Chapter One

Reviews of Thermodynamics

(1.1). Thermodynamic system

An isolated system is a system that exchanges neither mass nor energy with its
environment. An insulated rigid tank filled with air is an example of an isolated
system.

A closed system is a system that exchanges energy with its environment. However,
it does not exchange mass with its environment. In other words, mass is conserved
in the system. A cylinder and piston system is an example of a closed system.

An open system is a system that exchanges both energy and mass with its
environment. An air compressor is an example of an open system.

A simple system is one in which there is only one way to alter the energy by work.
Examples are simple compressible systems, simple elastic systems or simple electric
systems.

Single phase systems are formed by a single physical structure (solid, liquid or gas)
and a single chemical composition. Examples are ice, liquid water or vapor, a
water/alcohol mixture, etc.

Multiphase systems involve two or more phases either in physical structure or
chemical composition. Some examples are water/vapor and water/oil mixtures.

Pure substance systems are formed by a single chemical composition. Examples are
vapor, oxygen, nitrogen, etc.

Mixture systems involve two or more chemical compositions. Some examples are air,
air fuel mixture, etc.

A system may be composed of either pure substance or mixture. The
components of the system may constitute either single phase or multi phases.

Single phase Multiphase
Pure substance vapor water & vapor
Mixture air Air & fuel droplets


(1.2). Thermodynamic property

Properties are some numerical values used to describe the macroscopic
characteristics of the system. Not all properties are independent properties. Some
properties can be derived from other properties. Pressure(P), temperature(T), and
specific volume(v) are examples of thermodynamic properties.

Units of pressure: Pascal, bar, kg/cm
2
, mmH
2
O, mmHg, Torr, psi, atm
1 Pascal = 1 N/m
2
, 1 kPa = 1000 Pa, 1 MPa = 1000 kPa
1 bar = 100 kPa = 1000 mbar, 1 psi = 1 lbf/in
2
,
1 kg/cm
2
= 98 kPa
1 Torr = 1mmHg
1 atm = 101325 Pa = 14.6956 psi = 760 mmHg = 760 Torr


The properties can be classified in a) directly measurable (pressure, temperature), b)
defined by laws of thermodynamics (entropy) and c) defined as combination of other
properties (Gibbs function).

An extensive property is one that is dependent on the size of a system, e.g. mass and
volume.

An intensive property is independent of the size of the system. Examples are heat
capacity, temperature and pressure.

Specific properties are obtained by dividing extensive properties with mass.
V
v
m
= ,
H
h
m
= ,
U
u
m
= ,
S
s
m
=

(1.3). Thermodynamic state

A state is made up of several independent properties which can fully define the
status of the system. In a simple compressible system, a thermodynamic state can
be determined explicitly by two independent properties.

The state space is a multi dimensional space constructed by the independent
properties of a system. The dimensionality of state space is equal to the number of
independent properties of that system. A thermodynamic state is a point in the state
space. The state space of a simple compressible system is a two-dimensional space
in which a state is represented as a point.

P-v diagram or the T-s diagram is often used to represent the thermodynamic
state in a simple compressible system.
(1.4). Thermodynamic process

When a thermodynamic system changes its state as a result of exchange of
energy with other system or the environment, the location of the state in the state
space moves, and the locus of all the states that the system goes through make up a
process. A process is a curve in the state space.

The initial and final conditions of a system are the end states. Infinite number of
processes can connected between the same end states. The series of states between
end states define the path of the process.

The change in the properties when a system undergoes a process between two end
states is independent of the path. Thus, the value of a property is independent of the
process and depends only on the state of the system. Quantities that depend on the
nature of the process are not properties.


A process in PV diagram


(1.4.1) Reversible process

If a system undergoes a process from the initial state to the final state, and then
the system moves back to the initial state in a reversed direction along the same path.
If the process does not cause any net effect on either the system or its environment,
then this process is said to be a reversible process.

A reversible process is an ideal process. It would not happen in real world.
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Example , A piston and cylinder system undergoes a compression process, and then
expands to its original position. Both processes are adiabatic. Discuss that if the
processes are reversible or not.
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Example , A piston and cylinder system undergoes a constant pressure process by
heating the air inside the system to push a weight upwards a height of h, and then
lowers down the weight to its original position by cooling the air. Discuss that if
the process is reversible or not.
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(1.4.2). Irreversible process

An irreversible process is that when the system goes back to the initial state with
the reversed process, some definite changes happen in either the system or the
environment after the process is done.

Causes of irreversibility: friction, combustion, diffusion, mixing, chemical
reaction, free expansion, heat transfer with finite temperature difference.

Results of irreversible process: increases of entropy and loss of availability.

(1.5). Thermodynamic cycle

A system undergoes several processes, such that the start of the next process
coincide the end of the previous process, and the end of the last process coincides the
start of the first process. All the processes make up a cycle. A cycle is a closed loop
in the state space.

A cycle can be conducted continuously to either convert heat into work or
reversibly. Some well known cycles include Carnot cycle, Otto cycle, Diesel cycle,
Rankine cycle, Brayton cycle, Stirling cycle, etc.

(1.6). Work and Heat

Work output/input and heat transfer are the two principal ways of energy
exchange between a thermodynamic system and its environment.

Work transfer is conducted through ordered motion of atoms or molecules.
The motion of a piston driven by expansion gas is an example. Both the piston and
the gas are in a bulk motion in which all the atoms composing the piston and the
molecules contained in the gas move in a homogeneous way.

In contrast, heat transfer is carried out by means of random motion of atoms and
molecules.

The energy contained in ordered motion can be totally converted to random
motion. However, the energy contained in random motion can not be totally
converted to ordered motion. The inequality of the conversion between heat and
work is the basis of the second law of thermodynamics.

(1.6.1). Work of reversible process

rev
W Fdx YdX o = = ,
rev
W YdX =
}


Y: generalized force, X: generalized displacement

However, in an irreversible process, the work conducted is less than that of a
reversible process.

irr rev
W YdX W s =
}


(1.6.2). Work in a Simple Compressible Closed System

Y P = , X V = , e.g., piston and cylinder system.

Reversible work
rev
W PdV =
}


Irreversible work <
irr
W PdV
}

In generalW PdV s
}


The integration of pressure over volume is the projected area of the cure in the
PV diagram. Thus, the reversible work of a process is equal to the projected area of
this process represented in the PV diagram.

The work of a process depends on the path of the process. Work is a path
function, not a point function. As a result, work is not a thermodynamic property.

For a closed system consisting of ideal gas, the work and the heat transfer during a
specific process are given as the following.



The work conducted by the piston in a steam engine

Reversible work of an isothermal process:
2
1
ln
rev
mRT V
W PdV dV mRT
V V
= = =
} }

Heat transfer in an isothermal process:
2
1
ln
V
Q U W mRT
V
= A + =

Reversible work of an isobaric process
2 1
( )
rev
W PdV P dV P V V = = =
} }

Heat transfer in an isobaric process:
2 1 2 1 2 1
( ) ( ) ( )
p
v
c
Q U W mc T T P V V P V V
R
= A + = + =

Reversible work of a polytropic Process
.
n
PV const =
1 1 2 2
1
( )
1
rev
W PdV PV PV
n
= =

}

Heat transfer in a polytropic process:
n
Pv C =
n
C
P
v
=
1
1
n
n
Pv C C
T v
R Rv R

= = = (1 )
n
C
dT n dv
Rv
=
1
(1 ) ( 1)
1 1
v
n n n n
c C C n C k n C
q du Pdv n dv dv dv dv
R v v k v k v
o

= + = + = + =


If both k and n are constants, the amount of heat transfer of the process is
1 1
2 1 2 2 1 1
1
( ) ( )
1 1 1 1 1
n n
n
k n C k n C k n
q dv v v Pv Pv
k v k n k n


= = =

}
1
1 1 1
1 1 2 2
2
1
( ) [1 ( ) ]
1 1 1 1
n
k n k n Pv v
q Pv Pv
k n k n v

= =


1 1 2 2
( )
( 1)( 1)
k n
Q PV PV
k n

=



Table 1.1: The relationships among k, n, and the amount of heat transfer
& n k dv
q o

n k > 0 dv >
0 q o <
heat rejection
n k > 0 dv <
0 q o >
heat absorption
n k = 0 dv >
0 q o =
adiabatic process
n k = 0 dv <
0 q o =
adiabatic process
n k < 0 dv >
0 q o >
heat absorption
n k < 0 dv <
0 q o <
heat rejection


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ExampleCalculate the reversible work needed to compress 1 kg of air at 100 kPa
and 25 to a volume of 0.5 m
3
.
(1). Isothermal compression. (-45.91 kJ)
(2). Isobaric compression. (-35.53 kJ, )
(3). Polytropic process with n=1.5. (-52.67 kJ)
(4). Polytropic process with n=1.3. (-48.23 kJ)
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ExampleTwo kilograms of saturated water vapor at 150 is contained in a piston
and cylinder assembly. The system is compressed to 10 bars with a polytropic
process in which PV
1.5
=constant. Find the amount of heat transfer during this
process.
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Assignment 1.1 : Calculate the reversible work needed to compress 1 kg of helium at
100 kPa and 25 to a volume of 0.5 m
3
.
(1). Isothermal compression.
(2). Isobaric compression.
(3). Polytropic process with n=1.5.
(4). Polytropic process with n=1.3.
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Assignment 1.2 : Calculate the reversible work needed to expand 1 kg of air at 300
kPa and 250 to a volume of 1.5 m
3
.
(1). Isothermal compression.
(2). Isobaric compression.
(3). Polytropic process with n=1.5.
(4). Polytropic process with n=1.3.
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(1.6.3). Work in an open system

There are two modes of work that can be conducted in an open system. One is
conducted by changing the volume of the system, the same way as that happens in a
closed system. An example of this mode of work is the suction of air in a piston type
compressor while the intake valve is open and the piston is moving down.


Two modes of work: volume variation and shaft work

In a steady state steady flow system, the volume of the system remains the same.
Work can be conducted by rotating a shaft inside the system. The effect of the shaft
might be acting force on the working fluid, or varying volume inside the system.
This mode of work is called shaft work. Example of shaft work are pump, rotary
compressor, turbine, and expander.

The shaft work can be calculated as the following.
e
rev
i
W m vdP =
}

,
e
rev
i
w vdP =
}

For ideal gas, the shaft work for some reversible processes are as the following.

Reversible work of an isothermal process:
ln
i
rev
e
RT P
w vdP dP RT
P P
= = =
} }

ln
i
rev
e
P
W mRT
P
=

Reversible work of an isobaric process
0
rev
w vdP = =
}


Reversible work of a polytropic Process
.
n
Pv const =
1 1 2 2
( )
1
rev
n
w vdP Pv Pv
n
= =

}

1 1 2 2 1 2
( ) ( )
1 1
rev
n n
W m Pv Pv m RT RT
n n
= =

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ExampleCalculate the reversible work needed to compress air at 100 kPa and 25
to the pressure of 1 MPa. The flow rate of air is 0.1 m
3
/sec.
(1). Isothermal compression.
(2). Polytropic process with n=1.5.
(3). Polytropic process with n=1.3.
(4). Adiabatic process.
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Assignment 1.3 : Calculate the reversible work needed to compress hydrogen at 100
kPa and 25 to the pressure of 10 MPa. The flow rate is 0.5 m
3
/min.
(1). Isothermal compression.
(2). Adiabatic compression in single stage.
(3). Adiabatic compression in two stages with a perfect intercooler in between.
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(1.6.4). Simple Elastic System

The work is carried out by deformation of the system. Examples are spring
compression and bending of a beam.

, Y F X L = =
rev
W FdL =
}

,
F L
A L
o c
A
= =
rev
W FdL A Ld AL d V d o o c o c o c = = = =
Youngs modulus ( )
T
Y
o
c
c
=
c

d
d
Y
o
c =
rev
W d
w d
V Y
o o
o o c o = = =
2
2
rev
w d
Y Y
o o
o = =
}

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ExampleThe tensile force in a steel wire 1 m long and 1 mm diameter is increased
reversibly at constant temperature of 30 from zero to 100 N. Calculate the work
done. Assume that Y = 2 x 10
8
kN/m
2
.
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Assignment 1.4 : For a certain rubber band, the restoring force is related to its initial
length
0
L and the displacement x as follows:
2
0 0
3
x x
F
L L
(
| |
( = +
|
(
\ .

N
The initial length of the rubber band is 5 cm. Determine the work required to
stretch the band to a final length of 10 cm.
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(1.6.5). Simple Surface Tension System

The work is carried out by varying the surface area of the system. Examples are
formation of liquid droplets and bubble generation.
Y = , surface tension (N/m)
X A = , area (m
2
)
rev
W dA =
}

2 F L =
2
rev
F
W dA dA
L
o = =

Liquid Temperature C Surface tension, ( mN/m)
Water 0 75.64
Water 25 71.97
Water 50 67.91
Water 100 58.85
Ethanol 20 22.27
Mercury 15 487



Formation of liquid droplets from water pool:
Mass of droplets:
3
4
3
m r n
t
=
Number of droplets:
3
3
4
m
n
r t
=
Total work:
2 2
3
3 3 3
4 4
4
rev
m m V
W A r n r
r r r
t t
t
= = = = =
Specific work:
3 W
w
V r

= = (in volume)
Specific work:
3 3 W V
w
m mr r

= = = (in mass)

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ExampleAn atomizer shoots out water droplets of an average radius of 10
-4
cm into
the air. Estimate the work required when 1 kg of water is atomized isothermally at
25 . The surface tension of water in contact with air at 25 is 7.2x10
-4
N/cm.
ANS: 2.166 x 10
2
J/kg.
+
m
W P KE PE U

= A = A + A A
work = kinetic energy + potential energy + thermal energy

2
2
V
KE m A =
3m
PE A
r

A = =
m = 1 kgP = 250 kPa = 1000 kg/m
3

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Bubble formation:
2 2
2 2
i o
P R P R R t t t = +
4
i o
P P
R

=

Work of surface tension:
2
4
4 16
s
dw PdV r dr rdr
r

t t = = =
2 2
2 1 2 1
16 8 ( ) 2 ( )
s
W rdr R R A A t t = = =
}

Work to expel outside fluid:
2
0 0
4
o
dw PdV P r dr t = =
2 3
0 0 0 2 1
4
4 ( )
3
o
W P r dr P R P V V t t = = =
}

Total work for the bubble growth:
2 1 0 2 1
2 ( ) ( )
s o
W W W A A P V V = + = +

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ExampleFind the pressure inside a soap bubble of 1 cm in diameter. How much
work should be done to boost a bubble of this size?
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Assignment 1.5 : A spherical air bubble with a radius of 2.510
-6
m is suspended at
the bottom of a pool water of 10 meters deep. The surface tension of water in
contact with air at 25 is 7.2x10
-4
N/cm. Calculate the pressure of air inside the
bubble.
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Assignment 1.6: An atomizer shoots out water droplets into the air. The
distribution of droplet size is shown below. Estimate the work required when 1 kg of
water is atomized isothermally at 25 . The surface tension of water in contact
with air at 25 is 7.2x10
-4
N/cm.


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