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Product Research & Development

Session 16
Phase Diagrams Phase Rule & Phase Equilibria:
A Refresher
Part 3

Department of Chemical Engineering


2nd Semester 2017 - 2018

V. M. Naik
Session 15 : Home Work Exercise – Question 1

Discuss the number of components present in the


following systems:

i) NaH2PO4 dissolved in water, at equilibrium with


water vapour, but disregarding the fact that the
salt is ionized

ii) Same as above, but taking in to account the


ionization of salt

iii) A closed reactor containing following species:


NH4Cl(s), NH4Cl(aq), NH4+(aq), Cl-(aq), H2O(liq),
H+, H2O(g), NH3(g), OH-(aq), NH3(aq)
Session 15 : Home Work Exercise - Question 2
System cannot exist in shaded space System cannot exist in shaded space

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

Constant Pressure of 70 Atm


G
DF = 1
L+G
DF = 0
L
DF = 1
S+L
DF = 0
Temperature

System Can Exist


Only On The Red
S Line
DF = 1

Specific Volume
Phase Rule & Phase Equilibria :

Empirical Criteria for Equilibrium of a System

➢Does not change with time


➢Sensitive to changes in state variables
(operating parameters)
➢Arrives at the same state when state
variables are restored, from any direction
➢Has uniform composition and
properties, everywhere within a phase
Phase Rule & Phase Equilibria :
A Refresher
Empirical Criteria for Equilibrium of a System
➢Does not change with time
➢Sensitive to changes in state variables
(operating parameters)
➢Arrives at the same state when state
variables are restored, from any direction
➢Has uniform composition and
properties, everywhere within a phase

What Should Be the Thermodynamic Condition


for Equilibrium of a System ?
What Should Be the Thermodynamic Condition
for Equilibrium of a System ?

Let Us Begin by Examining the Empirical Criteria


for Equilibrium of a System
➢ Does not change with time
➢Sensitive to changes in state variables (operating
parameters)
➢ Arrives at the same state when state variables
are restored, from any direction
➢Has UNIFORM COMPOSITION and
properties, everywhere within a phase
What Drives Migration of Molecules from One Region to
Another Region of a Sub-System, So That Compositions
Become Uniform?

……?
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

Gradient in Chemical Potential Is the Real Driving Force


Behind Migration of Molecules

Flux = C (D/RT)(- µ/x )


Phase Rule & Phase Equilibria :

Empirical Criteria, and


Thermodynamic Condition for Equilibrium of a System

➢Arrives at the same state


when state variables are
At
restored, from any direction equilibrium
➢Does not change with time
➢Sensitive to changes in state
variables (operating µ
parameters) In all
Phases,
➢Has uniform composition and everywhere
properties, everywhere within
a phase
Phase Rule & Phase Equilibria :
A Refresher

In Case of a Pure, Single


Component System :
CO2 CO2
Solid Liquid
➢A Solid Melts in to a Liquid,
and a Liquid Vaporises in to a
Gas, as Temperature Is Raised,
If the Transformation Takes CO2
Gas
the System from Higher
Potential to Lower Potential

How Does Chemical Potential


of a Pure Component Vary with
Temperature & Pressure ?
Phase Rule & Phase Equilibria :
A Refresher
Empirical Criteria, and
Thermodynamic Condition for Equilibrium of a System
➢ Does not change with time
➢ Has uniform composition and
At
properties, everywhere within a equilibrium
phase
➢ Sensitive to changes in state
variables (operating parameters) µ
In all
➢ Arrives at the same state phases
when state variables
are restored, from any
direction

For Single Component, µ ≡ G


Phase Rule & Phase Equilibria :
A Refresher

Dependence of Gibbs Free Energy


with Temperature & Pressure

G = H - ST

dG = Vdp - SdT
Phase Rule & Phase Equilibria :
A Refresher
Variation of Gibbs Free Energy with Temperature & Pressure

dG = Vdp - SdT

G of All Phases of a Pure Component Decreases with Rise in


Temperature, and Increases with Rise in Pressure
Phase Rule & Phase Equilibria :
A Refresher
Temperature Dependence of Phase Stability
for Pure Components
Phase Rule & Phase Equilibria :
A Refresher
Temperature Dependence of Phase Stability

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

Note: Unlike a VAPOUR

single component V+L

system which V+L Bubble


Point
exists on a folded Interface
3D surface only, a LIQUID
Azeotropic
two component Temperature
LIQUID
system exists in a Composition
Line
3D solid space. VAPOUR
The 2D T-X or P- LIQUID
X phase diagrams
of a two
Bubble
component Point
system are cross- V+L Interface
V+L
sections of the 3D
space
VAPOUR
L- L Equilibrium Phase Diagram of a Binary System, at
a Given Pressure…1

(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

Two Solids  &  at Eqm With Each Other


S-S-L Equilibrium Phase Diagram of a Eutectic
Forming Binary System, with Mutually
“Insoluble” Solids
Next Task:
How Do We Prove The Phase Rule?

Step 1:
Identify/Define Parameters and
Conditions Which Drive Phase
Equilibrium

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