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KIMIA FISIKA I
The Phase Rule

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The Phase Rule

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The various type of heterogeneous equilibria : vaporation, sublimation, fusion, transition of one solid phase to another, solubility of solids, liquids, etc.

A unified standpoint : phase rule.

2010 Imam Siswanto

Kimia Fisika I

The Phase Rule

Definition
Three types of equilibrium :

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1. True equilibrium : exist in a system when the same state can be realized by approach from either direction.
2. Metastable equilibrium : can be realized by approach from either direction. 3. Unstable equilibrium : system appears to undergo no change with time.

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Kimia Fisika I

The Phase Rule

Definition

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The number of component : the smallest number of independently variable constituents, in term of whose formulas equations may be written expressing the composition of each of the possible phases that may be occurs.

Example :
Water can be in three form : ice, liquid water and water vapor Na2SO4 water can be in : Na2SO4, Na2SO4.7H2O, Na2SO4.10H2O

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Kimia Fisika I

The Phase Rule

Definition

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The degrees of freedom or the variance : the smallest number of independent variables (such as pressure, temperature, concentration) that must be specified in order to define completely the remaining variables of the system. Example : The density of water is 0.99973 gram per milliliter.

2010 Imam Siswanto

Kimia Fisika I

The Phase Rule

The Gibbs Phase Rule

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J. Willard Gibbs (1876) : There is a definite relation in a system between the number of degrees of freedom, the number of components, and the number of phase present.

F = number of variables number of equations = [P(C-1) + 2] [C(P-1)] =CP+2

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Kimia Fisika I

The Phase Rule

One-Component System

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The complexity of one-component system depends on the number of solid phases that can exist in the system.

2010 Imam Siswanto

Kimia Fisika I

The Phase Rule

One-Component System
The System Water

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2010 Imam Siswanto

Kimia Fisika I

The Phase Rule

Two-Component System

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When two components are present in a system, C = 2 and F = 4 P. If the temperature is constant, the remaining variance is F = 3 P, which has the maximum value of 2. One of these two remaining degrees of freedom is pressure and concentration.

2010 Imam Siswanto

Kimia Fisika I

The Phase Rule

Two-Component System
Vapour pressure diagrams

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Raoults law :

p A x A p* A

* p B xB p B

* * * * p p A pB x A p * x p p ( p p A B B B A B ) xA

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Kimia Fisika I

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The Phase Rule

Two-Component System
The Composition of the vapour

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The Daltons law for the gas :

yA

pA p

yB

pB p

x A p* A yA * * pB p * A pB x A yB 1 y A

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Kimia Fisika I

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The Phase Rule

Two-Component System
The Composition of the vapour

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Relation between the total vapour pressure to the composition of the vapour :
* p* A pB p * * p A pB p* A yA

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The Phase Rule

Two-Component System
The interpretation of the diagrams

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Relation between the total vapour pressure to the composition of the vapour :

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Kimia Fisika I

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The Phase Rule

Two-Component System
The interpretation of the diagrams

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Kimia Fisika I

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The Phase Rule

Two-Component System
The lever rule

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n l n l

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The Phase Rule

Two-Component System
Temperature-composition diagrams

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The Phase Rule

Two-Component System
The distillation of mixtures

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The efficiency of a fractionating column is expressed in terms of the number of the theoretical plates, the number of effective vaporation and condensation and steps that are required to archieve a condensate of given composition from a given distillate.

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Kimia Fisika I

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The Phase Rule

Two-Component System
Azeotropes = boiling without changing

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The Phase Rule

Two-Component System
Liquid-liquid phase diagrams, phase separation

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The Phase Rule

Two-Component System
Critical Temperature

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The Phase Rule

Two-Component System
Critical Temperature

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The Phase Rule

Two-Component System
Liquid-solid phase diagrams

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The Phase Rule

Two-Component System
Eutetics = easily melted

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Kimia Fisika I

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