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
Temperature – Volume diagram for water
showing liquid and vapor phases

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

Thermodynamics – Chapter 3 28
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
mf  mg
f used to designate a
property of saturated
liquid and g property
of a saturated vapor.

Thermodynamics – Chapter 3 29
 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 30
 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 31
V  Vliq  Vvap  Vf  Vg

V  mv  mv
t avg
 mf v f  mg vg
m f v f mg vg  m f   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 32
Quality is related to the horizontal distance on P-v
and T-v diagrams.
Thermodynamics – Chapter 3 33
 Page No:674/702 (24)

Thermodynamics – Chapter 3 34
 g - f = fg Process a: Ice at –20 oC to ice
e at 0 oC (no phase change)
d
100 oC 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

b steam at 100 oC (phase change)
0 oC
Process e: Steam at 100 oC to higher
-20 oC a temperature (no phase change)

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

Thermodynamics – Chapter 3 35
• 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 36
• 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 37
Some Solid – Liquid – Vapor Triple- Point Data

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

Thermodynamics – Chapter 3 39
Pressure – Temperature Diagram for
a Substance (Water)
Thermodynamics – Chapter 3 40
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 41
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 42
Phase Diagram for Carbon Dioxide (Dry Ice)

Thermodynamics – Chapter 3 43
 0 < P < 4 kPa : Vapor
0.004 MPa < P < 1000
MPa : Liquid
P >1000 MPa : Solid

Water Phase Diagram

Thermodynamics – Chapter 3 44
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 45
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 46
Phase Diagram

Pressure – Temperature Diagram of Pure Substance

Thermodynamics – Chapter 3 47
P-v Diagram of a Substance that Expands
on Freezing (such as water)

Thermodynamics – Chapter 3 48
 P-v Diagram of a Substance that
Contracts on Freezing

Thermodynamics – Chapter 3 49
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 50
The P-V-T Surface for a Real Substance

Substance which Contracts Upon Freezing

Thermodynamics – Chapter 3 51
The P-V-T Surface for a Real Substance

Substance which Expands Upon Freezing

Thermodynamics – Chapter 3 52
Substance that expands on freezing Substance that contracts on freezing

Thermodynamics – Chapter 3 53
Substance that expands on freezing

Thermodynamics – Chapter 3 54
Substance that contracts on freezing

Thermodynamics – Chapter 3 55
Equations of State
 Any equation that relates the temperature,
pressure, and specific volume of a substance is
called an equation of state.

 The simplest and best-known equation of state for

substances in a gas phase is the ideal-gas equation
of state.

 This equation predicts the P-v-T behavior of a gas

quite accurately within some properly selected
region.

Thermodynamics – Chapter 3 56
Ideal Gas Equation
The combination of Boyle’s and Charles’ laws for
gases at low pressure result in the equation of state
for the ideal gas as
T 
P  R 
v
where R is the constant of proportionality and is
called the gas constant and takes on a different
value for each gas. If a gas obeys this relation, it is
called an ideal gas. We often write this equation as
Pv  RT
Thermodynamics – Chapter 3 57
The gas constant (R) for ideal gases is related to the
universal gas constant (Ru) valid for all substances
through the molar mass (or molecular weight).
Then,
Ru 8.314 KJ/kg.K
R 
M M
The molar mass is defined as the mass of one mole
of a substance in grams and has the same value
regardless of the system of units.
g kg lbm
M air  28.97  28.97  28.97
gmol kmol lbmol

Thermodynamics – Chapter 3 58
The mass (m) of a system is equal to the product of
its molar mass M and the mole number n:

m  nM
The ideal gas equation of state may be written
several ways.
Pv  RT
V
P  RT
m
PV  mRT
Thermodynamics – Chapter 3 59
 A.5 (Page No:658/686)

Thermodynamics – Chapter 3 60
Is Water Vapor an Ideal Gas?
 At pressures below 10 kPa, water can be treated
as an ideal gas, regardless of its temperature.
 Steam can treated as an ideal gas when the
percentage error is less than 0.1.
Percentage Error    table  ideal /  table   100

 But at higher pressures, the ideal-gas assumption

yields unacceptable errors, particularly in the
vicinity of the critical point and the saturated
vapor line.
Thermodynamics – Chapter 3 61
Percentage of error involved in assuming steam to
be an ideal gas.
Thermodynamics – Chapter 3 62
Compressibility Factor
The deviation from ideal gas behavior at a given
temperature and pressure can accurately be
accounted for by the introduction of a correction
factor called the compressibility factor, Z defined as
P
P  Z RT or Z
RT
actual
It can also be expressed as Z 
ideal
For an ideal gas Z  1

Thermodynamics – Chapter 3 63
 Compressibility Chart for Nitrogen

Thermodynamics – Chapter 3 64
Thermodynamics – Chapter 3 65
 If we examine compressibility diagrams for other
pure substances, we find that the diagrams are all
similar in the characteristics described earlier, at
least in a qualitative sense.

 Quantitatively the diagrams are all different, since

the critical temperatures and pressures of different
substances vary over wide ranges.

 Is there a way in which we can put all of these

substances on a common basis?

Thermodynamics – Chapter 3 66
 Gases behave differently at a given temperature
and pressure, but they behave very much the same
at temperatures and pressures normalized with
respect to their critical temperature and pressures.
T
TR (reduced temperature) 
Tcr
P
PR (reduced pressure) 
Pcr

 The Z factor for all gases is approximately same

at the same reduced temperature and reduced
pressure, which is known as the principle of
corresponding states.
Thermodynamics – Chapter 3 67
The experimentally determined Z values plotted
against PR and TR for several gases (with simple
molecules, which means that it represents the
average behavior for a number of different simple
substances). The gases seem to obey the principle of
corresponding states reasonably well. By curve-
fitting all the data, we obtain the generalized
compressibility chart can be used for all gases.

Thermodynamics – Chapter 3 68
 Compressibility Chart based on Data for a
Large Number of Gases
Thermodynamics – Chapter 3 69
These charts show the conditions for which Z = 1
and the gas behaves as an ideal gas:

 At very low pressure (PR << 1), the gases behave

as an ideal gas regardless of temperature.

 At high temperature (TR > 2), ideal gas behavior

can be assumed with good accuracy to pressures
as high as four or five times Pc (except PR >> 1).

 The deviation of gas from ideal-gas behavior is

greatest in the vicinity of the critical point.

Thermodynamics – Chapter 3 70
At very low pressures, all gases approach ideal-
gas behavior regardless of their temperature.

Thermodynamics – Chapter 3 71
Gases deviate from the ideal-gas behavior the
most in the neighborhood of the critical point.

Thermodynamics – Chapter 3 72
Other Equations of State
Many attempts have been made to keep the
simplicity of the ideal gas equation of state but yet
account for the intermolecular forces and volume
occupied by the particles. Three of these are

Van der Waals:

a
( P  2 )(v  b)  R T
v
where
27 R 2 Tcr2 RTcr
a and b
64 Pcr 8 Pcr

Thermodynamics – Chapter 3 73
Beattie-Bridgeman:

where

Benedict-Webb-Rubin:

Thermodynamics – Chapter 3 74