Thermodynamics

Second Law
The Carnot Engine

Lana Sheridan

De Anza College

May 15, 2020

Last time

• entropy (microscopic perspective)

• heat engines

• heat pumps
Overview

• wrap up heat pumps

• Carnot engines

• efficiency of a Carnot engine

• entropy in a Carnot cycle (?)

Heat Engines

1
Diagram from http://www2.ignatius.edu/faculty/decarlo/
Heat Pump
Refrigerators work by taking electrical energy, converting it to
work, then pumping heat from a cold area to a hotter one.

This type of process, where work is converted into a heat transfer

from a colder object to a hotter one is called a heat pump.
1
Diagram from http://hyperphysics.phy-astr.gsu.edu
 22.2 Heat Pumps and Refrigerators 657
“Perfect” but Impossible Heat Pump

An impossible heat pump This heat pump (using no work) violates our
. first statement of the second law, since heat
Hot reservoir
spontaneously goes from a cooler reservoir to
at Th a hotter one.

Qh " Qc
More formally, the Clausius statement of the
second law:
Heat
pump Second Law of thermodynamics (Clausius)

Qc It is impossible to construct a cyclical machine

whose sole effect is to transfer energy
Cold reservoir continuously by heat from one object to
at Tc another object at a higher temperature
without the input of energy by work.
igure 22.5 Schematic diagram
an impossible heat pump or
efrigerator, that is, one that takes
energy from
1
a cold reservoir
Diagram from Serway and Jewett.
Question

Suppose you have a house with very excellent insulation. If you

leave the door to your refrigerator open for the day, what happens
to the temperature of your house?

(A) It increases.
(B) It decreases.
(C) It stays the same.
Question

Suppose you have a house with very excellent insulation. If you

leave the door to your refrigerator open for the day, what happens
to the temperature of your house?

(A) It increases. ←
(B) It decreases.
(C) It stays the same.
Carnot Engines

Sadi Carnot wanted to find the fundamental limit of how

efficient a heat engine could be.

He imagined a theoretical engine (now called the Carnot engine)

that was as efficient as possible.

He realized that no engine would be more efficient than a

reversible one.

Only in a reversible process will no energy be lost to friction or

turbulence in the fluid.
Carnot Engines
Carnot specified that his heat engine should use just two thermal
reservoirs, each at constant temperature, Th and Tc .

In order to be reversible, the heat must be exchanged in the cycle

only when the engine fluid’s temperature matches that of the
reservoir with which it is in contact. ⇒ Isothermal processes

The other parts of the cycle must be adiabatic (Q = 0).

(The Carnot engine is the reversible engine cycle you can operate
between just two thermal reservoirs at constant temperature.)
 and the PV dia
The Carnot Cycle of two adiabati

The work done 1. Process

P
during the cycle The gas
equals the area ture Th .
A enclosed by the path ervoir th
on the PV diagram.
piston.
2. In proce
thermal
Qh
energy e
B
peratur
Weng
raising t
Th
3. In proce
C
Tc
energy r
D Qc
V peratur
and the
Figure 22.11 PV diagram for the
Maximum Efficiency of an Engine

Assume a Carnot engine has efficiency eC .

Now supoose it was possible to construct an engine (reversible or

irreversible) that is even more efficient, with efficiency e > eC .

Since the Carnot cycle is reversible, we could run the Carnot

engine in reverse as a heat pump.
Maximum Efficiency of an Engine
Putting the imagined engine and the Carnot heat pump together:

Hot reservoir
at Th

Qh Q hC

Heat W WC Carnot
rn
engine heat
pump
Figure 22.9 A Carnot engine
Qc QcC operated as a heat pump and
another engine with a propose
Cold reservoir higher efficiency operate betwe
at Tc two energy reservoirs. The work
output and input are matched.

Now, the work from

maximum the hypothetical
possible engine
efficiency for drives theLet
real engines. Carnot heat that
us confirm
pump, engine
so W = W
is theC most efficient. We imagine a hypothetical engine with a
greater than that of the Carnot engine. Consider Figure 22.9, whic
hypothetical engine |W | the|WCleft
| connected between hot a
e > eC with⇒e 7 e C on>
|Qh | a |Q
ervoirs. In addition, let us attach hC | engine between the same
Carnot
Maximum Efficiency of an Engine
|W | |W |
e > eC ⇒ >
|Qh | |QhC |
This means
|Qh | < |QhC |
We also know that |W | = |Qh | − |Qc | (energy conservation). Since
the works are equal:
W = Wc
|Qh | − |Qc | = |QhC | − |QcC |

Rearranging:
|QhC | − |Qh | = |QcC | − |Qc |

But the LHS is positive if e > eC .

Heat arrives at the hot reservoir and leaves the cold one! ⇒
Violates the Second Law.
Maximum Efficiency of an Engine

Putting the imagined engine and the Carnot heat pump together:

Hot reservoir
at Th

|QhC | − |Qh | > 0 Qh Q hC

↑ Qh,net
Heat W WC Carnot
rn
engine heat
pump
Figure 22.9 A Carnot engine
Qc QcC operated as a heat pump and
|QcC | − |Qc | > 0
Cold reservoir
↑
another engine with a propose
Qc,net operate betwe
higher efficiency
at Tc two energy reservoirs. The work
output and input are matched.

maximum
Violates possible
the Second Law. efficiency for real engines. Let us confirm that
engine is the most efficient. We imagine a hypothetical engine with a
greater than that of the Carnot engine. Consider Figure 22.9, whic
Carnot’s Theorem

Carnot’s Theorem
No real heat engine operating between two energy reservoirs can
be more efficient than a Carnot engine operating between the same
two reservoirs.

But how efficient is a Carnot engine?

 and the PV dia
The Carnot Cycle of two adiabati

The work done 1. Process

P
during the cycle The gas
equals the area ture Th .
A enclosed by the path ervoir th
on the PV diagram.
piston.
2. In proce
thermal
Qh
energy e
B
peratur
Weng
raising t
Th
3. In proce
C
Tc
energy r
D Qc
V peratur
and the
Figure 22.11 PV diagram for the
Efficiency of a Carnot Engine

First, we can relate the volumes at different parts of the cycle.

In the first adiabatic process:

Th VBγ−1 = Tc VCγ−1

In the second adiabatic process:

Th VAγ−1 = Tc VDγ−1

Taking a ratio, then the γ − 1 root:

VB VC
=
VA VD
Efficiency of a Carnot Engine

First law: ∆Eint = Q + W = 0 gives for the first isothermal process

 
VB
|Qh | = nRTh ln
VA

Second isothermal process:

 
VC
|Qc | = nRTc ln
VD

We will take a ratio of these to find the efficiency. Noting that

VB VC
VA = VD :
|Qc | |Tc |
=
|Qh | |Th |
Efficiency of a Carnot Engine

Recall, efficiency of a heat engine:

|Qc |
e =1−
|Qh |

Efficiency of a Carnot engine:

Th − Tc Tc
e= =1−
Th Th

(T is measured in Kelvin!)

This is the most efficient that any heat engine operating between
two reservoirs at constant temperatures can be.
Third Law of Thermodynamics

3rd Law
As the temperature of a material approaches zero, the entropy
approaches a constant value.

The constant value the entropy takes is very small. It is actually

zero if the lowest energy state of the material is unique.

Another way to express the third law:

3rd Law - alternate
It is impossible to reach absolute zero using any procedure and
only a finite number of steps.
Heat Engine question

Consider and ocean thermal energy conversion (OTEC) power

plant that operates on a temperature difference between deep 4◦ C
water and 25◦ C surface water. Show that the Carnot (ideal)
efficiency of this plant would be about 7%.

0
Hewitt, page 331, problem 2.
Clausius Equality
Clausius found that the entropy change around any reversible cycle
(closed path) is zero.

This is called the Clausius Equality:

I
dQr
∆S = =0
T

This follows directly from the fact that entropy is a state variable
(though that was not obvious initially).

If a heat engine works in a cycle, the entropy change of the engine

over the cycle is zero.
Entropy in the Carnot Cycle
In the Carnot engine, since the working fluid returns to its initial
state, the change in the entropy for the whole cycle is
Entropy in the Carnot Cycle
In the Carnot engine, since the working fluid returns to its initial
state, the change in the entropy for the whole cycle is ∆Seng = 0.
Entropy in the Carnot Cycle
In the Carnot engine, since the working fluid returns to its initial
state, the change in the entropy for the whole cycle is ∆Seng = 0.

We can see this from an analysis also:

Z
1
∆S = dQr
T
In the reversible adiabatic processes
Entropy in the Carnot Cycle
In the Carnot engine, since the working fluid returns to its initial
state, the change in the entropy for the whole cycle is ∆Seng = 0.

We can see this from an analysis also:

Z
1
∆S = dQr
T
In the reversible adiabatic processes ∆S = 0.

In the reversible isothermal portions, T is constant so

Entropy in the Carnot Cycle
In the Carnot engine, since the working fluid returns to its initial
state, the change in the entropy for the whole cycle is ∆Seng = 0.

We can see this from an analysis also:

Z
1
∆S = dQr
T
In the reversible adiabatic processes ∆S = 0.

Q
In the reversible isothermal portions, T is constant so ∆S = T.

For the cycle

|Qh | |Qc |
∆Seng = −
Th Tc
Entropy in the Carnot Cycle
For the cycle
|Qh | |Qc |
∆Seng = −
Th Tc

We just found that

|Qh | Th
=
|Qc | Tc

So
|Qh | |Qc |
=
Th Tc

And for the cycle

∆Seng = 0
Entropy in the Carnot Cycle it is
is do
We can represent the Carnot Cycle on a TS diagram: area
QH
Figs.
quan
a b perf
TH
Temperature T

invo
Carn
d c
TL tere
QL gram
isoth
Entropy S cycle
stan
Fig. 20-10 The Carnot cycle of
ing t
Entropy in the Carnot Cycle it is
is do
We can represent the Carnot Cycle on a TS diagram: area
QH isothermal Figs.
expansion quan
a . b
perf
TH
Temperature T

adiabatic adiabatic
invo
compression expansion
Carn
d -c
TL tere
QL isothermal gram
compression isoth
Entropy S cycle
stan
EntropyFig. ThetheCarnot
20-10during cycle of
only changes isothermal processes.
ing t
Entropy in the Carnot Cycle
What is the energy change of the surroundings (the thermal
reservoirs) for a Carnot engine?
Hot reservoir:
|Qh |
∆Shot = −
Th

Cold reservoir:
|Qc |
∆Scold = +
Tc

However,
|Qh | |Qc |
=
Th Tc

The total entropy change of the surroundings over the cycle:

∆Ssurr = ∆Shot + ∆Scold = 0

Entropy in the Carnot Cycle
The total entropy change of the engine + surroundings over the
cycle:
∆Snet = ∆Seng + ∆Ssurr = 0
Entropy in the Carnot Cycle
The total entropy change of the engine + surroundings over the
cycle:
∆Snet = ∆Seng + ∆Ssurr = 0

Remember that the engine only exchanges heat with its

surroundings when they are at the same temperature. This is
necessary for the processes to be reversible.
Entropy in the Carnot Cycle
The total entropy change of the engine + surroundings over the
cycle:
∆Snet = ∆Seng + ∆Ssurr = 0

Remember that the engine only exchanges heat with its

surroundings when they are at the same temperature. This is
necessary for the processes to be reversible.

In any real, practical engine, some heat transfer occurs when the
engine’s working fluid is not at the same temperature as its
surroundings. These are irreversible effects.

The surroundings do not quite return to their initial state ⇒

entropy of the surroundings increases.

∆Snet > 0
Clausius Inequality

Since real engines always involve irreversible processes, the entropy

of the engine + surroundings will increase:
I
dQr
∆S = >0
T

This is called the Clausius Inequality.

Entropy in an isolated system

This gives us another way to state the second law:

2nd Law
dS
In an isolated system, entropy does not decrease. dt >0

In a non-isolated system (either closed or open) entropy can

decrease, but only by increasing the entropy of the environment at
least as much.

However, in an isolated system, such as when we include a heat

engine and its thermal reservoirs in the system, the entropy cannot
decrease.
Summary

• wrapped up heat pumps

• Carnot engines
• efficiency of a Carnot engine
• entropy in a Carnot cycle (?)

Homework
Serway & Jewett (additional problems you might like to look at):
• Ch 22, OQs: 1, 3, 7; CQs: 1; Probs: 20, 73