V=

X iV i

H= X i H i

S= X i Si R X i ln X i
G= X i GiRT X i ln X i

i=Gi+ RTln X i
Note that the last equation follows from the definition of fugacities, with the
standard state taken as the pure fluid at the same T,P.
Read liquid Mixtures - -Partial Molar and Excess Properties
Partial molar properties are defined by

1= nM
M
ni

( )

T, P,

nj

Thus, the partial molaar Gibbs free energy is the chemical potential:

( nGn )

1=

T, P,

nj

= Gi

Excess properties are defined by.

M E =M M id
Where the ideal solution value is at the same T, P, and composition as the actual
mixture, Thus, the enthalpy of a real mixture can be calculated from.

H=H id + H E= X i H i + H E

Fugacities in Mixtures Ideal Behavior

Gas Phase - - Ideal Gases

v
f^ i =P y i

Liquid Phase - - Ideal Solutions.

f^ iL =f Li x i
The coefficient on the RHS is the fugacity of the pure liquid at the same the actual
liquid mixture.
This relation is called the Lewis Randall rule.
Note: Ideal solutions exhibit no volumen change on mixing heat of mixing.

Fugacities in Mixtures - Real Gas and Liquid Bachavior.

Gas phase fugacity coefficients.

f^ iv =P y i ^ vi
^ vi 1 as P 0
P

ln ^ i=
0

n ( Z1 )
ni

P, T,

dP
P

nj

Liquid phase activity coeficients

f^ iL =f Li x i i

L
sat
^f L =Psat sat exp V i ( PPi )
i
i
i
RT

Henrys law approach for dilute componests

The activity coefficient can be very large near infinite dilution for a quite different).

f^ iL =k i x i
k i=f iL i
This can be taken as the ideal dilute solution (Henrys law), and corrected with a
different activity coeficiente:

f^ iL =k i x i i ( HL)

 i ( HL )=

i
i

The liquid- phase activity coefficients can be related to the excess Gibbs free
energy
f^ iL
id
^
^
i =GiGi =RTln L =RTln i
f i xi
id
i

^ i =RTln i
G
E

It can also be shown that the following hold

GE =RT x i ln i

x i dln i=0 at const , T , P

The first of these equations is used to calculate excess Gibbs enrgies from VLE
data.
The latter is used to test VLE data for thermodynamic consistency.
Fugacities in Liquid Mixtures Empirical Relations.
Empirical equations are often used to fit excess Gibbs free energy as a function of
coposition.

GE
=x1 x 2 [ A21 x 1 + A12 x 2 ]
RT
Margules:

ln 1=x 22 [ A12 +2 ( A 21 A12 ) x1 ]

ln 2=x 21 [ A 21+2 ( A12 A21 ) x 2 ]

Note that the constants are equal to the limiting values of the logrithms of the
activity coefficients for the Margules equations.

GE
=x1 x 2 [ A+ B(x 1x 2) ]
RT
Redlich Kister:

ln 1=?

ln 2=?

Note that this equation is identical to the two-suffix Margules equation:

GE
= A ( x 1+ x 2 ) + B(x 1x 2)
RT x 1 x 2
( A + B ) x 1 +( AB)x 2
A 21= A+ B
A 12= AB

Phase Equilibrium Raults Law.

Consider two phases, vapor and liquid, where the gas phase is a nidal gas mixture,
and the liquid phase is an ideal liquid solution.
The phase equlilibrium relations become
f^ Vi =f Li i=1,2, .. , N
L

P i =f i x i
Assume that the effect of pressure is negligible on the pure liquid fugacity, so that
is can be evaluated at the vapor pressure for component i rather tan at P.

f iL ( P ,T )=f iL (Pisat , T )

Since we are assuming that the gas phase behaves like an ideal gas, and since the
mole fraction of component i is unity.

f iL ( Pisat , T )=f Vi ( Pisat , T )=Pisat

Substituting this above, gives Raoutls Law:

sat

P i =P i x i

Bubble-point pressure problem T, x given P, y

Calculations Using Raoult's

Discuss the P-x-y diagram (Fig. 12.16, p. 445). It represents all possible
bubble and dew points for this system at the T given.
Bubble-point temperature problem - P,x given - T,y unknown.
A trial and error procedure must be followed, where T is assumed, the vapor
pressures calculated, and then see if the correct total pressure is obtained (or the
vapor mole fractions sum to unity).

Discuss the T-x-y diagram (Fig. 12.17, p. 447). It represents all possible dew and
bubble points for this system at the pressure given.
Dew-point pressure problem ~ T,y given P,x unknown.
No trial and error is needed, as P can be directly calculated.

Dew-point
unknown.

temperature

problem

--

P,

given

--

T,

Guess a T, find the vapor pressures, and see if the liquid mole fractions
sum to unity.

Discuss calculation of a y-x diagram for this system at

fixed P. K-values, flash calculations, and relative
volatilities

T, P,
and feed
compositions (Zi s) know. Trial and error for V (fraction to vapor stream). See Sec.

Relative volatility:
12.6 for derivation.
Modified Raoult's Law - Low Pressures

At low pressure, where gases can be considered ideal, it may be necessary to

correct for liquid-phase no idealities, using a "Modified Raoult's Law"

See pp. 449-56 for calculations of various phase equilibrium problems. Activity
coefficients come from experimental data (using empirical equations), or from
estimation techniques, such as the UNIFAC method presented in Append. G.