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Phase Rule

The Gibbs phase rule is a thermodynamic equation that relates the number of phases, components, and degrees of freedom in a system at equilibrium, expressed as F=C−P+2. In a three-component system, represented by a triangular phase diagram, the phase rule simplifies to F=4−P, with degrees of freedom varying from one to five phases. The document also discusses the concept of ternary eutectic points and provides examples of three-component systems.

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19 views3 pages

Phase Rule

The Gibbs phase rule is a thermodynamic equation that relates the number of phases, components, and degrees of freedom in a system at equilibrium, expressed as F=C−P+2. In a three-component system, represented by a triangular phase diagram, the phase rule simplifies to F=4−P, with degrees of freedom varying from one to five phases. The document also discusses the concept of ternary eutectic points and provides examples of three-component systems.

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20che147 SIRANJEEVI C
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PHASE RULE

Gibbs phase rule

The Gibbs phase rule is a thermodynamic equation that describes the relationship between the
number of phases, components, and degrees of freedom in a system in thermodynamic
equilibrium: The equation for the Gibbs phase rule is 𝐹=𝐶−P+2
 F: The number of independent thermodynamic variables

 C: The number of chemical components, or the number of atom or molecule types

 P : The number of phases

Phase Rule Derivation

Consider a heterogeneous system with Pn phases and Cn components in equilibrium. Also, let's
assume that there's no chemical reaction when a component moves from one phase to another.
The equilibrium state of this system can be characterized by the following parameters:

o Pressure: remains constant across all phases


o Temperature: remains constant across all phases
o Concentration
o The independent concentration variable for one phase in relation to the C components is
C – 1. Thus, the independent concentration variables for P phases with respect to C
components is P (C – 1).
o Hence, total number of variables = P (C – 1) + 2….. (1)
o b. The total number of equilibria:
o The multiple phases in the system can only maintain equilibrium if the chemical potential
(µ) of each component is identical across all phases, i.e.,

µ1, P1 = µ1, P2 = µ1, P3 = … = µ1, P

The number of equilibria for each P phases for each component is P – 1.

For C components, the number of equilibria for P phases is C ( P – 1).


Therefore, the total number of equilibria involved is E = C (P – 1)… (2)

Setting eq (1) and (2) equal to each other, we get

F=[P(C−1)+2]−[C(P−1)]
F=[CP−P+2−CP+C]
F=C−P+2

A three-component system

A three-component system, also known as a ternary system, is a system that contains


three components. The properties of a three-component system can be represented by a phase
diagram, which is a triangular graph that shows the phases that exist in equilibrium at a given
condition.

Here are some characteristics of a three-component system:

1.Phase diagram

The phase diagram of a three-component system is a triangular graph with each pure
component at the apex of the triangle. A point inside the triangle represents a three-component
system, while a point on the edge of the triangle represents a two-component system.

2.Phase rule
The phase rule for a three-component system is 𝐹=4−𝑃 , where 𝑃 is the number of phases

3.Degrees of freedom
A three-component system can have one to five phases. When there is one phase, there
are four degrees of freedom: temperature, pressure, and two of the component
concentrations. When there are five phases, there are no degrees of freedom.
4. Equilibrium

An invariant point is when there is equilibrium between four phases.


5. Ternary eutectic point
The ternary eutectic point is where crystals of A, B, and C are in equilibrium with a
liquid. Examples are
1. Alcohol, camphor, and water: A ternary phase diagram can be used to study the effect of
alcohol on the solubility of camphor in water

2. Chloroform, acetic acid, and water: A phase diagram can be created for this three-
component system.

The phase behavior of mixtures containing three components (ternary systems) is conveniently
represented in a triangular diagram, such as that shown in the figure. Such diagrams are based on
the property of equilateral triangles that the sum of the perpendicular distances from any point to
each side of the diagram is a constant and equal to the length on any of the sides. Thus,
the composition xi of the ternary system as represented by point A in the interior of the triangle
of the above figure.

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