CHAPTER 1

INTRODUCTION TO VLE

RAT N AWAT I
{1 The Nature of
Equilibrium }
Equilibrium is a static condition in
which no changes occur in the
macroscopic properties of a
system with time.
 State of a system

T S

P H

V G
Change of state of a thermodynamic system

Gradient Process
Temperature Heat transfer
Pressure Momentum transport or
convective transport of
mass
chemical potential Diffusive mass transfer
Criteria of thermodynamic equilibrium:
1. dT = 0  thermal equilibrium
2. dP = 0  mechanical equilibrium
3. d = 0 diffusive equilibrium
{2 The Phase Rule
}
T and P are common independent intensive variables

N components
1
No. of intensive variables = N – 1
2
N components
3 No. of intensive variables = N – 1
N components
No. of intensive variables = N – 1

Total number of variables =  (N – 1) + 2
The chemical potential of each component must be
equal in all phases.
Comp. 1 Comp. 2 Comp. N
 1  2  1  2  1  2
1  1 2  2  N  N
1 2   1 3   22    23    N 2   N 3 
  
  1    1    1  
1  1 2  2  N  N

Total number of equations/constraints = N ( – 1)

Degrees of freedom:
= no. of variables – no. of eqs.
F = { (N – 1) + 2} – N ( – 1)

F=2–+N (1.1)
{3 Single Component
System }
 F  2  N  3

P S+L
=2;F=1

P = 1 atm

=1;F=2 L+V
=1;F=2 =2;F=1
S+V
=2;F=1 Vapor
S+L+V =1;F=2
=3;F=0
{4 Two Component
System }
 F=2–+N=4–
Minimum number of phase = 1
F=3

3 dimensional diagram
(T – P – composition)
 Constant T compression

L = light comp.
H = heavy comp. L&
Constant T
H
P-V Diagram for a Binary Mixture
T

(H will condense first)

P-V Diagram for a Pure Component
Family of Isotherms on a P-V diagram of A Binary Mixture

Bubble point curve Dew point curve

P-T Phase Envelope For A Binary System
Cricondentherm (Tcc)

• The highest temperature in the

two-phase envelope.
• For T > Tcc, liquid and vapor cannot
co-exist at equilibrium, no matter
what the pressure is.
Cricondenbar (Pcc)

• The highest pressure in the two-

phase envelope.
• For P > Pcc, liquid and vapor cannot
co-exist at equilibrium, no matter
what the temperature is.
Isothermal Compression at T1 and T2
Effect of Composition on Phase Behavior

Vapor pressure curve (pure component)

(https://www.e-education.psu.edu/png520/m5_p2.html)
 P-T Graphs For The Pure Components A and B
(https://www.e-education.psu.edu/png520/m5_p2.html)
 50% 40%
60% 30%
20%
10%

PT diagram for methane – ethane

(https://www.e-education.psu.edu/png520/m5_p2.html)
 Px Diagram

(https://www.e-education.psu.edu/png520/m5_p3.html)
 Txy Diagram

(https://www.e-education.psu.edu/png520/m5_p3.html)
PTxy Diagram
xy Diagram
 Pxy Diagram
Px relation for ideal liquid
solutions
Pxy diagrams at
constant T of
tetrahydrofuran (1)/
carbon tetrachloride
(2) at 303.15 K
Pxy Diagram

Pxy diagrams
at constant T
of chloroform
(1)/tetrahy-
drofuran(2) at
303.15 K
x1 y1
Pxy Diagram

Pxy diagrams at
constant T of
ethanol (1)/
toluene (2) at
338.15 K
Txy Diagram

Pxy diagrams at
constant T of
tetrahydrofuran
(1 )/carbon
tetrachloride (2)
at 1 atm
Txy Diagram

Pxy diagrams at
constant T of
tetrahydrofuran
(1 )/carbon
tetrachloride (2)
at 1 atm
Txy Diagram

Pxy diagrams at
constant T of
furan(1)/carbon
tetrachloride(2)
at 1 atm
Txy Diagram

Pxy diagrams at
constant T of
ethanol (1)/
toluene (2) at 1
atm
 xy Diagram
yx diagrams at 1 atm:
(a) tetrahydrofuran
(1)/CCl4 (2); (b)
chloroform (1)/
tetrahydrofuran (2);
(c) furan (1)/ CCl4 (2);
(d) ethanol (1)/
toluene (2)
The Lever Rule
L F V

xA zA yA

L z A  x A   V  y A  z A 

F  L V
 V L
G  L 
F F
{5 The Clausius-
Clapeyron Equation }
Fundamental equation:
dG  S dT  V dP (1.2)

Phase change (vaporization) occurs at

constant T and P:
dG  0

GV  G L  0 GL  GV (1.3)
On taking a differential of eq. (1.3):

dGL  dGV

 S L dT  V L dP sat  SV dT  V V dP sat

On rearranging:

dPsat SV  SL Svap
 V L
 V
dT V V V  VL
using the second law: dS  dQ T

for a constant pressure process: dQ = dH

Thus: dH = T dS

Hvap = T Svap
 dPsat Hvap

dT 
T V V  VL  (1.4)

This is Clapeyron equation

 VL  V V V V  VL  V V

at low to moderate saturation pressures

V RT
V  sat
P

dP sat Hvap
 2 sat
dT RT P
 vap
sat  H 1
d ln P  d  (1.5)
R T 

This is Clausius-Clapeyron equation

Integrating eq. (1.5):

sat   H vap  1 
ln P      constant
 R  T 

sat B
ln P  A (1.6)
T
Modification of eq. (1.6) called the Antoine
Equation, is more accurate (including at
higher pressures):

sat B
ln P  A (1.7)
T C
THANK YOU