The Carnot Cycle (The Most Efficient

Heat Engine)
A reversible cycle described by Sadi Carnot in
1824.
The Carnot Theorem gives the theoretical limit
to the thermal efficiency of any heat engine.
The Carnot cycle consists of:
Operates between two temperatures:
2 reversible isothermal processes in which
2 reversible adiabatic processes in which
An Ideal Gas as its working substance
and
H C
T T
H C
T T
Q
Steps of the Carnot Cycle
animation
Details on the Carnot Cycle
The isothermal expansion (ab) and compression (cd):
0
isothermal
U A =
(T is constant and U(T) is a function
of T only for an Ideal Gas.)
ln
b
H ab H
a
V
Q W nRT
V
| |
= =
|
\ .
(ab : isothermal expansion)
ln ln ( )
d
C cd C C c d
c
c
d
V V
Q W nRT nRT V V
V V
| | | |
= = = >
| |
\ . \ .
(cd : isothermal compression)
Details on the Carnot Cycle
(by definition)
The adiabatic expansion (bc) and compression (da):
0
adiabatic
Q =
From Section 19.8, we learned that
1
for adiabatic processes. TV const

=
(bc: adiabatic expansion)
1 1
H b C c
T V T V

=
(da: adiabatic compression)
1 1
H a C d
T V T V

=
Dividing these two equations gives,
b c
a d
V V
V V
=
Efficiency of the Carnot Cycle
From definition, we have
1
C
H
Q
e
Q
=
Using our results for Q
C
and Q
H
from the isothermal processes,
( )
( )
( )
( )
ln ln
1 1
ln ln
C c d C c d
H b a H b a
nRT V V T V V
e
nRT V V T V V
= =
From the adiabatic processes, we have
1 1
C
H
C
H
T
e
Q T
Q
=
b a c d
V V V V =
( )
( )
ln
1
ln
c d
b a
V V
V V
=
(Carnot Cycle only)
(T must be in K)
Efficiency of the Carnot Cycle
1
C
carnot
H
T
e
T
=
(Carnot Cycle)
General Comments:
Higher efficiency if either T
C
is lower and/or T
H
is higher.
For any realistic thermal process, the cold reservoir is far
above absolute zero and T
C
> 0.
Thus, a realistic e is strictly less than 1! (No 100%
efficient heat engine)
Realistic heat engines must take in energy from the high T
reservoir for the work that it produces ANDsome heat
energy must be released back to the lower T reservoir.
(Kelvin-Plancks Statement)
skip
Internal Combustion Engine
The Otto Cycle
A fuel vapor can be compressed, then detonated to rebound
the cylinder, doing useful work.
animation
http://auto.howstuffworks.com/engine1.htm
The Otto Cycle
a b
b, c c d
2
( ) 0
H V c b
Q U nC T T = A = >
4
( ) 0
C V a d
Q U nC T T = A = <
r is the compression ratio (8 to 13)
intake
exhaust
intake exhaust
For the two constant V processes: 2 and 4,
we can calculate,
The Otto Cycle
Applying the definition of efficiency,
( )
( )
1 1 1
V a d
C a d
H V c b c b
nC T T
Q T T
e
Q nC T T T T

= + = + = +

Now, we can utilize the two adiabatic processes: 1 and 3,
1 1
a a b b
T V T V

=
and
1 1
c c d d
TV T V

=
( )
1
1
a b
T rV T V

=
( )
1
1
c d
TV T rV

=
1
a b
T r T

=
1
c d
T T r

=
The Otto Cycle
Substituting T
b
and T
c
into the efficiency equation, we have,
( )
1 1 1
1 1 1
a d a
d
a
c b d a
d d
a
T T T T T T
e
T T T r T r T T r


= + = + =

1
1
1 e
r

=
Using a typical value for the compression ratio r = 8 and
= 1.40 gives,
0.56 (or 56%) e =
Note: This is a theoretical value.
Realistic gasoline engine typically
has e ~35%.
The Diesel Cycle
Key difference:
No fuel in cylinder at the beginning of the
compression stroke (process 1)
Fuel is injected only moments before
ignition in the power stroke
No fuel until the end of the adiabatic
compression can avoid pre-ignition
Compression ratio r value can be higher (15
to 20)
Higher temperature can be reached during
the adiabatic compression
Higher e and no need for spark plugs
D
steamengine
Refrigerators
Refrigerators are basically heat engine running in reverse.
Heat from inside the refrigerator (cold T reservoir) is absorbed and released
into the room (high T reservoir) with the input of mechanical work.
Refrigerators
what you get
what you put in
C C
H C
Q Q
K
W Q Q
= = =

Coefficient of Performance for a Refrigerator

From 1
st
Law,
( ) ( )
0
cycle C H
H C
U Q Q W
Q Q W
A = =
= +
(Note: we have put in the explicit signs according to our sign convention.)
|Q
C
| (absorbed) positive
|Q
H
| (released) negative
|W| (work is done on working substance by motor) negative
explicit signs
A perfect Refrigerator
C C
H C
Q Q
K
W Q Q
= =

A perfect refrigerator means ( ).

This means that
0
H C
Q Q or W = =
No mechanical work W is needed to
transfer heat from the cold reservoir
to the hot reservoir.
The Clausiuss statement of the 2
nd
Law does not allow this !
realistic
K <
K =
Entropy
Recall from a Carnot Cycle, we have derived the following relationship:
C
C
H H
Q
T
Q T
=
0
H C
H C
Q Q
T T

+ =
Formally, we can rewrite this as,
0
cycle
Q
T
=

(We have absorbed the explicit

sign back into the Q variable.)
where Q represents the heat absorbed/released along the isotherm at temp T.
Entropy
Any reversible cycles can be approximated as a series
of Carnot cycles !
Entropy
This suggests that the following generalization to be true for any reversible
processes,
0
r
cycle
dQ
T
=
}
where,
dQ
r
is the infinitesimal heat absorbed/released by the system at an
infinitesimal reversible step at temp T.
denotes the integration evaluated over one complete cycle.
cycle
}
Entropy
We have seen this property previously,
0
cycle
dU =
}
Changes in the internal energy U over a
closed cycle is zero!
This is a consequence of the fact that U is a state variable and dU for any
processes depends on the initial and final states only.
Thus the result indicates that there is another state variable S
such that,
0
r
cycle
dQ
T
=
}
and
0
cycle
dS =
}
dQ
dS
T

This new state variable S is called the entropy of the system.

Entropy: Disorder
Recall that the 2
nd
Law of Thermodynamics is a statement on natures
preferential direction for systems to move toward the state of disorder.
Let see how Entropy is a quantitative measure of disorder.
Recalling our previous derivation, was from the isothermal branch of
the infinitesimal Carnot cycle. Let look at an isothermal expansion of an ideal
gas microscopically:
Intuitively, as the gas expands into a bigger
volume, the degree of randomness for the
system increases since molecules now have
more choices in position for them to move
about. One can associate the increase in
randomness to the ratio:
V dV
or
V V
A
/ dQ T
(T stays the same avg. KE stays the same)
Entropy: Disorder
Since this is an isothermal process, we have the following relation from the 1
st
Law:
nRT
dQ dW PdV dV
V
= = =
1 dQ dV
nR T V
=
So, the newly introduced macroscopic variable S (entropy),
dQ
dS
T

is proportion to the degree of disorder of the system.

f
i
dQ
S
T
A =
}
| |
/ S J K =
dS is an infinitesimal entropy change for a reversible process at temperature T.
For any finite reversible process, the total entropy change AS is,
2
nd
Law (Quantitative Form)
The total entropy (disorder) of an isolated system in any
processes can never decrease.
0
( 0 ; 0 )
tot sys env
tot tot
S S S
S reversible S irreversible
A = A + A >
A = A >
Nature always tends toward the most probable macrostates
[states with the highest S (disorder)] in any processes.
system
environment
Q
W
Entropy Changes for Different
Processes
1. General Reversible Processes:
V
i
f
P
f f
r
i i
dQ
S dS
T
A = =
} }
NOTE: in most applications,
it is the change in entropy AS
which one typically needs to
calculate and not S itself.
Note: S is a state variable, AS is the same for all processes
(including irreversibleones) with the same initial and final
states!
Entropy Changes for Different
Processes
2. Reversible Cycles:
3. AnyReversible Processes for an Idea Gas:
0
r
cycle
cycle cycle
dQ
S ds
T
A = = =
} }
( , ) ( , )
i i f f
T V T V
1
st
Law gives,
r
r V
r V
dU dQ dW
dQ dU dW nC dT PdV
nRT
dQ nC dT dV
V
=
= + = +
= +
(Note: Thru the Ideal Gas Law, P
is fixed for a given pair of T & V.)
Entropy Changes for Different
Processes
Dividing T on both sides and integrating,
f f
V r
i i
nC dT dQ dV
S nR
T T V
| |
A = = +
|
\ .
} }
We have,
ln ln
f f
V
i i
T V
S nC nR
T V
| | | |
A = +
| |
\ . \ .
Entropy Changes for Different
Processes
4. Calorimetric Changes:
f f
i i
dQ mcdT
dQ mcdT
S
T T
=
A = =
} }
If c is constant within temperature range,
ln
f
i
T
S mc
T
| |
A =
|
\ .
Entropy Changes for Different
Processes
5. During Phase Changes (or other isothermal
Processes):
1 dQ
S dQ
T T
A = =
} }
(T stays constant during a
phase change.)
Q mL
S
T T
A = =
Entropy Changes for Different
Processes
6. Irreversible Processes:
Although for a given an irreversible process, we cannot write
dS = dQ
r
/T, AS between a well definite initial state a and final state
b can still be calculated using a surrogate reversible process
connecting a and b. (S is a state variable!)
Example 20.8: (free expansion of an ideal gas)
Initial State a: (V,T)
Final State b: (2V,T)
Since Q=W=0, AU=0.
For an ideal gas, this
means that AT=0 also.
Although Q=0, but AS
is not zero!
AS in a Free Expansion
Important point: Since S is a state variable, AS is the same for
any processes connecting the same initial a and final b states.
In this case, since T does not change, we can use an surrogate isothermal
process to take the ideal gas from state a (V,T) to state b (2V,T) to calculate AS.
Surrogate
Isothermal Expansion
Applying our general formula,
ln ln
f f
V
i i
T V
S nC nR
T V
| | | |
A = +
| |
\ . \ .
we have,
ln
V
T
S nC
T
| |
A =
|
\ .
2
ln ln2 5.76 /
V
nR nR J K
V
| |
+ = =
|
\ .
(n=1)