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# The nature of equilibrium

## The phase rule: Duhems Theorem

VLE: Qualitative behavior
Simple models for vapor-liquid equilibrium
VLE by modified Raoults law
VLE from K-value correlations
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.

The Nature of Equilibrium
Measures of Composition
Most common measures of composition are mass
fraction, mole fraction and molar concentration

Mass or mole fraction is defined as the ratio of
mass or number of moles of a particular chemical
species in a mixture or solution to the total mass
or number of moles of mixture or solution:

-
-
=
m
m
m
m
x
i i
i -
-
=
n
n
n
n
x
i i
i
V
x
C
i
i

q
n
C
i
i
-
=
Molar concentration is defined as the ratio of mole
fraction of a particular chemical species in a mixture
or solution to molar volume of the mixture of solution

For flow process, gives the expression as a ratio of
rates:

where is the molar flow rate of species i, and q is the volumetric flow
rate.
n
-
moles of i
per unit
volume
The molar mass of a mixture or solution : mole
fraction-weighted sum of the molar masses of all
species

i
i i
M x M
The Phase Rule: Duhems Theorem
The no. of variables that may be independently fixed in a
system at equilibrium is the difference between total no. of
variables that characterize the intensive state of the system
and the no. of independent equations.
The intensive state of a PVT system containing N chemical
species and phases in equilibrium is characterize by the
intensive variables, temperature T, pressure P, and N1
mole fractions for each phase.
No. of phase-rule variables : 2 + (N-1)()
- masses of the phases are not phase-rule variable (no influence on intensive state of system)
No. of independent phase equilibrium equations : (1)(N)
Degree of freedom of the system, F
F = 2 + (N 1)() (1)(N)
Upon reduction, the phase rule becomes
F = 2 + N

Duhems theorem
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 : 2 + (N-1)t
Extensive phase rule variable (masses or mole no. of the phases) :
t
Total number of variables : 2 + (N-1)t + t = 2 + Nt
If the system is closed and formed from specified
amounts of each species,
No. of independent phase equilibrium equations: (t1)(N)+N =
tN
The difference between the no. of variables and the no.
of equations,
2 + NttN = 2

Duhems 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.
VLE: Qualitative Behavior
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- t + N = 2- t + 2 =4 - t
Because there must at least one phase (t = 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.

3D diagram: surfaces for VLE
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-x
1
]

Under surfaces contains sat. vapor
states [P-T-y
1
]

Surfaces intersect along the line
RKAC
1
& UBHC
2
: vapor P vs. T
curves for pure species 1 and 2
Rounded surfaces between C
1
and C
2
:
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

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.

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
-y
1

phase diagram at constant T
T
a
~ AEDBLA
Horizontal lines ~ tie line connecting
the compositions of phases in
equilibrium
T
b
and T
d
lie between two pure
species critical temperatures, T
c

identified by C
1
and C
2
.
Horizontal plane perpendicular to P axis
KJIHLK
The lines on this plane form T-x
1
-y
1

phase diagram at constant P
P
a
~ KJIHLK
P
b
~ lies between the critical
pressures, P
c
of two pure species at
point C
1
and C
2
P
d
~ above critical pressure, P
c
of
two pure species

Vertical & perpendicular to
composition axis SLMN and Q
UC
2
and RC
1
: 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.

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.

Fig. 10.4 shows the enlarged nose
section of a single P-T loop
Critical point at C
Point of maximum pressure ~ M
p
Point of maximum temperature~ M
T

Interior dashed curved ~ liquid
fraction in a two phase mixture

Pressure reduction along line BD ~
vaporization of liquid from
bubblepoint to dewpoint

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

Fig. 10.5: P-T diagram for typical mixtures
of non-polar substances such as
hydrocarbon. The P-T diagram for the
ethane/n-heptane system.

Fig. 10.6: y
1
-x
1
diagram of ethane/n-
heptane for several pressure.

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

Fig. 10.8 and Fig. 10.9: Display common types of P-x-y and t-x-y behavior at
condition well removed from the critical region

Explanation: Refer page 345-347
Fig. 10.10: The y
1
-x
1
diagrams at constant P four systems

Simple Models for Vapor/Liquid Equilibrium
Goal thermodynamics applied in VLE: To find the
temperatures, pressures and compositions of phases in
equilibrium.

Therefore, we need models for the behavior of systems
in vapor/liquid equilibrium

Two simplest:
Raoults Law
System at low to moderate pressures and only
for systems comprised of chemically similar
species.
Henrys Law
For any species present at low concentration
and limited to systems at low to moderate
pressures.

Raoults 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 Raoults Law:

10.1 Eq. ) 1,2,..., ( N i P x P y
sat
i i i
= =
system the of temp. at the species pure of pressure phase vapor
fraction mole phase vapor
fraction mole phase liquid
where;
i
sat
i
P
i
y
i
x
=
=
=
Dewpoint and Bubblepoint Calculations With Raoults Law
Because
i
y
i
= 1, Eq. (10.1) may be summed over all
species to yield

This equation applied in bubblepoint calculations, where
the vapor-phase composition is unknown.

For a binary system with x
2
= 1 x
1
,

10.2 Eq.

=
i
sat
i i
P x P
( )
1 2 1 2
x P P P P
sat sat sat
+ =
( )
1 2 1 2
2 1
1
1 1
2 2 1 1
x
sat
P
sat
P
sat
P P
sat
)P x (
sat
P x P
sat
P x
sat
P x P
+ =
+ =
+ =
P vs. x
1
at constant T straight line
connecting
P
2
sat
at x
1
=0 to P
1
sat
at x
1
=1
Equation (10.1) may also be solved for x
i
and summed
over all species. With
i
x
i
= 1, this yield

This equation applied in dewpoint calculations, where
the liquid-phase composition is unknown.

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

10.3 Eq.

1
sat
i
i
i
P y
P

=
i
i
sat
i
C K T
B
A kPa P
+
=
) (
) ( ln
Dew Point Pressure:
Given a vapor composition at a specified temperature,
find the composition of the liquid in equilibrium
Given T, y
1
, y
2
,... y
n
find P, x
1
, x
2
, ... x
n

Dew Point Temperature:
Given a vapor composition at a specified pressure,
find the composition of the liquid in equilibrium
Given P, y
1
, y
2
,... y
n
find T, x
1
, x
2
, ... x
n

Bubble Point Pressure:
Given a liquid composition at a specified temperature,
find the composition of the vapor in equilibrium
Given T, x
1
, x
2
, ... x
n
find P, y
1
, y
2
,... y
n

Bubble Point Temperature:
Given a liquid composition at a specified pressure,
find the composition of the vapor in equilibrium
Given P, x
1
, x
2
, ... x
n
find T, y
1
, y
2
,... y
n

Example 1
Binary system acetonitrile(1)/nitromethane(2) conforms
closely to Raoults law. Vapor pressures for the pure
species are given by the following Antoine equations:
15 . 64
64 . 2972
2043 . 14 ln
15 . 49
47 . 2945
2724 . 14 ln
2
1

=

=
T
P
T
P
sat
sat
a) Prepare a graph showing P vs. x
1
and P vs. y
1
for
a temperature of 75
o
C (348.15K).

b) Prepare a graph showing t vs. x
1
and t vs. y
1
for a
pressure of 70kPa.
Solution (a)
BUBL P calculations

1) Calculate P
1
sat
and P
2
sat
using Antoine equations
At 384.15K (75
o
C), P
1
sat
= 83.21kPa and P
2
sat
= 41.98kPa
2) Calculate P using equation for binary system:

3) Lets x
1
= 0.6,

4) Calculate value of y
1
using Raoults Law expression:

( )
1 2 1 2
x P P P P
sat sat sat
+ =
( ) kPa P 72 . 66 6 . 0 98 . 41 21 . 83 98 . 41 = + =
7483 . 0
72 . 66
) 21 . 83 )( 6 . 0 (
1 1
1
= = =
P
P x
y
sat
It means that at 75C (348.15K), a liquid mixture of 60mole%
acetonitrile and 40mole% nitromethane is in equilibrium with a
vapor containing 74.83mole% acetonitrile at a pressure of
66.72kPa.
DEW P calculations

1) Calculate P using Eq. 10.3:

2) Lets y
1
= 0.6 (at point c) and T = 348.15K, calculate P :

3) Calculate value of x
1
using Raoults Law expression:

sat sat
P y P y
P
2 2 1 1
1
+
=
kPa P 74 . 59
98 . 41 4 . 0 21 . 83 6 . 0
1
=
+
=
4308 . 0
21 . 83
) 74 . 59 )( 6 . 0 (
1
1
1
= = =
sat
P
P y
x
Liquid phase
composition at point c
The results of calculations for 75
o
C (348.15K) at a number of values of x
1
:
x
1
y
1
P(kPa)
0.0 0.0000 41.98
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
0.6 0.7483 66.72
0.7 0.8222 70.84
0.8 0.8880 74.96
0.9 0.9469 79.09
1.0 1.0000 83.21
States of sat. liquid
States of sat. vapor
Two phase region: sat.liq &
sat. vapor coexist in
equilibrium
States in calculation:
X
1
=0.6,P=66.72kPa, y
1
=0.7483
Bubblepoint
Locus of bubblepoint
Dewpoint
Locus of dewpoint
Solution (b)
1) Calculate T
1
sat
and T
2
sat
at the given pressure using Antoine
equations

For P = 70kPa, T
1
sat
/ t
1
sat
= 342.99K/69.84C and T
2
sat
/ t
2
sat
= 362.73K/89.58C

2) Select T
1
sat
<T<T
2
sat
, calculate P
1
sat
and P
2
sat
for these
temperature. For example take T = 78
o
C (351.15K),
At 351.15K (78
o
C), P
1
sat
= 91.76kPa and P
2
sat
= 46.84kPa

3) Lets evaluate x
1
using equation for binary system:

4) Calculate value of y
1
using Raoults Law expression:

i
i
i
sat
i
C
P A
B
T

=
ln
5156 . 0
84 . 46 76 . 91
84 . 46 70
2 1
2
1
=

=
sat sat
sat
P P
P P
x
6759 . 0
70
) 76 . 91 )( 5156 . 0 (
1 1
1
= = =
P
P x
y
sat
The results of this and similar calculations for P = 70kPa are as follows:
x
1
y
1
t (C)
1.0000 1.0000 69.84
0.8596 0.9247 72
0.7378 0.8484 74
0.6233 0.7656 76
0.5156 0.6759 78
0.4142 0.5789 80
0.3184 0.4742 82
0.2280 0.3614 84
0.1424 0.2401 86
0.0613 0.1098 88
0.0000 0.0000 89.58
States of sat. liquid
States of sat. vapor
Two phase region: sat.liq &
sat. vapor coexist in
equilibrium
Bubblepoint
Locus of bubblepoint
Dewpoint
Locus of dewpoint
Bubl T calculations
For x
1
= 0.6 and P = 70kPa, T is determine by iteration.
Equation (10.2) is written as

Subtract ln P
2
sat
from ln P
1
sat
as given by Antoine equations yield

Iterate as follow:
With the current value of o (found for an arbitrary intermediate T)
calculate P
2
sat
by using Eq. (B)
Calculate t from Antoine equation for species 2:

Find a new value of o by using Eq.(C)
Return to initial step and iterate to convergence for a final value of t

The result is t = 76.42
o
C (349.57K). From Antoine equation, P
1
sat
=87.17
kPa and by Eq. (10.1), y
1
= 0.7472
(B) Eq.
2 1
where
2 1
2
sat
P
sat
P
x x
P
P
sat
=
+
= o
o
(C) Eq.
00 . 209
64 . 2972
00 . 224
47 . 2945
0681 . 0 ln
+
+
+
=
t t
o
00 . 209
ln 2043 . 14
64 . 2972
2

=
sat
P
t
Dew T calculations
With o P
1
sat
/P
2
sat
, Eq. (10.3) is written as

The iteration steps are as before, but are based on P
1
sat
, with

The result is t=79.58
o
C (352.73K). From Antoine equation, P
1
sat
=
96.53kPa and from Eq. (10.1), x
1
= 0.4351

) (
2 1 1
o y y P P
sat
+ =
00 . 224
ln 2724 . 14
47 . 2945
1

=
sat
P
t
EXERCISE
Assuming the validity of Raoults law, do the following
calculation for the benzene (1)/toluene (2) system.

a) Given x
1
=0.33 and T=100C(373.15K), find y
1
and P
b) Given y
1
=0.33 and T=100C(373.15K), find x
1
and P
c) Given x
1
=0.33 and P=120kPa, find y
1
and T
d) Given y
1
=0.33 and P=120kPa, find x
1
and T