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CHAPTER
Thermodynamics

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Properties of
Pure Substances
 Faculty of Mechanical Engineering, UiTM

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

 A phase is a quantity of matter which is homogeneous
throughout in chemical composition and physical structure.
 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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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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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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The graphical representation of this relationship between temperature

and pressure at saturated conditions is called the vapor pressure curve

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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 17
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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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Example 2.1
Determine the saturated pressure, specific volume, internal energy
and enthalpy for saturated water vapor at 45 oC 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 ⁰ 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 m
3
kg
h h f  x h fg
vg 0.8858 m3
kg 504.7  (0.903)(2201.6)
kJ
2492.7
kg 25
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Example 2.4
Determine the internal energy of refrigerant-134a at a temperature
of 0C 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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MEC 451 – THERMODYNAMICS
 Faculty of Mechanical Engineering, UiTM

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:
 Theoretically: State 2:

v2 v1  Information :
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 The quality before pressure P2 8 MPa v2 0.031 mkg
increased (state 1).  From table A-5:
mg 1
x1  vg 2  v2
m f 1  mg 1
0.22 kg
 0.11
(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 1m 3.
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 m 3 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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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
constant
experiments, the following T
relationship can be obtained
 The constant in the above
equation is called the ideal gas
Pv  RT or PV mRT
constant and is designated by
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 
C v   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
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 10 3

123.15 kPa
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Example 2.7 Solution:

given
A closed assembly contains 2 kg
state1
of air at an initial pressure and
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 10 3

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 0.6m 2 
T 20  273K 293 K
287 kgNm. K 293K 
2.14 kg

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Supplementary Problems

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