MEC 189.

2 Thermal Science

Chapter 2. Properties of Pure Substance

Ram Bdr. Ale

Ritz College of Engineering and
Management(PU)
Department of Civil Engineering
 Pure Substance
Pure substance is a substance that has fixed chemical composition throughout .
A pure substance is a system which is:
a) Homogenous in composition b) Homogenous in chemical aggregation
c) Invariable in chemical aggregation
Homogenous in chemical composition means relative proportion of the chemical
elements is same throughout the system taken for analysis. It doesn’t matter how
the elements are combined.
Homogenous in chemical aggregation means chemical elements must be
combined chemically in the same way in all parts of the system.
-related to position.
Invariable chemical aggregation means that the state of chemical combination of
system doesn’t change with time. A mixture of hydrogen and oxygen, which
changed into steam during the time that the system was under consideration,
would not be a pure substance.
 Pure substance
Properties of fig(i)
The ratio of hydrogen atom and oxygen atoms are present in the ratio 2:1 in both
water and steam. So, system (i) is homogenous in composition.
Steam and water consists of identical molecules . So system(i) is homogenous in
chemical aggregation.
Properties of fig(ii)
Homogenous in composition.
Hydrogen and oxygen are not combined chemically in upper part, whereas the
hydrogen and oxygen are combined in the form of water in lower part. So system(ii)
is not homogenous in chemical aggregation.
Properties of fig(iii)
The ratio of hydrogen atom and oxygen atoms are present in the ratio 1:1 in
upper part but 2:1 in lower part ( i.e. in water). So, it is not homogenous in chemical
composition
Not homogenous in chemical aggregation as in system (ii).
 Phase-change Process of Pure Substance
The substance exist in different phases e.g. at room temperature and pressure,
copper is solid and mercury is a liquid.
 It can exist in different phases under variations of conditions.
There are 3 principal phases
Solid – strong intermolecular bond
Liquid – intermediate intermolecular bond
Gas – weak intermolecular bond
Each with different molecular structures.
 Terms in Phase-change Process
Saturation: It is defined as a condition in which a mixture of vapor and liquid can
exist together at a given temperature and pressure.
Saturation Temperature : Temperature at which vaporization takes place at a given
pressure is saturation temperature and the pressure is called the saturation pressure
for the given temperature.
Saturated Liquid: If a substance exists as liquid at the saturation temperature and
pressure, it is called saturated liquid. In this condition, the liquid is about to
vaporize.
Subcooled Liquid : If the temperature of the liquid is lower than the saturation
temperature for the existing pressure, it is called either a subcooled liquid or a
compressed liquid.
Saturated Vapor: If a substance exists entirely as vapor at saturation temperature, it
is called saturated vapor and it is about to condense.
A substance at states between saturated liquid and saturated vapor is referred to as a
saturated- vapor mixture since the liquid and vapor phases co-exists in equilibrium
at these states.
Superheated Vapor: When the vapor is at a temperature greater than the saturation
temperature, it is said to exist as superheated vapor and it is not about to condense.
The pressure and temperature of superheated vapor are independent properties,
since the temperature may increase while the pressure remains constant
 Phase-change Process in Pure Substance

Consider as a system 1 kg of water contained in the piston-cylinder arrangement.

Suppose the piston and the weight maintain a pressure of 1 atm in the cylinder and
the initial temperature is 10oC.
If the water is heated the temperature increases appreciably and specific volume
increases slightly and the pressure remains constant.
When the temperature reaches 99.6oC, additional heat transfer results in a change
of phase (i.e., some of the liquid becomes vapour and during this both the
temperature and pressure remains constant but the specific volume increases
considerably).
 Phase-change Process in Pure Substance
 When the last drop has been vaporized, further transfer of heat results in an
increase in both temperature and specific volume.

State 1- The water is liquid state which is below

saturation temperature i.e. it is not about to
vapourize. So, state 1 is subcooled or
Compressed liquid state.
State 2 – Any heat addition to the liquid water
at state 2 will cause some of the liquid
to vaporize i.e. water is about to vaporize.
So, state 2 is saturated liquid state.
Once boiling starts, the temperature stops
rising until the liquid is completely vaporized,
i.e. state(2) to state(3) and the states between these
are called saturated liquid-vapour mixture or two-phase
region states and substances at between these states are
called saturated liquid-vapour mixture.
 Phase-change Process in Pure Substance
State 4 – All the water is in vapor phase but any heat rejection of heat from this
vapor will cause some of the vapor to condense. So, it is saturated vapour state.
State -5 Any small rejection of heat from vapour at state 5 will not cause
condensation. So, state 5 is Superheated vapour phase.
The difference between the superheated temperature and the saturation
temperature at given pressure is called degree of superheat.

Here in the figure , P1<P2<P3<P4……

As the heat is transferred to the water,
the process at all the processes follow
paths that look alike but there are some
noticeable differences. As the pressure
increases:
The boiling point increases.
The specific volume of saturated
liquid also increases.
And specific volume of the saturated
decreases.
 Phase-change Process in Pure Substance
i.e., he horizontal line that connects the saturated
liquid and saturated vapour state becomes shorter and
shorter and shrinks to a point which is called critical
point. The critical temperature Tc of a pure substance
is the maximum temperature at which liquid and
vapour phases can coexist in equilibrium. The pressure
at the critical point is called the critical pressure, pc.
The specific volume at this state is the critical specific
volume.
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, and vcr = 0.003106 m3/kg

At supercritical pressures (P > Pcr), there is no

distinct phase-change (boiling) process.
 T-V diagram.

One transferring heat to the system, the process follows path as shown in figure
above.
 P-V diagram.

Pressure releasing gradually allowing the water to exchange heat with

surroundings to keep the temperature constant, the process follows the path as
shown in figure.
 P-T diagram.
A P-T diagram is the most common way to show
the phases of substance. A P-T diagram can be
constructed for any pure substance.
Sublimation line: The line that separates the solid
and vapour phases is called the sublimation line.
Fusion line: The line that separates the solid and
liquid phases is called the fusion line.
Vapourization line: The line that separates the
liquid and vapour phases is called the vapourization
line. The temperature, pressure, and
Triple point: The point where the three lines meet specific volume of a substance at
is called triple point. The triple point is the only the critical point are called,
point at which all three phases exist in equilibrium. respectively, the critical
temperature Tcr , critical pressure
Critical Point: The point where the vapourization
Pcr , and critical specific volume
line ends. At temperatures and pressures greater vcr . The critical-point properties
than those at the critical point, no substance can of water are Pcr = 22.06 MPa, Tcr
exist as liquid no matter how great pressure is = 373.95°C, and vcr = 0.003106
exerted upon on it. The region above the critical m3/kg.
point is called super critical region.
 Wet steam and Moisture Content
A mixture of dry steam and suspended water particles is wet steam. Then, when a
substance exists as part liquid and part vapor at the saturation temperature, its
dryness fraction or quality, x, is defined as the ratio of mass of vapor to the total
mass of both vapour and liquid. It is also called dryness factor.

The quality is zero for the saturated liquid and one for the saturated vapour ( 0 ≤
x ≥ 1 ). Although defined as a ratio, the quality is frequently given as a percentage.

The moisture content of a substance is the opposite of its quality. Moisture is

defined as the ratio of the mass of the liquid to the total mass of both liquid and
vapor.
 Specific Volume for Wet Steam
Let us consider m kg of wet steam having volume V m3. The steam consisting of mf
kg of suspended water and mg kg of dry saturated vapour with volumes Vf anf Vg
resply.
 Property Diagrams
For a pure substance there is a definite relationship
between saturation pressure and saturation temperature
i.e., Tsat= f(Psat). The higher the pressure, the higher
the saturation temperature. The graphical representation
of this relationship between temperature and pressure at
saturated conditions is called Vapour-pressure curve.
 Property Diagrams
As the elevation increases,
standard atm. pressure goes on
decreasing and, hence, boiling
temperature.
 Property Table
For most substances, the relationships among thermodynamic properties are
too complex to be expressed by simple equations. Therefore, properties are
frequently presented in the form of tables.
 Some thermodynamic properties can be measured easily, but others cannot and
are calculated by using the relations between them and measurable properties.
 The results of these measurements and calculations are presented in tables in a
convenient format.
In the table the subscript f is used to denote properties of a saturated liquid, and
the
subscript g to denote the properties of saturated vapor. Another subscript
commonly used is fg, which denotes the difference between the saturated vapor
and saturated liquid values of the same property.
Property Tables
Property Tables
Property Tables
Property Tables
Property Tables
Property Tables