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OUTLINE
 PHASE RULE
 WHAT IS MEANT BY PHASE
 WHAT IS MEANT BY COMPONENTS
 DEGREES OF FREEDOM
 DERIVATION
 ONE COMPONENT SYSTEM
 PHASE DIAGRAM
PHASE RULE
THE PHASE RULE IS AN IMPORTANT
GENERALIZATION DEALING WITH THE
BEHAVIOR OF HETEROGENEOUS SYSTEM.
IN GENERAL IT MAY BE SAID THAT WITH THE
APPLICATION OF PHASE RULE IT IS POSSIBLE
TO PREDICT QUALITATIVELY BY MEANS OF
DIAGRAM. THE EFFECT OF CHANGING
PRESSURE , TEMPERATURE AND
CONCENTRATION ON A HETEROGENEOUS
SYSTEM IN EQUILIBRIUM.
 HETEROGENEOUS EQUILIBRIUM IS
FIRST DISCOVERED BY AMERICAN
PHYSICIST “WILLARD GIBBS” IN 1874.
IT MAY BE MATHEMATICALLY STATED
AS:
F=C – P+2
F= DEGREE OF FREEDOM
C=COMPONENTS
P=NUMBER OF PHASES OF THE
SYSTEM
PHASE
IT MAY BE DEFINED AS:
“ANY HOMOGENOUS PART OF A SYSTEM HAVING
ALL PHYSICAL AND CHEMICAL PROPERTIES THE
SAME THROUGHOUT”.
A PHASE MAY BE OF THREE TYPES:
1. ONE PHASE SYSTEM
2. TWO PHASE SYSTEM
3.THREE PHASE SYSTEM
A SYSTEM CONSISTING OF ONE PHASE IS
CALLED HOMOGENOUS SYSTEM.
A SYSTEM CONSIST OF TWO OR MORE
SYSTEM IS CALLED HETEROGENOUS
SYSTEM.
GENERALY,LIQUID SLOID GASES ARE
THREE PHASES BUT IIN PHASE RULE “A
UNIFORM PART OF A SYSTEM IN
EQUILIBRIUM IS TERMED AS A PHASE.
EXAMPLES:
1.PURE SUBSTANCES, MAY BE LIQUID, SOLIS OR GAS
FORM 1 PHASE.
E.G, OXYGEN,BENZEN AND ICE ARE 1- PHASE.
2.MIXTURE OF GASES, IS ONE PHASE SYSTEM.E.G, ANY
MIXTURE OF GASES LIKE OXYGEN AND NITROGEN FORN
1-PHASE.
3.MISCIBLE LIQUIDS, TWO MISCIBLE LIQUIDS FORM ONE
PHASE.E.G, SOLUTION OF WATER AND ETHANOL IS ONE
PHASE SYSTEM.
4.NON-MISCIBLE LIQUIDS,SOLUTION OF TWO NON
MICIBLE LIQUIDS FORM TWO SEPRATE LAYER N IT WILL
2 PHASE SYSTEM.E.G, MIXTURE OF CHLOROFORM AND
WATER CONSTITUTE 2-PHASE SYSTEM.
5.AQUEOUS SOLUTION,AN AQOUES SOLUTION
LIKE WATER+ SUGER FORM AQUEOUS SOLUTION
AND IT WILL ONE PHASE SYSTEM.
BUT SATURATED SYSTEM OF THAT SOLUTION
WILL FORM 2 PHASE SYSTEM.
AQOUES SOLUTION OF SODIUM CHLORIDE IS 1-
PHASE SYSTEM WHILE ITS SATURATED SYSTEM
FORM 2-PHASE SYSTEM
6.MIXTURE OF SOLIDS:
A. A PHASE HAVE SAME PHYSICAL AND CHEMICAL
PROPERTIES.
A MONOCLINIC AND RHOMBIC SULPHUR ARE TWO
ALLOTROPIC FORMS WHICH ARE CHEMICALLY
SAME BUT PHYSICALLY DIFFERENT AND FORMS 2-
PHASE SYSTEM.
B. A MIXTURE OF TWO OR MORE CHEMICAL
SUBSTANCES CONTAINS AS MANY PHASES.EACH
OF THEM HAVE DIFFERENT CHEMICAL AND
PHYSICALL PROPERTIES.
A MIXTURE OF CALCIUM CARBONATE AND
CALCIUM OXIDE FORM TWO PHASES.WHILE THE
DECOMPOSITION OF CALCIUM CARBONATE
FORMS 3 PHASE SYATEM
WHAT ARE COMPONENTS ?
Defination:
The least number of independent chemical
constituents in terms of which compostion of
every phase can be expressed by means of a
chemical equation
RULES FOR FINDING A COMPONENT:
 Chemical formula representing the composition of a phase
is written on LHS.
 Rest of chemical constituents that are represented in
chemical equation are written on RHS.
 If quantities on RHS are made minus or zero then we get
compostion of phase on LHS.
NUMBER OF COMPONENTS IN A SYSTEM:
 1-Component System:
Only 1 constituent forms the compostion.
 Example :
Water
Suplhur
(ice) (water) (vapours)
 2-Component System:
When two components independently form a compostion then it is 2-
component System.
• Example:
(i) Mixture of two gasses like 02 and N2
Phase Component
Mixture of two = xO2 + yN2
Gases
(ii) Sodium Chloride Solution:
Phase Component
Aq. Sol of = xNaCl + yH2O
NaCl
(iii) Saturated Sol Of NaCl:
Phase Component
Aq.Sol of = xNaCl + yH20
NaCl
Solid NaCl = NaCl + 0H2O
(iv) Decomposition Of Calcium Carbonate:
Equation:
CaCO3 ⇌ CaO + CO2
(solid) (solid) (gas)
Phase Component
CaCO3 = CaO + CO2
CaO = 0CaCO3 + CaO
CO2 = CaCO3 – CaO
SATURATED SOLUTION OF NACL
Mixture of Aq. NaCl and Solid NaCl to form
saturated solution .That is a 2-Component System.
(v) Decomposition Of Ammonium Chloride:
Ammonium Chloride when heated in a closed vessel exisits in
equilibrium with the products of dissociation,ammonia and hydrogen
chloride gas.
Equation:
NH4Cl ⇌ NH3 + HCl
(solid) (gas) (gas)
Phase Components
Solid = NH4Cl
Gaseous = xNH3 + xHCl or NH4Cl
Thus dissociation of Ammonia is a 2-component system.
DEGREE OF FREEDOM :
The least number of variable factors
(concentration,temperature,pressure) which
must be specified so that the remaining
variables are fixed automatically and the
system is completely defined.
 F=0 Non variant.
 F=1 Univariant.
 F=2 Bivariant.
 A system is defined completely when it retain
the same same state of equilibrium with the
specified variables.
 For a pure gas F=2 :
a system containing a pure gas has two
degree of freedom.
 For a mixture of gases F=3:
a mixture of gases has 3 degree of
freedom (F=3)
 For water ⇌ water vapours, F=1:
the system containing water has 1
degree of freedom.
 For saturated NaCl Sol, F=1
NaCl ⇌ NaCl-Solution ⇌ water vapours
the system has 1 degree of Freedom .
 For ice-water -vapour System:
ice ⇌ water ⇌ vapours.
It has no degree of freedom so F=0
DERIVATION OF THE PHASE RULE
 The states of a system will depend upon a
temperature and pressure and these
variables are always there .
 The concentration,however,depend upon the
number of phases.
 The total number of variable of the system:
[P(C-1)+2]
 Thermodynamic Equilibrium:
when a system is in equilibrium the partial
molal free energy of each constituentsof a
phase is equal to the partialmolal free
energy of the same constituents in every
phase.
F=No. of variables – No. of Equations
= [P(C-1)+2] – [C(P-1)]
= PC-P+2-PC+C
F= C-P+2
PHASE DIAGRAM
 Plot showing the conditions of the pressure
and temperature under which two or more
physical states can exist together in a state
of dynamic equilbrium.
CHARACTERISTIC FEATURES:
1. Region or Areas:
Devided into solid liquid and gases.
2. Lines or Cures.
That separates two phases
3. Triple Point.
A triple point shows the conditions under which
all the three phases(solids liquid vapours) can
coexist in equilibrium.
GRAPH SHOWING PHASE DIAGRAM

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Phase rule

  • 1. OUTLINE  PHASE RULE  WHAT IS MEANT BY PHASE  WHAT IS MEANT BY COMPONENTS  DEGREES OF FREEDOM  DERIVATION  ONE COMPONENT SYSTEM  PHASE DIAGRAM
  • 2. PHASE RULE THE PHASE RULE IS AN IMPORTANT GENERALIZATION DEALING WITH THE BEHAVIOR OF HETEROGENEOUS SYSTEM. IN GENERAL IT MAY BE SAID THAT WITH THE APPLICATION OF PHASE RULE IT IS POSSIBLE TO PREDICT QUALITATIVELY BY MEANS OF DIAGRAM. THE EFFECT OF CHANGING PRESSURE , TEMPERATURE AND CONCENTRATION ON A HETEROGENEOUS SYSTEM IN EQUILIBRIUM.
  • 3.  HETEROGENEOUS EQUILIBRIUM IS FIRST DISCOVERED BY AMERICAN PHYSICIST “WILLARD GIBBS” IN 1874. IT MAY BE MATHEMATICALLY STATED AS: F=C – P+2 F= DEGREE OF FREEDOM C=COMPONENTS P=NUMBER OF PHASES OF THE SYSTEM
  • 4. PHASE IT MAY BE DEFINED AS: “ANY HOMOGENOUS PART OF A SYSTEM HAVING ALL PHYSICAL AND CHEMICAL PROPERTIES THE SAME THROUGHOUT”. A PHASE MAY BE OF THREE TYPES: 1. ONE PHASE SYSTEM 2. TWO PHASE SYSTEM 3.THREE PHASE SYSTEM
  • 5. A SYSTEM CONSISTING OF ONE PHASE IS CALLED HOMOGENOUS SYSTEM. A SYSTEM CONSIST OF TWO OR MORE SYSTEM IS CALLED HETEROGENOUS SYSTEM. GENERALY,LIQUID SLOID GASES ARE THREE PHASES BUT IIN PHASE RULE “A UNIFORM PART OF A SYSTEM IN EQUILIBRIUM IS TERMED AS A PHASE.
  • 6. EXAMPLES: 1.PURE SUBSTANCES, MAY BE LIQUID, SOLIS OR GAS FORM 1 PHASE. E.G, OXYGEN,BENZEN AND ICE ARE 1- PHASE. 2.MIXTURE OF GASES, IS ONE PHASE SYSTEM.E.G, ANY MIXTURE OF GASES LIKE OXYGEN AND NITROGEN FORN 1-PHASE. 3.MISCIBLE LIQUIDS, TWO MISCIBLE LIQUIDS FORM ONE PHASE.E.G, SOLUTION OF WATER AND ETHANOL IS ONE PHASE SYSTEM. 4.NON-MISCIBLE LIQUIDS,SOLUTION OF TWO NON MICIBLE LIQUIDS FORM TWO SEPRATE LAYER N IT WILL 2 PHASE SYSTEM.E.G, MIXTURE OF CHLOROFORM AND WATER CONSTITUTE 2-PHASE SYSTEM.
  • 7. 5.AQUEOUS SOLUTION,AN AQOUES SOLUTION LIKE WATER+ SUGER FORM AQUEOUS SOLUTION AND IT WILL ONE PHASE SYSTEM. BUT SATURATED SYSTEM OF THAT SOLUTION WILL FORM 2 PHASE SYSTEM. AQOUES SOLUTION OF SODIUM CHLORIDE IS 1- PHASE SYSTEM WHILE ITS SATURATED SYSTEM FORM 2-PHASE SYSTEM 6.MIXTURE OF SOLIDS: A. A PHASE HAVE SAME PHYSICAL AND CHEMICAL PROPERTIES. A MONOCLINIC AND RHOMBIC SULPHUR ARE TWO ALLOTROPIC FORMS WHICH ARE CHEMICALLY SAME BUT PHYSICALLY DIFFERENT AND FORMS 2- PHASE SYSTEM.
  • 8. B. A MIXTURE OF TWO OR MORE CHEMICAL SUBSTANCES CONTAINS AS MANY PHASES.EACH OF THEM HAVE DIFFERENT CHEMICAL AND PHYSICALL PROPERTIES. A MIXTURE OF CALCIUM CARBONATE AND CALCIUM OXIDE FORM TWO PHASES.WHILE THE DECOMPOSITION OF CALCIUM CARBONATE FORMS 3 PHASE SYATEM
  • 9. WHAT ARE COMPONENTS ? Defination: The least number of independent chemical constituents in terms of which compostion of every phase can be expressed by means of a chemical equation
  • 10. RULES FOR FINDING A COMPONENT:  Chemical formula representing the composition of a phase is written on LHS.  Rest of chemical constituents that are represented in chemical equation are written on RHS.  If quantities on RHS are made minus or zero then we get compostion of phase on LHS.
  • 11. NUMBER OF COMPONENTS IN A SYSTEM:  1-Component System: Only 1 constituent forms the compostion.  Example : Water Suplhur (ice) (water) (vapours)
  • 12.  2-Component System: When two components independently form a compostion then it is 2- component System. • Example: (i) Mixture of two gasses like 02 and N2 Phase Component Mixture of two = xO2 + yN2 Gases (ii) Sodium Chloride Solution: Phase Component Aq. Sol of = xNaCl + yH2O NaCl
  • 13. (iii) Saturated Sol Of NaCl: Phase Component Aq.Sol of = xNaCl + yH20 NaCl Solid NaCl = NaCl + 0H2O (iv) Decomposition Of Calcium Carbonate: Equation: CaCO3 ⇌ CaO + CO2 (solid) (solid) (gas) Phase Component CaCO3 = CaO + CO2 CaO = 0CaCO3 + CaO CO2 = CaCO3 – CaO
  • 14. SATURATED SOLUTION OF NACL Mixture of Aq. NaCl and Solid NaCl to form saturated solution .That is a 2-Component System.
  • 15. (v) Decomposition Of Ammonium Chloride: Ammonium Chloride when heated in a closed vessel exisits in equilibrium with the products of dissociation,ammonia and hydrogen chloride gas. Equation: NH4Cl ⇌ NH3 + HCl (solid) (gas) (gas) Phase Components Solid = NH4Cl Gaseous = xNH3 + xHCl or NH4Cl Thus dissociation of Ammonia is a 2-component system.
  • 16. DEGREE OF FREEDOM : The least number of variable factors (concentration,temperature,pressure) which must be specified so that the remaining variables are fixed automatically and the system is completely defined.
  • 17.  F=0 Non variant.  F=1 Univariant.  F=2 Bivariant.  A system is defined completely when it retain the same same state of equilibrium with the specified variables.
  • 18.  For a pure gas F=2 : a system containing a pure gas has two degree of freedom.  For a mixture of gases F=3: a mixture of gases has 3 degree of freedom (F=3)  For water ⇌ water vapours, F=1: the system containing water has 1 degree of freedom.
  • 19.  For saturated NaCl Sol, F=1 NaCl ⇌ NaCl-Solution ⇌ water vapours the system has 1 degree of Freedom .  For ice-water -vapour System: ice ⇌ water ⇌ vapours. It has no degree of freedom so F=0
  • 20. DERIVATION OF THE PHASE RULE  The states of a system will depend upon a temperature and pressure and these variables are always there .  The concentration,however,depend upon the number of phases.  The total number of variable of the system: [P(C-1)+2]
  • 21.  Thermodynamic Equilibrium: when a system is in equilibrium the partial molal free energy of each constituentsof a phase is equal to the partialmolal free energy of the same constituents in every phase. F=No. of variables – No. of Equations = [P(C-1)+2] – [C(P-1)] = PC-P+2-PC+C F= C-P+2
  • 22. PHASE DIAGRAM  Plot showing the conditions of the pressure and temperature under which two or more physical states can exist together in a state of dynamic equilbrium.
  • 23. CHARACTERISTIC FEATURES: 1. Region or Areas: Devided into solid liquid and gases. 2. Lines or Cures. That separates two phases 3. Triple Point. A triple point shows the conditions under which all the three phases(solids liquid vapours) can coexist in equilibrium.