Advanced Thermodynamics

Vapor/Liquid Equilibrium:
Introduction
 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.
 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 the system.
– Fixed temperature, pressure, and phase composition
 Phase rule vs. Duhem’s 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

• Duhem’s rule:
F  2   ( N  1)( )      (  1)( N )  N   2
– 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.
 VLE: qualitative behavior
N 2
• When two chemical species:
– phase rule: F  4  
– the maximum value of F = 3
(π = 1), namely, P, T, and one
mole fraction. All equilibrium
states of the system can be
represented in three-
dimensional P-T-composition
space.

Fig 10.1
• 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
• Fig 10.8 (a)(b), Negative departures from P-x1 linearity: strong liquid-
phase inter-molecular attractions between unlike than between like pairs
of molecules.
• Fig 10.8 (c)(d), Positive departures from P-x1 linearity: strong liquid-
phase inter-molecular attractions between like than between unlike pairs
of molecules.
• Fig 10.8 (b)(d), the “azeotrope”: the point where x1 = y1 the dewpoint
and bubblepoint curves are tangent to the same horizontal line. The
liquid does not change in composition as it evaporates. No separation of
such a constant-boiling solution is possible by distillation.

Fig 10.8
Fig 10.8
Fig 10.9
Fig 10.10
 Simple models for VLE
• The simplest are Raoult’s law and Henry’s law.
• Raoult’s 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 )
• 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.
 1
yi P  xi Pi sat
(i  1, 2, ..., N ) P (i  1, 2, ..., N )
 yi / Pi sat
x i 1 i

yi
i 1 i
For dewpoint calculation

P   xi Pi sat (i  1, 2, ..., N )
i
For bubblepoint calculation
Binary system
P  P2sat  ( P1sat  P2sat ) x1
Binary system acetonitrile (1)/nitromethane(2) conforms closely to Raoult’s law.
Vapor pressures for the pure species are given by the following Antoine equations:
2945.47 2972.64
ln P1
sat
/ kPa  14.2724   ln P2sat / 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 75°C.
(b) Prepare a graph showing t vs. x1 and t vs. y1 for a pressure of 70 kPa.

(a) BUBL P P  P2  ( P1  P2 ) x1
sat sat sat

At 75°C P1sat  83.21 P2sat  41.98

e.g. x1 = 0.6 x1 P1sat (0.6)(83.21)
P  41.98  (83.21  41.98) x1 y1    0.7483
P  66.72 P 66.72

At 75°C, 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
Fig. 10.11
(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

P1sat P  P2sat
Select t x1  sat t vs. x1 t vs. y1
P2sat P1  P2sat xP sat
y1  1 1
P

Fig. 10.12
 Henry’s 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

Table 10.1
Assuming that carbonated water contains only CO2 (species 1) and H2O (species
2) , determine the compositions of the vapor and liquid phases in a sealed can of
“soda” and the pressure exerted on the can at 10°C. Henry’s constant for CO 2 in
water at 10°C is about 990 bar.

Henry’s law for species 1: y1 P  x1 H1

Raoult’s law for species 2: y2 P  x2 P2sat

P  x1 H1  x2 P2sat
Assuming x1 = 0.01
P  (0.01)(990)  (0.99)(0.01227)  9.912
y1 P  x1 H1 assuming y1 = 1.0

Justified the assumption x1  0.01

y2 P  x2 P2sat
y2  0.0012

y1  0.9988 Justified the assumption

 VLE modified Raoult’s law
• Account is taken of deviation from solution
ideality in the liquid phase by a factor inserted into
Raoult’s 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
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
(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

(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
(c): for P = 101.33 kPa and x1 = 0.85
T1sat  337.71 T2sat  330.08
A iterative process is applied, with T  (0.85)T1sat  (0.15)T2sat  336.57

 1  ...  2  ...
3643.31
ln P1sat / kPa  16.59158 
T ( K )  33.424 P   xi i Pi sat
i

P1sat  ...
Converges at: T  331.20 K  1  1.0236  2  2.1182 y1  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
Bi
ln Pi sat / kPa  Ai 
T ( K )  Ci

P1sat  ... P2sat  ...

3643.31
ln P1sat / kPa  16.59158  P   xi i Pi sat
T ( K )  33.424
i

x1  ... x2  ...

 1  ...  2  ...

P1sat  ... P2sat  ...

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 exp(2.771  0.00523T )
sat

Since α12 is a continuous function of x1: from 2.052 to 0.224, α12 = 1 at some point
There exists the azeotrope!

 1 P1sat  1az P2sat

12  1  sat  1.4747
 2 P2sat
2 az
P1

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 ) x12 2
 1az  1.657
x  0.325  y
az
1
az
1
P az   1az P1sat  73.76kPa
 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.
– The Raoult’s law: P sat
Ki  i
P
– The modified Raoult’s law:  i Pi sat
Ki 
P
Fig 10.13
Fig 10.14
For a mixture of 10 mol-% methane, 20 mol-% ethane, and 70 mol-% propane at
50°F, 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:
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
Σ(yi /Ki) = 0.828 Σ(yi /Ki) = 1.174 Σ(yi /Ki) = 1.000

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

P = 380 (psia) P = 400 (psia) P = 385 (psia)
Species xi Ki xi 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
Σ(xi Ki) = 1.017 Σ(xi Ki) = 0.963 Σ(xi Ki) = 1.000
 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 zi  xi L  yiV zi  xi (1  V )  yiV

zi K i
The moles of vapor yi 
The vapor mole fraction 1  V ( K i  1)
The moles of liquid The liquid mole fraction zi K i
 1  V ( K  1)  1
i
 The system acetone (1)/acetonitrile (2)/nitromethane(3) at 80°C and 110 kPa has
the overall composition, z1 = 0.45, z2 = 0.35, z3 = 0.20, Assuming that Raoult’s 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} :
1
Pdew   101.52 kPa
y1 / P1sat  y2 / P2  y3 / P3
sat sat
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