PROPERTIES OF PURE

SUBSTANCES

Engr. William R. Salazar,PME

Instructor
 Properties of Pure Substances

• TOPICS

3.1 Definition of the pure substance. 3.12. Internal energy of steam.

3.2. Phase change of a pure substance. 3.13. Entropy of water.
3.3. p-T (pressuretemperature) diagram for a 3.14. Entropy of evaporation.
pure substance.
3.15. Entropy of wet steam.
3.4. p-V-T (pressure-volume- temperature)
surface.
3.16. Entropy of superheated steam.
3.5. Phase change terminology and 3.17. Enthalpy-entropy (h-s) chart or Mollier
definitions. diagram.
3.6. Property diagrams in common use. 3.18. Determination of dryness fraction of
3.7. Formation of steam. steam—Tank or bucket calorimeter—
throttling calorimeter— separating and
3.8. Important terms relating steam formation.
throttling calorimeter—
3.9. Thermodynamic properties of steam and
steam tables.
3.10. External work done during evaporation. Highlights—Objective Type Questions—
3.11. Internal latent heat. Theoretical Questions—Unsolved Examples.
 Properties of Pure Substances

3.1. DEFINITION OF THE PURE SUBSTANCE

A pure substance is a system which is (i) homogeneous in composition, (ii) homogeneous in chemical
aggregation, and (iii) invariable in chemical aggregation.

— “Homogeneous in composition” means that the composition of each part of the system is the
same as the composition of every other part.
“Composition” means the relative proportions of the chemical elements into which the sample can
be analysed. It does not matter how these elements are combined.

Fig. 3.1 system

(a), comprising steam and water, is
homogeneous in composition, since chemical
analysis would reveal that hydrogen and oxygen
atoms are presents in the ratio 2 : 1 whether the
sample be taken from the steam or from the
water. The same is true of system
(b) containing uncombined hydrogen and oxygen
gas in the atomic ratio 2 : 1 in the upper
part, and water in the lower part. System
(c) Is not homogeneous in composition, for the
hydrogen and oxygen are present in the ratio 1 :
1 in the upper part, but in the ratio 2 : 1 (as
water)
 Properties of Pure Substances

“Homogeneous in chemical “Invariable in chemical

aggregation” aggregation”
- means that the chemical elements must be - means that the state of chemical
combined chemically in the same way in all combination of the system does not
parts of the system. change with time (condition (ii)
- In Fig. 3.1 shows that the system in (a) referred to variation with position).
satisfies this condition also ; for steam and
- Thus a mixture of hydrogen and
water consist of identical molecules.
oxygen, which changed into steam
- System (b) on the other hand is not during the time that the system was
homogeneous in chemical aggregation under consideration, would not be a
since in the upper part of the system the
pure substance.
hydrogen and oxygen are not combined
chemically (individual atoms of H and O
are not uniquely associated), whereas in
the lower part of the system the hydrogen
and oxygen are combined to form water.
Properties of Pure Substances
 Properties of Pure Substances

 PHASE CHANGE OF A PURE SUBSTANCE

 Consider a 1 kg of liquid water at a temperature

of 20°C in a cylinder fitted with a piston, which
exerts on the water a constant pressure of one
atmosphere (1.0132 bar) as shown in Fig. 3.2 (i).

— As the water is heated slowly its temperature

rises until the temperature of the liquid water
becomes 100°C. During the process of heating, the
volume slightly increases as indicated by the line
1-2 on the temperature-specific volume diagram
(Fig. 3.3). The piston starts moving upwards.
 Properties of Pure Substances

 If the heating of the liquid, after it attains

a temperature of 100°C, is continued it
undergoes a change in phase.
 A portion of the liquid water changes
into vapour as shown in Fig. 3.2 (ii). This
state is described by the line 2-3 in Fig.
3.3.
 The amount of heat required to convert
the liquid water completely into vapour
under this condition is called the heat of
vapourisation.
 Saturation temperature – is the
temperature at which vapourisation
takes place at a given pressure.
 Saturation pressure – Is the given
pressure at which vapourisation takes
place at a given temperature.
 During the process represented by the
line 2-3 (Fig. 3.3) the volume increases
rapidly and piston moves upwards Fig.
3.2 (iii).
Properties of Pure Substances
Properties of Pure Substances
Properties of Pure Substances

 Saturation
 Saturation is defined as a condition in which a mixture of vapor and liquid can exist
together at a given temperature and pressure.
 Saturation pressure is the pressure at which the liquid and vapor phases are in
equilibrium at a given temperature
 For a pure substance there is a definite relationship between saturation pressure and
saturation temperature. The higher the pressure, the higher the saturation temperature

 Latent Heat
Latent heat: The amount of energy absorbed or released during a phase-change
process.
Latent heat of fusion: The amount of energy absorbed during melting. It is
equivalent to the amount of energy released during freezing.
Latent heat of vaporization: The amount of energy absorbed during
vaporization and it is equivalent to the energy released during
condensation.
At 1 atm pressure, the latent heat of fusion of water is 333.7 kJ/kg
and the latent heat of vaporization is 2256.5 kJ/kg.
 Properties of Pure Substances

• The graphical representation of this

relationship between temperature and pressure
at saturated conditions is called the vapor
pressure curve
 Properties of Pure Substances

 Subcooled Liquid -
If the temperature of the
liquid water on cooling becomes lower than the
saturation temperature for the given pressure, the
liquid water is called a subcooled liquid.
• In Fig 3.3, when the liquid water is cooled under
atmospheric pressure to a temperature of 20°C,
which is below the saturation temperature (100°C),
the water is subcooled.
• 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
• If, at point ‘1’ the temperature of liquid is 20°C
and corresponding to this temperature, the
saturation pressure is 0.0234 bar, which is The term compressed liquid or sub-cooled liquid is
lower than the pressure on the liquid water, used to distinguish it from saturated liquid. All
which is 1 atmosphere. If, the pressure on points in the liquid region indicate the states of the
the liquid water is greater than the
saturation pressure at a given compressed liquid.
temperature. In this condition, the liquid
water is known as the compressed liquid
 Properties of Pure Substances

 When all the liquid has been evaporated completely and heat
is further added, the temperature of the vapour increases.
 The curve 3-4 in Fig. 3.3 describes the process. When the
temperature increases above the saturation temperature (in
this case 100°C), the vapour is known as the superheated
vapour and the temperature at this state is called the
superheated temperature.
 There is rapid increase in volume and the piston moves
upwards [Fig. 3.2 (iii)].
 Degree of Superheat – Is the difference between the
superheated temperature and the saturation temperature at
the given pressure.
• If the above mentioned heating process is repeated at
different pressures a number of curve similar to 1-2-3-4 are
obtained. Thus, if the heating of the liquid water in the piston
cylinder arrangement takes place under a constant pressure of
12 bar with an initial temperature of 20°C until the liquid water
is converted into superheated steam, then curve 5-6-7-8 will
represent the process.
 Properties of Pure Substances

o Consider the heating process at a constant pressure of 225 bar

• represented by the curve 9-10-11 in Fig. 3.3, it can be seen that
there is no constant temperature vapourisation line.
o The specific volume of the saturated liquid and of the saturated
vapour is the same, i.e., = v . Such a state of the substance is
g

called the critical state. The parameters like temperature,

pressure, volume, etc. at such a state are called critical
parameters.
o The curve 12-13 (Fig. 3.3) represents a constant pressure heating
process, when the pressure is greater than the critical pressure.
At this state, the liquid water is directly converted into
superheated steam. As there is no definite point at which the
liquid water changes into superheated steam, it is generally
called liquid water when the temperature is less than the
critical temperature and superheated steam when the
temperature is above the critical temperature.
 Properties of Pure Substances

 p-T (Pressure-Temperature) DIAGRAM FOR

A PURE SUBSTANCE • The points representing the coexistence of 
• If the vapour pressure of a solid is measured at (i) solid and vapour lie on the ‘sublimation
various temperatures until the triple point is curve’,
reached and then that of the liquid is measured
until the critical point is reached, the result  (ii) liquid and vapour lie on the
when plotted on a p-T diagram appears as in ‘vapourisation curve’,
Fig. 3.5.
(iii) liquid and solid lie on the ‘fusion curve’.
In the particular case of water, 
 the sublimation curve is called the frost line,
 the vapourisation curve is called the steam line, 
and 
 the fusion curve is called the ice line.
 Properties of Pure Substances

 Triple point

The triple point is merely the point of intersection of sublimation and vapourisation curves. It m
be understood that only on p-T diagram is the triple point represented by a point. On p-V diagram it is a
line, and on a U-V diagram it is a triangle.
— The pressure and temperature at which all three phases of a pure substance coexist may be measured
with the apparatus that is used to measure vapour pressure.
— Triple-point data for some interesting substances are given in Table 3.1.
 Properties of Pure Substances

 p-v-t (Pressure-Volume-
Temperature) SURFACE
• The combined picture of change of pressure,
specific volume and temperature may be
shown on a three dimensional state model.
• Fig. 3.6 illustrates the equilibrium states for
a pure substance which expands on fusion.
• Water is an example of a substance that
exhibits this phenomenon.

 All the equilibrium states lie on the surface

of the model. States represented by the
space above or below the surface are not
possible.
 It may be seen that the triple point appears
as a line in this representation.
 The point C.P. is called the critical point and
no liquid phase exists at temperatures
above the isotherms through this point.
 Properties of Pure Substances

 PHASE CHANGE TERMINOLOGY AND DEFINITIONS

Suffices :
Solid -i
Liquid -f
Vapour -g
Phase change Name Process Process suffix
1. Solid-liquid Fusion Freezing, melting if
2. Solid-vapour Sublimation Frosting, defrosting ig
3. Liquid-vapour Evaporation Evaporating, Condensing fg
 Triple point—The only state at which the solid, liquid and vapour phases coexist in
equilibrium.
 Critical point (C.P.). - The limit of distinction between a liquid and vapour.
 Critical pressure. - The pressure at the critical point.
 Critical temperature - The temperature at the critical point.
 Gas—A vapour whose temperature is greater than the critical temperature.
Liquid-vapour terms : Refer Fig. 3.7.
 Saturation temperature - The phase change temperature corresponding to the
saturation pressure. Sometimes called the boiling
temperature.
 Saturation pressure - The phase change pressure.
 Compressed liquid - Liquid whose temperature is lower than the saturation
temperature. Sometimes called a sub-cooled liquid.
 Properties of Pure Substances

 Saturated liquid - Liquid at the saturation  FORMATION OF STEAM

temperature corresponding to the saturation pressure.
That is liquid about to commence evaporating,
represented by the point f on a diagram.
 Saturated vapour - A term including wet and dry
vapour.
 Dry (saturated) vapour - Vapour which has just
completed evaporation. The pressure and temperature
of the vapour are the saturation values. Dry vapour is
represented by a point g on a diagram.
 Wet vapour - the mixture of saturated liquid and dry
vapour during the phase change.
 Superheated vapour - Vapour whose temperature is
greater than the saturation temperature corresponding
to the pressure of the vapour.
 Degree of superheat - The term used for the
numerical amount by which the temperature of a If the heat is imparted to water, a rise in temperature
superheated vapour exceeds the saturation will be noticed and this rise will continue till boiling
temperature. point is reached. The temperature at which water
starts boiling depends upon the pressure and as such
 Consider a cylinder fitted with a piston which can for each pressure (under which water is heated)
move freely upwards and downwards in it. Let, for the there is a different
sake of simplicity, there be 1 kg of water at 0°C with boiling point. This boiling temperature is known as
volume vf m3 under the piston [Fig 3.9 (i)]. Further let the temperature of formation of steam or saturation
the piston is loaded with load W to ensure heating at temperature.
 Properties of Pure Substances

  During heating up to boiling point, there will be slight

increase in volume of water due to which piston moves
up and hence work is obtained as shown in Fig. 3.9 (ii).
This work is so small that is can be neglected.
 As heat supply to water is continued there will be no
rise of temperature after the boiling point is reached,
but piston starts moving upwards which indicates that
there is increase is volume which is only possible if
steam formation occurs.
 The heat being supplied does not show any rise of
temperature but changes water into vapour state
(steam) and is known as latent heat or hidden
heat.
 So long as the steam is in contact with water, it is
called wet steam [Fig. 3.9 (iii)] and if heating of  As heat is continuously supplied to the dry and
steam is further progressed [as shown in Fig. 3.9 (iv)] saturated steam at constant pressure there will
such that all the water particles associated with steam be increase in temperature and volume of steam.
are evaporated, the steam so obtained is called dry The steam so obtained is called superheated
and saturated steam. steam, illustrated in Fig. 3.9 (v). and it behaves
 If m³is the volume of 1 kg of dry and saturated steam like a perfect gas.
then work done on the piston will be:

Work = p(vg – vf) eq...(3.1)

Where:
p is the constant pressure (due to weight ‘W’ on the
 Properties of Pure Substances

The graphical representation of  
•  IMPORTANT TERMS RELATING STEAM FORMATION
formation of steam. 1. Sensible heat of water () - Defined as the quantity of
heat absorbed by 1 kg of water when it is heated from
0°C (freezing point) to boiling point. It is also called total
heat (or enthalpy) of water or liquid heat invariably. It 
is reckoned from 0°C where sensible heat is taken as 
zero. If 1 kg of water is heated from 0°C to 100°C the 
sensible heat added to it will be 4.18 kJ/kg-K  × 100 C° = 
418 kJ but if water is at say 20°C initially then sensible 
heat added will be 4.18 × (100 – 20) = 334.4 kJ. This 
type of heat is denoted by letter  and its value can be 
directly read from the steam tables.
• Note. The value of specific heat of water may be taken as 
4.18 kJ/kg - K at low pressures but at high pressures it is 
different from this value.
 Properties of Pure Substances

•   Latent heat or hidden heat (). - Is the

2.
• 
Thus if in 1 kg of wet steam 0.9 kg is the dry
amount of heat required to convert water at steam and 0.1 kg water particles then x = 0.9.
a given temperature and pressure into steam
Note. No steam can be completely dry and
at the same temperature and pressure. It is
saturated, so long as it is in contact with the water
expressed by the symbol and its value is from which it is being formed.
available from steam tables. The value of
latent heat is not constant and varies 4. Total heat or enthalpy of wet steam (h) - Is
according to pressure variation. defined as the quantity of heat required to
convert 1 kg of water at 0°C into wet steam at
3. Dryness fraction (x) - The term dryness constant pressure. It is the sum of total heat of
fraction is related with wet steam. It is water and the latent heat and this sum is also
defined as the ratio of the mass of actual called enthalpy.
dry steam to the mass of steam containing
it. It is usually expressed by the symbol ‘x’
or ‘q’. h = + x ...(3.3)
If = Mass of dry steam contained in steam If steam is dry and saturated, then x = 1 and hg = hf
considered, and + hfg.
= Weight of water particles in suspension in
the steam considered,
Then, eq…3.2
 Properties of Pure Substances

5.
•   Superheated steam -When steam is heated after it has   The advantages obtained by using ‘superheated’
become dry and saturated, it is called superheated steam 
and the process of heating is called superheating. steam are as follows :
Superheating - is always carried out at constant pressure. The  (i) By superheating steam, its heat content and hence 
additional amount of heat supplied to the steam during  its capacity to do work is increased without having to 
superheating is called as ‘Heat of superheat’ and can be calculated  increase its pressure. 
by using the specific heat of superheated steam at constant 
pressure (), the value of which varies from 2.0 to 2.1 kJ/kg K (ii) Superheating is done in a superheater which obtains 
depending upon pressure and temperature.  its heat from waste furnace gases which would have 
If ,  are the temperatures of superheated steam in K and wet or  otherwise passed uselessly up the chimney. 
dry steam, then ( – ) is called ‘degree of superheat’. The total heat 
of superheated steam is given by:
(iii) High temperature of superheated steam results in an 
increase in thermal efficiency. 
(iv) Since the superheated steam is at a temperature 
= + + (– ) eq...(3.4)
above that corresponding to its pressure, it can be 
considerably cooled during expansion in an engine 
• Superheated steam behaves like a gas and therefore it before its temperature falls below that at which it 
follows the gas laws.  will condense and thereby become wet. Hence, heat 
• The value of n for this type of steam is 1.3 and the law  losses due to condensation of steam on cylinder 
for the adiabatic expansion is  = constant.
walls etc. are avoided to a great extent.
 Properties of Pure Substances

6.
•   Volume of wet and dry steam - If the steam has dryness 
fraction of x, then 1 kg of this steam will contain x kg of dry 
• 
7. Volume of superheated steam - As
superheated steam behaves like a perfect
steam and (1 – x) kg of water. If  is the volume of 1 kg of water  gas its volume can be found out in the same
and  is the volume of 1 kg of perfect dry steam (also known as 
way as the gases.
specific volume), then volume of 1 kg of wet steam = volume of 
dry steam + volume of water. If, = Specific volume of dry steam at pressure
p,
            = x + (1 – x)                    eq...(3.5)
Note. The volume of  at low pressures is very small and is generally 
= Saturation temperature in K,
neglected.  = Temperature of superheated steam in
In general, the volume of 1 kg of wet steam is K, and
given by, x and density 1/x
= Volume of 1 kg of superheated steam at
pressure p,
Then,

eq…..(3.5 (a))

Or
eq…(3.6)
eq…..(3.5 (b))
 Properties of Pure Substances

 THERMODYNAMIC PROPERTIES OF STEAM AND

STEAM TABLES The thermodynamic properties of steam 
• In engineering problem, for any fluid which is used  which are tabulated in the form of table :
as working fluid, the six basic thermodynamic
properties required are : 
p (pressure), T (temperature), v (volume),
u (internal energy), h (enthalpy) and s (entropy).
These properties must be known at different 
pressure for analysing the thermodynamic cycles 
used for work producing devices. The values of these 
properties are determined theoretically or 
experimentally and are tabulated in the form of 
tables which are known as
‘Steam Tables’ -  The properties of wet steam are 
then computed from such tabulated data. Tabulated 
values are also available for superheated steam. It
may be noted that steam has only one saturation The internal energy of steam (u = h – pv) is also
temperature at each pressure. Also,
tabulated in some steam tables
 Properties of Pure Substances

  EXTERNAL WORK DONE DURING EVAPORATION

When water is evaporated to form saturated steam, its volume increases from to at a
constant pressure, and thus external work is done by steam due to increase in volume. The energy
for doing the work is obtained during the absorption of latent heat. This work is called external
work of evaporation and is given by p(– ).
i.e., External work of evaporation = p(– ). eq...(3.7)
As at low pressure is very small and hence neglected, work of evaporation is
p. eq...(3.8)
In case of wet steam with dryness fraction x, work of evaporation will be
px eq ...(3.9)
 Properties of Pure Substances


•   INTERNAL LATENT HEAT Where:
• The latent heat consists of true latent heat and  u is internal energy of 1
the work of evaporation. This true latent heat is  kg of steam at pressure p
called the internal latent heat and may also be 
found as follows :
Internal latent heat =  eq….3.10
J = 1 in SI units.

 INTERNAL ENERGY OF STEAM

• It is defined as the actual energy stored
in the steam. 
• The total heat of steam is sum of sensible heat, 
internal latent heat and the external work of 
evaporation
 Properties of Pure Substances

 ENTROPY OF WATER
• Consider 1 kg of water being heated from 
temperature T1 to T2 at constant pressure. The 
change in entropy will be given by,

• Integrating both sides, we get,

• eq….
(3.13)
• If 0°C is taken as datum, then entropy of
water per kg at any temperature T above
this datum will be,
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Properties of Pure Substances
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Example 3.7. 1000 kg of steam at • 

Solution.
a pressure of 16 bar and 0.9 dry is Mass of steam generated, m = 1000 kg/h
generated by a boiler per hour. The Pressure of steam, p = 16 bar
steam passes through a superheater
Dryness fraction, x = 0.9
via boiler stop valve where its
Temperature of superheated steam,
temperature is raised to 380°C. If
the temperature of feed water is = 380 + 273 = 653 K
30°C, determine : Temperature of feed water = 30°C

(i) The total heat supplied to feed Specific heat of superheated steam, = 2.2
kJ/kg K.
water per hour to produce wet
steam. At 16 bar.
From steam tables,
(ii) The total heat absorbed per hour
in the superheater. = 201.4°C ( = 201.4 + 273 = 474.4 K) ;
= 858.6 kJ/kg ; = 1933.2 kJ/kg
Take specific heat for superheated
steam as 2.2 kJ/kg K.
 Properties of Pure Substances

• 
Example 3.9.
•  (i) Heat supplied to feed water per A pressure cooker contains 1.5 kg of saturated
hour to produce wet steam is given by steam at 5 bar. Find the quantity of heat which
: must be rejected so as to reduce the quality to
H = m [( + x ) – 1 × 4.18 × (30 – 0)] 60% dry. Determine the pressure and
= 1000 [(858.6 + 0.9 × 1933.2) – 4.18 temperature of the steam at the new state.
× (30-0)] Solution.
= 1000(858.6 + 1739.88 – 125.4)
Mass of steam in the cooker = 1.5 kg
= 2473.08 × kJ. 3 (Ans.)
Pressure of steam, p = 5 bar
Initial dryness fraction of steam, x = 1
(ii) Heat absorbed by superheater per hour
1

Final dryness fraction of steam, x = 0.6 2

= m[(1 – x)  +  ( – )] Heat to be rejected :

= 1000[(1 – 0.9) × 1933.2 + 2.2 (653  Pressure and temperature of the steam at the
new state :
– 474.4)]
At 5 bar.
= 1000(193.32 + 392.92) From steam tables,
= 586.24 ×  kJ. (Ans.) = 151.8°C ; = 640.1 kJ/kg ;
 Properties of Pure Substances

Thus, the volume of pressure cooker
•  i.e.,
= 1.5 × 0.375 = 0.5625 m³
Internal energy of steam per kg at initial 
point 1,
 =   –  From steam tables corresponding to 0.625 m 3/kg,
p2 ~ 2.9 bar, ts = 132.4°C, hf = 556.5 kJ/kg, hfg = 2166.6 kJ/kg
Internal energy of steam per kg, at final point 2,
= (+   ) –   u2 = h2 – p2v2
= (hf2 + x2hfg2) – p2xvg2
( ) v xvg 2 = 2
….(  = ) = (556.5 + 0.6 × 2166.6) – 2.9 × 10 5 × 0.6 × 0.625 × 10–3
= 1856.46 – 108.75 = 1747.71 kJ/kg.

= (640.1 + 2107.4) – 5 ×  × 0.375 × 
Heat transferred at constant volume per kg
= u2 – u1 = 1747.71 – 2560 = – 812.29 kJ/kg
Thus, total heat transferred

= 2747.5 – 187.5 = 2560 kJ/kg = – 812.29 × 1.5 = – 1218.43 kJ. (Ans.)

Also, =
(= volume at final condition)
Negative sign indicates that heat has been rejected.
Properties of Pure Substances