Академический Документы
Профессиональный Документы
Культура Документы
Introduction
ERT 206: Thermodynamics
Miss Anis Atikah Ahmad
Email: anis atikah@unimap.edu.my
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
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.
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
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 ni
xi
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 ni ni Molar flow rate
Ci
V q q Volumetric flow rate
M xi M i
i
Similar to phase
F 2 N N 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
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
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
P i i
x
i
P sat
For bubble point calculation
3.2 Dewpoint & Bubblepoint
Calculations with Raoult’s Law
yi P xi Pi sat
1
P For dew point calculation
i
yi / Pi sat
3.2.1 BUBL P CALCULATION
(Calculate {yi} and P, given {xi} and T)
P i i
x
i
P sat
yi P xi Pi sat
PxP 1 1
sat
x2 P
2
sat y1 P x1 P1sat
x1 P1sat
PxP 1 1
sat
1 x1 P 2
sat
y1
P
P P2sat P1sat P2sat x1
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 P sat
/ kPa 14.2724
t / C 224.00
1
2972.64
ln P sat
/ kPa 14.2043
t / C 209.00
2
2945.47
ln Psat
/ kPa 14.2724
75C 224.00
1
P1sat 83.21kPa
2972.64
ln P sat
/ kPa 14.2043
75C 209.00
2
P2sat 41.98kPa
3.2.1 BUBL P CALCULATION
(Calculate {yi} and P, given {xi} and T)
P P2sat P1sat P2sat x1
P 41.98 83.21 41.98x1
Taking at any value of x1, say x1=0.6,
P 41.98 83.21 41.980.6
66.72kPa
3.2.1 BUBL P CALCULATION
(Calculate {yi} and P, given {xi} and T)
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/kPa
40
P2sat = 41.98
20
Superheated vapor
0
0 0.2 0.4 0.6 0.8 1
x1, y1
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'
c’ Points lying between b
60 c
and c are in two phase
P/kPa
d remaining.
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
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
c’
60 c c remains.
P/kPa
d
Further pressure
40 reduction leads to
superheated vapor at
point d
P2sat = 41.98
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 / P1sat y2 / P2sat
1
P/kPa
d
0.6 / 83.21 0.4 / 41.98
40
59.74kPa
P2sat = 41.98
20
Step 2: Calculate x1
y1 P
Superheated vapor x1
P1sat
0 0.659.74
0 0.2 0.4 0.6 0.8 1
83.21
x1, y1 0.4308
3.2.2 DEW P CALCULATION
(DEW P : Calculate {xi} and P, given {yi} and T)
1 yi P xi Pi sat
P
i
yi / Pi sat
y1 P x1 P1sat
1
P x1
y1 P
y1 / P1sat 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
sat
Bi
Ci yi P xi Pi sat
i i
Ti
Ai ln P P x P sat
i y1 P x1 P1sat
P x1P1sat x2 P2sat x1 P1sat
y1
P x1P1sat 1 x1 P2sat P
P P2sat P1sat P2sat x1
P P2sat
x1
P1sat P2sat
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 P sat
/ kPa 14.2724
t / C 224.00
1
2972.64
ln P sat
/ kPa 14.2043
t / C 209.00
2
Bi
Ti sat Ci
Ai ln P
2945.47
T1sat 224 69.84C
14.2724 ln 70
2972.64
T2sat 209 89.58C
14.2043 ln 70
T-x-y Diagram
Find P1sat
Find T1sat
& P2sat
& T2sat
using T Calculate Calculate
using
btween xi yi
Antoine
T1sat &
equation
T2sat
P P2sat
x1
P1sat P2sat
70 46.84
0.5156
91.76 46.84
T-x-y Diagram
Find P1sat
Find T1sat
& P2sat
& T2sat
using T Calculate Calculate
using
btween xi yi
Antoine
T1sat &
equation
T2sat
x1 P1sat
y1
P
0.515691.76
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)
T x y diagram for acetonitrile/nitromethane at 70 kPa as
given by Raoult’s law
90
85 Superheated vapor
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
85
What is y1 and T
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
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 x1P1sat x2 P2sat
2972.64
P x1P1sat 209.00
sat x2 14.2043 ln P2 sat
sat
P2 P2 2945.47 2972.64
ln 0.0681
P1sat t 224.00 t 209.00
sat
P2
P The substraction of ln P1sat & P2sat from
P2
sat
Antoine Equation
x1 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 P2sat
1 1.96
P2sat 70kPa P2sat 44.41kPa 1.9744.24
T 89.58C T 76.53C 87.17kPa
1.88 1.97
x1 P1sat
y1
Iteration 2 Iteration 4 P
1.88 1.97 0.687.17
P2sat 44.24kPa
P2sat 45.81kPa 70
T 77.38C T 76.43C 0.7472
1.96 1.97
3.2.4 DEW T CALCULATION
(Calculate {xi} and T, given {yi} and P)
90
Superheated vapor
85
What is x1 and T
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
Psat
224.00
P 14.2724 ln P1
y
1 sat
y1 P 1
sat
P2
sat
2
yi P xi 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 xi i Pi
sat
P x
i
i i Pi sat
assuming, i xi 1 thus,
yi
1
i Ki
yi
By trial, find the value of pressure that satisfy
i Ki
1
For a mixture of 10 mol-% methane, 20 mol-%
Example 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
y i K i 0.828 y i K i 1.174 y
i
i K i 1.000
i i
assuming i yi 1 , thus
K x
i
i i 1
K x i i 1.017 K x i i 0.963 K x
i
i i 1.000
i i