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1 - Introduction To Phase Equilibrium

This document provides an introduction to phase equilibrium, including the Gibbs phase rule and its applications to single and two-component systems. The Gibbs phase rule relates the number of degrees of freedom in a system to the number of components and phases. It is expressed as F = 2 - π + N, where F is the degrees of freedom, π is the number of phases, and N is the number of components. For a single-component system, F ranges from 1 to 2 depending on the number of phases. For a two-component system, F is generally 3, allowing representation in 3D phase diagrams of temperature, pressure, and composition. Several examples of phase diagrams for pure substances and binary mixtures are also shown.

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238 views42 pages

1 - Introduction To Phase Equilibrium

This document provides an introduction to phase equilibrium, including the Gibbs phase rule and its applications to single and two-component systems. The Gibbs phase rule relates the number of degrees of freedom in a system to the number of components and phases. It is expressed as F = 2 - π + N, where F is the degrees of freedom, π is the number of phases, and N is the number of components. For a single-component system, F ranges from 1 to 2 depending on the number of phases. For a two-component system, F is generally 3, allowing representation in 3D phase diagrams of temperature, pressure, and composition. Several examples of phase diagrams for pure substances and binary mixtures are also shown.

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CHAPTER 1

INTRODUCTION TO
PHASE EQUILIBRIUM
RATNAWATI
Sections:

1 Gibbs Phase Rule

2 Single Component System

3 Two Component System


{1 Gibbs Phase Rule
}
T P

V H

S G
Change of state of a thermodynamic system

Gradient Process
Pressure Momentum or convective
transport of mass
Temperature Heat transfer
Concentration/ Diffusive mass transfer
chemical potential
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
11 13 21 23 N1 N3

1 1 1
1 1 2 2 N N

Total number of equations/constraints = N ( 1)


Degrees of freedom:

F = (N 1) + 2 N ( 1)

FF =
=22
+
+NN (1.1)
{2 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
{3 Two Component
System }
F=2+N=4
Minimum number of phase = 1
F=3

3 dimensional diagram
(T P composition)
Constant T compression
P-V Diagram for a Binary Mixture
T
P-V Diagram for a Pure Component
Family of Isotherms on a P-V diagram of A Binary Mixture
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
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)
PT diagram for methane ethane
(https://www.e-education.psu.edu/png520/m5_p2.html)
(https://www.e-education.psu.edu/png520/m5_p3.html)
(https://www.e-education.psu.edu/png520/m5_p3.html)
Px relation for ideal liquid
solutions
Pxy diagrams at
constant T of
tetrahydrofuran (1)/
carbon tetrachloride
(2) at 303.15 K
Pxy diagrams
at constant T
of chloroform
(1)/tetrahy-
drofuran(2) at
303.15 K
Pxy diagrams at
constant T of
ethanol (1)/
toluene (2) at
338.15 K
Pxy diagrams at
constant T of
tetrahydrofuran
(1 )/carbon
tetrachloride (2)
at 1 atm
Pxy diagrams at
constant T of
tetrahydrofuran
(1 )/carbon
tetrachloride (2)
at 1 atm
Pxy diagrams at
constant T of
furan(1)/carbon
tetrachloride(2)
at 1 atm
Pxy diagrams at
constant T of
ethanol (1)/
toluene (2) at 1
atm
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)
L F V

xA zA yA

Lz A x A V y A z A

F L V
V L
G L
F F
THANK YOU

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