Phase Equilibrium

Phase equilibrium
BITS Pilani
K K Birla Goa Campus
Prof. Srinivas Krishnaswamy

Department of Chemical Engineering
BITS Pilani
K K Birla Goa Campus
Chemical Engineering
Thermodynamics (CHE C311)
2011 - 2012
Why study phase equilibrium?

Most chemical engineering operations involve transfer of
mass from one phase to another at different pressures
and temperatures
Understanding of these systems is important from
designing and analyzing the same
Knowledge of phase equilibrium and phase equilibrium
data a must
Correlations required for non-ideality and need validation
with experimental data
Our focus will be on vapour liquid equilibrium
BITS Pilani, K K Birla Goa Campus
Criteria for equilibrium

Consider a system placed in surroundings and exchanging
heat with a reservoir at temperature T and producing work
From First law: Q - W (PdV) = dU
From the 2nd law: dS >= dQ/T
dU + PdV TdS <= 0 (General eqm. criteria)
Isolated system, System at constant T and V,
System at constant T and V

At constant V dU TdS <= 0
Now A = U TS
Comparing 1 and 2
dA <= -PdV SdT
dA = dU TdS SdT
dU = dA + TdS + SdT --- 1
dU + PdV TdS <= 0 --- 2
At constant T and V
dAT,V <= 0
For a spontaneous process taking place at constant T and V is

accompanied by decrease in work function or Helmholtz free energy at
equilibrium
System at constant T and P

At constant V dU TdS <= 0
Comparing 3 and 4
Now G = H TS
dG = dH TdS SdT --- 1
dH = dU + PdV + VdP ---- 2
dG <= -VdP SdT

At constant T and P
Substituting 2 in 1
dU = dG PdV VdP + TdS + SdT -- 3
dGT,P <= 0
dU + PdV TdS <= 0 --- 4

For a spontaneous process taking place at constant T and P Gubbs free
energy is minimum at equilibrium
Phase rule for non-reacting

system
Gibbs Phase rule: The minimum number of independent
intensive variables that need to be fixed to define the state
of a system
F=CP+2
At the same temperature and pressure

chemical potential or partial molar free
energy of a component in every phase
must be the same under equilibrium
conditions
Ideal solution
Fugacity of each species in an
ideal solution is proportional to its
mole fraction, where fugacity of
pure species i is a proportionality
constant
Lewis & Randall Rule
Lewis Randall rule applied to

gaseous mixtures
For an ideal gas mixture (solution)
(Daltons Law)
(Amagats Law)
Phase equilibrium in Ideal

solutions
At equilibrium,
But
(Raoults Law)
Constraints
Raoults law: 2 unknowns 1 equation
Antoine equation for

calculating Psat (t in
Celsius and P in torr
T x y plot
The T vs x and y plot presents the temperature

equilibrium relationship for x and y.
Pressure is constant.
One normally
component.
plots
the
more
volatile
T x y plot
Temperature-Composition Diagram
for Ethanol-Water, P = 1 atm
100
95
Superheated Vapor Phase
Two Phase
T( oC)
90
85
80
Subcooled Liquid Phase
75
0.0
0.2
0.4
0.6
0.8
1.0
xEtOH or yEtOH
What does the T x y plot

tell us?
One now has two equilibrium curves a saturated liquid line and
saturated vapor line.
Any point below the saturated liquid line is a single-phase
composition of a sub-cooled liquid no vapor exists.
Any point above the saturated vapor line is a single-phase
composition of a superheated vapor no liquid exists.
Any point between the saturated liquid and saturated vapor lines is a
two- phase composition both vapor and liquid exist in equilibrium.
Thus, one can obtain a lot more information from the T vs. x,y plot
than from the y vs. x
Bubble point and dew point

temperatures
Any point on the saturated liquid line is the point at which the
liquid just begins to boil the first bubble of vapor is formed.
This temperature, for a given composition and pressure, is the
bubble-point temperature.
Any point on the saturated vapor line is the point at which the
vapor just begins to condense the first drop of liquid is
formed.
This temperature, for a given composition and
pressure, is the dew-point temperature.
T x y plot
100
95
Two Phase
T( oC)
90
85
80
75
0.0
0.2
0.4
0.6
0.8
1.0
xEtOH or yEtOH
How to use the T x y plot?

Assume one is given an ethanol-water mixture
concentration of 20% ethanol at P = 1 atm and T = 75oC.
with
Explain what happens as one heats the system to 80oC using the
T vs. x,y plot.
By convention for a feed, designate the mole fraction as xEtOH on
the diagram at 75oC and indicate heating to 80oC.
What is the phase of this mixture at 75oC and what is the phase at
80oC?
Saturated Liquid and Vapor Plot

Heating, xEtOH = 0.2
100
95
T( oC)
Two Phase
90
85
80
75
0.0
z EtOH
0.2
0.4
0.6
xEtOH or yEtOH
0.8
1.0
Solution
Starting with xEtOH = 0.2 at T = 75oC, one has a sub-cooled liquid.
As it is heated, this mixture remains a single-phase liquid until the
saturated liquid line is reached.
Once one reaches the saturated liquid line, the first vapor bubble
appears.
This is known as the Bubble Point Temperature the temperature

at which the mixture begins to boil.
What is the Bubble Point Temperature for a mixture containing
mole fraction xEtOH = 0.2? Indicate the isotherm line on the plot.

Bubble Point Temperature
100
95
Two Phase
T( oC)
90
85
83
80
75
0.0
zEtOH
0.2
0.4
0.6
xEtOH or yEtOH
0.8
1.0
What will be the vapour composition at

bubble point temperature?
What will be the vapor composition of this first bubble at

equilibrium? Indicate the method of determination on the
plot.
Remember that the temperature of the vapor and liquid
phase are the same at equilibrium

1st Vapor Bubble Composition
100
95
Two Phase
T( oC)
90
85
Isotherm
83
80
75
0.0
zEtOH
0.2
0.4
yEtOH
0.6
xEtOH or yEtOH
0.8
1.0
T x y plot
Assume that the mixture is heated further to T = 89oC.
What is the phase of the mixture at T = 89oC?
What are the liquid and vapor phase compositions of the
mixture at T = 89oC?
Indicate your method of determination on the plot.

Heating, xEtOH = 0.2
100
95
T( oC)
Two Phase
90
89
Isotherm
85
80
75
0.0
x EtOH
z EtOH
0.2
y EtOH
0.4
0.6
xEtOH or yEtOH
0.8
1.0
T x y plot
Assume that the mixture is heated further through the two phase
region.
Once one reaches the saturated vapor line, the last liquid drop
disappears.
This is known as the Dew Point Temperature.

Why Dew Point? because the system is reversible. If one
started in the superheated vapor region and cooled, this would be
the temperature at which the mixture begins to condense and the
first liquid drop would form.
What is the Dew Point Temperature, and what will be the liquid
composition of the last liquid drop before it disappears?
Indicate your method of determination on the plot.

Last Liquid Drop Composition
100
95
94.8
Isotherm
T( oC)
90
Two Phase
85
80
75
xEtOH
0.0
zEtOH
0.2
0.4
0.6
xEtOH or yEtOH
0.8
1.0
Phase equilibrium problems
Dew and Bubble Point Calculations

Dew Point Pressure:
Given a vapour composition at a specified temperature, find the composition of
the liquid in equilibrium
Given T, y1, y2,... yn find P, x1, x2, ... xn
Dew Point Temperature:
Given a vapour composition at a specified pressure, find the composition of the
liquid in equilibrium
Given P, y1, y2,... yn find T, x1, x2, ... xn
Bubble Point Pressure:
Given a liquid composition at a specified temperature, find the composition of
the vapour in equilibrium
Given T, x1, x2, ... xn find P, y1, y2,... yn
Bubble Point Temperature:
Given a vapour composition at a specified pressure, find the composition of the
liquid in equilibrium
Given P, x1, x2, ... xn find T, y1, y2,... yn
VLE Calculations - Introduction

For now, we are going to employ these calculations only for identifying
the state and composition of binary and ideal mixtures
As we are going to see later in the course, the aforementioned VLE
calculations are also applicable to non-ideal or/and multi-component
mixtures
The calculations revolve around the use of 2 key equations:
1) Raoults law for ideal phase behaviour:
2) Antoines Equation
sat
i
Pi
yi * P x i * P
sat
i
ln( P ) A i
Bi
T Ci
(1)
(2)
BUBL P Calculation (T, x1 known)

sat
2 from Antoines Equation
and P
- For the vapour-phase composition (bubble) we can write:
y1+y2=1
- Substitute y1 and y2 in Eqn (3) by using Raoults law:
sat
1
- Calculate P
x1 * P1sat
P
x 2 * P2sat
P
x1 * P1sat
P
( 1 x1 )* P2sat
P
(3)
(4)
- Re-arrange and solve Eqn. (4) for P

- Now you can obtain y1 from Eqn (1)
- Finally, y2 = 1 - y1
CHEE 311
Lecture 2
36
DEW P Calculation (T, y1 known)

P1satand P2sat from Antoines Equation
- Calculate
- For the liquid-phase composition (dew) we can write:
x1+x2=1
(5)
- Substitute x1 and x2 in Eqn (5) by using Raoults law:
y1 * P
P1sat
y2 * P
P2sat
y1 * P ( 1 y1 )* P
1
sat
sat
P1
P2
(6)
- Re-arrange and solve Eqn. (6) for P

- Now you can obtain x1 from Eqn (1)
- Finally, x2 = 1-x1
CHEE 311
Lecture 2
37
BUBL T Calculation (P, x1 known)

Since T is an unknown, the saturation pressures for the mixture components
cannot be calculated directly. Therefore, calculation of T, y1 requires an
iterative approach, as follows:
- Re-arrange Antoines equation so that the saturation temperatures
of the components at pressure P can be calculated:
Tisat
Bi
Ci
A i ln( P )
- Select a temperature T so that

- Calculate
T1sat
(7)
T' T2sat
P1sat ( T' ) and P2sat ( T' )
- Solve Eqn. (4) for pressure P

- If
P P'
, then P=P; If not, try another T-value
Calculate y1 from Raoults law
DEW T Calculation (P, y1 known)

Same as before, calculation of T, x1 requires an iterative approach:
- Re-arrange Antoines equation so that the saturation temperatures
of the components at pressure P can be calculated from Eqn. (7):
-Select a temperature T so that
sat
sat
T1
sat
sat
- Calculate P1 ( T' ) and P2 ( T'

- Solve Eqn. (6) for pressure P
- If
P P'
T' T2
from Antoines Eqn.
, then P=P; If not, try another T-value
- Calculate x1 from Raoults law
CHEE 311
Lecture 2
39
Flash calculations
Rearranging Raoults law expression,
Ki is the equilibrium ratio or K
factor of component i
material balance around

the flash drum
Practice Problems
1.
A binary liquid mixture consists of 60 mol per cent ethylene and 40 mol percent
propylene. At 423 K, the vapour pressures of ethylene and propylene are 15.2 atm
and 9.8 atm. Calculate the total pressure and equilibrium composition in the vapour
phase (13.04 atm, 0.7 and 0.3)
2.
The pure component vapour pressure of 2 organic liquids X and Y are given by the
Antoine equation
ln P1sat = 14.35 (2942 / T + 220) and ln P2sat = 14.35 (2960 / T + 210)
where pressures are in kPa and T is in oC. Calculate the composition of liquid and
vapour in equilibrium at 77 oC and 75 kPa (0.69, 0.787)
3.
The vapour pressure of acetone, acetonitrile and nitromethane cane be represented

by Antoine equation and T is in oC. ln P1sat = 14.3916 (2795.82 / T + 230) and ln
P2sat = 14.2724 (2945.47 / T + 224), ln P3sat = 14.2043 (2972.64 / T + 209).
where pressures are in kPa and T is in oC. Assume ideality, find P and y1 at 75 oC,
x1 = 0.3 and x2 = 0.4. Also find P and x1 at T = 80 oC, y1 = 0.45 y2 = 0.35
Practice Problems
1. For a system methanol methyl acetate, the activity coefficients for the components 1 and 2 are
represented by
ln
= Ax22 and ln
= Ax12
ln P1sat = 16.5915 (3643.41 / T 33.424) and ln P2sat = 14.2532 (2665.54 / T 53.424)

Where P is in kPa and T is in K
Calculate P and y1 at T = 318.15 K and x1 = 0.25
(0.282, 0.718)
2. For a binary system at 30 oC, GE/ / RT = 0.625 x1x2. The vapour pressures of 1 and 2 are given by
ln P1sat = 13.7 (3800 / T ) and ln P2sat = 14.01 (3800 / T )
Where P is in kPa and T is in K. Calculate the composition of the azeotrope (0.26)
Henrys law
For a species present as a very
dilute solute in the liquid
phase, the partial pressure
of the species in the vapor
phase is directly proportional
to its liquid-phase mole
fraction:
yi P
xi H i
Henrys law
Limiting law applicable to extremely dilute solutions
Not applicable for solutions where solute and solvent
react
Henrys law is applicable for solute and Raoults is for
solvent over solution
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Phase Equilibrium

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Phase Equilibrium

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Phase equilibrium

Prof. Srinivas Krishnaswamy

Why study phase equilibrium?

BITS Pilani, K K Birla Goa Campus

Criteria for equilibrium

BITS Pilani, K K Birla Goa Campus

System at constant T and V

For a spontaneous process taking place at constant T and V is

BITS Pilani, K K Birla Goa Campus

System at constant T and P

dH = dU + PdV + VdP ---- 2

dG <= -VdP SdT

dU + PdV TdS <= 0 --- 4

BITS Pilani, K K Birla Goa Campus

Phase rule for non-reacting

At the same temperature and pressure

BITS Pilani, K K Birla Goa Campus

Lewis Randall rule applied to