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VAPOR/LIQUID EQUILIBRIUM

CHE 407: ChE Thermodynamics 2

Prof. “Piolo Pascual”, NQE, RChE

OUTLINE
1. The Nature of Equilibrium
2. Duhem’s Theorem
3. Simple Models for VLE
4. VLE by Modified Raoult’s Law
5. VLE from K-value Correlations

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1. The Nature of Equilibrium

• Equilibrium is a static condition in which no
changes occur in the macroscopic properties
of a system with time.
– Eg: An isolated system consisting of liquid & vapor
phase reaches a final state wherein no tendency
exists for change to occur within the system. The
temperature, pressure and phase compositions
reach final values which thereafter remain fixed.

• At microscopic level, conditions are not static.

– Molecules with high velocities near the interface
overcome surface forces and pass into the other
phase.
– But the average rate of passage of molecules is
the same in both directions & no net interphase
transfer of material occurs.

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Measures of Composition
1. Mass fraction: the ratio of the mass of a particular chemical
species in a mixture or solution to the total mass of mixture or
solution.
mi m! i
xi º =
m m!
2. Mole fraction: the ratio of the number of moles of a
particular chemical species in a mixture or solution to the number
of moles of mixture or solution.
ni n!i
xi º =
n n!

Measures of Composition
3. Molar concentration: the ratio of the mole fraction of a
particular chemical species in a mixture or solution to the molar
volume of mixture or solution.
xi n!i n!i = Molar flow rate
Ci º =
V q q= Volumetric flow rate

4. Molar mass of mixture/solution: mole-fraction-

weighted sum of the molar masses of all species present.

M º å xi M i
i

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Similar to phase

2. Duhem’s Theorem rule, but it

considers
extensive state.

• 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.
– Applies to closed systems at equilibrium
– The extensive state and intensive state of system are fixed

F = 2 + Np - pN = 2
No of No of
variables equations

3. SIMPLE MODELS FOR

VAPOR/LIQUID EQUILIBRIUM
• Vapor/liquid equilibrium (VLE): the state of coexistence of
liquid and vapor phase.
• VLE Model: to calculate temperatures, pressures and
compositions of phases in equilibrium.
• The two simplest models are:
– Raoult’s law
– Henry’s law

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3. SIMPLE MODELS FOR

VAPOR/LIQUID EQUILIBRIUM
3.1 Raoult’s Law
• Assumptions:
– The vapor phase is an ideal gas (low to moderate pressure)
– The liquid phase is an ideal solution (the system are chemically similar)
*Chemically similar: the molecular species are not too different in size
and are of the same chemical nature.
eg: n-hexane/n-heptane, ethanol/propanol, benzene/toluene

yi P = xi Pi sat (i = 1,2..., N )
xi Liquid phase mole fraction Pi sat Vapor pressure of pure species i at
system temperature
yiVapor phase mole fraction

Pxy Diagram

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3.2 Dewpoint & Bubblepoint

Calculations with Raoult’s Law
yi P = xi Pi sat
4 Calculations
• 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

If the vapor-phase composition is unknown, åy i i = 1 may be assumed; thus

P= åx P
i
i i
sat
For bubble point calculation

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3.2 Dewpoint & Bubblepoint

Calculations with Raoult’s Law
yi P = xi Pi sat

If the liquid-phase composition is unknown, åxi i = 1 may be assumed; thus

1
P= For dew point calculation
å i
yi / Pi sat

3.2.1 BUBL P CALCULATION

(Calculate {yi} and P, given {xi} and T)

Find P1sat &

P2sat using
Find P Calculate yi
Antoine
equation

P= åx P
i
i i
sat
yi P = xi Pi sat

P = x1 P1sat + x2 P2sat y1 P = x1 P1sat

x1 P1sat
P=xP 1 1
sat
+ (1- x1 )P 2
sat
y1 =
P
(
P = P2sat + P1sat - P2sat x1 )

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Example 1
Binary system acetronitrile (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 / kPa = 14.2724 -
t / °C + 224.00

2972.64
ln P2sat / kPa = 14.2043 -
t / °C + 209.00
Prepare a graph showing P vs. X1 and P vs. Y1 for a temperature
of 75°C.

3.2.1 BUBL P CALCULATION

(Calculate {yi} and P, given {xi} and T)
Find P1sat &
P2sat using
Find P Calculate yi
Antoine
equation
At 75°C, by Antoine Equations,

2945.47
ln P1sat / kPa = 14.2724 -
75°C + 224.00
P1sat = 83.21kPa

2972.64
ln P2sat / kPa = 14.2043 -
75°C + 209.00
P2sat = 41.98kPa

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3.2.1 BUBL P CALCULATION

(Calculate {yi} and P, given {xi} and T)

Find P1sat &

P2sat using
Find P Calculate yi
Antoine
equation

(
P = P2sat + P1sat - P2sat x1 )
P = 41.98 + (83.21 - 41.98)x1
Taking at any value of x1, say x1=0.6,
P = 41.98 + (83.21 - 41.98)(0.6 )
= 66.72kPa

3.2.1 BUBL P CALCULATION

(Calculate {yi} and P, given {xi} and T)

Find P1sat &

P2sat using
Find P Calculate yi
Antoine
equation
x1 P1sat
y1 =
P
0.6(83.21)
= = 0.7483
66.72

At 75°C, a liquid mixture of 60 mol-% acetonitrile and 40 mol-%

nitromethane is in equilibrium with a vapor containing 74.83 mol-%
acetonitrile at a pressure of 66.72 kPa

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P-x-y Diagram
To draw P-x-y graph, repeat the calculation with different values of x;

x1 y1 P/kPa
0.0 0.0000 41.98
0.2 0.3313 50.23
0.4 0.5692 58.47
0.6 0.7483 66.72
0.8 0.8880 74.96
1.0 1.0000 83.21

P x y diagram for acetonitrile/nitromethane at 75°C as given by

Raoult’s law
100
T= 75°C P1sat = 83.21

80

Subcooled liquid

60
P-x 1
P/kPa

P-y 1
40

P2sat = 41.98
20
Superheated vapor

0
0 0.2 0.4 0.6 0.8 1
x1, y1

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P x y diagram for
acetonitrile/nitromethane at 75°C as Point a is a subcooled
given by Raoult’s law liquid mixture of 60 mol-
100 % acetonitrile and 40
T= 75°C P1sat = 83.21 mol-% of nitromethane
at 75°C.
a
80 Subcooled liquid Point b is saturated
b liquid.
b'
60 c’ Points lying between b
c
P-x 1 and c are in two phase
P/kPa

d region, where saturated

P-y 1 liquid and saturated
40
vapor coexist in
equilibrium.
P2sat = 41.98
20 Saturated liquid and
Superheated vapor saturated vapor of the
pure species coexist at
vapor pressure P1sat and
0
P2sat
0 0.2 0.4 0.6 0.8 1
x1, y1

P x y diagram for
acetonitrile/nitromethane at 75°C as
given by Raoult’s law
100 Point b: bubblepoint
T= 75°C P1sat = 83.21
P-x1 is the locus of
a bubblepoints
80 Subcooled liquid
b As point c is approached,
b' the liquid phase has
60 c’
c almost disappeared, with
P-x 1 only droplets (dew)
P/kPa

d remaining.
P-y 1
40
Point c: dewpoint
P2sat = 41.98 P-y1 is the locus of
20 dewpoints.
Superheated vapor

0
0 0.2 0.4 0.6 0.8 1
x1, y1

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P x y diagram for
acetonitrile/nitromethane at 75°C as
given by Raoult’s law
100
T= 75°C P1sat = 83.21
a
80 Subcooled liquid
Once the dew has
b evaporated, only
b' saturated vapor at point
60 c’
c c remains.
P-x 1
P/kPa

d
Further pressure
P-y 1 reduction leads to
40
superheated vapor at
P2sat = 41.98 point d

20
Superheated vapor

0
0 0.2 0.4 0.6 0.8 1
x1, y1

3.2.2 DEW P CALCULATION

(DEW P : Calculate {xi} and P, given {yi} and T)
100 What is x1 & P
T= 75°C P1sat = 83.21 at point c’?
a
80 Subcooled liquid
Step 1: Calculate P
b 1
b' P=
60 c’
c y1 / P1 + y2 / P2sat
sat

P-x 1 1
P/kPa

d =
P-y 1 0.6 / 83.21 + 0.4 / 41.98
40
= 59.74kPa
P2sat = 41.98
20
Step 2: Calculate x1
y P
Superheated vapor x1 = 1sat
P1
0 0.6(59.74 )
0 0.2 0.4 0.6 0.8 1 =
83.21
x1, y1 = 0.4308

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3.2.2 DEW P CALCULATION

(DEW P : Calculate {xi} and P, given {yi} and T)

Find P from Raoult’s

Law assuming Calculate xi
å i
xi = 1

1 yi P = xi Pi sat
P=
å i
yi / Pi sat
y1 P = x1 P1sat
1 y1 P
P= x1 =
y1 / P 1
sat
+ y2 / P2sat P1sat

T-x-y Diagram
Find P1sat
Find T1sat
& P2sat
& T2sat
using T Calculate Calculate
using
btween xi yi
Antoine
T1sat &
equation
T2sat

Bi yi P = xi Pi sat
Ti sat = - Ci
Ai - ln P P= åx P
i
i i
sat

y1 P = x1 P1sat
P = x1 P1sat + x2 P2sat x1 P1sat
y1 =
P = x1 P1sat + (1- x1 )P2sat P

(
P = P2sat + P1sat - P2sat x1 )
P - P2sat
x1 =
(
P1sat - P2sat )

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Example 2
Binary system acetronitrile (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 / kPa = 14.2724 -
t / °C + 224.00

2972.64
ln P2sat / kPa = 14.2043 -
t / °C + 209.00
Prepare a graph showing T vs. X1 and T vs. Y1 for a pressure of
of 70kPa.

T-x-y Diagram
Find P1sat
Find T1sat
& P2sat
& T2sat
using T Calculate Calculate
using
btween xi yi
Antoine
T1sat &
equation
T2sat

Bi
Ti sat = - Ci
Ai - ln P

2945.47
T1sat = - 224 = 69.84°C
14.2724 - ln 70

2972.64
T2sat = - 209 = 89.58°C
14.2043 - ln 70

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T-x-y Diagram
Find P1sat
Find T1sat
& P2sat
& T2sat
using T Calculate Calculate
using
btween xi yi
Antoine
T1sat &
equation
T2sat

T1sat = 69.84°C, T2sat = 89.58°C

Let T=78°C,
2945.47 2972.64
ln P1sat / kPa = 14.2724 - ln P2sat / kPa = 14.2043 -
78°C + 224.00 78°C + 209.00
P1sat = 91.76kPa P2sat = 46.84kPa

T-x-y Diagram
Find P1sat
Find T1sat
& P2sat
& T2sat
using T Calculate Calculate
using
btween xi yi
Antoine
T1sat &
equation
T2sat

P1sat = 91.76kPa, P2sat = 46.84kPa

P - P2sat
x1 =
(
P1sat - P2sat )
70 - 46.84
= = 0.5156
91.76 - 46.84

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T-x-y Diagram
Find P1sat
Find T1sat
& P2sat
& T2sat
using T Calculate Calculate
using
btween xi yi
Antoine
T1sat &
equation
T2sat

P1sat = 91.76kPa, x = 0.5156

x1 P1sat
y1 =
P
0.5156(91.76 )
= = 0.6759
70

T-x-y Diagram
To draw T-x-y graph, repeat the calculation with different values of T;

x1 y1 T/°C
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)

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T x y diagram for acetonitrile/nitromethane at 70 kPa as

given by Raoult’s law
90

T-y
85 1 Superheated vapor

T-x
1 T1sat = 69.84°c
80
T2sat = 89.58°C
T/°C

75 Subcooled liquid

70

65
0 0.2 0.4 0.6 0.8 1
x1, y1

3.2.3 BUBL T CALCULATION

(Calculate {yi} and T, given {xi} and P)
90
Superheated vapor
T-y
85
What is y1 and T
1
T-x
1 T1sat = 69.84°c
80 T2sat = 89.58°C c
at point b’
c’
(with x1=0.6 and
T/°C

b b'
75 P= 70 kPa)?
Subcooled liquid
70

65
0 0.2 0.4 0.6 0.8 1
x1, y1

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3.2.3 BUBL T CALCULATION

(Calculate {yi} and T, given {xi} and P)

Find T using
Repeat step
Antoine eq Find P1sat &
Find new α 1 by using
Start with & find y1
by new α until
α=1, find substitute using
substituting similar
P2sat P2sat Raoult’s
T value of α
obtained in law
is obtained
step 1
B
T= -C
A - ln P2sat
P = x1 P1sat + x2 P2sat
2972.64
P x1 P1sat = - 209.00
= + x2 14.2043 - ln P2sat
P2sat P2sat 2945.47 2972.64
ln a = 0.0681 - +
P sat t + 224.00 t + 209.00
a = 1sat
P2
P The substraction of ln P1sat & P2sat from
P2sat = Antoine Equation
x1a + x2

3.2.3 BUBL T CALCULATION

(Calculate {yi} and T, given {xi} and P)
Find T using
Repeat step
Antoine eq Find P1sat &
Find new α 1 by using
Start with & find y1
by new α until
α=1, find substitute using
substituting similar
P2sat P2sat Raoult’s
T value of α
obtained in law
is obtained
step 1
Iteration 1 Iteration 3
P1sat = aP2sat
a =1 a = 1.96
P2sat = 70kPa P2sat = 44.41kPa = 1.97(44.24 )
T = 89.58°C T = 76.53°C = 87.17 kPa
a = 1.88 a = 1.97
x1 P1sat
y1 =
Iteration 2 Iteration 4 P
a = 1.88 a = 1.97 0.6(87.17 )
sat
= 44.24kPa =
P 2
sat
= 45.81kPa P 2 70
T = 77.38°C T = 76.43°C = 0.7472
a = 1.96 a = 1.97

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3.2.4 DEW T CALCULATION

(Calculate {xi} and T, given {yi} and P)
90
Superheated vapor
T-y
85
What is x1 and T
1
T-x
1 T1sat = 69.84°c
80
T2sat = 89.58°C
c
at point c’
c’
(with y1=0.6 and
T/°C

b b'
75 P= 70 kPa)?
Subcooled liquid
70

65
0 0.2 0.4 0.6 0.8 1
x1, y1

3.2.4 DEW T CALCULATION

(Calculate {xi} and T, given {yi} and P)

Find T using
Repeat step
Antoine eq
Find new α 1 by using
Start with & by new α until
α=1, find substitute Find x1
substituting similar
P1sat P1sat
T value of α
obtained in
is obtained
step 1

B
1 T= -C
P= A - ln P1sat
y1 P1sat + y2 P2sat
2945.47
P1sat = - 224.00
P= 14.2724 - ln P1sat
(
y1 + P1sat P2sat y2 )
Psat
2945.47 2972.64
a = 1
ln a = 0.0681 - +
P
2
sat
t + 224.00 t + 209.00
P1sat = P( y1 + y2a )

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3.3 Henry’s Law

• Used for a species whose critical temperature
is less than the temperature of application, in
which Raoult’s Law could not be applied (since
Raoult’s Law requires a value of Pisat).

yi P = xi H i
Where Hi is Henry’s constant and obtained from experiment.

4. VLE by Modified Raoult’s Law

• Used when the liquid phase is not an ideal
solution.

yi P = xig i Pi
sat

Where ɣi is an activity coefficient

(deviation from solution ideality in liquid phase).

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4. VLE by Modified Raoult’s Law

• For bubblepoint calculation, (assuming åi yi = 1 )

P= åxg i
i i Pi sat

• For dewpoint calculation, (assuming åi xi = 1 )

1
P=
åyi
i g i Pi sat

5. VLE from K-value Correlations

• Equilibrium ratio, Ki
y
Ki = i
xi
• When Ki > 1, species exhibits a higher
concentration of vapor phase

• When Ki < 1, species exhibits a higher

concentration of liquid phase (is considered as heavy
constituent.)

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5. VLE from K-value Correlations

• K value for Raoult’s Law
yi Pi sat
Ki = = since yi P = xi Pi sat
xi P

• K value for modified Raoult’s Law

g i Pi sat
Ki = since yi P = xi g i Pi sat
P

5. VLE from K-value Correlations

• For bubblepoint calculations, åi yi = 1
y
Ki = i
xi
åi K i xi = 1

• For dewpoint calculations åi xi = 1

yi yi
Ki =
xi åK
i
=1
i

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Example
For a mixture of 10 mol-% methane, 20 mol-%
ethane, and 70 mol-% propane at 50°F, determine:

(a) The dewpoint pressure

(b) The bubblepoint pressure

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

ethane, and 70 mol-% propane at 50°F,
determine:

(a) The dewpoint pressure

When the system at its dewpoint, only an insignificant amount
of liquid is present.
Thus 10 mol-% methane, 20 mol-% ethane, and 70 mol-%
propane are the values of yi.
yi
assuming, åxi i = 1 thus,
åK =1
i i

yi
By trial, find the value of pressure that satisfy åK
i
=1
i

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

ethane, and 70 mol-% propane at 50°F,
determine: (a) The dewpoint pressure
Species yi P=100psia P=150psia P=126psia
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

åy i K i = 0.828 åy i K i = 1.174 åy
i
i K i = 1.000
i i

Thus, the dewpoint pressure is 126 psia.

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

ethane, and 70 mol-% propane at 50°F,
determine:

(b)The bubblepoint pressure

assuming åi yi = 1 , thus

åK x
i
i i =1

By trial, find the value of pressure that satisfy åK x

i
i i =1

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

ethane, and 70 mol-% propane at 50°F,
determine: (b) The bubble point pressure
Species xi P=380psia P=400psia P=385psia
Ki Kixi Ki Kixi Ki Kixi
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

åK x i i = 1.017 åK x i i = 0.963 åK x
i
i i = 1.000
i i

Thus, the bubblepoint pressure is 385 psia.

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