Chapter 22

Heat Engines, Entropy and the

Second Law of Thermodynamics
First Law of Thermodynamics
– Review
 Review: 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 law makes no distinction between
the results of heat and the results of
work
First Law – Missing Pieces
 There is an important distinction
between heat and work that is not
evident from the first law
 The first law makes no distinction
between processes that occur
spontaneously and those that do not
 An example is that it is impossible to
design a device that takes in energy and
converts it all to energy
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
Irreversible Processes
 An irreversible process is one that
occurs naturally in one direction only
 No irreversible process has been
observed to run backwards
 An important engineering implication is
the limited efficiency of heat engines
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
 Heat Engine, cont.
 The working substance
absorbs energy by heat
from a high temperature
energy reservoir (Qh)
 Work is done by the engine
(Weng)
 Energy is expelled as heat
to a lower temperature
reservoir (Qc)
 Heat Engine, cont.
 Since it is a cyclical process,
ΔEint = 0
 Its initial and final internal
energies are the same
 Therefore, Qnet = Weng
 The work done by the engine
equals the net energy
absorbed by the engine
 The work is equal to the area
enclosed by the curve of the
PV diagram
 If the working substance is a gas
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   1
Qh Qh Qh
 We can think of the efficiency as the
ratio of what you gain to what you give
More About Efficiency
 In practice, all heat engines expel 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 other effect than the
absorption of energy from a reservoir
and the performance of an equal
amount of work
 Means that Qc cannot equal 0
 Some Qc must be expelled to the environment
 Means that e cannot equal 100%
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 an impossible
engine
 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
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
 Or – energy does not transfer
spontaneously by heat from a cold
object to a hot object
Perfect Heat Pump
 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)
 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
COP, Heating Mode
 COP is similar to efficiency
 Qh is typically higher than W
 Values of COP are generally greater than 1
 It is possible for them to be less than 1
 We would like the COP to be as high as
possible
COP, Cooling Mode
 In cooling mode, you “gain” energy
from a cold temperature reservoir
Qc
COP 
W
 A good refrigerator should have a high
COP
 Typical values are 5 or 6
 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
 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
 Reversible and Irreversible
Processes, cont
 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
Reversible and Irreversible
Processes, Summary
 The reversible process is an idealization
 All real processes on Earth are
irreversible
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
 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
 Carnot Cycle, B to C
 B -> C is an adiabatic
expansion
 The base of the cylinder is
replaced by a thermally
nonconducting wall
 No heat enters or leaves
the system
 The temperature falls from
Th to Tc
 The gas does work WBC
 Carnot Cycle, C to D
 The gas is placed in
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 gas is again placed
against 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
 Efficiency of a Carnot Engine
 Carnot showed that the efficiency of the engine
depends on the temperatures of the reservoirs
Qc Tc Tc
 and ec  1 
Qh Th 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
COPC  
W Th  Tc
 In cooling mode:

Qc Tc
COPC  
W Th  Tc
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
 Otto Cycle
 The PV diagram of an
Otto cycle is shown at
right
 The Otto cycle
approximates the
processes occurring in
an internal combustion
engine
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
as potential energy in the
fuel
 O -> A in the Otto cycle
 Gasoline Engine –
Compression Stroke
 The piston moves upward
 The air-fuel mixture is
compressed adiabatically
 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
 Gasoline Engine – Spark
 Combustion occurs when
the spark plug fires
 This is not one of the
strokes of the engine
 It occurs very quickly
while the piston is at its
highest position
 Conversion from potential
energy of the fuel to
internal energy
 B -> C in the Otto cycle
 Gasoline Engine – Power
Stroke
 In the power stroke, the
gas expands adiabatically
 This causes a temperature
drop
 Work is done by the gas
 The work is equal to the
area under the curve
 C -> D in the Otto cycle
Gasoline Engine – Valve
Opens
 This is process D -> A in the Otto cycle
 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 begins to be expelled from the
interior of the cylinder
 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
 A -> O in the Otto cycle
 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 
 1

  is the ratio of the molar specific heats

 V1 / V2 is called the compression ratio
Otto Cycle Efficiency, cont
 Typical values:
 Compression ratio of 8
  = 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
 Operate on a cycle similar to the Otto cycle
without a spark plug
 The 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
 The importance of entropy grew with the
development of statistical mechanics
 A main result is isolated systems tend
toward disorder and entropy is a
natural measure of this disorder
Microstates vs. Macrostates
 A microstate is a particular
configuration of the individual
constituents of the system
 A macrostate is a description of the
conditions from a macroscopic point of
view
 It makes use of macroscopic variables such
as pressure, density, and temperature for
gases
Microstates vs. Macrostates,
cont
 For a given macrostate, a number of
microstates are possible
 It is assumed that all microstates are
equally probable
 When all possible macrostates are
examined, it is found that macrostates
associated with disorder have far more
microstates than those associated with
order
 Microstates vs. Macrostates,
Probabilities
 The probability of a system moving in time from
an ordered macrostate to a disordered
macrostate is far greater than the probability of
the reverse
 There are more microstates in a disordered
macrostate
 If we consider a system and its surroundings to
include the Universe, the Universe is always
moving toward a macrostate corresponding to
greater disorder
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
 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, S is
dQr
S 
T
Entropy and Heat, cont
 The change in entropy depends only on
the endpoints and is independent of the
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,
f f dQ
S   dS   r
i i T
Change in Entropy, cont
 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
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
S for a Quasi-Static,
Reversible Process
 Assume an ideal gas undergoes a quasi-
static, reversible process
 Its initial state has Ti and Vi
 Its final state has Tf and Vf
 The change in entropy is
f dQr Tf Vf
S    nCV ln  nR ln
i T Ti Vi
 This demonstrates that S depends on only
the initial and final states and not the path
between the states
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 Changes in
Irreversible Processes, cont
 In general, the total entropy and
therefore the total disorder always
increases in an irreversible process
 The total entropy of an isolated system
undergoes a change that cannot
decrease
 This is another statement of the second
law of thermodynamics
Entropy Changes in
Irreversible Processes, final
 If the process is irreversible, then the
total entropy of an isolated system
always increases
 In a reversible process, the total entropy of
an isolated system remains constant
 The change in entropy of the Universe
must be greater than zero for an
irreversible process and equal to zero
for a reversible process
Heat Death of the Universe
 Ultimately, the entropy of the Universe should
reach a maximum value
 At this value, the Universe will be in a state of
uniform temperature and density
 All physical, chemical, and biological
processes will cease
 The state of perfect disorder implies that no
energy is available for doing work
 This state is called the heat death of the Universe
S in Thermal Conduction
 The cold reservoir absorbs 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 a Free Expansion
 Consider an adiabatic free expansion
 Q = 0 but cannot be used since that is
for an irreversible process
f dQr 1 f
S     dQr
i T T i
S in Free Expansion, cont
 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
S in Calorimetric Processes
 The process is irreversible because the system
goes through a series of nonequilibrium states
 Assuming the specific heats remain constant and
no mixing takes place:

Tf Tf
S  m c ln  m c ln
 If mixing takes1 place,
1
Tc this resultTapplies
2 2
h
only to
identical substances
S will be positive and the entropy of the Universe
increases
Entropy on a Microscopic
Scale
 We can treat entropy from a microscopic
viewpoint through statistical analysis of
molecular motions
 A connection between entropy and the number
of microstates (W) for a given macrostate is S =
kB ln W
 The more microstates that correspond to a given
macrostate, the greater the entropy of that
macrostate
 This shows that entropy is a measure of disorder
 Entropy, Molecule Example

 One molecule in a two-sided container has a 1-in-2 chance of

being on the left side
 Two molecules have a 1-in-4 chance of being on the left side
at the same time
 Three molecules have a 1-in-8 chance of being on the left
side at the same time
Entropy, Molecule Example
Extended
 Consider 100 molecules in the container
 The probability of separating 50 fast
molecules on one side and 50 slow
molecules on the other side is (½)100
 If we have one mole of gas, this is
found to be extremely improbable
Entropy, Marble Example
 Suppose you have a bag with 50 red
marbles and 50 green marbles
 You draw a marble, record its color,
return it to the bag, and draw another
 Continue until four marbles have been
drawn
 What are possible macrostates and
what are their probabilities?
Entropy, Marble Example,
Results

 The most ordered are the least likely

 The most disorder is the most likely