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Lecture 2a

Lecture 2a: Properties of Pure Substances

A Pure Substance

Pure substance: a material with homogeneous and invariable composition.

A substance that has a fixed chemical composition throughout is called pure
substance. Water, helium carbon dioxide, nitrogen are examples.

To elaborate,

Pure substances can have multiple phases: an ice-water mixture is still a pure
substance.
An air-steam mixture is not a pure substance.
Air, being composed of a mixture of N2, O2, and other gases, is formally not a pure
substance. However, experience shows that we can often treat air as a pure substance
with little error.

Phases of a Pure Substance

There are three principle phases solid, liquid and gas, but a substance can have several other
phases within the principle phase. Examples include solid carbon (diamond and graphite)
and iron (three solid phases). Nevertheless, thermodynamics deals with the primary phases
only.
In general:

Solids have strongest molecular bonds.

Solids are closely packed three dimensional crystals.
Their molecules do not move relative to each other
Intermediate molecular bond strength
Liquid molecular spacing is comparable to solids but their molecules can float about
in groups.
There is molecular order within the groups
Weakest molecular bond strength.
Molecules in the gas phases are far apart, they have no ordered structure
The molecules move randomly and collide with each other.
Their molecules are at higher energy levels, they must release large amounts of
energy to condense or freeze.

Vapour-liquid-solid phase equilibrium

Often different phases of pure substances can exist in equilibrium with one another. Let us
consider an important gedanken experiment (Latin-German for thought experiment) in
which we boil water in an open container. However, this ordinary experiment has constraints
which are too loose. Most importantly, the mass of water leaks into the atmosphere; thus, the
water vapour and the air become a mixture and no longer a pure substance.

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Lecture 2a

Let us instead consider a more controlled piston-cylinder arrangement. Inside the cylinder,
we begin with pure liquid water at T = 20C. The piston is free to move in the cylinder, but it
is tightly sealed, so no water can escape. On the other side of the piston is a constant pressure
atmosphere, which we take to be at P = 100 kPa = 0.1 MP a = 105 Pa = 1 bar.
Slowly add heat to the cylinder, and observe a variety of interesting phenomena. A sketch of
what is observed is given in Fig. 2.1. The following behaviour is noticed:

Figure 2.1: Sketch of experiment in which heat is added isobarically to water in a closed
piston-cylinder arrangement.
The pressure remains at a constant value of 100 kPa. This is an isobaric process.

The total volume increases slightly as heat is added to the liquid.

The temperature of the liquid increases significantly as heat is added to the liquid.
At a special value of temperature, observed to be T = 99.62C, it is all liquid, but
cannot add any more heat and retain all liquid. This state is called the saturated liquid
state. The temperature T = 99.62C is the saturation temperature at P = 100 kPa. As
heat is continuously added,
The temperature remains constant (this is isothermal now as well as isobaric).
The total volume continues to increase.
We notice two phases present: liquid and vapour, with a distinct phase
boundary. The liquid is dense relative to the vapour. That is f > g, where f
denotes fluid or liquid and g denotes gas or vapour. Thus, vg > vf.
As more heat is added, more vapour appears, all while P = 100 kPa and T =
99.62C.
At a certain volume, there is all vapour and no liquid, still at P = 100 kPa, T =
99.62C. We call this state the saturated vapour state.
As heat is added, both the temperature and the volume rise, with the pressure
remaining constant. The water remains in the all vapour state.

This is called boiled water! This process is sketched on the temperature-specific volume
plane, that is, the plane, in Fig. 2.2. Note that the mass m of the water is constant in
this problem, so the extensive V is strictly proportional to specific volume, = / .
Next repeat this experiment at lower pressure (such as might exist on a mountain top) and at a
higher pressure (such as might exist in a valley below sea level). For moderate pressures, we
find qualitatively the exact same type of behaviour. The liquid gets hotter, turns into vapour

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isothermally, and then the vapour gets hotter as the heat is added. However, the following
important facts are noted:

The saturation temperature (that is the

boiling point) increases as pressure
increases, as long as the pressure
increase is not too high.
As pressure increases becomes
closer to .
Above a critical pressure, =
=
22.089
, there is no phase
change observed! At the critical
pressure, the temperature takes on a
critical temperature of
=
374.14. At the critical pressure
and temperature, the specific volume
takes the value
=
=
=
0.003155
/ .

Fig. 2.3 shows the boiling point changes with

pressure by plotting the saturation pressure as
a function of saturation temperature in the
plane. This is the called vapour
pressure curve. Here, focus is on liquidvapour mixtures and T is kept high enough to
prevent freezing. Note the curve terminates
abruptly at the critical point.

Figure 2.2: Isobar in the T v plane for our

thought experiment in which heat is added
isobarically to water in a piston-cylinder
arrangement.

The following nomenclature is adopted:

SATURATED LIQUID: the material

is at
and is all liquid.
SATURATED VAPOR: the material is
at
and is all vapour.
COMPRESSED (SUBCOOLED)
LIQUID: the material is liquid with
<
.
SUPERHEATED VAPOR: the
material is vapour with >
.
TWO-PHASE MIXTURE: the
material is composed of co-existing
liquid and vapour with both at
.

Figure 2.3: Saturation pressure versus

saturation temperature sketch.

For two-phase mixtures, we define a new property to characterize the relative concentrations
of liquid and vapour. We define the

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QUALITY =
mixture mass:

: as the ratio of the mass of the mixture which is vapour (vap) to the total

Mass of saturated vapour

=
Total mass

The total mass to be the sum of the liquid and vapour masses:
=

So
=

There are two important limits to remember:

= 0: corresponds to
is the all liquid limit.
= 1: corresponds to
This is the all gas limit.

= 0. This
=

We must have
0
Note, quantity 1
mixture becomes

Figure 2.4: Specific volumes at constant

temperature and states within the vapour
dome in a liquid-vapour system

is often given the name moisture. The specific volume of the saturated
= (1 )

The form that we use most often is

+

The waters T v plane is sketched

again for a wide variety of isobars in
Fig. 2.5.
The waters P v plane for a wide
variety of isotherms is sketched in Fig.
2.6. A similar thought experiment can be
performed for ice. Start ice at =
100
and add heat to it. Now
observe the ices temperature rise until
=
0 . At that temperature,
the ice begins to melt and the
temperature remains constant until all
the ice is melted. At this point the liquid
Figure 2.5: Sketch of T v plane for water for a
variety of isobars.

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temperature begins to rise. If continued to add heat, the water would boil.
If this experiment is performed
for P < 0.6113
the ice in
fact goes directly to vapour. It is
said to have undergone
sublimation. There exists a
second important point where ice
being heated isobarically can
transform into either liquid or
gas. This is the so called triple
point. At the triple point we find
the saturation pressure and
temperature are Ptp =
0.6113
and Ttp = 0.01,
respectively. It is better described
as a triple line, because in the
P T space, it appears as
Figure 2.6: Sketch of P v plane for water for a variety of
a line with constant P and T, but
isotherms.
variable v. In the P T
projected plane of the P T volume, it projects as a point. We sketch waters P T
plane again for a wider range to include the vapour-liquid-solid phase behaviour in Fig. 2.7.
These characteristics apply to all pure substances. For example, nitrogen has a triple point
and a critical point. Note also that phase transitions can occur within solid phases. This
involves a re-arrangement of the crystal structure. This has important implications for
material science, but will not be considered in detail in this course.

Figure 2.7: Sketch of P T plane for water.