10/26/2016

ChE 307

Thermodynamics-II

Instructor:
Dr. Md. Easir Arafat Khan
Assistant Professor
Department of Chemical Engineering, BUET,
Dhaka-1000

July, 2016

Vapor/Liquid Equilibrium
Content:
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 two simplest formulations that allow calculation of
temperatures, pressures, and phase compositions for systems 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. The second, Henrys
law, is valid for any species present at low concentration
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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Vapor/Liquid Equilibrium

Content:

The Nature of Equilibrium

The Phase Rule

VLE Quantitative Behavior

Raoults Law

Henrys Law

VLE by Modified Raoults Law

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 inter-phase 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 the system.

Fixed temperature, pressure, and phase composition

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Measure of Composition

1. Mass Fraction

2. Molar Fraction

3. Molar Concentration

The Phase Rule

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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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 the variable):
Phase rule: F 2 ( N 1)( ) ( 1)(N ) 2 N

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 be extensive.

F 2 ( N 1)( ) ( 1)( N ) N 2

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VLE: Qualitative Behavior

Fig.10.1: PTxy diagram for vapor/liquid equilibrium 9

VLE: Qualitative Behavior

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 UBHC1 and KAC2, which
represent the vapor pressure-vs.-T curves for pure species 1 and 2.

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VLE: Qualitative Behavior

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.
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VLE: Qualitative Behavior

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VLE: Qualitative Behavior

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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VLE: Qualitative Behavior

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VLE: Qualitative Behavior

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
Txy diagram at constant P
PT diagram at constant composition
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VLE: Qualitative Behavior

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VLE: Qualitative Behavior

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VLE: Qualitative Behavior

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VLE: Qualitative Behavior

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VLE: Qualitative Behavior

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VLE: Qualitative Behavior

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VLE: Qualitative Behavior

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VLE: Qualitative Behavior

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VLE: Qualitative Behavior

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Simple models for VLE

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 vapor-phase 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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Simple models for VLE

Raoults law:

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.

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Dewpoint and Bubblepoint Calculations

Engineering interest centers on dewpoint and bubblepoint

calculations; there are four classes:

BUBL P : Calculate {yi} and P, for given {xi} and T

DEW P : Calculate {xi} and P, for given {yi} and T
BUBL T : Calculate {yi} and T, for given {xi} and P
DEW T : Calculate {xi} and T, for given {yi} and P

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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Dewpoint and Bubblepoint Calculations

1
yi P xi Pi sat (i 1, 2, ..., N ) P (i 1, 2, ..., N )
yi / Pi sat
x i 1 i

yi 1
i
i
For dewpoint calculation

P xi Pi sat (i 1, 2, ..., N ) For bubble point calculation

i

Binary system

P P2sat ( P1sat P2sat ) x1

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(a) BUBL P P P2sat ( P1sat P2sat ) x1

At 75C P1sat 83.21 P2sat 41.98
e.g. x1 = 0.6 x1P1sat (0.6)(83.21)
P 41.98 (83.21 41.98) x1 y1 0.7483
P 66.72 P 66.72

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(b) BUBL T, having P = 70 kPa

2945.47 2972.64
ln P1sat / kPa 14.2724 ln P2sat / kPa 14.2043
t / C 224.00 t / C 209.00

x1 P1sat
y1
P P2sat
sat
P1 P
Select t x1 t vs. x1 t vs. y1
P2sat P1sat P2sat

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Henrys law
Assumption
A species present in the liquid phase as a very dilute solute
Vapor phase is assumed as ideal gas

Henrys law states that the partial pressure of the species in the vapor phase
is directly proportional to its liquid phase mole fraction. Thus,

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Henrys law

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Henrys law

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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
i i Pi sat
y
i
/

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VLE modified Raoults law

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VLE modified Raoults law

Solution: 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:
3643.31 2665.54
ln P1sat / kPa 16.59158 ln P2sat / kPa 14.25326
T ( K ) 33.424 T ( K ) 53.424

Calculate
(a): P and {yi} for T = 318.15 K and x1 = 0.25

(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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VLE modified Raoults law

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

P1sat 44.51 P2sat 65.64

1
P
An iterative process is applied, with 1 1 2 1
yi / i Pi sat
i

y1 P
x1 x2 1 x1
1 P1sat

Converges at: P 62.89 kPa 1 1.0378 2 2.0935 x1 0.8169

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VLE modified Raoults law

(c): for P = 101.33 kPa and x1 = 0.85
Bi
T1sat 337.71 T2sat 330.08 Ti sat Ci
Ai ln P
An iterative process is applied, with
T (0.85)T1sat (0.15)T2sat 336.57
Bi
ln Pi sat / kPa Ai
T ( K ) Ci

T
B1
C1 A 1 ... 2 ... P1sat

A1 ln P1sat P2sat

P
P1sat
P1sat ... x1 1 x2 2 /
Converges at:
T 331.20 K 1 1.0236 2 2.1182 y1 0.670 y2 0.330

x P sat
y1 1 1 1
P
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(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 Initial
Bi
ln Pi sat / kPa Ai
T ( K ) Ci
P1sat
P1sat ... P2sat ...
P2sat
B1
T C
A1 ln P1sat
y1 P
x1 x2 1 x1
1 P1sat

1 ... 2 ...

y1 y2
P1sat P( )
1 2
Converges at: T 326.70 K 1 1.3629 2 1.2523 x1 0.4602 x2 0.5398

(e): the azeotropic pressure and the azeotropic composition for T = 318.15 K

y1
x1 yi P xi i Pi sat 1 P1sat
Define the relative volatility: 12 12
y2 2 P2sat
x2

Azeotrope y1 x1 y2 x2 12 1

P1sat exp( 2.771 0.00523T ) P1sat

12 x1 0 2.052 12 x1 1 0.224
P2sat P2
sat
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 1az P2sat

12 1 1.4747
2 P2sat 2az P1sat
ln 1 (2.771 0.00523T ) x22 1
ln (2.771 0.00523T )( x2 x1 ) (2.771 0.00523T )(1 2 x1 )
ln 2 (2.771 0.00523T ) x 2 2
1
1az 1.657
x1az 0.325 y1az
P az 1az P1sat 73.76kPa

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VLE from K-value correlations

A convenient measure, the K-value:

yi
Ki
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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VLE from K-value correlations

Pi sat
The Raoults law: Ki
P

The modified Raoults law: i Pi sat

Ki
P

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Solution:

P = 100 (psia) P = 150 (psia) P = 126 (psia)

Species yi 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
(yi /Ki) = 0.828 (yi /Ki) = 1.174 (yi /Ki) = 1.000

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VLE from K-value correlations

P = 380 (psia) P = 400 (psia) P = 385 (psia)

Species xi Ki x i Ki Ki x i Ki Ki x i Ki
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
(xi Ki) = 1.017 (xi Ki) = 0.963 (xi Ki) = 1.000

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Flash Calculations

A liquid at a pressure equal to or greater than its bubble point

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 non-reacting
chemical species:

L V 1 zi xi L yiV zi xi (1 V ) yiV

zi K i
The moles of vapor The vapor mole fraction yi
1 V ( K i 1)
zi K i
1 V (K
The moles of liquid The liquid mole fraction
1
i 1)

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Flash Calculations

Solution:

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} :
1
Pdew 101.52 kPa
y1 / P1sat y2 / P2sat y3 / P3sat

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Flash Calculations
Do a DEW P calculation, with {zi} = {yi} :
1
Pdew 101.52 kPa
y1 / P1
sat
y2 / P2sat y3 / P3sat L 1 V 0.2636 mol
Since Pdew < P = 110 kPa < Pbubl, the system is in the two-phase region,

Pi sat zi K i
Ki K1 1.7795 K 2 0.8895 K 3 0.4575 1 V (K 1)
1 V 0.7364 mol
P i

zi K i
yi
1 V ( K i 1)
yi
x1 0.2859 Ki y1 0.5087
xi
x2 0.3810 y2 0.3389
x3 0.3331 y3 0.1524

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