Chapter 3: Properties of a

Pure Substance

Thermodynamics 1
 Steam Power Plant

Thermodynamics – Chapter 3 2
 Refrigerator
Thermodynamics – Chapter 3 3
 Jet Engine

Thermodynamics – Chapter 3 4
Pure Substance
A pure substance is one that has a homogeneous and
invariable chemical composition and it may exist in
more than one phase but the chemical composition is
the same in all phases.
Examples:
1. Water (solid, liquid, and vapor phases)
2. Carbon dioxide, CO2
3. Nitrogen, N2
4. Mixtures of gases, such as air, as long as there is
no change of phase.

Thermodynamics – Chapter 3 5
 Nitrogen and gaseous air are pure substances.

A mixture of liquid and gaseous water are pure

substances, but a mixture of liquid and gaseous air
is not.
Thermodynamics – Chapter 3 6
 In this text the emphasis will be on simple
compressible substances.
 Simple compressible substances are substances
whose surface effects, magnetic effects, and
electrical effects are insignificant when dealing
with the substances.
 But changes in volume, such as those associated
with the expansion of a gas in a cylinder, are very
important.
 We will refer to a system consisting of a simple
compressible substance as a simple compressible
system.
Thermodynamics – Chapter 3 7
Vapor –Liquid – Solid – Phase
Equilibrium in a Pure Substance
Consider as a system 1 kg of water. The piston and
weight maintain a pressure of 0.1 MPa in the cylinder
and that the initial temperature is 20oC.

Constant – pressure change from liquid to vapor phase for a

pure substance

Thermodynamics – Chapter 3 8
The temperature at which vaporization takes place at
a given pressure is called saturation temperature.
This pressure is called the saturation pressure for
the given temperature.

A typical curve is called vapor-pressure curve.

Thermodynamics – Chapter 3 9
If the temperature of the liquid is lower than the
saturation temperature for the existing pressure, it
called either a subcooled liquid or a compressed
liquid.

Thermodynamics – Chapter 3 10
Thermodynamics – Chapter 3 11
Thermodynamics – Chapter 3 12
Thermodynamics – Chapter 3 13
Thermodynamics – Chapter 3 14
Thermodynamics – Chapter 3 15
If the substance exists as liquid at the saturation
temperature and pressure is called a saturated
liquid.

Thermodynamics – Chapter 3 16
When a substance exists as part liquid and part
vapor at the saturation temperature, its quality (x) is
defined as the ratio of the mass of vapor to the total
mass.

Thermodynamics – Chapter 3 17
If a substance exists as vapor at the saturation
temperature and pressure is called saturated vapor.

Thermodynamics – Chapter 3 18
When the vapor is at a temperature greater than the
saturation temperature, it is said to exist as
superheated vapor.

Thermodynamics – Chapter 3 19
Thermodynamics – Chapter 3 20
Thermodynamics – Chapter 3 21
Temperature – Volume diagram for the heating process of
water at constant pressure

Thermodynamics – Chapter 3 22
 374.14oC

311.1oC

179.9oC

99.6oC

Temperature – Volume diagram for water

showing liquid and vapor phases

Line NJFB represents the saturated-liquid line and

line NKGC represents the saturated-vapor line.
Thermodynamics – Chapter 3 23
Critical Point:
It is defined as the
point at which the
saturated liquid and
saturated vapor states
are identical (co-
exiting).
 At pressures
above the critical
pressure, there is
not a distinct
process.

Thermodynamics – Chapter 3 24
 The specific volume of the substance
continually increases, and all times there is only
one phase present.
 Eventually, it resembles a vapor, but we can
never tell when the change has occurred.
 Above the critical state, there is no line
separates the compressed liquid region and the
superheated vapor region.
 However, it is customary to refer the substance
as superheated vapor at temperatures above the
critical temperature and as compressed liquid at
temperatures below the critical temperatures.

Thermodynamics – Chapter 3 25
Thermodynamics – Chapter 3 26
 Explaining the Critical Point

Thermodynamics – Chapter 3 27
Temperature – Volume diagram for water
showing liquid and vapor phases

Thermodynamics – Chapter 3 28
Pressure – Volume diagram for water showing
liquid and vapor phases

Thermodynamics – Chapter 3 29
Conditions for Compressed or Sub-cooled liquid state

Thermodynamics – Chapter 3 30
Conditions for Saturated or Mixture State

Thermodynamics – Chapter 3 31
Conditions for Superheated Vapour State

Thermodynamics – Chapter 3 32
Saturated Liquid-Vapor Mixture
The specific volume of a two-phase liquid-vapor
mixture can be determined by using the saturation
tables and the definition of quality (x).

mg
x
m f  mg
f used to designate a
property of saturated
liquid and g property
of a saturated vapor.

Thermodynamics – Chapter 3 33
 During a vaporization process, a substance exists
as part liquid and part vapor. That is, it is a
mixture of saturated liquid and saturated vapor.
 The properties of the saturated liquid are the same
whether it exists alone or in a mixture with
saturated vapor.
 During vaporization process, only the amount of
saturated liquid changes, not its properties. The
same can be said about a saturated vapor.

Thermodynamics – Chapter 3 34
 The amount of mass for each phase is usually not
known. Therefore, it is often more convenient to
imagine that the two phases are mixed very well,
forming a homogenous mixture.
 Then the properties of this mixture will simply be
the average properties of the saturated liquid-vapor
mixture under consideration.

Thermodynamics – Chapter 3 35
V  Vliq  Vvap  V f  Vg

V  mv  mt vavg  m f v f  mg vg
mf v f mg vg
 mf   mg 
vavg     v f    vg
mt mt  mt   mt 
v  (1  x)v f  xvg  v f  x(vg  v f )

v  v f  xv fg Where v fg  vg  v f
Thermodynamics – Chapter 3 36
 v  v f  xv fg
v  v f AB
x 
v fg AC

Quality is related to the horizontal distance on P-v

and T-v diagrams.
Thermodynamics – Chapter 3 37
 Page No:674/702 (24)

Thermodynamics – Chapter 3 38
(E3.1) Determine the phase for each of the
following water states.
a. 120oC, 500 kPa

Enter table B.1.1(Page No: 22) with 120o C

Enter table B.1.2(Page No: 26) with 500 kPa

Thermodynamics – Chapter 3 39
 Page No: 22

Psat @120o C  198.5kPa  Since Psat < 500Kpa

 state is compressed liquid
Thermodynamics – Chapter 3 40
 Page No: 26

Tsat@500kPa  151.86o C Since Tsat > 120o C  

 state is subcooled liquid
Thermodynamics – Chapter 3 41
Thermodynamics – Chapter 3 42
(E3.1) Determine the phase for each of the
following water states.
b. 120oC, 0.5 m3/kg

Enter table B.1.1 (Page No: 22) with 120oC

Thermodynamics – Chapter 3 43
 Page No: 22

3
v f  0.001060m /kg
3
vg  0.89186m /kg
v  v f  x vg  v f 
x  0.56
3 3
v f  0.00106  v  0.5 m /kg  vg  0.89186 m /kg
so the state is a mixture of liquid and vapor.
Psat @120 C  198.5kPa 
o

Thermodynamics – Chapter 3 44
Thermodynamics – Chapter 3 45
(E3.2) Determine the phase for each of the
following states.
a. Ammonia 30oC, 1000 kPa
b. R-22 200 kPa, 0.15 m3/kg

a.Enter table B.2.1 (Page No: 40) with 30oC.

Thermodynamics – Chapter 3 46
a. Ammonia 30oC, 1000 kPa

B.2.1 (Page No: 40) with 30oC

Psat = 1167 kPa > P = 1000 kPa

it is superheated vapor state.

Thermodynamics – Chapter 3 47
a. Ammonia 30oC, 1000 kPa
B.2.2 (Page No: 44) with 30oC

It is superheated by 5oC

Thermodynamics – Chapter 3 48
 

Thermodynamics – Chapter 3 49
b)R-22 200 kPa, 0.15 m3/kg
enter table B.4.2 (Page No: 52) with 200 kPa.

Thermodynamics – Chapter 3 50
b) R-22 200 kPa, 0.15 m3/kg Page No:52

3
v  vg  0.11237 m /kg
it is superheated

Thermodynamics – Chapter 3 51
 (E3.3) Determine the temperature and quality (if
defined) for water at a pressure of 300 kPa and
at each of these specific volumes:
a. 0.5 m3/kg b. 1.0 m3/kg

a. 300 kPa, 0.5 m3/kg refer table

B.1.2 (Page No:26)

Thermodynamics – Chapter 3 52
 Page No:26

3 3
v f  0.001073  v  0.5 m /kg  vg  0.60582 m /kg
so the state is a mixture of liquid and vapor

Thermodynamics – Chapter 3 53
a. 300 kPa, 0.5 m3/kg (B.1.2 Page No:26)

o
Tsat@300 kPa  133.6 C
3
v f  0.001073m /kg
3
vg  0.60582m /kg
3
v fg  0.60475m /kg
v  v f  xv fg

vf vg x  0.825

Thermodynamics – Chapter 3 54
b. 300 kPa,1.0 m3/kg  table B.1.2 Page No:26

3 3
v  1.0 m /kg  vg  0.60582 m /kg
so the state is superheated vapor
 The quality(x) is undefined

55
b. 300 kPa,1.0 m3/kg  table B.1.3 Page No:31

56
b. 300 kPa,1.0 m3/kg
In this case, T is found by linear interpolation
between the 300 kPa specific volume values at
300oC and 400oC
T  T1 T2  T1
Slope 
v  v1 v2  v1
 v  v1 
T  T1    T2  T1 
 v2  v1 
 1.0  0.8753 
T  300     400  300 
 1.0315  0.8753 
o
 379.8 C

57
(E3.7) Determine the pressure for water at 200oC
with v = 0.4 m3/kg.

Table B.1.1 (Page No:24) with 200oC

Thermodynamics – Chapter 3 58
H2O at 200oC, v = 0.4 m3/kg Table B.1.1 (Page No:24)

3
Since v  vg  0.12736 m /kg
 it is superheated

Thermodynamics – Chapter 3 59
Water at 200oC with v = 0.4 m3/kg (Page No:31)

A linear interpolation between these

3
500 kPa  v  0.42492 m /kg two pressures is done to get P at the
600 kPa  v  0.35202 m3 /kg desired v  0.4 m3 / kg

Thermodynamics – Chapter 3 60
  v  v1 
P  P1     P2  P1 
 v2  v1 
 0.4  0.42492 
P  500     600  500   534.2 kPa
 0.35202  0.42492 

Thermodynamics – Chapter 3 61
Thermodynamics – Chapter 3 62
 g - f = fg Process a: Ice at –20 oC to ice
e at 0 oC (no phase change)
d
100 Co Process b: Ice at 0 oC to
water at 0 oC (phase change)
Process c: Water at 0 oC to water at
T c 100 oC (no phase change)

Process d: Water at 100 oC to

0 oC
b steam at 100 oC (phase change)

Process e: Steam at 100 oC to higher

-20 Co
a temperature (no phase change)

NOTE: PRESSURE
f  g CONSTANT
Pressure – volume diagram of a substance, which
expands on freezing

Thermodynamics – Chapter 3 63
• Suppose the cylinder contains 1 kg of ice at -20oC,
100 kPa. It is heated at constant pressure. The
temperature increases until it reaches 0oC, at which
point the ice melts and temperature remains
constant. In this state the ice is called a saturated
solid.
• If the initial pressure of the ice at -20oC is 0.26
kPa, heat transfer to the ice results in an increase in
temperature to -10oC. At this point, the ice passes
directly from the solid phase to the vapor phase in
the process is known as sublimation.

Thermodynamics – Chapter 3 64
• Finally, consider an initial pressure of the ice of
0.6113 kPa and a temperature of -20oC. Through
heat transfer let the temperature increases until it
reaches 0.01oC.
• At this point, further heat transfer 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, which is defined as the state in
which all three phases are in equilibrium.

Thermodynamics – Chapter 3 65
Some Solid – Liquid – Vapor Triple- Point Data

Thermodynamics – Chapter 3 66
 Page No:688/716 (38)

Thermodynamics – Chapter 3 67
Pressure – Temperature Diagram for
a Substance (Water)
Thermodynamics – Chapter 3 68
Why does increasing pressure decrease the freezing point
of water?

Ans: Generally increasing the pressure increases

the freezing point (not decreases). This is because
generally solids are more compact than liquids, so
increasing the pressure makes it harder to melt as
the heat has to work against the compression to
expand the substance. Therefore, you have to raise
the temperature higher to melt it. Therefore the
freezing point is higher.

Thermodynamics – Chapter 3 69
Why does increasing pressure decrease the freezing point
of water?

Ans: Water ice forms crystals with more empty

space than water, so it is less dense than liquid
water. Therefore, increasing the pressure tends to
force it into a more dense liquid state. Yet more
pressure (6175 atmospheres) forces it to freeze
again, into a new, more compact type of ice called
ice VI. There are at least eight types of water ice
(ice I thru ice VIII) that form at various different
temperatures and pressures.

Thermodynamics – Chapter 3 70
Phase Diagram for Carbon Dioxide (Dry Ice)

Thermodynamics – Chapter 3 71
Carbon dioxide phase diagram
Figure shows the three-phase diagram for carbon
dioxide, the triple-point pressure is greater than
normal atmospheric pressure. Therefore, the
commonly observed phase transition under
conditions of atmospheric pressure of about 100
kPa is a sublimation from solid directly to vapor,
without passing through a liquid phase, which is
why solid carbon dioxide is commonly referred to
as dry ice. The phase transformation at 100 kPa
occurs at a temperature below 200 K.

Thermodynamics – Chapter 3 72
 0 < P < 4 kPa : Vapor
0.004 MPa < P < 1000
MPa : Liquid
P >1000 MPa : Solid

Water Phase Diagram

Thermodynamics – Chapter 3 73
Water phase diagram
A pure substance can exist in a number of different
solid phases. A transition from one solid phase to
another is called an allotropic transformation. A
pure substance can have a number of triple points,
but only one triple point has a solid, liquid, and
vapor equilibrium. Other triple points for a pure
substance can have two solid phases and a liquid
phase, two solid phases and a vapor phase, or three
solid phases.

Thermodynamics – Chapter 3 74
Independent Properties of a Pure Substance
 The state of a simple compressible pure substance
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.
 In a saturation state, 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.

Thermodynamics – Chapter 3 75
Phase Diagram
 The p-T diagram of a pure substance is often
called phase diagram since all three phases are
separated from each other by three lines.
 The sublimation line separates the solid and vapor
regions, the vaporization line separates the liquid
and vapor regions, and the fusion line separates
the solid and liquid regions. These three lines
meet at the triple point, where all three phases
coexist in equilibrium.
 The vaporization line ends at the critical point
because no distinction can be made between
liquid and vapor phase above the critical point.
Thermodynamics – Chapter 3 76
Phase Diagram

Pressure – Temperature Diagram of Pure Substance

Thermodynamics – Chapter 3 77
P-v Diagram of a Substance that Expands
on Freezing (such as water)

Thermodynamics – Chapter 3 78
 P-v Diagram of a Substance that
Contracts on Freezing

Thermodynamics – Chapter 3 79
The P-V-T Surface for a Real Substance
The equilibrium states of any simple, compressible
substance can be represented as a surface in a
rectangular, three-dimensional space.

Thermodynamics – Chapter 3 80
The P-V-T Surface for a Real Substance

Substance which Contracts Upon Freezing

Thermodynamics – Chapter 3 81
The P-V-T Surface for a Real Substance

Substance which Expands Upon Freezing

Thermodynamics – Chapter 3 82
Substance that expands on freezing Substance that contracts on freezing

Thermodynamics – Chapter 3 83
Substance that expands on freezing

Thermodynamics – Chapter 3 84
Substance that contracts on freezing

Thermodynamics – Chapter 3 85