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  Vf  Vg

V  mv  mt vavg  m f 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 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 120 o 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

500 kPa  v  0.42492 m /kg two pressures is done to get P at the
3

600 kPa  v  0.35202 m 3 /kg desired v  0.4 m 3 / 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 Process b: Ice at 0 oC to
100 Co
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
(3.53/3.59)A boiler feed pump delivers 0.05 m3/s of
water at 240oC, 20 MPa. What is the mass flow
rate (kg/s)? What would be the percent error if
the properties of saturated liquid at 240oC were
used in the calculation? What if the properties of
saturated liquid at 20 MPa were used?
o
State 1: T1  240 C, P1  20 MPa
3
Compressed liquid B.1.4  v  0.001205 m /kg
V 3
0.05 m /s
m   3
 41.5 kg/s
v 0.001205 m /kg

Thermodynamics – Chapter 3 86
 3
v f @ 240 C  0.001229 m /kg  m  40.68 kg/s
o

 error 2%
3
v f @ 20MPa  0.002036 m /kg  m
  24.56 kg/s
 error 41%

Thermodynamics – Chapter 3 87
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 88
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 89
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/kmol.K
R  KJ/kg.K   
M M  kg / kmol 
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 90
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 91
 A.5 (Page No:658/686)

Thermodynamics – Chapter 3 92
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 93
Percentage of error involved in assuming steam to
be an ideal gas.
Thermodynamics – Chapter 3 94
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 95
 Compressibility Chart for Nitrogen

Thermodynamics – Chapter 3 96
Thermodynamics – Chapter 3 97
 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 98
 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 99
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 3 100

 Compressibility Chart based on Data for a
Large Number of Gases
Thermodynamics – Chapter 3 101
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 3 102

At very low pressures, all gases approach ideal-
gas behavior regardless of their temperature.

Thermodynamics – Chapter 3 103

Gases deviate from the ideal-gas behavior the
most in the neighborhood of the critical point.

Thermodynamics – Chapter 3 104

 Figure D.1
P. No. 728/755

Generalized Compressibility Chart

Thermodynamics – Chapter 3 105
(E3.12) Determine the specific volume for R-134a
at 100oC, 3.0 MPa, for the following models:
a. The R-134a tables, Table B.5
o
From Table B.5.2 (P 61) at 100 C, 3 MPa,
3
v  0.00665 m /kg (most accurate value)
b. Assuming ideal gas Table A.5 (P 6)
Ru 8.3145 kJ/kmol.K
R   0.08149 kJ/kg.K
M 102.03 kg/kmol
RT 0.08149 kJ/kg.K  373.2 K 3
v   0.01014 m /kg
P 3000 kPa
which is more than 50% too large.
Thermodynamics – Chapter 3 106
c. Using the generalized chart, Fig. D.1
From Table A.2 (P 4) for R-134a 
Tcri  374.2K and Pcri  4.06MPa
T 373.2
Tr    1.0
Tcri 374.2
P 3
Pr    0.74
Pcri 4.06

 Z  0.67
RT 3
vZ  0.67  0.01014  0.00679 m /kg
P
which is only 2% too large.
Thermodynamics – Chapter 3 107
 Tr  1.0
Z  0.67

Pr  0.74

Thermodynamics – Chapter 3 108

(E3.13) Propane in a steel bottle of volume 0.1 m3
has a quality of 10% at a temperature of 15oC. Use
the generalized compressibility chart to estimate the
total propane mass and to find the pressure.

From Table A.2 for propane,

Pc  4250 kPa and Tc  369.8 K.

The reduced temperature is

T 273.15  15
Tr    0.7792  0.78
Tc 369.8

Thermodynamics – Chapter 3 109

For the two-phase state the pressure is the saturated
pressure
P  PR  Pc  0.2  4250 kPa  850 kPa

Thermodynamics – Chapter 3 110

 Tr  0.78
Z g  0.83

P  Pr  Pc
 0.2  4250 kPa
 850 kPa

Z f  0.035
Pr  0.2

Thermodynamics – Chapter 3 111

The overall compressibility factor becomes
Z  Z f  x  Z g  Z f   0.035  0.1   0.83  0.035 
 0.1145
The gas constant from Table A.5  R  0.1886 kJ/kg.k
PV  mZRT
PV
m
ZRT
3
850 kPa  0.1 m

0.1145  0.1886 kJ/kg.k  288.15 K
 13.66 kg

Thermodynamics – Chapter 3 112

(3.82/3.89) A new refrigerant R-125 is stored as a
liquid at -20oC with a small amount of vapor. For a
total of 1.5 kg R-125 find the pressure and volume.

From Table A.2 for R-125

 Pc  3620 kPa and Tc  339.2 K

T 253.15 K
Tr  
Tc 339.2 K
 0.746

Thermodynamics – Chapter 3 113

Z g  0.86 Tr  0.746

Z f  0.03
Pr  0.16

Thermodynamics – Chapter 3 114

From Fig. D.1 for Tr  0.746
 Pr  0.16, Z g  0.86, Z f  0.03
P  Pr  Pc  0.16  3620 kPa
 579 kPa

Z f mliq RT
Vliq 
P
0.03  1.5 kg  0.06927 kJ/kg.K  253.15 K

579 kPa
3
 0.00136 m

Thermodynamics – Chapter 3 115