Examples of One Component System

I. The Water System

Water is a three-phase, one-component system. The three phases involved are liquid water, ice, water
vapor. All these phases can be represented by one chemical entity H2O and hence one component of the
system. The number of phases which can exist in equilibrium any time depends on the conditions of
temperature and pressure. The phase diagram or PT-graph of the system/ water/ice/vapour is shown in
Fig. The salient features of the phase diagram are listed below.

(1) The Curves OA, OB, OC

(2) The Triple Point O

(3) The Areas AOC, AOB, BOC

Figure 1: The phase diagram of water

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Let us proceed to discuss the significance of each of these features.

1. The Curves OA, OB, OC

These three curves meet at the point O and divide the diagram into three regions or areas.
 Curve OA, the Vapour Pressure curve of Water.

It represents the vapour pressure of liquid water at different temperatures. The two phases water and
water vapour coexist in equilibrium along this curve. The curve OA terminates at A, the critical point
(218 atm, temp. 374ºC) when the liquid and vapour are indistinguishable from each other and there is left
one phase only. When the vapour pressure is equal to one-atmosphere, the corresponding temperature, as
indicated on the phase diagram is the boiling point (100ºC) of water.

 Curve OB, the Sublimation curve of Ice.

It shows the vapour pressure of solid ice at different temperatures. The two phases solid ice and vapour
coexist in equilibrium along this curve. At the lower limit the curve OB terminates at absolute zero (–
273ºC) where no vapour exists.

 Curve OC, the Fusion curve of Ice

It depicts the effect of pressure on the melting point of ice. Here ice and water coexist in equilibrium.
The fact that OC slopes to the left indicates that the melting point of ice decreases with increase of
pressure. Since ice melts with decrease in volume by Le-Chatelier’s principle the melting point is lowered
by an increase of pressure. It may be noted that the 1.0 atmosphere line meets the fusion curve at 0ºC
which is the normal melting point of ice. Along the curves OA, OB, OC there are two phases in
equilibrium and one component.

Therefore,

F=C–P+2=1–2+2=1

Hence each two-phase system: water/water vapour represented by OA ice/water vapour represented by
OB ice/water represented by OC has one degree of freedom i.e., is monovariant.

2. The Triple point ‘O’

The curves OA, OB and OC meet at the triple point ‘O’ where all the three phases liquid water/
ice/vapour are in equilibrium. This occurs at 0.0076ºC and vapour pressure 4.58 mm Hg. Since there are
three phases and one component, we have

F = C– P + 2 = 1 – 3 + 2 = 0

i.e., the system at the triple point is nonvariant. Thus if either pressure or temperature is changed, the
three phases would not exist and one of the phases would disappear.
 3. Area AOC, AOB, BOC

The areas or regions between the curves show the conditions of temperature and pressure under which a
single phase–ice, water or vapour is capable of stable existence. Thus, Area AOC represents conditions
for the one-phase system water.

 Area AOB represents conditions for the one-phase system water vapour
 . Area BOC represents conditions for the one-phase system ice.

In all the three areas there being one-phase and one-component, we have

F=C–P+2=1–1+2=2

Thus each system water, water vapour, or ice has 2 degrees of freedom i.e., the system is bivariant.

Metastable system: Super cooled Water/Vapour System

The vapour pressure curve of water AO can be continued past the triple point as shown by the dashed line
OA'. That is, water can be super cooled by carefully eliminating solid particles. The super cooled
water/vapour system is metastable (unstable). It at once reverts to the stable system ice/vapour on the
slightest disturbance or introducing a crystal of ice.

II. The Sulphur System

It is a one-component, four-phase system. The four phases are :

i. Two solid polymorphic forms

 Rhombic Sulphur (SR)
 Monoclinic Sulphur (SM)
ii. Sulphur Liquid (SL)
iii. Sulphur Vapour (SV)

All the four phase can be represented by the only chemical individual ‘Sulphur’ itself and hence one
component of the system. The two crystalline forms of Sulphur S R and SM exhibit enantiotropy with a
transition point at 95.6ºC. Below this temperature SR is stable, while above it SM is the stable variety. At
95.6ºC each form can be gradually transformed to the other and the two are in equilibrium. At 120ºC, SM
melts. Thus,

SR ⇌ SM ⇌ SL
The phase diagram for the Sulphur system is shown in Fig. The salient features of the phase diagram are
described below.

i. The six curves AB, BC, CD, BE, CE, EG

ii. The three Triple points B, C, E
iii. The four areas
 ABG marked ‘solid Rhombic’
 BEC marked ‘solid Monoclinic’
 GECD marked ‘liquid Sulphur’
 ABCD marked ‘Sulphur vapour’

Let us now proceed to discuss the significance of these features

(1) The curves AB, BC, CD, BE, CE, EG

These six curves divide the diagram into four areas. Curve AB, the Vapour Pressure curve of SR. It
shows the vapour pressure of solid rhombic sulphur (S R) at different temperatures. Along this curve
the two phases SR and sulphur vapour (SV) are in equilibrium. The system SR/SV has one degree of
freedom
F=C–P+2=1–2+2=1
i.e., it is monovariant.

Figure 2: The phase diagram of Sulphur

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  Curve BC, the Vapour Pressure curve of SM.

It shows variation of the vapour pressure of monoclinic sulphur (S M) with temperature. SM and SV coexist
in equilibrium along this curve. The system SM/SV is monovariant.

 Curve CD, the Vapour Pressure curve of SL

It depicts the variation of the vapour pressure of liquid Sulphur (S L) with temperature. SL and SV are in
equilibrium along CD. The two phase system S L/SV is monovariant. One atmosphere line meets this curve
at a temperature (444.6ºC) which is the boiling point of Sulphur.

 Curve BE, the Transition curve

It shows the effect of pressure on the transition temperature for S R and SM. As two solid phases are in
equilibrium along the curve, the system S R/SM is monovariant. The transformation of SR and SM is
accompanied by increase of volume (density of SR = 2.04; SM = 1.9) and absorption of heat i.e.,

SR + Q (heat energy) ⇌ SM

Thus the increase of pressure will shift the equilibrium to the left (Le Chatelier’s Principle) and the
transition temperature will, therefore, be raised. This is why the line BE slopes away from the pressure
axis showing thereby that the transition temperature is raised with increase of pressure.

 Curve CE, the Fusion curve of SM.

It represents the effect of pressure on the melting point of SM. The two phases in equilibrium along this
curve are SM and SL. The system SM/SL is monovariant. As the melting or fusion of S M is accompanied by
a slight increase of volume, the melting point will rise by increase of pressure (Le Chatelier’s principle).
Thus the curve CE slopes slightly away from the pressure axis. The curve ends at E because S M ceases to
exist beyond this point.

 Curve EG, the Fusion curve for SR.

Here the two phases in equilibrium are S R and SL. The number of phases being two, the system S R/SL is
monovariant.

(2) The Triple points B, C, E

Triple point B. This is the meeting point of the three curves AB, BC and BE. Three phases, solid S R, solid
SM and SV are in equilibrium at the point B. There being three phases and one component, the system
SR/SM/SL is nonvariant.
 F=C–P+2=1–3+2=0

At B, SR is changed to SM and the process is reversible. Thus the temperature corresponding to B is the
transition temperature (95.6ºC). Triple point C. The curves BC, CD, CE meet at this point. The three
phases in equilibrium are S M, SL and SV. There being three phases and one component, the system
SM/SL/SV is nonvariant. The temperature corresponding to C as indicated on the phase diagram is 120ºC.
This is the melting point of SM. Triple point E. The two lines CE and BE, having different inclinations
away from the pressure axis, meet at E where a third line EG also joins. The three phases S R, SM and SL
are in equilibrium and the system at the point E is nonvariant. This point gives the conditions of existence
of the system SR/SM/SL at 155ºC and 1290 atmospheres pressure.

(3) The Areas

The phase diagram of the Sulphur system has four areas or regions. These are labelled as rhombic
Sulphur, monoclinic Sulphur, liquid Sulphur and vapour. These represent single phase systems which
have two degrees of freedom

F=C–P+2=1–1+2=2

That is, each of the systems SR, SM, SL, and SV are bivariant.

(4) Metastable Equilibria

The change of SR to SM takes place very slowly. If enough time for the change is not allowed and SR is
heated rapidly, it is possible to pass well above the transition point without getting SM. In that case,
there being three phases (SR, SL, SV) only and one component, the phase diagram, like that of water
system, will consist of three curves, one triple point and three areas.

 The dashed curve BF, the Vapour Pressure curve of metastable SR.

This is a continuation of the vapour pressure curve AB of stable S R. The metastable phases S R and SV
are in equilibrium along this curve. It is a monovariant system.

 The dashed curve CF, the Vapour Pressure curve of supercooled SL.

On supercooling liquid sulphur, the dashed curve CF is obtained. It is, in fact, the back prolongation of
DC. The curve CF represents the metastable equilibrium between supercooled S L and SV. Thus it may be
designated as the vapour pressure curve of supercooled SL. It meets the dashed curve BF at F.

 The dashed curve FE, the Fusion curve of metastable SR.

The two metastable phases SR and SL are in equilibrium along this curve and the system is monovariant.
This shows that the melting point of metastable S R is increased with pressure. Beyond E, this curve
depicts the conditions for the stable equilibrium SR/SL as the metastable SR disappears.

 The metastable Triple point F.

At this point, three metastable phases S R, SL and SV are in equilibrium. The system is a metastable triple
point with no degree of freedom. The corresponding temperature is the melting point of metastable S R
(114ºC).