2.2. Phase Equilibria
2.2. Phase Equilibria
2.2. Phase Equilibria
phase rule
Phase equilibria and the phase rule
Phase equilibria: the equilibria exist between the
phase of a system. Example: the equilibrium exists
between water and steam.
Phase is a homogeneous, physically distinct portion
of a system that is separated from other portions of
the system by bounding surfaces.
The three primary phases (solid, liquid, and gaseous)
are defined individually under different conditions.
But in most systems we encounter phases in
coexistence.
For example, a glass of ice water on a hot summer
day comprises three coexisting phases: ice(solid),
water (liquid), and vapour (gaseous). 2
The phase rule
The Phase Rule expresses the relation between
phases, phase compositions, and intensive variables
(e.g. temperature and pressure) in a system of a
given composition at equilibrium.
J. Willard Gibbs formulated the phase rule, which is a
relationship for determining the least number of
intensive variables (independent variables that do
not depend on the size of the phase, e.g.,
temperature, pressure, density, and concentration),
the least number required to define the state of the
system.
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The phase rule (cont’d)
This critical number is called F, the number of
degrees of freedom of the system, and the rule is
expressed as follows:
F = C-P+2
Where, C is the number of components and P is the
number of phases present.
The degree of freedom is the least number of
intensive variables that must be known to describe
the system completely.
Although a large number of intensive properties are
associated with any system, it is not necessary to
report all of these to define the system. 4
The phase rule (cont’d)
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The phase rule (cont’d)
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The phase rule (cont’d)
In any one of the three regions of phase diagram of
water, in which pure solid, liquid, or vapor exists, the
phase rule gives
F = 1-1+2 = 2
Therefore, we must fix two conditions, namely
temperature and pressure, to specify or describe
the system completely.
This statement means that if we were to record the
results of a scientific experiment involving a given
quantity of water, it would not be sufficient to state
that the water was kept at, say, 76 oC.
The pressure would also have to be specified to
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define the system completely.
The phase rule (cont’d)
– Melting/freezing
– Vaporization/condensation
– Sublimation/deposition
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Phase equilibria of two- component
system
A maximum of three degrees of freedom is possible
in a two-component system, for example,
temperature, pressure and concentration.
Because in practice we are primarily concerned with
liquid and/or solid phases in the particular system
under examination, we frequently choose to
disregard the vapor phase and work under normal
conditions of 1 atm ( 760 mm Hg) of pressure.
In this manner we reduce the number of degrees of
freedom by one.
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Phase equilibria of two- component
system (cont’d)
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Two- component systems containing
liquid phases
The curve gbhci shows the limits of temperature and
concentration within which two liquid phases exist in
equilibrium.
The region outside this curve contains systems having
one liquid phase.
Starting at the point a, equivalent to a system
containing 100% water (i.e., pure water) at 50 oC,
Adding known increments of phenol to a fixed weight
of water, the whole being maintained at 50 oC, will
result in the formation of a single phase until the point
b is reached, at which a minute amount of second
phase appears i.e. at 11% by weight of phenol in water 16
Two- component systems containing
liquid phases (cont’d)
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Applications of phase diagram
The phase diagram is used in practice to formulate
systems containing more than one component where
it may be advantageous to achieve a single phase
product.
A number of solutions containing different
concentrations of phenol are official in several
pharmacopeias.
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Three component systems (ternary system)
For three component (A, B, C) systems at
constant temperature and pressure, the
composition can be expressed in terms of the
coordinates of an equilateral triangle.
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Three component systems…
In figure each corner of the triangle represents a
pure component, i.e. 100% A, 100% B and 100% C.
Each side represents a binary mixture and the
interior represents all ternary compositions.
A line parallel to one side of the triangle represents a
constant percentage of one component.
For e.g., DE (parallel to BC) represents 20% A with
varying amounts of B and C.
Similarly, line FG (parallel to AC) represents all
mixtures containing 50% of B.
These lines intersect at K which must be 20% of A,
50% of B, and therefore 30% of C.
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Three component systems…
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