1

IRREVERSIBILITY
IRREVERSIBILITY
AND
AND
CARNOT PRINCIPLES
CARNOT PRINCIPLES
2
IRREVERSIBILITY
At the end of a real process, it is
impossible to return both the system
and its surroundings to their original
conditions or states.
3
DEFINITIONS
A reversible process is a process at the end of
which the system and the surroundings can be
restored exactly to the initial states.
An irreversible process is a process at the end
of which the system and the surroundings
cannot be restored exactly to the initial states.
Real processes are irreversible!
4
In an irreversible process, some sign or
signature will be left in the system or
surroundings indicating that something has
occurred.
The system can often be restored to its initial
state, but the surroundings cannot.
Internal irreversibilities exist within the
system only, and are not in the surroundings .
External irreversibilities exist in the
surroundings and are not within the system.
5
EXAMPLES OF
IRREVERSIBLE PROCESSES
Heat transfer through a finite temperature difference.
Unrestrained expansion of a gas or liquid to a lower
pressure.
Spontaneous chemical reaction.
Spontaneous mixing of matter at different compositions
or states.
Friction --- sliding friction as well as friction in flow of
fluids.
Flow of electrical current through a resistor.
Inelastic deformation.
6
TEAMPLAY
Discuss among yourselves the
meaning of irreversibility. Give
examples of irreversible processes.
7
CARNOT PRINCIPLES
The thermal efficiency of an irreversible
heat engine is always less than the
thermal efficiency of a reversible heat
engine when each operates between the
same two reservoirs.
All reversible heat engines operating
between the same two reservoirs have the
same thermal efficiency.
8
CARNOT PRINCIPLES
For the same T
H
and T
L
,
2 1 R R
R I


=
<
A reversible
engine has a
higher value.
Two reversible
engines have
the same
value.
where R = reversible, and I = irreversible.
9
EFFICIENCIES OF REVERSIBLE
AND IRREVERSIBLE ENGINES
H
LR
H
LR H
H
R
R
Q
Q
Q
Q Q
Q
W
&
&
&
& &
&
&
=

= = 1
H
LI
H
LI H
H
I
I
Q
Q
Q
Q Q
Q
W
&
&
&
& &
&
&
=

= = 1
10

H
Q
&
T
H
T
L

H
Q
&
R I

LI
Q
&
LR
Q
&

I
W
&
R
W
&
The irreversible engine
produces less power and
rejects heat at a higher rate
than the reversible engine!
.
LR LI
R I
Q Q and
W W that Note
& &
& &
>
<
11
PROOF OF
CARNOT PRINCIPLES
Assume that the irreversible heat engine is
more efficient then the reversible heat engine.
That is, assume that the irreversible heat
engine produces more power and rejects heat
at a lower rate than the reversible heat
engine.
Let and
.
LR LI R I
Q Q W W
& & & &
< >
Violation of the first part of the Carnot Principles.
12

H
Q
&
T
H
T
L

H
Q
&
R
I

LI
Q
&
LR
Q
&

I
W
&
R
W
&
REVERSING THE REVERSIBLE HEAT
ENGINE AND USING IT AS A HEAT PUMP
13

H
Q
&
T
H
T
L

H
Q
&
R
I

LI
Q
&
LR
Q
&

I
W
&
R
W
&
SUPPLYING HEAT TO THE IRREVERSIBLE
HEAT ENGINE FROM THE HEAT PUMP

H
Q
&
T
L
New device

H
Q
&
R
I

LI
Q
&
LR
Q
&

I
W
&
R
W
&
14
THE NEW DEVICE PRODUCES WORK WHILE
RECEIVING HEAT FROM THE RESERVOIR AT T
L
.

LI
Q
&
LR
Q
&

H
Q
&
T
L
New device

H
Q
&
R I

I
W
&
R
W
&
T
L
New device

LI LR
Q Q
& &


R I
W W
& &

15
PROOF (CONT.)
Note that and .
LR LI R I
Q Q W W
& & & &
< >
The new device receives heat from a low
temperature reservoir at T
L
and produces work.
The new device violates the 2nd Law of
Thermodynamics. Thus, the assumption was
incorrect.
The thermal efficiency of an irreversible heat
engine may not be higher than that of a
reversible heat engine.
16
TEAMPLAY
By studying the following eight (8) slides
as a team, continue the proof of the
Carnot Principles by comparing the
efficiencies of two reversible engines
operating between the same two
reservoirs at T
H
and T
L
to show that their
efficiencies are the same.
17

H
Q
&
T
H
T
L

H
Q
&
R1
R2

2 LR
Q
&
1 LR
Q
&

2 R
W
&
1 R
W
&
NOW, CONSIDERING TWO REVERSIBLE
HEAT ENGINES, R1 AND R2
18
PROOF (CONT.)
Assume that the reversible heat engine
R2
R2 is
more efficient then the reversible heat engine
R1. That is, assume that the reversible heat
engine
R2
R2 produces more power and rejects
heat at a lower rate than the reversible heat
engine R1.
Let and
.
1 2 1 2 LR LR R R
Q Q W W
& & & &
< >
19
REVERSING THE REVERSIBLE HEAT ENGINE
R1 AND USING IT AS A HEAT PUMP

H
Q
&
T
H
T
L

H
Q
&
R1
R2

2 LR
Q
&
1 LR
Q
&

2 R
W
&
1 R
W
&
20

H
Q
&
T
H
T
L

H
Q
&
R1
R2

2 LR
Q
&
1 LR
Q
&

2 R
W
&
1 R
W
&
SUPPLYING HEAT TO THE REVERSIBLE
HEAT ENGINE R2 FROM THE HEAT PUMP

H
Q
&
T
L
New device

H
Q
&
R1 R2

2 LR
Q
&
1 LR
Q
&

2 R
W
&
1 R
W
&
21
THE NEW DEVICE PRODUCES WORK WHILE
RECEIVING HEAT FROM THE RESERVOIR AT T
L
.

H
Q
&
T
L
New device

H
Q
&
R1 R2

2 LR
Q
&
1 LR
Q
&

2 R
W
&
1 R
W
&
T
L
New device

2 1 LR LR
Q Q
& &


2 R
W
&

1 R
W
&
22
Recall that and .
The new device receives heat from a low
temperature reservoir at T
L
and produces work.
The new device violates the 2nd Law of
Thermodynamics. Thus, the assumption was
incorrect.
The thermal efficiency of reversible heat
engine
R2
R2 may not be higher than that of
reversible heat engine R1.
1 2 1 2 LR LR R R
Q Q W W
& & & &
< >
PROOF (CONT.)
23
PROOF (CONT.)
Now, switch R1 and R2. Assume that R1 has a
higher thermal efficiency than R2.
Operate R2 as a heat pump, and show that the
new device consisting of R1 and R2 violates the
2nd Law of Thermodynamics.
The thermal efficiency of reversible heat engine
R1 may not be higher than that of reversible
heat engine
R2
R2.
24
PROOF (CONT.)
, and If
R R R R 2 1 1 2
< <
2 1 R R
=
Two reversible engines operating
between the same two reservoirs
must have the same value.
25
CARNOT PRINCIPLES APPLY TO
REFRIGERATORS AND HEAT PUMPS
It may be shown in a similar manner that:
The coefficient of performance of an irreversible
refrigerator or heat pump is always less than the
coefficient of performance of a reversible
refrigerator or heat pump operating between the
same two reservoirs.
The coefficients of performance of two
reversible refrigerators or heat pumps operating
between the same two reservoirs are the same.
26
CARNOT PRINCIPLES
A reversible
refrigerator or
heat pump has
a higher COP
value.
Two reversible
refrigerators
or heat pumps
have the same
COP value.
For the same T
H
and T
L
,
2 1 R R
R I
COP COP
COP COP
=
<
where R = reversible,
and I = irreversible.
27
COEFFICIENTS OF PERFORMANCE
OF REV. AND IRREV. REFRIGERATORS
L HR
L
R
L
R
Q Q
Q
W
Q
COP
& &
&
&
&

= =
L HI
L
I
L
I
Q Q
Q
W
Q
COP
& &
&
&
&

= =
. ,
R I I R
W W COP COP Since
& &
> >
An irreversible refrigerator requires more power.
28
COEFFICIENTS OF PERFORMANCE
OF REV. AND IRREV. HEAT PUMPS
LR H
H
R
H
R
Q Q
Q
W
Q
COP
& &
&
&
&

= =
LI H
H
I
H
I
Q Q
Q
W
Q
COP
& &
&
&
&

= =
. ,
R I I R
W W COP COP Since
& &
> >
An irreversible heat pump requires more power.
29
KELVIN TEMPERATURE SCALE
KELVIN TEMPERATURE SCALE
AND
AND
CARNOT CYCLE
CARNOT CYCLE
30
REVIEW --- CARNOT PRINCIPLES
According to the Carnot Principles, all
reversible heat engines operating between
the same two reservoirs have the same
thermal efficiency, .
The thermal efficiency does not depend on
the type of heat engine, the cycle, the
working medium, or the energy transport
mechanism.
31
KELVIN TEMPERATURE SCALE
) , (
H L
R
H
L
T T f
Q
Q
=
|
|
.
|

\
|
The thermal efficiency is dependent on
the temperatures of the reservoirs only,
= (T
L
, T
H
)
Since = 1 (Q
L
/Q
H
)
R
,
R = reversible
heat engine
32
KELVIN TEMPERATURE SCALE (CONT.)
The previous equation provides the basis for
a thermodynamic temperature scale.
It may be shown that
) (
) (
H
L
R
H
L
T f
T f
Q
Q
=
|
|
.
|

\
|
H
L
R
H
L
T
T
Q
Q
=
|
|
.
|

\
|
We were free to pick the functions any way we
wish. Lord Kelvin proposed that f (T
L
) = T
L
and f (T
H
) = T
H
. Thus,
33
KELVIN TEMPERATURE SCALE (CONT.)
In 1954, the triple point of water was assigned
the value of 273.16 on the Kelvin temperature
scale.
One degree on the Kelvin temperature scale is
identical to one degree on the Celsius
temperature scale: 1C 1 K.
Since the triple point of water is 0.01C, the
temperatures on the Kelvin and Celsius scales
differ by 273.15 degrees.
34
KELVIN TEMPERATURE SCALE (CONT.)
The Kelvin temperature scale with a zero value
at 273.15 C may be validated experimentally.
For a reversible heat engine, also called a
Carnot heat engine,
H
L
R
H
L
R
T
T
Q
Q
=
|
|
.
|

\
|
= 1 1
The temperatures must
be in degrees K (or R).
35
CARNOT EFFICIENCY
The thermal efficiency of a reversible heat
engine (or Carnot heat engine) is also
called the Carnot efficiency.
Carnot I
H
L
I
H
L
I
H
L
R
H
L
max Carnot
or
T
T
Q
Q
T
T
Q
Q


< <
|
|
.
|

\
|
=
=
|
|
.
|

\
|
= =
1 1
1 1
36
TEAMPLAY
Many plants for electric power generation
operate with a steam supply at about 1,000F
and heat rejection to a reservoir at about 70F.
What is the maximum thermal efficiency of
these power plants?
What do you think is the typical thermal
efficiency of a power plant? Why are the
maximum and actual thermal efficiencies
different?
37
CARNOT CYCLE
A Carnot cycle consists of the following
four reversible processes:
1 - 2 an adiabatic compression process;
2 - 3 an isothermal expansion process;
3 - 4 an adiabatic expansion process;
4 - 1 an isothermal compression process
38
STEAM POWER
PLANT OPERATING
ON A CARNOT
CYCLE
Boiler
Condenser
Turbine
q
41
2
q
23
w
34
w
12
Pump
4
1
3
The cycle consists of the following four
reversible processes:
1 - 2 an adiabatic expansion process;
2 - 3 an isothermal heat removal process;
3 - 4 an adiabatic compression process;
4 - 1 an isothermal heat addition process.
39
CARNOT REFRIGERATOR/
AIR CONDITIONER
Maximum coefficient of performance (or
Carnot COP) of a refrigerator or air
conditioner:
L H
L
R
L H
L
max
T T
T
Q Q
Q

=
|
|
.
|

\
|

=
& &
&

40
CARNOT HEAT PUMP
Maximum coefficient of performance (or
Carnot COP) of a heat pump:
L H
H
R
L H
H
max
T T
T
Q Q
Q

=
|
|
.
|

\
|

=
& &
&

41
TEAMPLAY
Given the COP and of a household refrigerator, what is
L
Q
&
L H
L L
Q Q
Q
W
Q
COP
& &
&
&
&

= =
For the
refrigerator
? Q and W
H
& &
Refrigerator
Q
Q
L
L
W
W
Q
Q
H
H
.
.
.
. Q Q W that Note
L H
& & &
=
42
TEAMPLAY
Work problems 5.52 and 5.63 from text.
W
Q
COP
H
&
&
=
For the
heat pump
Given the COP of a heat pump, the rate of heat loss through
the walls, and the heat generated in the house, what is ? W
&
.
Heat
Pump
Q
Q
L
L
W
W
Q
Q
H
H
.
.
H
Q
&
Note that = (rate of heat loss -
rate of heat generated).
43
TAKE HOME TEAM PROJECT
Prepare three (3) engineering quality plots that show
the following:
Carnot thermal efficiency of a heat engine as a
function of T
H
, for 300 < T
H
< 2,000 K and T
L
of
300 and 400 K.
Carnot coefficient of performance of a heat pump
as a function of T
H
, for 400 < T
H
< 1,000 K and T
L
of 250 and 300 K.
Carnot coefficient of performance of a refrigerator
as a function of T
L
, for 100 < T
L
< 300 K and T
H
of
300 and 400 K.
44
CLAUSIUS INEQUALITY
CLAUSIUS INEQUALITY
AND
AND
ENTROPY
ENTROPY
45
CLAUSIUS INEQUALITY
Clausius Inequality --- For a closed
system, the cyclic integral of is
always less than or equal to zero.
T / Q
0

T
Q
The symbol means integrating over the
entire cycle.

46
PREVIEW
We need Clausius Inequality to define a property called
entropy, S [in kJ/K, and specific entropy, s, in (kJ/kg.K)].
For the universe (considered as an irreversible, isolated
system that is adiabatic), dS
universe
0. The total entropy of
the universe always increases. This is called the principle
of increase of entropy. When a natural process takes
place, the total entropy must increase.
By examining the values of the total entropy (for the system
and its surroundings) at the beginning and at the end of a
process, one may tell if a process is possible or not.
47
PROOF OF CLAUSIUS INEQUALITY
--- HEAT ENGINE
T
H
|Q
H
|
T
L
|Q
L
|
|W|
Heat engine
0
1 1


<
L
L
H
H
H
L
H
L
H
L
H
L
R I
T
Q
T
Q
or
T
T
Q
Q
T
T
Q
Q

T
Q
, is That

48
T
H
|Q
H
|
T
L
|Q
L
|
|W|
Refrigerator
or
heat pump
0

<
H
H
L
L
H
L
H
L
L H
L
L H
L
R I
T
Q
T
Q
or
T
T
Q
Q
T T
T
Q Q
Q

0

<
H
H
L
L
H
L
H
L
L H
H
L H
H
R I
T
Q
T
Q
or
T
T
Q
Q
T T
T
Q Q
Q

PROOF OF CLAUSIUS INEQUALITY
--- REFRIGERATOR/HEAT PUMP
0

T
Q
, is That

49
CLAUSIUS INEQUALITY
0
T
Q
(<) for irreversible cycle
(=) for reversible cycle
50
ENTROPY
Consider a reversible cycle 1-2-1, and A, B, and C are any
three different paths between states 1 and 2.
From the Clausius Inequality,
A
B
1
2
C
0 =

T
Q
0
1
2
2
1
1
2
2
1
=
|
.
|

\
|
+
|
.
|

\
|
=
|
.
|

\
|
+
|
.
|

\
|


C A
B A
T
Q
T
Q
T
Q
T
Q


C B A
T
Q
T
Q
T
Q
|
.
|

\
|
=
|
.
|

\
|
=
|
.
|

\
|

2
1
2
1
2
1

51
ENTROPY (CONT.)
We conclude that the integral is independent
of the path chosen, if we choose a reversible path.
Thus, the integral depends on the end states only.

2
1
T
Q

We can associate a property, entropy, S, in kJ/K or
Btu/R, with each state, such that
R
T
Q
S S
(

=

2
1
1 2

52
SPECIFIC ENTROPY
R
T
q
s s
(

=

2
1
1 2

We can defined specific entropy, s, in kJ/(kg.K)
or Btu/(lbm.R), such that s = S/m,
and
53
SPECIFIC ENTROPY (CONT.)
Entropy values are tabulated in a similar
manner as those of u, v, and h.
) (
f g f
s s x s s + = Also, for a mixture,
And, for compressed or subcooled liquids,
) ( ) ( T s p , T s
f

54
TEAMPLAY
Use the tables in your book to
find the entropy of water at 0.06 bar and
500C.
find the entropy of water at 100C and a
quality of 50%.
find the entropy of water at 0.5 bar and
20C.