The Second Law of

Thermodynamics
Lecture Hour 12
• Describe the operation of an actual engine (esp. Otto
engine).
• Develop and describe a cyclic process (esp. the Otto
process) representing such an engine.
• Illustrate per cycle operation of an engine using the
Energy Reservoir Model (ERM).
• Solve for the efficiency of a heat engine.
• Calculate for the power generated and various
thermodynamic quantities in a given engine cycle (esp.
Otto cycle).
• Discuss impossibility of developing a ‘perpetual heat
engine’.
• State the Heat engine form of the 2nd law and illustrate
meaning using ERM and efficiency.
Heat Engine
Energy Reservoir Model for a
Heat Engine
Engine

|𝑄𝐶 |
|𝑄𝐻 |
𝑇𝐻 𝑇𝐶

|𝑊|

𝑊 |𝑄𝐶 |
𝑒= =1−
𝑄𝐻 |𝑄𝐻 |
 Otto Engine
1 Intake Stroke 𝑝 𝑐

2 Compression Stroke

3 Ignition 𝑑
𝑏

4 Power Stroke
𝑎
5 Exhaust Stroke 𝑉 𝑟𝑉 𝑉
 Otto Engine
𝑝 𝑐

Efficiency
1
𝑒 =1− 𝑏
𝑑
𝑟 𝛾−1
𝑎
𝑉 𝑟𝑉 𝑉
Second Law of Thermodynamics:
Heat Engine Statement

• It is impossible for a heat engine

working in a cycle to produce no
other effect than that of extracting
thermal energy from a reservoir
and performing an equivalent
amount of work.
Perpetual Engine
• An electric motor has its shaft
coupled to that of an electric
generator. The motor drives the
generator, and some current from
the generator is used to run the
motor. The excess current is used
to light a home. What is wrong
with this scheme?
Ex.
1. A gasoline engine has a power
output of 180 kW. Its thermal
efficiency is 28.0%. (a) How
much heat must be supplied to
the engine per second? (b) How
much heat is discarded by the
engine per second?
Activity
• Find a Match!
• Answer the three problems on your quiz
by group. (Express in % and 3 sig fig)
• Your magic number is equal to the sum
of the answers for #1, #2, #3
• Find another group with the same magic
number.
• First pair of group that finishes the
search, wins a prize!
 Activity
• An Otto engine compresses a
diatomic gas up to 1/10 of its
volume, what is its efficiency?
• The ERM of a certain
motor protein is
shown by the figure
below. What is its
efficiency?
Activity
• A heat engine uses a diatomic gas as its
working substance. Find its efficiency if one
cycle of the heat engine is represented by
the following pV-diagram.
Lecture Hour 13
• Describe the operation of a refrigerator.
• Illustrate the ERM of a refrigerator.
• Solve for the coefficient of performance of a
refrigerator.
• Solve problems relating heat engine with
refrigerator.
• Calculate the coefficient of performance if given
the efficiency of an engine that is run in reverse
as a refrigerator.
• State the Refrigerator form of the 2nd law and
illustrate meaning using COP and efficiency.
Refrigerator

|𝑄𝐶 |
𝑇𝐻 |𝑄𝐻 | 𝑇𝐶

|𝑊|
Refrigerator
Expansion Valve

Evaporator

Condenser

Compressor
Refrigerator
• Coefficient of Performance
𝑄𝐶 𝐻
•𝐾 = =
|𝑊| 𝑃
Refrigerator
• Can you cool your house by
leaving the refrigerator open?
Refrigerator
• A refrigerator absorbs 5 kJ of energy
from a cold reservoir and rejects 8 kJ
to a hot reservoir. (a) Find the
coefficient of performance of the
refrigerator. (b) The refrigerator is
reversible and is run backward as a
heat engine between the same two
reservoirs. What is its efficiency?
Second Law of Thermodynamics
• It is impossible for any process to
have as its sole result the transfer
of heat from a cooler to a hotter
body.
• Clausius statement (Refrigerator
Statement)
• Imagine a special air filter placed in a
window of a house. The tiny holes in the
filter allow only air molecules moving faster
than a certain speed to exit the house, and
allow only air molecules moving slower
than that speed to enter the house from
outside. Explain why such an air filter
would cool the house, and why the second
law of thermodynamics makes building
such a filter an impossible task.
Announcement
• Probset 1-3 Feb. 20, 2015
11:59PM
Quiz 12
• A 50% efficient heat engine is used
in conjunction with a refrigerator
to increase the COP of the system.
50% of the work input to the
refrigerator comes from the
engine. What is the resulting COP
of the system if the COP of the
refrigerator is 4?
Lecture Hour 14
• Enumerate conditions necessary for a reversible
process to take place.
• Develop an equivalent reversible process for a given
irreversible process.
• Illustrate irreversibility in natural processes.
• Describe the Carnot cycle (enumerate the processes
consisting the cycle as well as illustrate the cycle on a
PV diagram for an engine and a refrigerator).
• State Carnot’s theorem and use it to calculate
maximum possible efficiency of a real engine.
• Explain how reversible cycles are used to design a
substance-independent thermometer scale.
Second Law of Thermodynamics

• Heat Engine Statement

• Refrigerator Statement

• Irreversibility of Natural Process

Carnot’s Theorem
• No engine working between two
given heat reservoirs can be more
efficient than a reversible engine
working between those two
reservoirs
 Carnot’s Theorem
𝑇𝐻
100 J 105 J 100 J 5J

Super
Carnot Engine Efficient Carnot Perfect
40 J 45 J
Refrigerator 40 J
Engine 5J
Engine

60 J 60 J 60 J 0J
𝑇𝐶
Carnot Engine
• How to make processes reversible?
• Irreversible processes
• Mechanical Energy → Heat
• Friction, Viscous forces, Dissipative Forces
• Heat conduction: Hot → Cold
• Difference in temperature
• Non-equilibrium states
• Turbulence, gas explosion
 Carnot Engine
• Carnot cycle:
1. Quasi static isothermal
absorption of heat from a
hot reservoir
2. Quasi static adiabatic
expansion to a lower
temperature
3. Quasi static isothermal
exhaustion of heat to
cold reservoir
4. Quasi static compression 𝑇𝐶𝐶|
|𝑄
back to the original state. 𝑒𝑒=
= 1−
−𝑄
𝑇𝐻𝐻
Carnot Refrigerator
• Coefficient of Performance of a
Carnot Refrigerator
1−𝑒
•𝐾 =
𝑒
𝑇𝐶
•𝐾 =
𝑇𝐻 −𝑇𝐶
Carnot Engine
• A heat engine takes 2000 J of heat
from a reservoir at 500 K, does
some work and discards some
heat to a reservoir at 350 K. What
is the maximum work that it can
do, how much heat is discarded,
what is its maximum efficiency?
Carnot Engine
𝑇𝐶
•𝑒 =1−
𝑇𝐻
• Carnot efficiency is independent of
the working substance
• Kelvin Temperature Scale:
Redefined
𝑇𝐶 𝑄𝐶
• =
𝑇𝐻 𝑄𝐻
Carnot Engine as a Thermometer
• A Carnot engine is used as a
thermometer. If it extracts 300 J of
heat from a hot reservoir of 500 K,
what is the temperature reading of
the thermometer if at a certain
reservoir, it rejects 120 J of heat?
Announcement
• Probset 1-3 Feb. 20, 2015.
11:59PM
 Quiz 13
• A Carnot refrigerator is operated between two
heat reservoirs at temperatures of 320 K and
270 K. (a) What is the coefficient of
performance of the refrigerator? (b) If in each
cycle the refrigerator receives 415 J of heat
energy from the reservoir at 270 K, how many
joules of heat energy does it deliver to the
reservoir at 320 K?(c) If the refrigerator
completes 165 cycles each minute, what
power input is required to operate it (in
Watts)?
Quiz 13
• A Carnot engine works between two
heat reservoirs at temperatures 𝑇ℎ =
300 K and 𝑇𝑐 = 200 K. (a) What is its
efficiency? (b) If it absorbs 100 J from
the hot reservoir during each cycle,
how much work does it do? (c) How
much heat does it give off during each
cycle? (d) What is the COP of this
engine when it works as a refrigerator
between the same two reservoirs?
Lecture Hour 15
• Mathematically describe entropy for
reversible processes and cite consequences
of entropy being a state function.
• Solve for entropy changes for various
processes: isothermal process, free
expansion, inelastic collision, constant
pressure process, heat conduction, Carnot
cycle
• State 2nd Law in terms of entropy of the
universe and explain significance for
naturally occurring processes.
Second Law of Thermodynamics
• Statement of Impossibility
• Spontaneous Direction
• Increasing Disorder
Second Law of Thermodynamics
 Second Law of Thermodynamics
Heat Conduction Q
TH TC

Conversion of ME to Heat
ME → Heat
Mixing of Fluids
Entropy
• Infinitesimal Reversible Process
𝑑𝑄
• 𝑑𝑆 =
𝑇
• State Function
• Δ𝑆 = 𝑆2 − 𝑆1

2 𝑑𝑄
• Δ𝑆 = (reversible process)
1 𝑇
Entropy
• Heat added 𝑄 at an isothermal
process with temperature 𝑇
• Δ𝑆 = 𝑄/𝑇
• Melting / Freezing
𝑚𝐿𝑓
• Δ𝑆 = ±
𝑇𝑓

• Boiling / Condensing
• Δ𝑆 = ±𝑚𝐿𝑣 /𝑇𝑣
Entropy

• Ideal Gas Isothermal Expansion

• Δ𝑆 = 𝑛𝑅 ln 𝑉2 /𝑉1
• Quasi Static Adiabatic Expansion
• Δ𝑆 =0
Entropy
• Free expansion
𝑉2
• Δ𝑆 = 𝑛𝑅 ln
𝑉1
• Ex. One mole of an ideal gas
undergoes a free expansion from
an initial volume 𝑉 to 2𝑉. What is
the change in entropy?
Entropy
𝑝 𝑑𝑄
Irreversible 2
1

Reversible
Reversible
𝑑𝑄
3

𝑉
Entropy
• Constant Pressure Process
𝑇2
• Δ𝑆 = 𝑚𝑐 ln
𝑇1
𝑇2
• Δ𝑆 = 𝑛𝐶𝑝 ln
𝑇1
• Ex. 1 kg of water is heated from
0°C to 100°C. What is its change in
entropy?
Entropy
• Heat Conduction
• Δ𝑆 = 𝑄/𝑇
• Ex. What is the change of entropy
of the universe when 500 J of
energy is conducted from a hot
reservoir of temperature 500 K to
a cold reservoir of 200 K?
Entropy
• Carnot Cycle
• What is the change of entropy of
the universe after a Carnot Engine
completes one cycle?
Entropy
• Inelastic Collision
• Ex. A 60-kg reckless boy traveling
at 27.8m/s slams into the asphalt
road. If the temperature of the
environment is 30 °C, calculate the
entropy change of the universe
due to his crash.
Second Law of Thermodynamics:
Entropy Statement
• When all systems taking part in a
process are included, the entropy
either remains constant or increases.
• No process is possible in which the
total entropy decreases, when all
systems taking part in the process are
included.
• Δ𝑆𝑠𝑦𝑠 ≥ 0
Announcement
• Problem Set: Deadline Feb. 27,
2015. 11:59 PM
• Online Recit! Deadline Feb. 27,
2015. 11:59 PM
• First Long Exam Mar. 2, 2015.
7AM-9AM.
Quiz 14
• 1 kg of boiling water is placed in a
freezer of temperature 0°C. The
water is allowed to freeze until all
becomes ice. What is the change
of entropy of the universe during
this process?
Lecture Hour 16
• Differentiate ‘useful’ from ‘useless’ forms of
energy.
• Differentiate macroscopic from microscopic
interpretation of entropy and illustrate their
equivalence as well as use in explaining
various physical phenomena.
• Describe ‘order’ and ‘disorder’ in terms of
the number of available (i.e. accessible)
microstates for a given macrostate.
‘Useful’ & ‘Useless’ Energy

Q
TH TC
Microscopic Interpretation of
Entropy

Leo Lio
Microscopic Interpretation of
Entropy
 Microscopic Interpretation of
Entropy
Macroscopic View
Leo Lio


 Microscopic Interpretation of
Entropy
Macroscopic View
Leo Lio


Microscopic Interpretation of
Entropy
• Microscopic View

1 3

2 4
Microscopic Interpretation of
Entropy
• Calculating Entropy Using
Microstates:
• 𝑆 = 𝑘 ln 𝑤
• 𝑤 − # of microstates
• 𝑘 − Boltzmann Constant
• 1.38065 x 10−23 J/K

𝑤2
• Δ𝑆 = 𝑘 ln
𝑤1
Microscopic Interpretation of
Entropy
• Ex. 𝑛 moles of gas at temperature
𝑇 undergoes a free expansion to
twice its volume. What is the
entropy change of this process?
• What is the probability that after
the partition is broken, all of the
gas remains on one side?
Microscopic Interpretation of
Entropy
• Entropy and Probability
• High order = Low Probability
• Low order = High Probability

• Ex. 2 toblerone for both Leo & Lio

Announcements
• Recit & Probset: Feb. 27, 2015
11:59PM
• 1st LE Mar 2, 2015 7AM-9AM
• Review Class tomorrow!
Quiz
• A box is separated by a partition into two
parts of equal volume. The left side of the
box contains 500 molecules of nitrogen gas;
the right side contains 100 molecules of
oxygen gas. The two gases are at the same
temperature. The partition is punctured, and
equilibrium is eventually attained. (a) What
is the change in entropy of the system when
the partition is punctured? (b) What is the
probability that the molecules will be found
in same distribution as they were before the
partition was punctured?