PHASE DIAGRAMS

Chapter 5
(part 1)

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In this chapter, the following topics will be discussed

 Phases, components, and degrees of freedom

 The phase rule
 One component systems
 Two-component systems

Vapour pressure diagrams

Temperature-composition diagrams
Liquid-liquid phase diagrams
Liquid-solid phase diagrams

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 Introduction
• Thermodynamics of simple mixtures can be applied to
discuss the physical changes of mixtures when they are
heated or cooled and when their compositions are
changed.

• The phase rule of Gibbs allow us to discuss the phase

diagrams and determine the phases composition.

• Phase diagrams can be used to judge whether two

substances are mutually miscible or not under certain
conditions of T, P and composition.
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• We will see whether equilibrium can exist over a range of
conditions or whether a system must be bought to a definite
pressure, temperature and composition before equilibrium is
established.

• Phase diagrams are industrially and commercially important.

• Semiconductor, ceramics, steel and alloy industries rely heavily

on phase diagrams to ensure uniformity of a product.

• Phase diagrams are also the basis for separation procedures in

the petroleum industry and the formulation of foods and
cosmetic preparations.
• Then we can say that phase diagrams are extremely useful for
chemical engineering.

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 Phases, components, and degrees of freedom
Definitions:
1. A phase is a state of matter that is uniform, not only in
composition but also in physical state. The number of
phase in a system is denoted P.

– Examples of single phase system

A pure gas, A gaseous mixture, Two totally miscible liquids,
A crystal , A solution of sodium chloride , Ice.

– Examples of two phase system

A mixture of ice and water.
An alloy is a mixture of two metals, like Fe + Cu, is a two phase
system if the metals are immiscible, but a single phase system if
they are miscible.
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2. A constituent of a system is a chemical species (ion or
molecule) that is present. A mixture of water and ethanol has
two constituents. A solution of sodium chloride has three
constituents: Na+, Cl-, H2O.

3. A component is a chemically independent constituent of a

system. The number of components in a system is the
minimum number of independent species necessary to
define the composition of all the phases present in the
system.

Remark: When no reaction takes place and there are no other

constraints, the number of components is the equal to the
number of constituents.

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Phase Rule
• The number of phases, is denoted P.
• The number of components, is denoted C.
• The variance (degree of freedom) of the system, denoted F is
the number of intensive variables (e.g. p and T) that can be
changed independently without disturbing the number of
phases in equilibrium.
F=C–P+2
• This is not an empirical rule based upon observations, it can
be derived from chemical thermodynamics .
• For a one component system F = 3 – P
• When only one phase is present, F = 2 and both p and T can
be varied without changing the number of phases.
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 C=c–r
C: Number of components
c : Number of constituents
r : Number of reactions (+ the electrical neutrality reaction in the case of aqueous
solutions).

C
F = C – P + 2 = (c – r) – P +2

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Examples:
1) Perfect gas : F = 1 – 0 – 1 + 2

2) Aqueous solution of NaCl:

Na+ , Cl- , H3O+, OH- and H2O

c=5,r=2;P=1; 2 intensive parameters (P and T)

F=5–2–1+2=4
4 independent intensive parameters can be chosen arbitrarily without changing the
number of phases present.

3) Saturated aqueous solution of NaCl:

Na+ , Cl- , H3O+, OH- ; H2O and NaCl

c=6,r=3;P=2; 2 intensive parameters (P and T)

F = 6 – 3 – 2 +2 = 3

Only 3 independent intensive parameters can be chosen arbitrarily without changing the
number of phases present.
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• When two phases are present, F = 1 which implies that only
one variable can be varied independently (p or T). This is
why at a given temperature a liquid has a characteristic vapor
pressure.

• When three phases are present, F = 0 (no independent

variable, degree of freedom =0). This special case occurs
only at a definite temperature and pressure it is characteristic
of the substance.

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 One Component Systems
The location of phase boundaries for monocomponent diagrams P = f(T)
when two phases are in equilibrium, their chemical potentials must be equal. Therefore, where
the phases α and β are in equilibrium,
μ(α; p,T) =μ(β; p,T)
dμ(α) = dμ(β).

We know that : μ = Gm <==> dGm = dμ

dGm=dμ =Vmdp − SmdT

−Sm(α)dT + Vm(α)dp = −Sm(β)dT + Vm(β)dp

where Sm(α) and Sm(β) are the molar entropies of the phases and Vm(α) and Vm(β) are their
molar volumes. Hence

{Vm(β) − Vm(α)}dp = {Sm(β) − Sm(α)}dT

which rearranges into the Clapeyron equation:

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The Clapeyron equation is an exact expression for the slope of the tangent to the boundary
at any point and applies to any phase equilibrium of any pure substance. It implies that
we can use thermodynamic data to predict the appearance of phase diagrams and to
understand their form. A more practical application is to the prediction of the response of
freezing and boiling points to the application of pressure.
The solid–liquid boundary

We can obtain the formula for the phase boundary by integrating dp/dT, assuming that ΔfusH
and ΔfusV change so little with temperature and pressure that they can be treated as constant.
If the melting temperature is T* when the pressure is p*, and T when the pressure is p, the
integration required is

When T is close to T*, the logarithm can be approximated by using:

Therefore:

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This expression is the equation of a steep straight line when p is plotted against T

A typical solid–liquid phase boundary slopes steeply upwards. This

slope implies that, as the pressure is raised, the melting temperature
rises. Most substances behave in this way.
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 The liquid–vapour boundary

For a gas : ΔvapV ≈ Vm(g). if the gas behaves perfectly, Vm(g) = RT/p. These two
approximations turn the exact Clapeyron equation into

which rearranges into the Clausius–Clapeyron equation for the variation of vapour pressure
with temperature:

this equation can be integrated as follows:

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where p* is the vapour pressure when the temperature is T* and p the vapour pressure
when the temperature is T. Therefore, because the integral on the left evaluates to ln(p/p*),
the two vapour pressures are related by:

Equation 4.12 is plotted as the liquid–vapour boundary in Fig. 4.17. The line does
not extend beyond the critical temperature Tc, because above this temperature
the liquid does not exist.

A typical liquid–vapour phase boundary.

The boundary can be regarded as a plot of
the vapour pressure against the
temperature.

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 The solid–vapour boundary

The only difference between this case and the last is the replacement of the enthalpy of
vaporization by the enthalpy of sublimation, ΔsubH.

Typical one component phase diagram

plotted from Clapeyron equation

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 One Component Systems
Given below the diagram of pure water (F = 3 - P)

The phase diagram for water , T3 marks the temperature of the triple
point, Tb the normal boiling point (p = 1atm), and Tf the normal
freezing point.
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• When only phase is present F = 2, (p and T can be varied
independently without changing the number of phases). A
single phase is represented by an area on a phase diagram.

• When two phases are in equilibrium F = 1, (p or T can be

varied independently) the equilibrium of two phases is
represented by a line in the phase diagram.

• When three phases are in equilibrium, F= 0 and the system is

invariant. The equilibrium of three phases is represented by
a point, the triple point, on a phase diagram.

• Four phases cannot be in equilibrium in a one-component

system because F cannot be negative.
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This diagram summarizes the changes that take place when a
sample is cooled at constant pressure. At a, the sample remains
entirely gaseous until the temperature reaches b, when liquid
appears. Two phases are now in equilibrium (Liq/gas).
Lowering the temperature takes the system to c in the one phase,
liquid region, the temperature can now be varied around the
point c. Ice appears at d and two phases are now in equilibrium
(Solid/Liquid). Then lowering the temperature takes the system
to e in the one phase solid region.

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• Thermal analysis: a sample is allowed to cool and its
temperature is monitored. When a phase transition occurs,
cooling may stop until the phase transition is complete and
is easily observed on a thermogram.

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