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ERT 206/4 THERMODYNAMICS

SEM 1 (2012/2013)

VAPOR LIQUID
EQUILIBRUIM
Dr. Hayder Kh. Q. Ali
hayderali@unimap.edu.my
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The Nature of Equilibrium


The Phase rule.
VLE Quantitative Behavior
Raoults Law
VLE by Modified Raoults Law

In this chapter we first discuss the nature of equilibrium, and then


consider two rules that give the number of independent variables required
to determine equilibrium states.
Then a qualitative discussion of vapor/liquid phase behavior.
Introduce the simplest formulations
temperatures,

pressures,

and

that

allow

phase compositions

calculation
for

systems

of
in

vapor/liquid equilibrium. The first, known as Raoult's law, is valid only


for systems at low to moderate pressures and in general only for systems
comprised of chemically similar species.
A modification of Raoult's law that removes the restriction to chemically
similar species is treated.
Finally the calculations based on equilibrium ratios or K-values are
considered.
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Phase equilibrium
Application
Distillation, absorption, and extraction bring
phases of different composition into contact.

Both the extent of change and the rate of


transfer depend on the departure of the
system from equilibrium.
Quantitative treatment of mass transfer
the equilibrium T, P, and phase
compositions must be known.
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The nature of equilibrium


A static condition in which no changes
occur in the macroscopic properties of a
system with time.
At the microscopic level, conditions are not
static.
The average rate of passage of molecules is
the same in both directions, and no net
interphase transfer of material occurs.

An isolated system consisting of liquid and


vapor phases in intimate contact
eventually reaches a final state wherein no
tendency exists for change to occur within
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the system.

Phase rule vs. Duhems


theorem

(The number of variables that is independently


fixed in a system at equilibrium) = (the number of
variables that characterize the intensive state of
the system) - (the number of independent
equations connecting
F 2 ( N 1)(the
) variable):
( 1)( N ) 2 N
Phase rule:
F 2 ( N 1)( ) ( 1)( N ) N 2

Duhems rule:
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.
Two ? When phase rule F = 1, at least one of the two
variables must be extensive, and when F = 0, both must
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be extensive.

VLE: QUALITATIVE BEHAVIOR


Vapor/Liquid equilibrium (VLE) is the state of coexistence of liquid and
vapor phases. In this qualitative discussion, we limit consideration to systems
comprised of two chemical species, because systems of greater complexity
cannot be adequately represented graphically.
When N = 2, the phase rule becomes F = 4 - . Since there must be at least
one phase ( = 1), the maximum number of phase-rule variables which must be
specified to fix the intensive state of the system is three: namely, P, T, and
one mole (or mass) fraction. All equilibrium states of the system can therefore
be represented in three dimensional P-T- composition space. Within this space,
the states of pairs of phases coexisting at equilibrium (F = 4 - 2 = 2) define
surfaces. A schematic three-dimensional diagram illustrating these surfaces for
VLE is shown in Fig. below:
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This figure shows schematically the P-T-composition surfaces


which contain the equilibrium states of saturated vapor and
saturated liquid for a binary system:
The under surface contains the saturated-vapor states; it is
the P-T-yl surface.
The upper surface contains the saturated-liquid states; it is
the P-T-xl surface.
These surfaces intersect along the lines UBHC2 and RKAC1,
which represent the vapor pressure-vs.-T curves for pure species
1 and 2.

Because of the complexity of Fig. 10.1, the detailed characteristics


of binary VLE are usually depicted by two-dimensional graphs. The
three principal planes, each perpendicular to one of the coordinate
axes.
A vertical plane perpendicular to the temperature axis is outlined
as ALBDEA. The lines on this plane form a P-x1-y1 phase diagram at
constant T.
A horizontal plane perpendicular to the P axis is identified by
HIJKLH. Viewed from the top, the lines on this plane represent a
T-x1-y1 diagram at constant P.

10

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The third plane, vertical and perpendicular to the


composition axis, is indicated by MNQRSLM, this is the P-T
diagram.
At points A and B in Fig. 10.3 saturated-liquid and
saturated-vapor lines intersect. At such points a saturated
liquid of one composition and a saturated vapor of another
composition have the same T and P, and the two phases are
therefore in equilibrium.

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13

14

Within this space, the states of pairs of phases


coexisting at equilibrium define surfaces.
The subcooled-liquid region lies above the upper
surface; the superheated-vapor region lies below the
under surface.
UBHC1 and KAC2 represent the vapor pressure-vs.-T
curves for pure species 1 and 2.
C1 and C2 are the critical points of pure species 1 and
2.
L is a bubble point and the upper surface is the
bubblepoint surface.
Line VL is an example of a tie line, which connects
points representing phases in equilibrium.
W is a dewpoint and the lower surface is the dewpoint
surface.

Pxy diagram at constant T

15

16

Fig 10.8

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Fig 10.9

Simple models for VLE


When thermodynamics is applied to vapor liquid
equilibrium, the goal is to find by calculation the temperatures,
pressures, and compositions of phases in equilibrium.

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Raoults law:
the vapor phase is an ideal gas (apply for low to
moderate pressure)
the liquid phase is an ideal solution (apply when
the species that are chemically similar)

yi P xi Pi sat

(i 1, 2, ..., N )

where xi is a liquid-phase mole fraction, yi is a vaporphase mole fraction, and Pi sat is the vapor pressure
of pure species i at the temperature of the system. The
product yi P on the left side of Eq. is known as the partial
pressure of species i

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Ideal-solution behavior is often approximated by liquid


phases wherein the molecular species are not too different
in size and are of the same chemical nature
although it provides a realistic description of actual
behavior for a small class of systems, it is valid for any
species present at a mole fraction approaching unity,
provided that the vapor phase is an ideal gas.

20

Dewpoint and Bubblepoint


Calculations with Raoult's Law
Engineering interest centers on dewpoint and bubblepoint calculations;
there are four classes:

In each case the name suggests the quantities to be calculated: either a


BUBL (vapor) or a DEW (liquid) composition and either P or T. Thus,
one must specify either the liquid-phase or the vapor-phase composition
and either T or P.
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yi P xi Pi

sat

(i 1, 2, ..., N )

P xi Pi sat

(i 1, 2, ..., N )

1
yi / Pi sat

(i 1, 2, ..., N )

For dewpoint calculation

For bubblepoint calculation

Binary system

P P2sat ( P1sat P2sat ) x1

22

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Binary system acetonitrile (1)/nitromethane(2) conforms closely to Raoults law. Vapor


pressures for the pure species are given by the following Antoine equations:
sat
1

ln P

2945.47
2972.64
sat
/ kPa 14.2724
ln P2 / kPa 14.2043
t / C 224.00
t / C 209.00

(a) Prepare a graph showing P vs. x1 and P vs. y1 for a temperature of 75C.
(b) Prepare a graph showing t vs. x1 and t vs. y1 for a pressure of 70 kPa.
(a) BUBL P

P P2sat ( P1sat P2sat ) x1


At 75C

P1sat 83.21 P2sat 41.98

P 41.98 (83.21 41.98) x1

e.g. x1 = 0.6

P 66.72

x1 P1sat (0.6)(83.21)
y1

0.7483
P
66.72

At 75C, a liquid mixture of 60 mol-% (1) and 40 mol-% (2) is in equilibrium with a vapor
containing 74.83 mol-% (1) at pressure of 66.72 kPa.

Fig. 10.11
24

25

Fig. 10.11

(b) BUBL T, having P = 70 kPa

ln P1sat / kPa 14.2724

Select t

P1sat
P2sat

2945.47
2972.64
sat
ln
P
/
kPa

14
.
2043

2
t / C 224.00
t / C 209.00

P P2sat
x1 sat
P1 P2sat

t vs. x1

y1

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sat
1 1

xP
P

t vs. y1

Fig. 10.12

VLE modified Raoults law


Account is taken of deviation from solution
ideality in the liquid phase by a factor
inserted into Raoults law:
yi P xi i Pi sat

(i 1, 2, 3, ...N )

The activity coefficient, f (T, xi)


P xi i Pi sat
i

1
P
yi / i Pi sat
i

27

28

For the system methanol (1)/methyl acetate (2), the following equations provide a reasonable
correlation for the activity coefficients:

ln 1 (2.771 0.00523T ) x22 ln 2 (2.771 0.00523T ) x12


The Antoine equations provide vapor pressures:

ln P1sat / kPa 16.59158

3643.31
T ( K ) 33.424

ln P2sat / kPa 14.25326

2665.54
T ( K ) 53.424

Calculate
(a): P and {yi} for T = 318.15 K and x1 = 0.25
(b): P and {xi} for T = 318.15 K and y1 = 0.60
(c): T and {yi} for P = 101.33 kPa and x1 = 0.85
(d): T and {xi} for P = 101.33 kPa and y1 = 0.40
(e): the azeotropic pressure and the azeotropic composition for T = 318.15 K
(a) for T = 318.15, and x1 = 0.25
P1sat 44.51 P2sat 65.64 1 1.864 2 1.072

P xi i Pi sat (0.25)(1.864)( 44.51) (0.75)(1.072)(65.64) 73.50


i

yi P xi i Pi sat

y1 0.282 y2 0.718
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(b): for T = 318.15 K and y1 = 0.60


P1sat 44.51 P2sat 65.64
An iterative process is applied, with

1
P
yi / i Pi sat

1 1 2 1

x1
Converges at: P 62.89 kPa 1 1.0378

y1 P
1 P1sat

x2 1 x1

2 2.0935 x1 0.8169

(c): for P = 101.33 kPa and x1 = 0.85


T1sat 337.71 T2sat 330.08
A iterative process is applied, with

ln P1sat / kPa 16.59158

T (0.85)T1sat (0.15)T2sat 336.57

3643.31
T ( K ) 33.424

1 ... 2 ...

P xi i Pi sat
i

P1sat ...
Converges at:

T 331.20 K

1 1.0236 2 2.1182

y1 30
0.670

y2 0.330

(d): for P = 101.33 kPa and y1 = 0.40


T1sat 337.71 T2sat 330.08
A iterative process is applied, with

T (0.40)T1sat (0.60)T2sat 333.13

1 1 2 1
ln Pi sat / kPa Ai

ln P1sat / kPa 16.59158

3643.31
T ( K ) 33.424

P1sat ...

Bi
T ( K ) Ci

P2sat ...
P xi i Pi sat
i

x1 ...

x2 ...

1 ... 2 ...
P1sat ...
Converges at:

T 326.70 K

1 1.3629 2 1.2523

P2sat ...
x1 31
0.4602 x2 0.5398

(e): the azeotropic pressure and the azeotropic composition for T = 318.15 K
y1
Define the relative volatility:

Azeotrope

12

x1 0

12

y2

y1 x1 y2 x2

yi P xi i Pi sat

x1
x2

1 P1sat
12
2 P2sat

12 1

P1sat exp( 2.771 0.00523T )

2.052 12
sat
P2

P1sat
0.224
x1 1
sat
P2 exp( 2.771 0.00523T )

Since 12 is a continuous function of x1: from 2.052 to 0.224, 12 = 1 at some point


There exists the azeotrope!

1 P1sat
12
1
sat
2 P2

1az P2sat
sat 1.4747
az
2
P1

ln 1 (2.771 0.00523T ) x22


ln 2 (2.771 0.00523T ) x12

ln

1
(2.771 0.00523T )( x2 x1 ) (2.771 0.00523T )(1 2 x1 )
2

x 0.325 y
az
1

az
1

1az 1.657
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P az

1az P1sat 73.76kPa

VLE from K-value


correlations
A convenient measure, the K-value:
Ki

yi
xi

the lightness of a constituent species, i.e., of


its tendency to favor the vapor phase.
When Ki is greater than unity, species i
exhibits a higher concentration in the vapor
phase; when less, a higher concentration in
the liquid phase, and is considered a "heavy"
constituent.
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The Raoults

Pi sat
law:K i P

The modified Raoults

i Pi sat
Ki
law:
P

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Fig 10.13
35

Fig 10.14
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For a mixture of 10 mol-% methane, 20 mol-% ethane, and 70 mol-% propane at 50F,
determine: (a) the dewpoint pressure, (b) the bubblepoint pressure. The K-values are given by
Fig. 10.13.
(a) at its dewpoint, only an insignificant amount of liquid is present:
Species
Methane
Ethane
Propane

yi
0.10
0.20
0.70

P = 100 (psia)
Ki
yi /Ki
20.0
0.005
3.25
0.062
0.92
0.761
(yi /Ki) = 0.828

P = 150 (psia)
Ki
yi /Ki
13.2
0.008
2.25
0.089
0.65
1.077
(yi /Ki) = 1.174

P = 126 (psia)
Ki
yi /Ki
16.0
0.006
2.65
0.075
0.762
0.919
(yi /Ki) = 1.000

(b) at bubblepoint, the system is almost completely condensed:

Species
Methane
Ethane
Propane

xi
0.10
0.20
0.70

P = 380 (psia)
Ki
x i Ki
5.60
0.560
1.11
0.222
0.335
0.235
(xi Ki) = 1.017

P = 400 (psia)
Ki
xi Ki
5.25
0.525
1.07
0.214
0.32
0.224
(xi Ki) = 0.963

P = 385 (psia)
Ki
x i Ki
5.49
0.549
1.10
0.220
0.33
0.231
(xi Ki) = 1.000
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Flash calculations
A liquid at a pressure equal to or greater than its
bubblepoint pressure flashes or partially
evaporates when the pressure is reduced,
producing a two-phase system of vapor and liquid
in equilibrium.
Consider a system containing one mole of
nonreacting chemical species:
L V 1
The moles of vapor
The moles of liquid

zi xi L yiV

zi xi (1 V ) yiV

The vapor mole fraction


The liquid mole fraction
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yi

zi K i
1 V ( K i 1)

zi K i
1 V ( K 1) 1
i

The system acetone (1)/acetonitrile (2)/nitromethane(3) at 80C and 110 kPa has the overall
composition, z1 = 0.45, z2 = 0.35, z3 = 0.20, Assuming that Raoults law is appropriate to this
system, determine L, V, {xi}, and {yi}. The vapor pressures of the pure species are given.
Do a BUBL P calculation, with {zi} = {xi} :

Pbubl x1 P1sat x2 P2sat x3 P3sat (0.45)(195.75) (0.35)(97.84) (0.20)(50.32) 132.40 kPa


Do a DEW P calculation, with {zi} = {yi} :

Pdew

1
101.52 kPa
sat
sat
sat
y1 / P1 y2 / P2 y3 / P3

L 1 V 0.2636 mol

Since Pdew < P = 110 kPa < Pbubl, the system is in the two-phase region,

Pi sat
Ki
P

zi K i
1 V ( K 1) 1
i

K1 1.7795 K 2 0.8895 K 3 0.4575

yi

x1 0.2859
x2 0.3810
x3 0.3331

Ki

yi
xi

V 0.7364 mol

zi K i
1 V ( K i 1)

y1 0.5087
y2 0.3389
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y3 0.1524