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Pure Substance
Prepared by:
Engr. Marvin V. Rosales

References:
Titles, authors, and editions of textbooks and other materials,
required and recommended

1. Richard E. Sonntag et al. Fundamental of Thermodynamics.6th Edition.

New York: John Wiley and Sons. C. 2003
2. Michael J. Moran and Howard N. Shapiro. Fundamentals of Engineering
Thermodynamics. 4th Edition. United States of America: John Wiley and
Sons, Inc. C. 1999
3. M. David Burghardt and James A. Harbach. Engineering
Thermodynamics.3rd Edition. New York: Harper & Row Publisher, Inc. C.
1993
4. Yunus A. Cengel and Michael A. Boles. Thermodynamics: An Engineering
Approach. 1st Edition. United States of America: McGraw-Hill, Inc. C.
1989

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Phase and Pure Substance

Phase
➢ Refers to a quantity of matter that is homogeneous throughout in both
chemical composition and physical structure. Homogeneity in physical
structure means that the matter is all solid, or all liquid, or all vapor

Pure substance

➢ is one that is uniform and invariable in chemical composition. A pure

substance can exist in more than one phase, but its chemical composition
must be the same in each phase.

VAPOR–LIQUID–SOLID-PHASE
EQUILIBRIUM IN A PURE
SUBSTANCE

✓ Consider as a system 1 kg of water contained in the piston/cylinder arrangement shown in Fig. a. Suppose that the
piston and weight maintain a pressure of 0.1 MPa in the cylinder and that the initial temperature is 20◦C. As heat is
trans ferred to the water, the temperature increases appreciably, the specifi c volume increases slightly, and the pressure
remains constant.

✓ When the temperature reaches 99.6◦C, additional heat transfer results in a change o f phase, as indicat ed in Fig. b. That
is, some of the liquid becomes vapor, and during this process both the temperature and pressure remain constant, but
the specific volume increases considerably.

✓ When the last drop of liquid has vaporized, further trans fer o f heat results in an increase in both the temperature and
specific volume of the vapor, as shown in Fig. c.

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➢ saturation temperature designates the temperature at which

vaporization takes place at a given pressure. This pressure is called the
saturation pressure for the given temperature.

Example:
For water at 99.6 ◦ C the saturation pressure is 0.1 MPa, and for water
at 0.1 MPa the saturation temperature is 99.6◦C.

In pure substance there is a definite relation between saturation pressure and

saturation temperature. A typical curve, called the vapor-pressure curve

➢ If a substance exists as liquid at the saturation temperature and pressure, it is

called a saturated liquid.

➢ If the temperature of the liquid is lower than the saturation temperature for the
existing pressure, it is called either a subcooled liquid (implying that the
temperature is lower than the saturation temperature for the given pressure)
or a compressed liquid (implying that the pressure is greater than the
saturation pressure for the given temperature).

➢ When a substance exists as part liquid and part vapor at the saturation
temperature, its quality is defined as the ratio of the mass of vapor to the total
mass.

➢ If a substance exists as vapor at the saturation temperature, it is called saturated

vapor. (Sometimes the term dry saturated vapor is used to emphasize that the
quality is 100%.)

➢ When the vapor is at a temperature greater than the saturation temperature, it is

said to exist as superheated vapor.

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➢ At the critical point the saturated-liquid and saturated-vapor states are

identical. The temperature, pressure, and specific volume at the critical
point are called the critical temperature, critical pressure, and critical
volume. The critical-point data for some substances

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Properties of pure substance

Subscripts used/symbols used.
f – represents properties of saturated liquid
g – represents of saturated vapor
fg – represents to a change by evaporation
v - specific volume, m3kg
v=v+v
g f fg v = v -v
fg g f

Specific volume of a wet mixture

v = specific volume of its saturated liquid

content + specific volume or its saturated
vapor content.

= yvf + x vg

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➢ consider an initial pressure of the ice of 0.6113 kPa and a temperature of

−20 ◦C. Through heat transfer, let the temperature increase until it reaches
0.01 ◦C. At this point, however, further heat transfer may cause some of the
ice to become vapor and some to become liquid, for at this point it is
possible to have the three phases in equilibrium. This point is called the
triple point, defined as the state in which all three phases may be present in
equilibrium.

➢ Along the sublimation line the solid and vapor phases are in equilibrium

➢ Along the fusion line the solid and liquid phases are in equilibrium

➢ Along the vaporization line the liquid and vapor phases are in equilibrium.

➢ The only point at which all three phases may exist in equilibrium is the triple
point.

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INDEPENDENT PROPERTIES
OF A PURE SUBSTANCE
➢ important reason for introducing the concept of a pure substance is that the
state of a simple compressible pure substance (that is, a pure substance in the
absence of motion, gravity, and surface, magnetic, or electrical effects) is
defined by two independent properties.
For example,
✓ if the specific volume and temperature of superheated steam are specified, the
state of the steam is determined.

➢ To understand the significance of the term independent property, consider the

saturated-liquid and saturated-vapor states of a pure substance. These two
states have the same pressure and the same temperature, but they are definitely
not the same state.
✓ In a saturation state, therefore, pressure and temperature are
not independent properties.

✓ Two independent properties, such as pressure and specific volume or pressure

and quality, are required to specify a saturation state of a pure substance.

VAPOR PHASE PROPERTIES –

EQUATION OF STATE
➢ Ideal gas –is one which strictly obeys all gas laws under all conditions of
temperature and pressure. No gas known is perfect, i.e., no gas laws obeys the gas
laws but within the temperature limits of applied thermodynamics many gases
like hydrogen, oxygen, nitrogen and even air may be regarded as perfect gases.

Laws of perfect gases

The following three variables control the physical properties of a gas:
1. The pressure ( p ) exerted by the gas.
2. The volume( v ) occupied by it.
3. Its temperature( T ).

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EXAMPLE:
For water at 100 kPa with a quality of 10% find the volume fraction of vapor.

Solution:

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EXAMPLE:
Determine whether water at each of the following states is a compressed liquid,
a superheated vapor, or a mixture of saturated liquid and vapor.
a. P = 10 MPa, v = 0.003 m3/kg b. 1 MPa, 190°C
c. 200°C, 0.1 m3/kg d. 10 kPa, 10°C
Solution:

EXAMPLE:
Consider two tanks, A and B, connected by a valve. Each has a volu me o f 200 L and tank A
has R-12 at 25°C, 10% liquid and 90% vapor by volu me, while tank B is evacuated. The
valve is now opened and saturated vapor flo ws fro m A to B until the pressure in B has
reached that in A, at which point the valve is closed. This process occurs slowly such that
all temperatures stay at 25°C throughout the process. How much has the quality changed in
tank A during the process?

Solution:

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EXAMPLE:
A rigid tank contains 20 lbm of air at 20 psia and 70°F. More air is added
to the tank until the pressure and temperature rise to 35 psia and 90°F,
respectively. Determine the amount of air added to the tank.

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