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Phase Equilibria
Group 03
01
Table of
CONTENTS
1. Introduction
2. One component system
3. Miscible, partially miscible & immiscible liquid
mixtures
4. Condensed phase
5. Eutectic systems and compounds formation
6. Solid solutions
7. Simple three component systems
8. Distillation of liquid mixtures
(Congruent and non-congruent)
02
INTRODUCTION
What is Phase?
Any part of a system which is physically
separated from other part of the system by
a distinct boundary.
A phase can be a;
Solid, Liquid, Vapor (gas) or aqueous.
03
What is Phase Equilibrium?
• Thermodynamic Definition
A system is at equilibrium if it’s free
energy is at a minimum.
• Characteristics of the system do not
change with time, the system is stable.
04
Phase Equilibrium
Phase equilibrium is the study of the equilibrium
which exists between or within different states of
matter namely solid, liquid and gas. Equilibrium is
defined as a stage when chemical potential of any
component present in the system stays steady
With time.
05
Phase Rule
This rule is very useful to understand the effect of intensive
variables, such as temperature, pressure as well as
between chemical constituents.
The phase rule is stated as;
F - Number of degrees of freedom
C - Number of components
P – Number of phases
F = C – P + 2
06
Degrees of freedom (F)
Is the least number of intensive variables
that must be fixed/known to describe the
system completely.
Intensive variables are:
- Temperature, pressure, concentration.
07
Number of Component is defined as
the smallest number of
independently variable constituents,
by means of which the composition
of each phase can be expressed in
the form of a chemical equation.
Number of Components (C)
08
One component system is a system involving one pure
chemical.
Ex: At freezing point of water, three phases are in equilibrium.
Ice(s) Water (aq) Water vapor(g)
The chemical composition of all the phases is H2O ,
it is one component system.
One Components System
09
One component system mean , C=1,
From phase rule,
F = C – P + 2
F = 1 – P +2
F = 3 – P
Degree of freedom is depend on the number of phases present
at equilibrium.
Three different cases are possible;
• P=1, F=2 ( Bivariant system)
• P=2, F=1 (Univariant System)
10
Miscibility
Miscibility means how completely two or more liquids dissolve in
each other. It is a qualitative rather than quantitative observation,
• Miscible
• Partially miscible
• Immiscible
Miscibility depend on the force of the attraction between the
molecules of the different liquids. 11
Miscible
The ability of liquid to completely dissolve in
another liquid solution . A distinct layer between
two liquid will not form I this type of solutions.
12
Partially Miscible
• A liquid is partially miscible in another liquid if,
when mixed, the two liquids makes (liquid)
phases that contain some fraction of each liquid in
each phase.
• Partially miscible refers to those liquids which are
partially soluble in each other.
e.g. : Water and Triethylamine solution
13
Immiscible Liquid Mixture
• Immiscible liquids are liquids which are completely
insoluble in each other.
• Immiscibility is the property where two substances are not
capable of combining to form a homogeneous mixture.
• Components of an immiscible mixture will separate from
each other.
14
Condensed Phases
Condensed phase of matter are two ; Solid and
Liquids. These phases of matter are said to be
condensed phases .
Because the inter-molecular phases are fairly
strong as compared to those in gases.
15
● In two component system there
are four possible phases solid
Ag, solid Pb, solution of Ag, + Pb
and vapour.
● Since the pressure has no effect
on equilibrium so the system can
be represented by temperature
concentration diagram at
constant atmospheric pressure.
16
Eutectic System
(Eutectic comes a Greek word EUTEKTOS)
A binary system in which two or more components are miscible in all
proportions in the liquid state, but do not react chemically and each
component has the property of lowering each others melting point is
known as eutectic (easy to melt) system.
A eutectic system only forms when there is a specific ratio between
the components.
Example:
• Sodium chloride and water; The system is used to make ice cream
and to melt ice and snow.
17
Eutectic – Easy to melt. Consider a binary system
in which two components are miscible
in all proportions in the liquid (molten)
state. They do not react chemically and
each component has the property of
lowering each other’s freezing point. Such
a binary system is called Eutectic System.
A eutectic system is a homogeneous(A system consists of one
phase only) solid mixture.
● A eutectic system only forms when there is specific ratio
between the components.
● That has lower solidification point.
18
Examples of Eutectic Systems
Several examples of eutectic systems or eutectoids
exist, both in metallurgy and involving nonmetallic
components:
•NaCl and H2O form a eutectoid when the mixture is
23.3% salts by mass with a eutectic point at 21.2 0C.
The system is used to make ice cream and melt ice
and snow.
19
The minimum freezing point
attainable corresponding to the
eutectic mixture is known
as “Eutectic Point”
20
Solid Solution
What is Solvent and Solute…
Solvent : the component of a solution that is present in
the greatest amount. It is the substance in which the
solute is dissolve.
Ex: the solvent for seawater is water
the solvent for air is nitrogen
Solute : the substance that is dissolved in a solution. For
solution of fluid the solvent is present greater then solute.
Ex: salt in water
21
What is a solid Solution
 When in a solid, the atoms of solute are
present in the lattice of the solvent, it is
known as solid solution.
A solid solution is basically a crystalline phase that can
have variable composition.
often, it have certain properties of material
eg: conductivity, ferromagentism
22
Type of Solid Solution
The solid solution can be of two types.
1. Substitution solid solution
i. Disordered
ii.Ordered
2. Interstitutional solid solution
Examples:
•Al2O3 – Cr2O3 (substitutional, complete)
•Si - Ge (substitutional, complete)
•Fe - C (interstitial, partial)
23
Substitutional Solid Solution
One type of atoms for another so that
solute(Cu) enter the crystal to take positions
normally occupied by solvent atoms (Ni).
The great majority of the solid solution are substitutional
type.
Ex: Cu-Ni , Cd-Mg.
24
Disordered Substitutional Solid Solution
Solute atoms do not occupy specific position
random in the lattice structure of the solvent, it
is known as disordered solid solution.
Most of the solid solutions are disordered solid
solution.
Ex: Alloy
25
Ordered Substituional Solid Solution
If the atoms of the solute occupy certain
preferred sites in the lattice of the solvent, an
ordered solid solution is formed. It may ocure
only at certain fixed ratios of the solute atoms.
The alloy in the disordered condition, if in I cooled slowly,
under –goes a re-arrange meant of the atoms because of
the diffusion that takes place during cooling.
26
Interstitial Solid Solution
When the atoms of the solute occupy the
interstitial space in the lattice of the solvent, it is
known as interstitial solid solution.
• This type of reaction occurs when the solute atom is
equal to or the slightly smaller than the solvent atom.
• More common for C,N,O and H as solutes.
• More easily dissolved in transition metal solvent .
• Solubility is limited.
27
Ex: An example of interstitial solid
solution is C in iron
28
Simple Three Component Systems
In systems containing three components but only one
phase, F = 3 - 1 + 2 = 4 for a noncondensed system.
• The four degrees of freedom are temperature, pressure, and
the concentrations of two of the three components.
• Only two concentration terms are required because the sum
of these subtracted from the total will give the concentration
of the third component.
29
Use of The Three Component System
• Because we are dealing with a three-
component system, it is more convenient to
use triangular coordinate graphs,
• several areas of pharmaceutical processing
such as crystallization, salt form selection, and
chromatographic analyses rely on the use of
ternary systems for optimization.
30
Distillation
● Distillation is a process in which the components of a
substance or liquid mixture are separated by heating it to a
certain temperature and condensing the resulting vapor.
● Distillation is based on the different boiling points or volatility
values of the components and it is a physical process.
● Types of distillation include simple distillation, fractional
distillation, vacuum distillation and so on.
31
Simple Distillation
Simple distillation may be
used when the boiling points
of two liquids are
significantly different from
each other or to separate
liquids from solids or non-
volatile components.
32
● In simple distillation the only one chain of
vaporization and condensation takes place.
● Its only applicable if difference of boiling points
is very large like 25-35 0C.
● This is the sequence of events in distillation:
heating → evaporating → cooling → condensing
33
Fractional Distillation
• This method of distillation is used to separate two (or more)
miscible liquids.
• A fractionating column is used to separate the components.
● This is a another common type of distillation.
● It is used to separate liquids having very close boiling points.
● It requires more evaporation/condensation cycles.
● For fractional distillation one fractionating column is introduced
between flask and condenser. Each gap works as one cycle.
● It is use to petro chemical industry.
34
35
Vacuum Distillation
• Vacuum distillation is used to separate components
that have high boiling points.
• This method of distillation is particularly useful when
the normal boiling point exceeds the decomposition
temperature of a compound.
36
Use Of Distillation
• Purification of alcohol
• Crude oil refining
• Making liquefied gases from air
Ex: Nitrogen, Oxygen, and Argon are distilled from air.
• Distillation is used for many commercial processes, such as
the production of gasoline, paraffin, distilled water and
many other liquids.
37
RESOURCES
• Atkins, Peter.Paula,julio de; keeler ,James(2018)
.Atkins’ Physical chemistry (11th edition) oxford
university press. Pp 123 – 125 , ISBN 9780198769866.
• https://www.wattco.com/casestudy/phase-equllibrium/
• https://www.springer.com/referenceworkentry/10.1007
%2F1-4020-4496-8_252/
38
THANK
YOU
Any Questions ?
39
T.D.Jayawickrama 16APP2648
K.A.H. Navodya 16APP2666
W.S.H.Fernando 16APP2679
M.P.P.Chethiya 16APP2642
Group Members
40

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phase equilibrium

  • 2. Table of CONTENTS 1. Introduction 2. One component system 3. Miscible, partially miscible & immiscible liquid mixtures 4. Condensed phase 5. Eutectic systems and compounds formation 6. Solid solutions 7. Simple three component systems 8. Distillation of liquid mixtures (Congruent and non-congruent) 02
  • 3. INTRODUCTION What is Phase? Any part of a system which is physically separated from other part of the system by a distinct boundary. A phase can be a; Solid, Liquid, Vapor (gas) or aqueous. 03
  • 4. What is Phase Equilibrium? • Thermodynamic Definition A system is at equilibrium if it’s free energy is at a minimum. • Characteristics of the system do not change with time, the system is stable. 04
  • 5. Phase Equilibrium Phase equilibrium is the study of the equilibrium which exists between or within different states of matter namely solid, liquid and gas. Equilibrium is defined as a stage when chemical potential of any component present in the system stays steady With time. 05
  • 6. Phase Rule This rule is very useful to understand the effect of intensive variables, such as temperature, pressure as well as between chemical constituents. The phase rule is stated as; F - Number of degrees of freedom C - Number of components P – Number of phases F = C – P + 2 06
  • 7. Degrees of freedom (F) Is the least number of intensive variables that must be fixed/known to describe the system completely. Intensive variables are: - Temperature, pressure, concentration. 07
  • 8. Number of Component is defined as the smallest number of independently variable constituents, by means of which the composition of each phase can be expressed in the form of a chemical equation. Number of Components (C) 08
  • 9. One component system is a system involving one pure chemical. Ex: At freezing point of water, three phases are in equilibrium. Ice(s) Water (aq) Water vapor(g) The chemical composition of all the phases is H2O , it is one component system. One Components System 09
  • 10. One component system mean , C=1, From phase rule, F = C – P + 2 F = 1 – P +2 F = 3 – P Degree of freedom is depend on the number of phases present at equilibrium. Three different cases are possible; • P=1, F=2 ( Bivariant system) • P=2, F=1 (Univariant System) 10
  • 11. Miscibility Miscibility means how completely two or more liquids dissolve in each other. It is a qualitative rather than quantitative observation, • Miscible • Partially miscible • Immiscible Miscibility depend on the force of the attraction between the molecules of the different liquids. 11
  • 12. Miscible The ability of liquid to completely dissolve in another liquid solution . A distinct layer between two liquid will not form I this type of solutions. 12
  • 13. Partially Miscible • A liquid is partially miscible in another liquid if, when mixed, the two liquids makes (liquid) phases that contain some fraction of each liquid in each phase. • Partially miscible refers to those liquids which are partially soluble in each other. e.g. : Water and Triethylamine solution 13
  • 14. Immiscible Liquid Mixture • Immiscible liquids are liquids which are completely insoluble in each other. • Immiscibility is the property where two substances are not capable of combining to form a homogeneous mixture. • Components of an immiscible mixture will separate from each other. 14
  • 15. Condensed Phases Condensed phase of matter are two ; Solid and Liquids. These phases of matter are said to be condensed phases . Because the inter-molecular phases are fairly strong as compared to those in gases. 15
  • 16. ● In two component system there are four possible phases solid Ag, solid Pb, solution of Ag, + Pb and vapour. ● Since the pressure has no effect on equilibrium so the system can be represented by temperature concentration diagram at constant atmospheric pressure. 16
  • 17. Eutectic System (Eutectic comes a Greek word EUTEKTOS) A binary system in which two or more components are miscible in all proportions in the liquid state, but do not react chemically and each component has the property of lowering each others melting point is known as eutectic (easy to melt) system. A eutectic system only forms when there is a specific ratio between the components. Example: • Sodium chloride and water; The system is used to make ice cream and to melt ice and snow. 17
  • 18. Eutectic – Easy to melt. Consider a binary system in which two components are miscible in all proportions in the liquid (molten) state. They do not react chemically and each component has the property of lowering each other’s freezing point. Such a binary system is called Eutectic System. A eutectic system is a homogeneous(A system consists of one phase only) solid mixture. ● A eutectic system only forms when there is specific ratio between the components. ● That has lower solidification point. 18
  • 19. Examples of Eutectic Systems Several examples of eutectic systems or eutectoids exist, both in metallurgy and involving nonmetallic components: •NaCl and H2O form a eutectoid when the mixture is 23.3% salts by mass with a eutectic point at 21.2 0C. The system is used to make ice cream and melt ice and snow. 19
  • 20. The minimum freezing point attainable corresponding to the eutectic mixture is known as “Eutectic Point” 20
  • 21. Solid Solution What is Solvent and Solute… Solvent : the component of a solution that is present in the greatest amount. It is the substance in which the solute is dissolve. Ex: the solvent for seawater is water the solvent for air is nitrogen Solute : the substance that is dissolved in a solution. For solution of fluid the solvent is present greater then solute. Ex: salt in water 21
  • 22. What is a solid Solution  When in a solid, the atoms of solute are present in the lattice of the solvent, it is known as solid solution. A solid solution is basically a crystalline phase that can have variable composition. often, it have certain properties of material eg: conductivity, ferromagentism 22
  • 23. Type of Solid Solution The solid solution can be of two types. 1. Substitution solid solution i. Disordered ii.Ordered 2. Interstitutional solid solution Examples: •Al2O3 – Cr2O3 (substitutional, complete) •Si - Ge (substitutional, complete) •Fe - C (interstitial, partial) 23
  • 24. Substitutional Solid Solution One type of atoms for another so that solute(Cu) enter the crystal to take positions normally occupied by solvent atoms (Ni). The great majority of the solid solution are substitutional type. Ex: Cu-Ni , Cd-Mg. 24
  • 25. Disordered Substitutional Solid Solution Solute atoms do not occupy specific position random in the lattice structure of the solvent, it is known as disordered solid solution. Most of the solid solutions are disordered solid solution. Ex: Alloy 25
  • 26. Ordered Substituional Solid Solution If the atoms of the solute occupy certain preferred sites in the lattice of the solvent, an ordered solid solution is formed. It may ocure only at certain fixed ratios of the solute atoms. The alloy in the disordered condition, if in I cooled slowly, under –goes a re-arrange meant of the atoms because of the diffusion that takes place during cooling. 26
  • 27. Interstitial Solid Solution When the atoms of the solute occupy the interstitial space in the lattice of the solvent, it is known as interstitial solid solution. • This type of reaction occurs when the solute atom is equal to or the slightly smaller than the solvent atom. • More common for C,N,O and H as solutes. • More easily dissolved in transition metal solvent . • Solubility is limited. 27
  • 28. Ex: An example of interstitial solid solution is C in iron 28
  • 29. Simple Three Component Systems In systems containing three components but only one phase, F = 3 - 1 + 2 = 4 for a noncondensed system. • The four degrees of freedom are temperature, pressure, and the concentrations of two of the three components. • Only two concentration terms are required because the sum of these subtracted from the total will give the concentration of the third component. 29
  • 30. Use of The Three Component System • Because we are dealing with a three- component system, it is more convenient to use triangular coordinate graphs, • several areas of pharmaceutical processing such as crystallization, salt form selection, and chromatographic analyses rely on the use of ternary systems for optimization. 30
  • 31. Distillation ● Distillation is a process in which the components of a substance or liquid mixture are separated by heating it to a certain temperature and condensing the resulting vapor. ● Distillation is based on the different boiling points or volatility values of the components and it is a physical process. ● Types of distillation include simple distillation, fractional distillation, vacuum distillation and so on. 31
  • 32. Simple Distillation Simple distillation may be used when the boiling points of two liquids are significantly different from each other or to separate liquids from solids or non- volatile components. 32
  • 33. ● In simple distillation the only one chain of vaporization and condensation takes place. ● Its only applicable if difference of boiling points is very large like 25-35 0C. ● This is the sequence of events in distillation: heating → evaporating → cooling → condensing 33
  • 34. Fractional Distillation • This method of distillation is used to separate two (or more) miscible liquids. • A fractionating column is used to separate the components. ● This is a another common type of distillation. ● It is used to separate liquids having very close boiling points. ● It requires more evaporation/condensation cycles. ● For fractional distillation one fractionating column is introduced between flask and condenser. Each gap works as one cycle. ● It is use to petro chemical industry. 34
  • 35. 35
  • 36. Vacuum Distillation • Vacuum distillation is used to separate components that have high boiling points. • This method of distillation is particularly useful when the normal boiling point exceeds the decomposition temperature of a compound. 36
  • 37. Use Of Distillation • Purification of alcohol • Crude oil refining • Making liquefied gases from air Ex: Nitrogen, Oxygen, and Argon are distilled from air. • Distillation is used for many commercial processes, such as the production of gasoline, paraffin, distilled water and many other liquids. 37
  • 38. RESOURCES • Atkins, Peter.Paula,julio de; keeler ,James(2018) .Atkins’ Physical chemistry (11th edition) oxford university press. Pp 123 – 125 , ISBN 9780198769866. • https://www.wattco.com/casestudy/phase-equllibrium/ • https://www.springer.com/referenceworkentry/10.1007 %2F1-4020-4496-8_252/ 38
  • 40. T.D.Jayawickrama 16APP2648 K.A.H. Navodya 16APP2666 W.S.H.Fernando 16APP2679 M.P.P.Chethiya 16APP2642 Group Members 40