11/15/2011

1
THERMODYNAMICS
Prepared By:
Prof. Rene D. Estember
THERMODYNAMICS
branch of physical science that treats various phenomena of energy and
the related properties of matter, especially of the law of transformation
of heat into other forms of energy and vice-versa.
Examples of everyday transformation:
Process of converting heat into electrical work (electrical power
generation)
Process of converting electrical work into cooling (air conditioning)
Process of converting work into kinetic energy (automotive
transportation)
THERMODYNAMIC S YSTEM (or simply a SYSTEM)
refers to the quantity of matter or certain volume in space chosen for
study.
Surroundings - the mass or region outside the system.
Boundary the real or imaginary surface that separates the system
from the surroundings. The boundary of the system can either be
fixed or movable.
Kinds of Thermodynamic System
1. Closed system (also known as control mass)
a system in which there is no transfer of matter across the boundary. It
consists a fixed amount of mass, and no mass can cross its boundary.
That is, no mass can enter or leave a closed system.
2. Open system (also known as control volume)
a system in which there is a flow of matter through the boundary. It
usually encloses the device that involves mass flow such as
compressor, turbine, or nozzle.
Kinds of Thermodynamic System
3. Isolated System
A system in which neither mass nor energy crosses the boundaries and it
is not influenced by the surroundings. (m = 0, W=0, Q=0)
PROPERTIES OF A SYSTEM
Any characteristic of a system is called a property.
Types of Thermodynamic Properties
A. Static Properties
refer to the physical condition of the working substance such as
temperature, pressure, density, specific volume, specific gravity, or
relative density.
B. Transport Properties
refer to the measurement of diffusion within the working medium
resulting from molecular activity, like viscosities, thermal
conductivities, etc.
Classification of Thermodynamic Properties
A. Intensive Properties
independent of the mass such as temperature, pressure, density, and
voltage.
B. Extensive Properties
dependent upon the mass of the system and are total values such as total
volume and total internal energy.
The State Properties
1. Temperature
An indication or degree of hotness and coldness and therefore a
measure of intensity of heat.
Absolute temperature the temperature measured from absolute
zero.
Absolute zero the temperature at which the molecules stop
moving. The absolute zero equivalent to 0
o
K (-273.15
o
C) or 0
o
R (-
460
o
F).
Conversion Formulas
The Temperature Interval (Change)
The difference between two temperature readings from the same scale,
and the change in temperature through which the body is heated.
Note: The degree must be written after the temperature scale for it to
indicate that it is a change in temperature
ZEROTH LAW OF THERMODYNAMICS
When any two bodies are in thermal equilibrium with the third body, they
are in thermal equilibrium with each other. (Note: the third body is
usually a thermometer)
32
5
9
+ = C F
o
( ) 32
9
5
= F C
o
460 + = F R
o
273 + = C K
o
o o
C K
T T A = A
o o
C F
T T A = A
5
9
O O
F R
T T A = A o o
C F
T T A = A
5
9
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2. Density (Specific Weight)
Mass density the mass per unit volume.
where: m = mass (kg
m
, g, slug, lb
m
)
V = volume (m
3
, cm
3
, ft
3
)
= density (kg
m
/m
3
, g/cm
3
, lb
m
/ft
3
)
Weight density (Specific Weight) the weight per unit volume.
where: Fg = force due to gravity /weight (kg
f
,N, g, lb
f
)
V = volume (m
3
, cm
3
, ft
3
)
= specific weight (kg
f
/m
3
, N/m
3
, g/cm
3
, lb
f
/ft
3
)
3. Specific Volume
The volume per unit mass
where: m = mass (kg
m
, g, lb
m
)
V = volume (m
3
, cm
3
, ft
3
)
= specific volume (m
3
/kg
m
, cm
3
/g, ft
3
/lb
m
)
V
F
g
=

1
= =
m
V
v
V
m
=
4. Pressure
The force exerted per unit area.
Absolute pressure - the true pressure measured above a perfect
vacuum.
Gage Pressure
pressure measured from the level of atmospheric pressure by most pressure
recording measurement like pressure gage and ope-ended manometer.
Atmospheric pressure
pressure obtained from barometric reading.
where: p
abs
= absolute pressure
p
gage
= gage pressure
p
atm
= atmospheric pressure
atm psi p
atm
1 7 . 14 = =
mmHg kPa p
atm
760 325 . 101 = =
inHg
cm
kg
p
atm
92 . 29 032 . 1 = =
2
6
10 013 . 1 013 . 1
cm
dyne
x bar p
atm
= =
atm gage abs
p p p =
atm abs
p p > = +) (
atm abs
p p < = ) (
h
A
Ah
A
V
A
F
p
g
gage


= = = =
v
gh
gh h p
g
g g gage
= = =
Critical Pressure
Minimum pressure needed to liquefy gas at its critical temperature.
5. Specific Gravity (Relative Density)
Also known as relative density. It is the ratio of the density of a certain
gas/substance to the density of air/water at the same temperature.
CONSERVATION OF MASS
The law of conservation of mass states that the mass is indestructible. Mass
(m
1
) entering the system is equal to the sum of the stored mass (m) and
the mass (m
2
) that leaves the system.
Where: A = cross sectional area of the
stream
= average speed
= density
gas
air
water air
subs gas
water air
subs gas
water air
subs gas
R
R
MW
MW
G S = = = =
/
/
/
/
/
/
. .

2 2 2 1 1 1
2 1
u u A A
m m
=
=
CONSERVATION OF ENERGY
The law of conservation of energy states that energy is neither created nor
destroyed.
The fist law of Thermodynamics states that one form of energy may be
converted into another.
Gravitational Potential Energy is its energy due to its position or elevation.
Where: z = height
F
g
= weight
m = mass
g = acceleration due to gravity
P = Potential energy, P = change in potential energy
Kinetic Energy the energy or stored capacity for performing work possessed
by a moving body, by virtue of its momentum.
Where: m = mass
= velocity
K = kinetic energy
K = change in kinetic energy
) (
1 2 1 2
z z mg P P P
mgz z F P
g
= = A
= =
( )
2
1
2
2 1 2
2
2
2
u u
u
= = A
=
m
K K K
m
K
CONSERVATION OF ENERGY
Internal Energy is energy stored within the body or substance by virtue of the
activity and configuration of its molecules and of the vibration of the atoms
within the molecules.
u = specific internal energy (unit mass): u = u
2
u
1
U = mu = total internal energy (m mass): U = U
2
- U
1
Work (W) is the product of the displacement of the body and the component
of the force in the direction of the displacement. Work is energy in
transition; that is, it exists only when a force is moving through a
distance.
Work of a Nonflow System
Work doneby the system is positive (outflow of energy).
Work doneonthe system is negative (inflow of energy).
}
=
2
1
pdV W
CONSERVATION OF ENERGY
Flow Work (W
f
) of work flow energy is work done in pushing a fluid across a
boundary, usually into or out of a system.
Where: W
f
= change in flow
work
Heat (Q) is energy in transit (on the move) from one body or system to
another solely because of temperature difference between the bodies or systems.
Q is positivewhen heat is added to the body or system.
Q is negativewhen heat is rejected by the body or system.
1 1 2 2 1 2
V p V p W W W
pV W
pAL FL W
f f f
f
f
= = A
=
= =
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CONSERVATION OF ENERGY
Steady Flow Energy Equation
Characteristics of steady flow system
1. There is neither accumulation nor dimunition of mass within the system.
2. There is neither accumulation nor dimunition of energy within the system.
3. The state of the working substance at any point in the system remains
constant.
Energy Entering the System = Energy Leaving the System
W U W K P Q U W K P
f f
+ + + + = + + + +
2 2 2 2 1 1 1 1
CONSERVATION OF ENERGY
Enthalpy (H, h) - is a composite property applicable to all fluids . It is the
heat energy transferred to a substance at a constant pressure process. It is
defined by:
Thus, the steady flow energy equation becomes:
pV U H
mh H
pv u h
+ =
=
+ =
W H K P Q H K P + + + = + + +
2 2 2 1 1 1
THE IDEAL GAS
An ideal gas is ideal only in the sense that it conforms to the simple perfect
gas laws.
Boyles Law
If the temperature of a given quantity of gas is held constant, the volume of
a gas varies inversely with the absolute pressure during a change of state.
2 2 1 1
1
V p V p
C pV
p
C
orV
p
V
=
=
= =
THE IDEAL GAS
Charles Law
(1) If the pressure on a particular quantity of gas is held constant, then, with
any change of state, the volume will vary directly as the absolute
temperature.
or
or
(2) If the volume of a particular quantity of gas is held constant, then, with any
change of state, the pressure will vary directly as the absolute temperature.
or
or
C
T
p
T p
=
=
2
2
1
1
T
p
T
p
CT p
=
=
C
T
V
T V
=
=
2
2
1
1
T
V
T
V
CT V
=
=
THE IDEAL GAS
Equation of State or Characteristic Equation of a Perfect Gas
Combining Boyles and Charles Laws,
, a constant
where: p = absolute pressure
V = volume
v = specific volume
m = mass
T = absolute temperature
R = specific gas constant or gas constant
(unit mass) = universal gas constant
n = no. of moles
M = molecular weight
mR
T
pV
=
mRT pV =
RT pv =
T
R
n pV

=
R

M
R
R

=
M
m
n =
THE IDEAL GAS
Equation of State or Characteristic Equation of a Perfect Gas
The values of Universal Gas constant:
= 8.314 kJ/mol
o
K
= 1545 ft. lb./mol
o
R
= 1.986 BTU/mol
o
R
= 0.0821 L. atm/mol
o
K
Gas constant of diatomic oxygen:
= 0.2598 kJ/kg.K
= 48.28 ft.lb
f
/lb
m
.
o
R
Gas constant for air:
R
w
= 0.287 kJ/kg.K = 53.34 ft.lb
f
/lb
m
.
o
R
R

) (
) (
2
2
O M
R
O R

=
mol kg
K mol kJ
O R
/ 32
. / 314 . 8
) (
2
=
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THE IDEAL GAS
Specific Heat
The specific heat of a substance is defined as the quantity of heat required
to change the temperature of unit mass through one degree.
c
or dQ = mcdT
And for a particular mass m,
If the mean or instantaneous value of specific heat is used,
) _ _ )( (
) _ (
e temperatur of change mass
units energy Heat
mdT
dQ
c =
}
=
2
1
cdT m Q
( )
1 2
2
1
T T mc dT mc Q = =
}
THE IDEAL GAS
Constant Volume Specific Heat (c
v
)
Constant Pressure Specific Heat (c
p
)
( )
1 2
T T mc Q
U Q
v v
v
=
A =
( )
1 2
T T mc Q
p p
=
}
+ A = + A =
2
1
pdV U W U Q
p
( )
1 2
1 1 2 2 1 2
1 2
H H Q
V p V p U U Q
V V p U Q
p
p
p
=
+ =
+ A =
THE IDEAL GAS
Ratio of Specific Heats
Internal Energy of an Ideal Gas
Joules law states that the change of internal energy of an ideal gas is a
function of only the temperature change.
Therefore, U is given by the formula,
whether the volume remains constant or not.
1 > =
v
p
c
c
k
( )
1 2
T T mc U
v
= A
THE IDEAL GAS
Enthalpy of an Ideal Gas
The change of enthalpy of an ideal gas is given by the formula,
whether the pressure remains constant or not.
Relations between c
p
and c
v
From h = u + pv and pv = RT
dh = du + R dT
( )
1 2
T T mc H
p
= A
RdT dT c dT c
v p
+ =
R c c
v p
+ =
1
1

=

=
k
kR
c
k
R
c
p
v
THE IDEAL GAS
Entropy (S, s)
Entropy is that property of a substance which remains constant (if no heat
enters or leaves the substance, while it does work or alters its volume, but
which increase or diminishes should a small amount of heat enter or leave.
The change of entropy of a substance receiving (or delivering) heat is
defined by
Where: dQ = heat transferred at the temperature T
S = total change of entropy
(constant specific heat)
}
= A
=
2
1
T
dQ
S
T
dQ
dS
1
2
2
1
2
1
ln
T
T
mc
T
dT
mc S
T
mcdT
S
= = A
= A
}
}
THE IDEAL GAS
Temperature Entropy Coordinates
dQ = TdS
Other Energy Relations
(Reversible steady flow, P=0)
}
=
2
1
TdS Q
K W Vdp
s
A + =
}
2
1
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5
PROCESSES OF IDEAL GAS
Thermodynamic Processes
Thermodynamic process is any change that a system undergoes from one
equilibrium state to another. It can be reversible or irreversible.
Pathis the series of states through which a system passes during a
process.
a) Reversible Process (Quasi-equilibrium process)
It is the process that can be reversed without leaving any trace on the
surroundings. That is, both the system and the surroundings are returned o
their initial states at the end of the process.
b) Irreversible Process
It is the process that proceed spontaneously in one direction but the other.
Once having taken place, the process cannot reverse itself and always
results in an increase of molecular disorder.
PROCESSES OF IDEAL GAS
Constant Volume Process (Isometric Process)
An isometric process is a reversible constant volume process. A constant
volume process may be reversible or irreversible.

Process Formula Process Formula

p, V, T relations
n
(W
n
) 0 (reversible)
Q U (irreversible)
Specific heat
c
c
v
(W
s
) V(p
1
p
2
) H
2
H
1
mc
p
(T
2
T
1
)
U
2
U
1
mc
v
(T
2
T
1
) S
2
S
1
Q mc
v
(T
2
T
1
)
1
2
1
2
p
p
T
T
=

1
2
ln
T
T
mc
v
}
2
1
pdV
}

2
1
Vdp
PROCESSES OF IDEAL GAS
Isobaric Process
An isobaric process is an internally reversible process of a substance during
which the pressure remains constant.

Process Formula Process Formula

p, V, T relations
n 0
P(v
2
V
1
)
Specific heat
c
c
p
0 H
2
H
1
mc
p
(T
2
T
1
)
U
2
U
1
mc
v
(T
2
T
1
) S
2
S
1
Q mc
p
(T
2
T
1
)
}
2
1
pdV
}

2
1
Vdp
1
2
1
2
V
V
T
T
=
1
2
ln
T
T
mc
p
PROCESSES OF IDEAL GAS
Isothermal Process
An isothermal process is an internally reversible constant temperature
process of a substance.

Process Formula Process Formula

p, V, T relations
n 1
Specific heat
c
H
2
H
1
0
U
2
U
1
0 S
2
S
1
Q
}
2
1
pdV
}

2
1
Vdp
2 2 1 1
V p V p =
1
2
1 1
ln
V
V
V p
1
2
1 1
ln
V
V
V p

2
1
1
2
ln ln
p
p
mR
V
V
mR =
2
1
1
2
1 1
ln ln
p
p
mRT
V
V
V p =
PROCESSES OF IDEAL GAS
Isentropic Process
An isentropic process is a reversible adiabatic process. Adiabatic simply
means no heat. A reversible adiabatic is one of constant entropy.

Process Formula Process Formula

p, V, T
relations n k
Specific heat
c 0
H
2
H
1
mc
p
(T
2
T
1
)
U
2
U
1
mc
v
(T
2
T
1
) S
2
S
1
0
Q 0
}
2
1
pdV
}

2
1
Vdp
k k
V p V p
2 2 1 1
=
k
k
k
p
p
V
V
T
T
1
1
2
1
2
1
1
2

=
(

=
( )
k
T T mR
k
V p V p

1 1
1 2 1 1 2 2
( )
k
T T mR k
k
V p V p k

1
) (
1
) (
1 2 1 1 2 2
PROCESSES OF IDEAL GAS
Polytropic Process
A polytropic process is an internally reversible process during which
and

Process Formula Process Formula

p, V, T
relations n - to +
Specific heat
c
H
2
H
1
mc
p
(T
2
T
1
)
U
2
U
1
mc
v
(T
2
T
1
) S
2
S
1
Q mc
v
(T
2
T
1
)
}
2
1
pdV
}

2
1
Vdp
n n
n
V p V p
C pV
2 2 1 1
=
=
n n
V p V p
2 2 1 1
=
n
n
n
p
p
V
V
T
T
1
1
2
1
2
1
1
2

=
(

=
( )
n
T T mR
n
V p V p

1 1
1 2 1 1 2 2
( )
n
T T mR n
n
V p V p n

1
) (
1
) (
1 2 1 1 2 2

(

=
n
n k
c c
v n
1
1
2
T
T
mc
n
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General Equation for Thermodynamic Curves
The general equation of any process is:
If
n = 0 ; Isobaric process
n = 1 ; Isothermal process
n = k ; Isentropic process
n = - to + ; Polytropic process
n = ; Isometric process
Note: pV
k
is steeper than pV curve.
C pV
n
=

OTHER DEFINITION OF TERMS

1) Saturation temperature
Saturation temperature is the temperature at which liquids start to boil or
the temperature at which vapors begin to condense.
The saturation temperature of a given substance depends upon its pressure.
It is directly proportional to the pressure, i.e., it increases as the pressure is
increased and decreases as the pressure is decreased.
Examples:
Water boils at 100
o
C at atmospheric conditions (101.325 kPa).
Water boils at 179.91
o
C at a pressure of 1000 kPa.
Steam condenses at 311.06
o
C at 10 MPa.
Steam condenses at 39
o
C at 0.0070 Mpa.
OTHER DEFINITION OF TERMS
2. Subcooled Liquid
A subcooled liquid is one which has a tempeature lower than the saturation
temperature corresponding to the existing pressure.
Example:
Liquid water at 60
o
C and 101.325 kPa is a subcooled liquid. The saturation
temperature at 101.325 kPa is 100
o
C. Since the actual temperature of liquid
water of 60
o
C is less than 100
o
C, therefore, it is a subcooled liquid.
3. Compressed Liquid
A compressed liquid is one which has pressure higher than the saturation
pressure corresponding to the existing temperature.
Example
Liquid water at 110 kPa and 100
o
C is a compressed liquid since the actual
liquid water pressure of 110 kPa is greater than the saturation pressure of
101.325 kPa at 100
o
C.
OTHER DEFINITION OF TERMS
4. Saturated Liquid
A saturated liquid is a liquid at the saturations (saturation temperature or
saturation pressure) which has temperature equal to the boiling point
corresponding to the existing pressure. It is a pure liquid, i.e., it has no
vapor content.
Examples:
Liquid water at 100oC and 101.325 kPa.
Liquid water at 333.90oC and 3 Mpa.
Liquid water at 324.75oC and 12 Mpa.
5. Vapor
Vapor is the name given to a gaseous phase that is in contact with the liquid
phase, or that is in the vicinity of a state where some of it might be
condensed.
OTHER DEFINITION OF TERMS
6. Saturated Vapor
A saturated vapor is a vapor at the saturation conditions (saturation
temperature and saturation pressure). It is 100% vapor, i.e., has no liquid or
moisture content.
Examples:
Steam (water vapor) at 100
o
C and 101.325 kPa.
Steam at 212.42oC and 2 Mpa.
7. Superheated Vapor
A superheated vapor is a vapor having a temperature higher than the
saturation temperature corresponding to the existing pressure.
Examples:
Steam at 200
o
C and 101.325 kPa. (t
sat
at 101.325 kPa= 100
o
C)
Steam at 300oC and 5 Mpa (t
sat
at 5 Mpa = 263.99
o
C)
OTHER DEFINITION OF TERMS
8. Degrees of Superheat,
o
SH
The degrees of superheat is the difference between the actual temperature of
superheated vapor and the saturation temperature for the existing pressure.
In equation form:
o
SH = Actual superheated temperature t
sat
at existing pressure
9. Degrees Subcooled,
o
SB
The degrees subcooled of a subcooled liquid is the difference between the
saturation temperature for the given pressure and the actual subcooled
liquid temperature.
In equation form:
o
SB = t
sat
at a given pressure actual liquid temperature
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7
OTHER DEFINITION OF TERMS
10. Wet Vapor
A wet vapor is a combination of saturated vapor and saturated liquid.
11. Quality, x
The quality of wet vapor or wet steam is the percent by weight that is
saturated vapor.
12. Percent moisture, y
The percent moisture of wet vapor is the percent by weight that is saturated
liquid.
13. Latent Heat of Vaporization
The latent heat of vaporization of a pure substance is the amount of heat
added to/removed from the substance in order to convert it from saturated
liquid/saturated vapor to saturated vapor/saturated liquid with the
temperature remaining constant. It is inversely proportional to the
temperature or pressure of the substance.
OTHER DEFINITION OF TERMS
14. Critical point
The critical point represents the highest pressure and highest temperature at
which liquid and vapor can coexist in equilibrium. The state of water at
critical conditions whether it is saturated liquid or saturated vapor is
unknown. Hence, the latent heat of vaporization of water at this condition
is either zero or undefined.
15. Sensible Heat
Heat that causes change in temperature without a change in phase.
16. Sublimation
The term used to describe the process of changing solid to gas without
passing to the liquid state.
17. Deposition
The reverse of sublimation. It is the process of changing gas to solid
without passing to the liquid state.
OTHER DEFINITION OF TERMS
18. Latent heat of fusion
It is the heat needed by the body to change from solid to liquid without
changing is temperature.
19. Second Law of Thermodynamics
Heat cannot be transferred from cold body to a hot body without an input of
work. It similarly states that heat cannot be converted 100% into work.
The bottom line is that an engine must operate between a hot and a cold
reservoir. Also indicated is that energy has different levels of potential to
do work, and that energy cannot naturally move from realm of lower
potential to a realm of higher potential.
20. Third law of Thermodynamics
The total entropy of pure substances approached zero as the absolute
thermodynamic temperature approaches zero.
OTHER DEFINITION OF TERMS
21. Daltons Law of Partial Pressure
The pressure exerted in a vessel by a mixture of gases is equal to the sum of
the pressures that each separate gas would exert if it alone occupied the
whole volume of the vessel.
22. Avogadros Law
At equal volume, at the same temperature and pressure conditions, the
gases contain the same number of molecules.
23. The Carnot Cycle
The Carnot Cycle is the most efficient cycle conceivable. It consists of two
isothermal processes and two isentropic processes.
24. Mean effective pressure
It is the average constant pressure that, acting through one stroke, will do
on the piston the net work of a single stroke.
OTHER DEFINITION OF TERMS
25. Expansion ratio
The ratio between the volume at the end of expansion and the volume at the
beginning of expansion.
26. Compression ratio
The ratio between the volume at the beginnign of compression and the
volume at the end of compression.
27. Internal Combustion Engine
It is a heat engine deriving its power from the energy liberated by the
explosion of a mixture of some hydrocarbon, in gaseous or evaporated
form, with atmospheric air.
28. Four-stroke cycle
The four-stroke cycle is one wherein four strokes of the piston, two
revolutions, are required to complete the cycle.
OTHER DEFINITION OF TERMS
29. Heat engine or thermal engine
It is a closed system (no mass crosses its boundaries) that exchanges only
heat and work with its surrounding and that operates in cycle.
30. Elements of a thermodynamic heat engine with a fluid as the working
substance:
A working substance, matter that receives heat, rejects heat, and does
work;
A source of heat (also called a hot body, a heat resevoir, or just source),
from which the working substance receives heat;
A heat sink (also called receiver, a cold body, or ject sink), to which the
working substance can reject heat; and
An engine, wherein the woking substance may do work or have work
done on it.
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OTHER DEFINITION OF TERMS
31. Thermodynamic cycle
It occurs when the working fluid of a system experiences a number of
processes that eventually return the fluid to its initial state.
32. Available energy
It is that part of the heat that was converted into mechanical work.
33. Unavailable energy
It is the remainder of the heat that had to be rejected into the receiver (sink).
34. Otto Cycle
It is the ideal prototype of spark-ignition engine.
35. Spark-Ignition engine
It is also referred to as gasoline engine.
OTHER DEFINITION OF TERMS
36. Compression-Ignition Engine
It is also referred to as diesel engine.