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Session 16
Phase Diagrams Phase Rule & Phase Equilibria:
A Refresher
Part 3
V. M. Naik
Session 15 : Home Work Exercise – Question 1
CO2
Solid
CO2
CO2
Liquid
CO2 Liquid
Solid
CO2
Gas
CO2
Gas
a) Draw phase diagram for the system with (specific) Volume as X axis and
Temperature as Y axis
b) Draw “phase diagram” under a constraint that the pressure is 70 atm
Answer to Q 2a – Session 18 Exercise
System
Cannot
Exist in T = 67 C
This Sp V = 2.144 Cm3/g
Region (P = 72.9 Atm)
G
L DF = 2
DF = 2
L+G
Temperature
DF = 1
S+L
Sp V = 0.848 Cm3/g
DF = 1 S+L+G
T = -56.4 C DF = 0
(P = 5.11 Atm)
T = -78.4 C
Sp V = 0.64 Cm3/g
S+G
(P = 1 Atm)
S DF = 1
DF = 2
Specific Volume
Answer To Q 2b – Session 18 Exercise
Specific Volume
Phase Rule & Phase Equilibria :
……?
What Drives Migration of Molecules from One Region to
Another Region of a Sub-System, So That Compositions
Become Uniform?
Flux = D(- C / x )
C1 C2
What Should
+ We Expect After ?
Equilibrium
Demonstration:
When a red coloured dye “D & C Red 33” is dissolved at two
different concentrations in pre equilibrated and separated
layers of water and n-butyl alcohol, and the two solutions are
contacted with each other, the dye diffuses from lower
concentration in butanol layer to higher concentration in water
D & C Red 33
layer. Hence equalization of concentration cannot be
the driving force for attainment of equilibrium
Attainment of Equilibrium
+
The Dye Migrated
Against
Concentration
Gradient
G = H - ST
dG = Vdp - SdT
Phase Rule & Phase Equilibria :
A Refresher
Variation of Gibbs Free Energy with Temperature & Pressure
dG = Vdp - SdT
CO2 CO2
Solid Liquid
CO2
Gas
Effect of Pressure on Melting Point of Solids
Phase Rule & Phase Equilibria :
A Refresher
What Would Be the Temperature Dependence of µ, for the
Three Phases below 1 atm?
CO2 CO2
Solid Liquid
CO2
Gas
A Pitfall in Interpretation of Phase Diagrams
If Water Is Filled In A Bottle, Pressure Is 1 Atm , Temperature Is 30 Deg C,
Water Vapour Is Also Present In The Overhead Space. Is This Not
Inconsistent With The Phase Diagram?
S L G
S+L+G
Some Typical Phase Diagrams for
Two component Systems
V-L-E of an Ideal Binary System
Gibbs Phase Rule : F = C – P + 2
A simple vapour-liquid equilibrium phase diagram of an ideal binary
system, at a given pressure.
Since one state variable is already fixed, the available F = C – P + 1
y2 or 1. F = 2 where single phases L or
G are shown. Phase
composition (same as system
composition) and temperature
can vary independently of each
other. Once composition and T
are fixed system is completely
Tie Line G defined; and other intensive
properties such as specific
volume, refractive index etc.
are also fixed.
2. F = 1 in the region bound by
L dew point and bubble point
curves where two phases
(L+G) are shown. Once one of
the two phase compositions or
T is fixed, the system is
completely defined
y1 or
T
Tie Line
A Typical Non Ideal Binary V-L Phase Diagram With Max Boiling Azeotrope
Formation, at a Given Constant Pressure
Tie Lines
P=1
P=2
P=1
3D Space of a Binary V-L Phase Diagram for System showing Max Boiling Azeotrope
(292 deg K)
Tie Line
in Hexane
L - L Equilibrium Phase Diagram of a Binary System, at
a Given Pressure…..2
Tie Line
L - L Equilibrium Phase Diagram of a Binary System, at
a Given Pressure…..3
V – L Phase Diagram of a Binary Min Boiling Azeotropic
System, at a Given Pressure, When the BP Is Close to
L-L Phase Separation Temperatures
A Nearly Ideal V-L-E Binary Phase Diagram at a Constant, Given
Pressure, Together with S-L Phases at Low Temperature
When Phase Diagram of the Binary Min Boiling
Azeotropic System, at a Given Pressure, Overlaps L-L
Phase Separation Temperatures We Get Heterogeneous
Min Boiling Azeotrope
P=2
P=2
Solid-Liquid Equilibrium Phase Diagram of a
Mutually soluble Two Component System, at a
Given Pressure
S-S-L Equilibrium Phase Diagram of a Eutectic
Forming Binary System, with Partial Mutual
Solubility of Solids
Solid Soln of Sn in Pb Tie Line Eutectic Point Solid Soln of Pb in Sn
Molten Liquid
Step 1:
Identify/Define Parameters and
Conditions Which Drive Phase
Equilibrium