Chapter
TME 213
2 Thermodynamics
Properties of
Pure Dr S.K. Fasogbon & Dr Temilola T. Olugasa
Substances
University of Ibadan
What is a Pure Substance?
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
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This constant
pressure heating
process can be
illustrated as:
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Property Diagram
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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
Saturation Temperature: At a given pressure, the
temperature at which a pure substance changes phase.
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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
Mixture of liquid and vapor
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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 xv g
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
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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 47⁰ 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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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 26
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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)
u g 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:
mg 1 m3
x1 v f, 2 0 .001384
kg vg 2 v2
m f 1 mg 1
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 150°C. 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
350°C.
(a) what is the initial temperature of the water,
(b) determine the total mass of the water,
(c) calculate the final volume, and
(d) show the process on a P-v diagram with respect to
saturation lines.
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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.
• Triple point - the temperature and pressure at which all three
phases can exist in equilibrium. For water, the triple-point
temperature and pressure are 0.01°C and 0.6117 kPa,
respectively
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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Important Definition
o Critical point - the temperature and pressure above which there
is no distinction between the liquid and vapor phases.
Triple point - the temperature and pressure at which all three phases
can exist in equilibrium. For water, the triple-point temperature and
pressure are 0.01°C and 0.6117 kPa, respectively
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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This diagram is often called the phase diagram since all three phases are separated
from each other by three lines. 34
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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 gases, 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 Δu and Δh of ideal gases can be expressed as
u u 2 u1 C v (T2 T1 )
h h2 h1 C P (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
temperature drops to 150C, T2 15 273 288 K
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 2V1
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 20°C.
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 25°C, 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 50°C. 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 25°C and 500 kPa is connected through a
valve to another tank containing 5 kg of air at 35°C and 200 kPa. Now
the valve is opened, and the entire system is allowed to reach thermal
equilibrium with the surroundings, which are at 20°C. 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 25°C. To what
pressure should it be charged if there should be 1.2 kg of carbon
dioxide?
[ 2152 kPa]
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