Chapter 4 Thermodynamics 1 1

Thermodynamics I
Introduction
1. Basic Concepts of Thermodynamics
2. Energy, Energy Transfer, and General Energy Analysis
3. Properties of Pure Substances
4. Energy Analysis of Closed Systems
5. Energy and Mass Analysis of Control Volumes
6. The Second Law of Thermodynamics
7. Entropy
8. Steam Power Cycle
Applications
Examples
Chapter 4 Thermodynamics 1 2
Overview
4-1 Specific Heats
4-2 Moving Boundary Work
4-3 Internal Energy, Enthalpy and Specific Heats
of Ideal Gases
4-4 Internal Energy, Enthalpy and Specific Heats
of Solids and Liquids
4-5 Energy Balance for Closed System



Chapter 4 Thermodynamics 1 3
Specific Heat Capacity and Heat
Capacity
Specific heat is the
energy required to
raise the temperature
of a unit mass of a
substance by one
degree in a specified
way.

Chapter 4 Thermodynamics 1 4
Specific Heat Capacity
V=const: ( , )
P=const: ( , )
differentiated:
V T
u u v T
h h p T
u
du d d
u
T
T
v
v

| |
|

=
=

| |
= +
|

\ . \ .

P T
h
dh dT
T
dP
P
h
| |
= +
|

\
|
|
. .
|

\
V V
V V
P P
P P
u U
c C
T T
h H
c C
T T

| | | |
= =
| |

\ . \ .

| | | |
= =
| |

\ . \ .

or
or

Chapter 4 Thermodynamics 1 5
Specific Heat for Ideal Gases
, ,
( )
( )
( ) ( )
v av p a
V P
V P
V
v
P
u u T
h u Pv
h u RT h h T
Pv RT
du dh
du dT dh dT
dT dT
du c dT d
u u c T T h h c T T
h c dT
u u u c dT h h h c dT
=
= +

= + =
`
=
)
| | | |
= =

| |
\ . \ .
= =
= = = =


From Joule's experiment:
therefore:
differentiated:
2 2
2 1 2
2 1 2 1 2 1 2
1
1
1
1
, ,
( ) ( )
v av p av
v p
U U C T T H H C T T
u c T h c T



2 1 2 1 2 1 2 1
Chapter 4 Thermodynamics 1 6
Specific Heat Relations for Ideal
Gases
P V
P V
P
V
V P
h u RT
dh du RdT
c dT c dT RdT
c c R
c
k
c
k
c R c R
k k
= +
= +
= +
= +
=
= =

Specific Heat Ratio
and
1
1 1
k=1.667 for monatomic gases
k=1.4 for diatomic gases
Chapter 4 Thermodynamics 1 7
(kJ/kg)
For small temperature intervals,
the specific heats may be assumed
to vary linearly with temperature.
Internal energy and enthalpy
change when specific heat is
taken constant at an average
value
The relation u = c
v
T is valid
for any kind of process,
constant-volume or not.
Chapter 4 Thermodynamics 1 8
Internal Energy, Enthalpy and
Specific Heats of Solids and Liquids
( )
( ) ( )
P V
V
av
av
c c c
du c dt c T dT
u u u c T dT c T T
dh du vdP P du vdP
dv
h u v P c T v P
= =
= =
= =
= + + = +
= + = +

Internal Energy Changes:

Enthalpy Changes:
2
2 1 2 1
1
0
Constant spec. volume -> incompressible

Chapter 4 Thermodynamics 1 9
Internal Energy, Enthalpy and
Specific Heats of Solids and Liquids
@ , @
@ , @ @
:
:
( )
(
av
av
av
P T f T
P T f T f T
h u v P c T v P
h u c T
P const h u c T
T const h v P
h h v P P
h h
h h v P
= + +
=
= =
= =
=

+
For Solids:
For Liquids:
(e.g. heaters)
(e.g. pumps)

Enthalpy for compressed liquid:
2 1 2 1
)
sat
P
Chapter 4 Thermodynamics 1 10
Moving Boundary Work
Moving boundary work (P dV work):
The expansion and compression work in
a piston-cylinder device.
The work
associated
with a
moving
boundary is
called
boundary
work.
A gas does a
differential
amount of
work W
b
as
it forces the
piston to
move by a
differential
amount ds.
Quasi-equilibrium process:
A process during which the
system remains nearly in
equilibrium at all times.
W
b
is positive for expansion
W
b
is negative for compression
Chapter 4 Thermodynamics 1 11
Moving Boundary Work
The area under the
process curve on a P-V
diagram represents the
boundary work.
The boundary
work done
during a
process
depends on
the path
followed as
well as the
end states.
The net work
done during a
cycle is the
difference
between the
work done by the
system and the
work done on the
system.
Chapter 4 Thermodynamics 1 12
Isochoric/Isometric Process
Constant Volume Process:




Ideal Gas





P
V
1
2
b
W PdV
PV mRT
PV mRT
P T P
or const
P T T
= =
=
=
= =

2
1
1 1
2 2
1 1
2 2
0
Chapter 4 Thermodynamics 1 13
Isochoric/Isometric Process
With the moving boundary work
W=0 for the isochoric process to
work heat needs to be extracted:






Only the internal energy of the
system changes.




P
V
1
2
( )
T
v
T
T
v
T
Q U U
m c dT
mc T T
= =
= =
=

2
1
2
1
12 2 1
2 1
Chapter 4 Thermodynamics 1 14
Isobaric Process
Constant Pressure Process:






Ideal Gas





V
P
V
1
2
( )
( )
b
W PdV P dV
P V V
mR T T
PV mRT
PV mRT
V T V
or const
V T T
= = =
=
=
=
=
= =

2 2
1 1
2 1
2 1
1 1
2 2
1 1
2 2
Law of
Gay-Lussac
Chapter 4 Thermodynamics 1 15
Isobaric Process
The isobaric process needs a heat
transfer that compensates for the
volume change while keeping the
pressure constant:







The heat transfer is equal to the
enthalpy change of the system.





V
P
V
1
2
( )
T
p
T
T
p T
Q H H
m c dT
mc T T
= =
= =
=

2
1
2
1
12 2 1
2 1
Chapter 4 Thermodynamics 1 16
Isothermal Process
Constant Temperature Process:









P
V
1
2
ln ln
b
mRT
P
V
mRT
W PdV dV
V
V P
mRT PV
V P
PV mRT
PV mRT
PV PV or PV const
=
= = =
| | | |
= =
| |
\ . \ .
=
=
= =

2 2
1 1
2 1
1 2
1 1
2 2
1 1 2 2
Law of
Boyle-Mariotte
Chapter 4 Thermodynamics 1 17
Isothermal Process
Since the temperature of the system is
constant, the internal energy of the
system does not change. This implies
that the heat transfer associated with
an isothermal process must be:







The heat transfer is equivalent to the
moving boundary work.








P
V
1
2
ln ln
b
Q W
V P
mRT PV
V P
= =
| | | |
= =
| |
\ . \ .
12
2 1
1 2
Chapter 4 Thermodynamics 1 18
Polytropic Processes
Constant PV
n
Process:
Ideal gas









,
ln ln ln ,
( )
, for ideal gas
n
b
n
b
PV const
const
W PdV dV
V
PV PV
n
n
V V V
PV PV PV n
V V V
mR T T
W n
n
=
= = =

| | | | | |
= = = =
| | |
\ . \ . \ .

2 2
1 1
2 2 1 1
2 2 2
1 1 2 2
1 1 1
2 1
1
1
1
1
1
Chapter 4 Thermodynamics 1 19
Polytropic Processes
Special polytropic processes:
Constant pressure: n=0
Constant volume: n=
Isothermal & ideal gas: n=1
Adiabatic & ideal gas: n=k=C
p
/C
v

The last process is know as isentropic. C
p
and C
V
are specific
heats of the substance at constant pressure and constant
volume.
Chapter 4 Thermodynamics 1 20
Isentropic Process
Since the isentropic process is adiabatic no
heat transfer will occur:




For isentropic processes the following
relationships are valid:












P
V
1
2
k
k
k
Q
T V P
T V P

=
| | | |
= =
| |
\ . \ .
12
1
1
1 2 1
2 1 2
0
Chapter 4 Thermodynamics 1 21
Isentropic Process
The work for isentropic processes is
given by:
















P
V
1
2 b
k
k
k
k
k
W PdV
dV
PV
V
PV V
k V
PV T PV P
k T k P

= =
= =
(
| |
= =
(
|

\ .
(

(
( | | | |
(
= =
( | |
(

\ . \ .
(

2
1
2
1 1
1
1
1 1 1
2
1
1 1 2 1 1 2
1 1
1
1
1 1
1 1
Chapter 4 Thermodynamics 1 22
Isentropic Process
The work for isentropic processes is also
given by:









The moving boundary work is completely
converted into internal energy and vice
versa.
P
V
1
2
( )
( )
( )
b
v
PV T
W
k T
mR
T T
k
PT PT
k
mc T T
( | |
= =
( |

\ .
= =

= =

=
1 1 2
1
2 1
2 2 1 1
2 1
1
1
1
1
1
Chapter 4
Thermodynamics 1 23
Energy Balance for Closed System

>Heat Transfer< >Work Transfer< >Mass flow<
A closed system
involves only heat
transfer and work.
Chapter 4 Thermodynamics 1 24
Energy balance for a constant-pressure
expansion or compression process
H W U
b
= +
For a constant-pressure expansion or
compression process:
An example of constant-pressure process
General analysis for a closed
system undergoing a quasi-
equilibrium constant-pressure
process. Q is to the system and
W is from the system.
Chapter 4 Thermodynamics 1 25











A piston cylinder contains 25g of saturated water vapour at a
constant pressure of 300kPa. An electric heater (0.2A and
120V) heats the water for 5 mins. There is a heat loss of
3.7kJ. Determine the final temperature of the steam.
Closed System - Example
Chapter 4 Thermodynamics 1 26
Examples

A 0.1 m
3
rigid tank contains steam initially at 500 kPa and
200C. The steam is now allowed to cool until its temperature
drops to 50 C. Determine the amount of heat transfer during
this process and the final pressure in the tank.


A piston-cylinder device initially contains 0.5 m
3
of nitrogen
gas at 400 kPa and 27C. An electric heater with the device is
turned on and is allowed to pass a current of 2A for 5 min
from a 120V source. Nitrogen expands at constant pressure,
and a heat loss of 2800 J occurs during the process.
Determine the final temperature of the nitrogen.