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# PETROVIETNAM UNIVERSITY

## FACULTY OF FUNDAMENTAL SCIENCES

Fundamental Physics
Chapter 9
Pham Hong Quang

E-mail: quangph@pvu.edu.vn

## Chapter 9. Heat Engines and the Second

Law of Thermodynamics
9.1 Heat Engines and the Second
Law of Thermodynamics
9.2 Heat Pumps and Refrigerators
9.3 Reversible and Irreversible Processes
9.4 The Carnot Engine
9.5 Entropy
9.6 Entropy Changes in Irreversible
Processes
9.7 Entropy on a Microscopic Scale

## Faculty of Fundamental Sciences

Law of Thermodynamics
First Law of Thermodynamics
Review
The first law is a statement of Conservation of
Energy.
The first law states that a change in internal
energy in a system can occur as a result of
energy transfer by heat, by work, or by both.
The first law makes no distinction between
processes that occur spontaneously and those
that do not.
Only certain types of energy-conversion and
energy-transfer processes actually take place
Pham Hong Quang

## 9.1 Heat Engines and the Second

Law of Thermodynamics
The Second Law of
Thermodynamics

## Establishes which processes do and which do not

occur
Some processes can occur only in one direction
according to the first law.
This directionality is governed by the second law.
These types of processes are irreversible.
An irreversible process is one that occurs
naturally in one direction only.
No irreversible process has been observed to run
backwards.

## 9.1 Heat Engines and the Second

Law of Thermodynamics
William Thomson, Lord
Kelvin
1824 1907
British physicist and
mathematician
First to propose the use
of an absolute scale of
temperature
His work in
thermodynamics led to
the idea that energy
cannot pass
spontaneously from a
colder object to a hotter
object.

## 9.1 Heat Engines and the Second

Law of Thermodynamics
Heat Engine
A heat engine is a device
that takes in energy by heat
and, operating in a cyclic
process, expels a fraction of
that energy by means of
work.
A heat engine carries some
working substance through a
cyclical process.
The working substance
absorbs energy by heat from
a high temperature energy
reservoir (Qh).
Work is done by the engine
(Weng).

## 9.1 Heat Engines and the Second

Law of Thermodynamics

## Since it is a cyclical process, Eint = 0

Its initial and final internal energies are
the same.
Therefore, Weng = Qnet = |Qh| - |Qc|
The net work done by a heat engine equals
the net energy transferred to it.

## 9.1 Heat Engines and the Second

Law of Thermodynamics
Thermal Efficiency of a Heat
Engine
Thermal efficiency is defined as the ratio of
the net work done by the engine during one
cycle to the energy input at the higher
temperature. Weng Qh Qc
Qc
e

Qh

Qh

Qh

## We can think of the efficiency as the ratio of

what you gain to what you give.
In practice, all heat engines expel only a
fraction of the input energy by mechanical
work.
Therefore, their efficiency is always less than
100%.
Pham Hong
Quang
Faculty of Fundamental Sciences

## 9.1 Heat Engines and the Second

Law of Thermodynamics
Second Law: Kelvin-Planck
Form
It is impossible to construct a heat engine
that, operating in a cycle, produces no
effect other than the input of energy by
heat from a reservoir and the performance
of an equal amount of work.
Weng can never be equal to |Qh|
Means that Qc cannot equal 0
Some energy |Qc| must be expelled to the
environment
Means that e cannot equal 100%
Pham Hong Quang

## 9.1 Heat Engines and the Second

Law of Thermodynamics
Perfect Heat Engine
No energy is expelled to the
cold reservoir.
It takes in some amount of
energy and does an equal
amount of work.
e = 100%
It is impossible to
construct such an
engine.

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## 9.2 Heat Pumps and Refrigerators

Heat Pumps and Refrigerators
Heat engines can run in
reverse.
This is not a natural
direction of energy
transfer.
Must put some energy
into a device to do this
Devices that do this are
called heat pumps or
refrigerators
Examples
A refrigerator is a
common type of heat
pump.
Pham Hong Quang
Faculty of Fundamental Sciences

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## 9.2 Heat Pumps and Refrigerators

Second Law - Clausius statement for
refrigerator
It is not possible for
heat to flow from a
colder body to a
warmer body without
any work having
been done to
accomplish this flow.
Energy will not flow
spontaneously from a
low temperature
object to a higher
temperature object.
Pham Hong Quang
Faculty of Fundamental Sciences

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## 9.2 Heat Pumps and Refrigerators

Coefficient of Performance
The effectiveness of a heat pump is described
by a number called the coefficient of
performance (COP).
Similar to thermal efficiency for a heat engine
It is the ratio of what you gain (energy
transferred to or from a reservoir) to what
you give (work input).
In cooling mode,
you gain
energy
Qc
energy transferred
at low
temp removed

from aCOP
cold temperature
reservoir.
work done on the pump
W

## A good refrigerator should have a high COP.

Pham Hong Typical
Quang
Facultyare
of Fundamental
values
5 or 6 Sciences

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## 9.2 Heat Pumps and Refrigerators

COP, Heating Mode
In heating mode, the COP is the ratio of
the heat transferred in to the work required.
energy transferred at high temp Qh
COP =

W

## Qh is typically higher than W

Values of COP are generally about 4
For outside temperature about 25 F
The use of heat pumps that extract energy
from the air is most satisfactory in
moderate climates.
Pham Hong Quang

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## 9.3 Reversible and Irreversible Processes

Reversible and Irreversible
Processes
A reversible process is one in which both
the system and its environment can be
returned to exactly the states they were in
before the process occurred.
A reversible process is one in which every point
along some path is an equilibrium state.
An irreversible process does not meet these
requirements.
All natural processes are known to be
irreversible.
Reversible processes are an idealization, but
some real processes are good approximations.
Pham Hong Quang

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## 9.3 Reversible and Irreversible Processes

A real process that is a good approximation of
a reversible one will occur very slowly.
The system is always very nearly in an
equilibrium state.
A general characteristic of a reversible
process is that there are no dissipative effects
that convert mechanical energy to internal
energy present.
No friction or turbulence, for example

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## 9.4 The Carnot Engine

Carnot Engine
A theoretical engine developed by Sadi
Carnot
A heat engine operating in an ideal,
reversible cycle (now called a Carnot
cycle) between two reservoirs is the
most efficient engine possible
This sets an upper limit on the
efficiencies of all other engines.

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## 9.4 The Carnot Engine

Carnots Theorem
No real heat engine operating between
two energy reservoirs can be more
efficient than a Carnot engine
operating between the same two
reservoirs.
All real engines are less efficient than a
Carnot engine because they do not
operate through a reversible cycle.
The efficiency of a real engine is further
reduced by friction, energy losses
through conduction, etc.
Pham Hong Quang

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Carnot
Cycle

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## 9.4 The Carnot Engine

A B is an
isothermal
expansion.
The gas is placed in
contact with the high
temperature
reservoir, Th.
The gas absorbs
heat |Qh|.
The gas does work
WAB in raising the
piston.

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## 9.4 The Carnot Engine

B C is an adiabatic
expansion.
The base of the
cylinder is replaced
by a thermally
nonconducting wall.
No energy enters or
leaves the system
by heat.
The temperature
falls from Th to Tc.
The gas does work
WBC.
Pham Hong Quang

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thermal contact
with the cold
temperature
reservoir.
C D is an
isothermal
compression.
The gas expels
energy |Qc|.
Work WCD is done
on the gas.
Pham Hong Quang

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## 9.4 The Carnot Engine

D A is an adiabatic
compression.
The base is replaced by
a thermally
nonconducting wall.
So no heat is
exchanged with the
surroundings.
The temperature of the
gas increases from Tc
to Th.
The work done on the
gas is WDA.
Pham Hong Quang

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## 9.4 The Carnot Engine

The work done by the engine is
shown by the area enclosed by
the curve, Weng.
The net work is equal to |Qh| |
Qc|.
Eint = 0 for the entire cycle
Carnot showed that the
W of the
Q engine
efficiency
T
e eng 1 c 1 c
depends
of
Qhon theQtemperatures
Th
h
the reservoirs.

## Temperatures must be in Kelvins

All Carnot engines operating
between the same two
temperatures will have the
same efficiency.

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## 9.4 The Carnot Engine

Notes About Carnot
Efficiency
Efficiency is 0 if Th = Tc
Efficiency is 100% only if Tc = 0 K
Such reservoirs are not available
Efficiency is always less than 100%
The efficiency increases as Tc is lowered and
as Th is raised.
In most practical cases, Tc is near room
temperature, 300 K
So generally Th is raised to increase
efficiency.

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## 9.4 The Carnot Engine

Carnot Cycle in Reverse
Theoretically, a Carnot-cycle heat
engine can run in reverse.
This would constitute the most
effective heat pump available.
This would determine the maximum
possible COPs for a given combination
of hot and cold reservoirs.

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## 9.4 The Carnot Engine

Carnot Heat Pump COPs
In heating mode:
COPC

Qh
W

Th
Th Tc

In cooling mode:
COPC

Qc
W

Tc
Th Tc

values below 10

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9.5 Entropy
Entropy and
Heat

## The original formulation of entropy dealt with the

transfer of energy by heat in a reversible process.
Let dQr be the amount of energy transferred by heat
when a system follows a reversible path.
The change in entropy, dS is
dQr
dS
T
The change in entropy depends only on the
endpoints and is independent of the actual path
followed.
The entropy change for an irreversible process can
be determined by calculating the change in entropy
for a reversible process that connects the same
Pham
Hong Quang
Faculty of Fundamental Sciences
initial
and final points.

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9.5 Entropy
Entropy and Heat,
Cont. along a reversible path, even if the
dQr is measured
system may have followed an irreversible path.
For a finite process, T is generally not constant
during process.
f
f dQ
r
S dS
i
i
T

## The finite change in entropy depends only on the

properties of the initial and final equilibrium states.
Therefore we are free to choose a particular
reversible path over which to evaluate the
entropy rather than the actual path, as long as
the initial and final states are the same.

## Faculty of Fundamental Sciences

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9.5 Entropy
S for a Reversible Cycle
S = 0 for any reversible
cycle
In general,dQr

T 0
This integral symbol
indicates the integral is
over a closed path.

## Faculty of Fundamental Sciences

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9.5 Entropy
Entropy Changes in
Irreversible Processes
To calculate the change in entropy in a real
system, remember that entropy depends only on
the state of the system.
We find a reversible process which has the same
initial and final equilibrium states and calculate
the change in entropy for this process
Do not use Q, the actual energy transfer in the
process.
Distinguish this from Qr , the amount of
energy that would have been transferred by
heat along a reversible path.
Qr is the correct value to use for S.
Pham Hong Quang

## Faculty of Fundamental Sciences

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9.5 Entropy
Entropy and the
Second Law
Entropy is a measure of disorder.
The entropy of the Universe
increases in all real processes.
This is another statement of the
second law of thermodynamics.
It is equivalent to the KelvinPlanck and Clausius statements.

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9.5 Entropy
S in Thermal
Conduction

## The cold reservoir absorbs energy Q and its

entropy changes by Q/Tc.
At the same time, the hot reservoir loses Q
and its entropy changes by -Q/Th.
Since Th > Tc , the increase in entropy in the
cold reservoir is greater than the decrease in
entropy in the hot reservoir.
Therefore, SU > 0
For the system and the Universe
Pham Hong Quang

## Faculty of Fundamental Sciences

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9.5 Entropy
S in a Free Expansion
Consider an adiabatic free
expansion.
This process is irreversible
since the gas would not
spontaneously crowd into
half the volume after filling
the entire volume .
Q = 0 but we need to find
Qr
Choose an isothermal,
reversible expansion in
which the gas pushes
slowly against the piston
while
enters
from
a
Pham
Hongenergy
Quang
Faculty
of Fundamental
Sciences

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9.5 Entropy
S in Free Expansion, cont
For an isothermal process, this
becomes
Vf
S nr ln
Vi

## Since Vf > Vi , DS is positive

This indicates that both the entropy
and the disorder of the gas increase
as a result of the irreversible
adiabatic expansion .
Pham Hong Quang

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Thank you!

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