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CHAPTER 2
Properties of
Pure Substances
 What is Pure Substances?
A substance that has a fixed
chemical composition throughout
is called a pure substance.

A pure substance does not have

to be of a single chemical
element or compound, however.
A mixture of various chemical
elements or compounds also
qualifies as a pure substance as
long as the mixture is
homogeneous.

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 A mixture of liquid and water vapor is a pure substance, but a
mixture of liquid and gaseous air is not.

Examples:
Water (solid, liquid, and vapor phases)
Mixture of liquid water and water vapor
Carbon dioxide, CO2
Nitrogen, N2
Mixtures of gases, such as air, as long as there is no
change of phase.

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 Phases of A Pure Substance
The substances 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 condition.

There are 3 Principal phases

solid
Liquid
gas
Each with different molecular structures.

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 Phase-change Processes of Pure Substances
There are many practical situations where two phases of a pure
substances coexist in equilibrium.
E.g. water exists as a mixture of liquid and vapor in the boiler and etc.
Solid: strong intermolecular bond
Liquid: intermediate intermolecular bonds
Gas: weak intermolecular bond

Solid Liquid Gas

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 Phase-change Processes

Compressed liquid- Saturated liquid- Saturated liquid-vapor

Water exist in the water exist as liquid mixture part of
liquid phase and ready to vaporize saturated liquid vaporize

Saturated vapor- T Superheated vapor -

remains constant T of vapor start to
until the last drop of rise.
liquid vaporized
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Compressed Liquid Water that is not vaporize
/ Subcooled Liquid

Saturated Liquid A liquid that is about to vaporize

Saturated vapor A vapor that is about to

condense

Saturated liquid- Liquid and vapor phases coexist

vapor mixture in equilibrium at these states.

Superheated A vapor that is not about to

vapor condense
This constant
pressure heating
process can be
illustrated as:

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Property Diagram

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 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

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The graphical representation of this relationship between temperature
and pressure at saturated conditions is called the vapor pressure curve

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 Saturated and Sub-cooled Liquids

If a substance exists as a liquid at the

saturation temperature and pressure,
it is called a saturated 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

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Saturated and Superheated Vapors
If a substance exists entirely as
vapor at saturation temperature, it
is called saturated vapor.

When the vapor is at a temperature

greater than the saturation
temperature, it is said to exist as
superheated vapor.
The pressure and temperature of
superheated vapor are independent
properties, since the temperature
may increase while the pressure
remains constant
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 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.

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 Quality

When a substance exists as part liquid and part vapor at

saturation conditions, its quality (x) is defined as the
ratio of the mass of the vapor to the total mass of both
vapor and liquid.
The quality is zero for the saturated liquid and one for
the saturated vapor (0 x 1)

For example, if the mass of vapor is 0.2 g and the mass

of the liquid is 0.8 g, then the quality is 0.2 or 20%.

masssaturated vapor mg
x
masstotal m f mg

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 Quality

A two phase system can be treated as

a homogenous mixture for
convinience
The relative amounts of liquid and
vapor phase in saturated mixture are
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specified by the quality x
 Moisture Content

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
mg mg
Recall the definition of quality x x
m m f mg
Then
mf m mg
1 x
m m

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 Moisture Content
Take specific volume as an example. The specific volume of the
saturated mixture becomes
v (1 x)v f xvg
The form that is most often used

v v f x (v g v f )
Let Y be any extensive property and let y be the corresponding
intensive property, Y/m, then
Y
y y f x( yg y f )
m
y f x y fg
where y fg y g y f 18
 Property Table

For example if the pressure

and specific volume are
specified, three questions are
asked: For the given pressure,

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 Property Table
If the answer to the first question is yes,
the state is in the compressed liquid
region, and the compressed liquid table is v vf
used to find the properties. (or using
saturation temperature table)

If the answer to the second question is

yes, the state is in the saturation region, v f v vg
and either the saturation temperature table
or the saturation pressure table is used.

If the answer to the third question is yes,

the state is in the superheated region and
vg v
the superheated table is used.

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 Property Table

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Example 2.1
Determine the saturated pressure, specific volume, internal energy
and enthalpy for saturated water vapor at 45oC and 50oC.

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Example 2.2
Determine the saturated pressure, specific volume, internal energy
and enthalpy for saturated water vapor at 47 C .

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Solution:

Extract data from steam table

T Psat v u h
45 9.5953 15.251 2436.1 2582.4
47 Psat v u h
50 12.352 12.026 2442.7 2591.3

Interpolation for Psat

Psat 9.5953 47 45

12.352 9.5953 50 45 Interpolation Scheme for Psat
Psat @ 47 10.698 kPa

Do the same principal to

others!!!!
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 EXAMPLE

A RIGID TANK CONTAINS 50KG OF SATURATED LIQUID WATER AT 900C.

DETERMINE THE PRESSURE IN THE TANK AND THE VOLUME OF THE
TANK.
A PISTON CYLINDER DEVICE CONTAINS 0.057 M3 SATURATED WATER
VAPOR AT 350KPA PRESSURE. DETERMINED THE TEMPERATURE AND
THE MASS OF THE VAPOR CYLINDER.
Exercises

1. Fill in the blank using R-134a

2. Determine the saturated temperature, saturated pressure and

enthalpy for water at specific volume of saturated vapor at
10.02 m3/kg .

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Example 2.3 Is v v f ? No
Determine the enthalpy of 1.5 Is v f v v g ? Yes
kg of water contained in a Is v g v ? No
volume of 1.2 m3 at 200 kPa.
Find the quality
Solution: v v f x (v g v f )
v vf
Specific volume for water x
vg v f
Volume 12. m3 m3 0.8 0.001061
v 0.8
mass 15
. kg kg 0.8858 0.001061
From table A-5: 0.903 (What does this mean?)
The enthalpy
v f 0.001061 m3
kg
h h f x h fg
vg 0.8858 m3
kg 504.7 (0.903)(2201.6)
kJ
2492.7
kg 27
Example 2.4
Determine the internal energy of refrigerant-134a at a temperature
of 0C and a quality of 60%.

Solution:

From table A-5: The internal energy of R 134a

at given condition:
kJ
u f 51.63 u u f x (u g u f )
kg
kJ 51.63 (0.6)(230.16 51.63)
ug 230.16
kg kJ
158.75
kg

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Example 2.5

Consider the closed, rigid container of

water as shown. The pressure is 700 mg, Vg
kPa, the mass of the saturated liquid is Sat. Vapor
1.78 kg, and the mass of the saturated
vapor is 0.22 kg. Heat is added to the
water until the pressure increases to 8 mf, Vf
MPa. Find the final temperature, Sat. Liquid

enthalpy, and internal energy of the

water

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Solution:
State 2:
Theoretically:
v2 v1 Information :
P2 8 MPa v2 0.031 mkg
3

The quality before pressure

increased (state 1). From table A-5:
mg1 m3
x1 v f,2 0.001384
vg 2 v2
m f 1 mg1 kg
m3
0.22 kg v g,2 0.02352
0.11 kg
(1.78 0.22) kg Since that it is in superheated
Specific volume at state 1 region, use table A-6:
v1 v f 1 x1 (vg1 v f 1 ) T2 361.8o C
0.001108 (0.11)(0.2728 0.001108) h2 3024 kJ
kg
m3 u2 2776 kJ
0.031 kg
kg
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Exercises
1. Four kg of water is placed in an enclosed volume of 1m3.
Heat is added until the temperature is 150C. Find ( a )
the pressure, ( b )the mass of vapor, and ( c ) the volume
of the vapor.

2. A piston-cylinder device contains 0.1 m3 of liquid water and

0.9 m3 of water vapor in equilibrium at 800 kPa. Heat is
transferred at constant pressure until the temperature reaches
350C.
(a) what is the initial temperature of the water,
(b) determine the total mass of the water,
(c) calculate the final volume, and

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Exercises
3. For a specific volume of 0.2 m3/kg, find the quality of steam
if the absolute pressure is (a) 40 kPa and ( b ) 630 kPa. What
is the temperature of each case?

4. Water is contained in a rigid vessel of 5 m3 at a quality of

0.8 and a pressure of 2 MPa. If the a pressure is reduced to
400 kPa by cooling the vessel, find the final mass of vapor
mg and mass of liquid mf.

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 Important Definition
o Critical point - the temperature and pressure above which there
is no distinction between the liquid and vapor phases.

o Triple point - the temperature and pressure at which all three

phases can exist in equilibrium.

o Sublimation - change of phase from solid to vapor.

o Vaporization - change of phase from liquid to vapor.

o Condensation - change of phase from vapor to liquid.

o Fusion or melting - change of phase from solid to liquid.

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34
 Ideal Gas Law
Robert Boyle formulates a well-known law that states the pressure of a
gas expanding at constant temperature varies inversely to the volume,
or

P1V1 P2V2 constant

As the result of experimentation, Charles concluded that the pressure of

a gas varies directly with temperature when the volume is held
constant, and the volume varies directly with temperature when the
pressure is held constant, or

V1 T1 P1 T1
or
V2 T2 P2 T2
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 By combining the results of
Charles' and Boyle's Pv
experiments, the following constant
T
relationship can be obtained

The constant in the above

equation is called the ideal gas
constant and is designated by Pv RT or PV mRT
R; thus the ideal gas equation
becomes

In order to make the equation

applicable to all ideal gas, a RU
R
universal gas constant RU is M
introduced
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 For example the ideal gas constant for air, Rair

( RU ) air 8.3144
Rair 0.2871kJ / kg.K
( M ) air 28.96

The amount of energy needed to raise the temperature of a unit of

mass of a substance by one degree is called the specific heat at
constant volume Cv for a constant-volume process and the specific
heat at constant pressure Cp for a constant pressure process. They
are defined as

u h
Cv and C P
T v T P

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 Using the definition of enthalpy (h = u + Pv) and writing the
differential of enthalpy, the relationship between the specific heats
for ideal gases is

h u Pv
dh du RT
CP dt CV dt RdT
CP CV R

The specific heat ratio, k is defined as

CP
k
Cv
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 For ideal gases u, h, Cv, and Cp are functions of temperature alone.
The u and h of ideal gases can be expressed as

u u 2 u1 Cv (T2 T1 )

h h2 h1 CP (T2 T1 )

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Example 2.6 Solution:
given
An ideal gas is contained in a state1
closed assembly with an initial
pressure and temperature of 220 P1 220 kPa
kPa and 700C respectively. If T1 70 273K 343 K
the volume of the system is state 2
increased 1.5 times and the
T2 15 273 288 K
temperature drops to 150C,
determine the final pressure of V2 1.5V1
the gas. From ideal-gas law:
PV PV
1 1
2 2
T1 T2
V1 288
P2

1.5V1 343
220 103

123.15 kPa
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Example 2.7 Solution:
given
A closed assembly contains 2 kg
of air at an initial pressure and state1
temperature of 140 kPa and P1 140 kPa
2100C respectively. If the T1 210 273K 483 K
volume of the system is doubled
state 2
and temperature drops to 370C,
determine the final pressure of T2 37 273 310 K
the air. Air can be modeled as an V2 2 V1
ideal gas. From ideal-gas law:
PV P2V2
1 1

T1 T2
V1 310
P2
2V1 483
140 103

44.93 kPa
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Example 2.8
An automobile tire with a volume
of 0.6 m3 is inflated to a gage
pressure of 200 kPa. Calculate the
mass of air in the tire if the
temperature is 20C.
Solution: From ideal-gas law:
given
PV
state1 m
RT
P 200 100 kPa


300 103 mN3 0.6m2
T 20 273K 293 K
287 kgNm.K 293K
2.14 kg

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Supplementary Problems
1. The pressure in an automobile tire depends on the temperature of the air
in the tire. When the air temperature is 25C, the pressure gage reads 210
kPa. If the volume of the tire is 0.025 m3, determine the pressure rise in
the tire when the air temperature in the tire rises to 50C. Also, determine
the amount of air that must be bled off to restore pressure to its original
value at this temperature. Assume the atmospheric pressure is 100 kPa.
[ 26 kPa, 0.007 kg]

2. A 1-m3 tank containing air at 25C and 500 kPa is connected through a
valve to another tank containing 5 kg of air at 35C and 200 kPa. Now
the valve is opened, and the entire system is allowed to reach thermal
equilibrium with the surroundings, which are at 20C. Determine the
volume of the second tank and the final equilibrium pressure of air.
[ 2.21 m3, 284.1 kPa]

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3. A 1 m3 rigid tank has propane at 100 kPa, 300 K and connected by a
valve to another tank of 0.5 m3 with propane at 250 kPa, 400 K. The
valve is opened and the two tanks come to a uniform state at 325 K.
What is the final pressure?
[ 139.9 kPa]

4. A cylindrical gas tank 1 m long, inside diameter of 20 cm, is

evacuated and then filled with carbon dioxide gas at 25C. To what
pressure should it be charged if there should be 1.2 kg of carbon
dioxide?
[ 2152 kPa]

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The ideal gas equation of state is used when (1) the pressure is small compared to
the critical pressure or (2) when the temperature is twice the critical temperature and
the pressure is less than 10 times the critical pressure. The critical point is that state
where there is an instantaneous change from the liquid phase to the vapor phase for
a substance. Critical point data are given in Table A-1.

Compressibility Factor

To understand the above criteria and to determine how much the ideal gas equation
of state deviates from the actual gas behavior, we introduce the compressibility factor
Z as follows.
Pv Z Ru T
or
Pv
Z
Ru T
For an ideal gas Z = 1, and the deviation of Z from unity measures the deviation of
the actual P-V-T relation from the ideal gas equation of state. The compressibility
factor is expressed as a function of the reduced pressure and the reduced
temperature. The Z factor is approximately the same for all gases at the same
reduced temperature and reduced pressure, which are defined as
T P
TR and PR
Tcr Pcr
where Pcr and Tcr are the critical pressure and temperature, respectively. The
critical constant data for various substances are given in Table A-1. This is
known as the principle of corresponding states. Figure 3-51 gives a comparison of Z
factors for various gases and supports the principle of corresponding states.
When either P or T is unknown, Z can be determined from the compressibility chart
with the help of the pseudo-reduced specific volume, defined as
vactual
vR
R Tcr
Pcr
Figure A-15 presents the generalized compressibility chart based on data for a large
number of gases.
 These charts show the conditions for which Z = 1 and the gas behaves as an
ideal gas:

1.PR < 10 and TR > 2 or P < 10Pcr and T > 2Tcr

2.PR << 1 or P << Pcr

Note: When PR is small, we must make sure that the state is not in the
compressed liquid region for the given temperature. A compressed liquid state is
certainly not an ideal gas state.

For instance the critical pressure and temperature for oxygen are 5.08 MPa and
154.8 K, respectively. For temperatures greater than 300 K and pressures less than
50 MPa (1 atmosphere pressure is 0.10135 MPa) oxygen is considered to be an ideal
gas.

Example 2-6

Calculate the specific volume of nitrogen at 300 K and 8.0 MPa and compare the
result with the value given in a nitrogen table as v = 0.011133 m3/kg.

From Table A.1 for nitrogen

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 Tcr = 126.2 K, Pcr = 3.39 MPa R = 0.2968 kJ/kg-K
T 300 K
TR 2.38
Tcr 126.2 K
P 8.0 MPa
PR 2.36
Pcr 3.39 MPa
Since T > 2Tcr and P < 10Pcr, we use the ideal gas equation of state
Pv RT
kJ
0.2968 (300 K ) 3
RT kg K m MPa
v
P 8.0 MPa 103 kJ
m3
0.01113
kg
Nitrogen is clearly an ideal gas at this state.

If the system pressure is low enough and the temperature high enough (P and T are
compared to the critical values), gases will behave as ideal gases. Consider the T-v
diagram for water. The figure below shows the percentage of error for the volume
([|vtable videal|/vtable]x100) for assuming water (superheated steam) to be an ideal
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gas.
We see that the region for which water behaves as an ideal gas is in the superheated
region and depends on both T and P. We must be cautioned that in this course,
when water is the working fluid, the ideal gas assumption may not be used to solve
problems. We must use the real gas relations, i.e., the property tables.

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 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

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Beattie-Bridgeman:

where

The constants a, b, c, Ao, Bo for various substances are found in Table 3-4.

Benedict-Webb-Rubin:

The constants for various substances appearing in the Benedict-Webb-Rubin

equation are given in Table 3-4.

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