CHAPTER 3
HEAT ENGINES, ENTROPY AND
THE SECOND 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 SECOND LAW OF THERMODYNAMICS
Establishes which processes do and which do not occur
Some processes can occur in either direction according to
the first law.
They are observed to occur only in one direction.
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.
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.
Section 22.1
HEAT ENGINE, CONT.
[Link] working substance absorbs
energy by heat from a high temperature
energy reservoir (Qh).
[Link] is done by the engine (Weng).
[Link] is expelled as heat to a lower
temperature reservoir (Qc).
Section 22.1
HEAT ENGINE, CONT.
Since it is a cyclical process, ΔEint = 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.
Section 22.1
THERMAL EFFICIENCY OF A HEAT ENGINE
• 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≡ = = 1−
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 release only a fraction of the input energy
by mechanical work.
• Therefore, their efficiency is always less than 100%.
To have e = 100%, QC must be 0
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 released to the environment
Means that e cannot equal 100%
PERFECT HEAT ENGINE: IMPOSSIBLE
• 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.
Section 22.1
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.
An air conditioner is another example of a heat pump.
HEAT PUMP PROCESS
• Energy is extracted from
the cold reservoir, |QC|
• Energy is transferred to
the hot reservoir |Qh|,
work must be done on the
engine, W
• For example: refrigerator
SECOND LAW – CLAUSIUS FORM
It is impossible to construct a cyclical machine whose sole
effect
is to transfer energy continuously by heat from one object
to another object
at a higher temperature without the input of energy by
work.
Section 22.2
PERFECT HEAT PUMP: IMPOSSIBLE
• Takes energy from the cold
reservoir
• Expels an equal amount of
energy to the hot reservoir
• No work is done
• This is an impossible heat pump
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).
COP, COOLING MODE
In cooling mode, you “gain” energy removed from a cold
temperature reservoir.
energy transferred at low temp Qc
COP =
work done on the pump W
A good refrigerator should have a high COP.
Typical values are 5 or 6
Section 22.2
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 = =
work done by heat pump W
Qh is typically higher than W
Values of COP are generally about 4
Section 22.2
REVERSIBLE AND IRREVERSIBLE
PROCESSES
A reversible process is one in which every point along some
path is an equilibrium state.
And one for which the system can be returned to its
initial state along the same path.
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.
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.
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.
CARNOT CYCLE
Overview
of the
processes in
a Carnot
cycle
Section 22.4
CARNOT CYCLE, A TO B
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.
Section 22.4
CARNOT CYCLE, B TO C
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.
CARNOT CYCLE, C TO D
The gas is placed in
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.
CARNOT CYCLE, D TO A
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.
CARNOT CYCLE, PV DIAGRAM
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
Section 22.4
EFFICIENCY OF A CARNOT ENGINE
Carnot showed that the efficiency of the engine depends on the
temperatures of the reservoirs.
W Q T
e =eng =
1− c =
1− c
Qh Qh Th
Temperatures must be in Kelvins !!!!!!
All Carnot engines operating between the same two
temperatures will have the same efficiency.
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.
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.
CARNOT HEAT PUMP COPS
In heating mode:
Qh Th
=
COP =
Th − Tc
C
W
In cooling mode:
Qc Tc
=
COP =
W Th − Tc
C
In practice, the COP is limited to values below 10.
GASOLINE ENGINE
• In a gasoline engine, six processes occur during each cycle.
• For a given cycle, the piston moves up and down twice.
• This represents a four-stroke cycle.
• The processes in the cycle can be approximated by the
Otto cycle.
THE CONVENTIONAL GASOLINE ENGINE
GASOLINE ENGINE – INTAKE STROKE
During the intake stroke, the
piston moves downward.
A gaseous mixture of air and
fuel is drawn into the cylinder.
Energy enters the system by
matter transfer as potential
energy in the fuel.
The volume increases from V2
to V1.
O → A in the Otto cycle PV
diagram.
GASOLINE ENGINE – COMPRESSION STROKE
The piston moves upward.
The air-fuel mixture is compressed
adiabatically.
The volume changes from V1 to V2.
The temperature increases.
The work done on the gas is
positive and equal to the negative area
under the curve.
A → B in the Otto cycle PV diagram.
GASOLINE ENGINE – SPARK
Combustion occurs when the spark plug
fires.
It occurs very quickly while the piston is
at its highest position.
The combustion represents a rapid
energy transformation from potential
energy to internal energy.
The temperature changes from TB to TC
but the volume remains approximately the
same.
B → C in the Otto cycle PV diagram.
GASOLINE ENGINE – POWER STROKE
In the power stroke, the gas expands
adiabatically.
Volume changes from V2 to V1
The temperature drops from Tc to
TD.
Work is done by the gas
The work is equal to the area under
the curve.
C → D in the Otto cycle PV diagram
GASOLINE ENGINE – VALVE OPENS
This is process D → A in the Otto cycle PV
diagram
An exhaust valve opens as the piston
reaches its bottom position.
The pressure drops suddenly.
The volume is approximately constant.
So no work is done
Energy is expelled from the interior of the
cylinder.
It continues to be expelled during the
next process.
GASOLINE ENGINE – EXHAUST STROKE
In the exhaust stroke, the piston
moves upward while the exhaust
valve remains open.
Residual gases are expelled to the
atmosphere
The volume decreases from V1 to V2.
A → O in the Otto cycle PV
diagram
The cycle then repeats
OTTO CYCLE EFFICIENCY
If the air-fuel mixture is assumed to be an ideal gas, then
the efficiency of the Otto cycle is
1
e= 1−
(V1 V2 )
γ −1
γ is the ratio of the molar specific heats.
V1 / V2 is called the compression ratio.
OTTO CYCLE EFFICIENCY, CONT
Typical values:
Compression ratio (V1 / V2 ) of 8
γ = 1.4
e = 56%
Efficiencies of real engines are 15% to 20%
Mainly due to friction, energy transfer by conduction,
incomplete combustion of the air-fuel mixture
DIESEL ENGINES
• Similar cycle to the Otto cycle without a spark plug.
• Compression ratio is much greater and so the cylinder
temperature at the end of the compression stroke is much
higher.
• Fuel is injected and the temperature is high enough for the
mixture to ignite without the spark plug.
• Diesel engines are more efficient than gasoline engines.
ENTROPY
Entropy, S, is a state variable related to the second law of
thermodynamics.
Do not confuse entropy with energy !!
They are very different concepts
Isolated systems tend towards disorder and entropy is a
natural measure of this disorder.
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.
dQ dS is
The change in entropy,
dS = r
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 initial and final points.
MORE ABOUT CHANGE IN ENTROPY
dQr is measured along a reversible path, even if the system may have followed an irreversible path.
The meaningful quantity is the change in entropy and not the entropy itself.
For a finite process, T is generally not constant during process.
f f dQr
∆=
S ∫i
=
dS ∫
i T
The change in entropy of a system going from one state to another has the same value for all paths
connecting the two states.
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.
∆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.
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.
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.
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 Kelvin-Planck and Clausius
statements.
ENTROPY CHANGES IN NON-ISOLATED
SYSTEMS
The increase in entropy described in the second law is that of
the system and its surroundings.
When a system and its surroundings interact in an irreversible
process, the increase in entropy of one is greater than the
decrease in entropy of the other.
The change in entropy of the Universe must be greater than
zero for an irreversible process and equal to zero for a reversible
process.
∆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
∆S IN FREE EXPANSION
For an isothermal process, this becomes
Vf
∆S =nr ln
Vi
Since Vf > Vi , ∆S is positive
This indicates that both the entropy and the disorder of
the gas increase as a result of the irreversible adiabatic
expansion .