Chemical Engineering

Thermodynamics-II

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
• When two chemical species: N  2
– 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.
 Critical point for
component 2 (x1=0)

Liquid region
Critical point for
component 1 (x1=1)
Constant temperature
regions are vertical Vapor & Liquid in
slices equilibrium is
within the thumb
Vapor region
• 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.
Vapor Liquid Equilibrium: VLE
2 chemical species, 2 phases (liquid and vapor)
N = 2,  = 2
F=2-+N=2–2+2=2
The intensive properties of the system is 2.
PT diagram

Pxy diagram
Txy diagram


8
Bubblepoint

dewpoint

11
 dewpoint

Bubblepoint

12
 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
(a) Prepare a graph showing P vs. x1 and P vs. y1 for a temperature of 75°C.

2945.47 2972.64
ln P1 sat
/ kPa  14.2724   ln P2sat / kPa  14.2043 
t / C  224.00 t /  C  209.00

(a) BUBL P P  P2  ( P1sat  P2sat ) x1

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.
(b) Prepare a graph showing t vs. x1 and t vs. y1 for a pressure of 70 kPa.

BUBL T, having P = 70 kPa

2945.47 2972.64
ln P1 sat
/ 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
 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
 i ii
y /
i
 P sat
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
(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 y 2  0.718

(b): for T = 318.15 K and y1 = 0.60
P1sat  44.51 P2sat  65.64
1
P
A iterative process is applied, with  1  1  2  1
 i ii
y / 
i
P sat

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 y 2  0.330
(b): for T = 318.15 K and y1 = 0.60
P1sat  44.51 P2sat  65.64
1
P
A iterative process is applied, with  1  1  2  1
 i ii
y / 
i
P sat

y1 P
x1  x2  1  x1
 1 P1sat
Converges at: P  62.89 kPa  1  1.0378  2  2.0935 x1  0.8169
(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

 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 The vapor mole fraction yi 
1  V ( K i  1)
The moles of liquid The liquid mole fraction zi K i
 1  V ( K  1)  1
i