PURE SUBSTANCE

A substance that has a fixed chemical composition throughout is called a pure substance. Water,
nitrogen, helium, and carbon dioxide, for example, are all pure substances.

PHASE-CHANGE PROCESSES OF PURE SUBSTANCES

There are many practical situations where two phases of a pure substance coexist in equilibrium. Water
exists as a mixture of liquid and vapor in the boiler and the condenser of a steam power plant.

Compressed Liquid and Saturated Liquid

Consider a piston–cylinder device containing liquid

water at 20°C and 1 atm pressure (state 1, Fig.1).
Under these conditions, water exists in the liquid
phase, and it is called a compressed liquid, or a
subcooled liquid, meaning that it is not about to
vaporize. Heat is now transferred to the water. As the
temperature rises, the liquid water expands slightly,
and so its specific volume increases. The pressure in
Fig 1: At 1 atm and 20°C, water exists in the
the cylinder remains constant at 1 atm during this
liquid phase (compressed liquid).
process.

As more heat is transferred, the temperature keeps

rising until it reaches 100°C (state 2, Fig. 2). At this
point water is still a liquid, but any heat addition will
cause some of the liquid to vaporize. That is, a phase-
change process from liquid to vapor is about to take
place. A liquid that is about to vaporize is called a
saturated liquid. Therefore, state 2 is a saturated
liquid state.

Fig 2: At 1 atm pressure and 100°C, water

exists as a liquid that is ready to vaporize
(saturated liquid).
 Saturated Vapor and Superheated Vapor

Once boiling starts, the temperature stops rising until

the liquid is completely vaporized. That is, the
temperature will remain constant during the entire
phase-change process if the pressure is held constant.
During a boiling process, the only change we will
observe is a large increase in the volume and a steady
decline in the liquid level as a result of more liquid
turning to vapor.

Fig 3: As more heat is transferred, part of the Midway about the vaporization line (state 3, Fig. 3),
saturated liquid vaporizes (saturated liquid– the cylinder contains equal amounts of liquid and
vapor mixture). vapor. As we continue transferring heat, the
vaporization process continues until the last drop of
liquid is vaporized (state 4, Fig. 4). A vapor that is
about to condense is called a saturated vapor.
Therefore, state 4 is a saturated vapor state. A
substance at states between 2 and 4 is referred to as a
saturated liquid–vapor mixture since the liquid and
vapor phases coexist in equilibrium at these states.

Once the phase-change process is completed, we are

back to a singlephase region again (this time vapor),
Fig 4: At 1 atm pressure, the temperature
and further transfer of heat results in an increase in
remains constant at 100°C until the last drop
both the temperature and the specific volume (Fig. 5).
of liquid is vaporized (saturated vapor).
At state 5, the temperature of the vapor is, let us say,
300°C; and if we transfer some heat from the vapor, the
temperature may drop somewhat but no condensation
will take place as long as the temperature remains above
100°C (for P = 1 atm). A vapor that is not about to
condense (i.e., not a saturated vapor) is called a
superheated vapor. Therefore, water at state 5 is a
superheated vapor. This constant-pressure phase-
change process is illustrated on a T-v diagram in Fig.
6.
Fig 5: As more heat is transferred, the If the entire process described here is reversed by
temperature of the vapor starts to rise cooling the water while maintaining the pressure at the
(superheated vapor). same value, the water will go back to state 1, retracing
the same path, and in so doing, the amount of heat
released will exactly match the amount of heat added
during the heating process.

Saturation Temperature and Saturation Pressure

It probably came as no surprise to you that water started to boil at 100°C. Strictly speaking, the
statement “water boils at 100°C” is incorrect. The correct statement is “water boils at 100°C at 1 atm
pressure.” The only reason water started boiling at 100°C was because we held the pressure constant
at 1 atm (101.325 kPa). If the pressure inside the cylinder were raised to 500 kPa by adding weights
on top of the piston, water would start boiling at 151.8°C.

The temperature at which water starts boiling depends on the pressure; therefore, if the pressure is
fixed, so is the boiling temperature.

At a given pressure, the temperature at which a pure substance changes phase is called the saturation
temperature Tsat. Likewise, at a given temperature, the pressure at which a pure substance changes
phase is called the saturation pressure Psat. At a pressure of 101.325 kPa, Tsat is 99.97°C.
Conversely, at a temperature of 99.97°C, Psat is 101.325 kPa.
Fig 6: T-v diagram for the heating process of water at constant pressure

The T-v Diagram

The phase-change process of water at 1 atm pressure was described in detail in the last section and
plotted on a T-v diagram in Fig. 6. Now we repeat this process at different pressures to develop the
T-v diagram.

Let us add weights on top of the piston until the pressure inside the cylinder reaches 1 MPa. At this
pressure, water has a somewhat smaller specific volume than it does at 1 atm pressure. As heat is
transferred to the water at this new pressure, the process follows a path that looks very much like the
process path at 1 atm pressure, as shown in Fig. 7, but there are some noticeable differences. First,
water starts boiling at a much higher temperature (179.9°C) at this pressure. Second, the specific
volume of the saturated liquid is larger and the specific volume of the saturated vapor is smaller than
the corresponding values at 1 atm pressure. That is, the horizontal line that connects the saturated
liquid and saturated vapor states is much shorter. As the pressure is increased further, this saturation
line continues to shrink, as shown in Fig. 7, and it becomes a point when the pressure reaches 22.06
MPa for the case of water. This point is called the critical point, and it is defined as the point at
which the saturated liquid and saturated vapor states are identical.

The temperature, pressure, and specific volume of a substance at the critical point are called,
respectively, the critical temperature Tcr, critical pressure Pcr, and critical specific volume vcr. The
critical-point properties of water are Pcr = 22.06 MPa, Tcr = 373.95°C.
Fig 7: T-v diagram of constant-pressure phase-change processes of a pure substance at various
pressures (numerical values are for water).

The saturated liquid states in Fig. 7 can be connected by a line called the saturated liquid line, and
saturated vapor states in the same figure can be connected by another line, called the saturated vapor
line. These two lines meet at the critical point, forming a dome as shown in Fig. 8. All the compressed
liquid states are located in the region to the left of the saturated liquid line, called the compressed
liquid region. All the superheated vapor states are located to the right of the saturated vapor line,
called the superheated vapor region. In these two regions, the substance exists in a single phase, a
liquid or a vapor. All the states that involve both phases in equilibrium are located under the dome,
called the saturated liquid–vapor mixture region, or the wet region.
Fig 8: T-v diagram of a pure substance.

The P-v Diagram

The general shape of the P-v diagram of a pure
substance is very much like the T-v diagram, but the
T _ constant lines on this diagram have a downward
trend, as shown in Fig. 10. Consider again a piston–
cylinder device that contains liquid water at 1 MPa
and 150°C. Water at this state exists as a compressed
liquid. Now the weights on top of the piston are
removed one by one so that the pressure inside the
cylinder decreases gradually (Fig. 9). The water is
allowed to exchange heat with the surroundings so its
Fig 9: The pressure in a piston–cylinder temperature remains constant. As the pressure
device can be reduced by reducing the weight decreases, the volume of the water increases slightly.
of the piston. When the pressure reaches the saturation-pressure
value at the specified temperature (0.4762 MPa), the
water starts to boil. During this vaporization process,
 both the temperature and the pressure remain
constant, but the specific volume increases. Once the
last drop of liquid is vaporized, further reduction in
pressure results in a further increase in specific
volume. Notice that during the phase-change process,
we did not remove any weights. Doing so would
cause the pressure and therefore the temperature to
drop [since Tsat = f (Psat)], and the process would no
longer be isothermal.

When the process is repeated for other temperatures,

similar paths are obtained for the phase-change
processes. Connecting the saturated liquid and the
saturated vapor states by a curve, we obtain the P-v
diagram of a pure substance, as shown in Fig. 10.

Fig 10: P-v diagram of a pure substance.