THE SECOND LAW OF

THERMODYNAMICS

THE SECOND LAW OF THERMODYNAMICS:

THE HEAT FLOW STATEMENT
Fungsi Hukum Kedua
Heat flows spontaneously from a substance at a higher
temperature to a substance at a lower temperature and
does not flow spontaneously in the reverse direction
The second law is a statement about the natural
tendency of heat to flow from hot to cold, whereas the
first law deals with energy conservation and focuses on
both heat and work.
Hukum Kedua membicarakan konversi kalor-kerja dan
berapa efisiensinya.

Proses lingkar dan mesin kalor

Untuk mengubah panas menjadi kerja, kita membutuhkan mesin
termodinamika yang akan mengkonsumsi panas dan menghasilkan
kerja. Jika ingin membahas efisiensi konversi, mesin harus dapat
dikembalikan ke keadaan semula (melakukan proses lingkar). Mesin
yang mengandung sistem dan mekanisme lingkar disebut sebagai
MESIN KALOR (heat engine).
Secara umum, mesin kalor akan menyerap dan mengeluarkan
panas selama proses yang merupakan bagian dari proses lngkar.
Jika mesin dapat merubah kalor menjadi 100% kerja, maka mesin
yang bersangkutan merupakan mesin kalor ideal dan mustahil
terjadi.

Since it is a cyclical process, U = 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

CARNOT'S PRINCIPLE: AN
ALTERNATIVE STATEMENT OF THE
SECOND LAW OF THERMODYNAMICS
No irreversible engine operating between two
reservoirs at constant temperatures can have a greater
efficiency than a reversible engine operating between
the same temperatures. Furthermore, all reversible
engines operating between the same temperatures
have the same efficiency.

Heat Engine and Refrigerators

A heat engine is any device that uses heat to perform
work. It has three essential features:
1. Heat is supplied to the engine at a relatively high
Temperature from a place called the hot reservoir.
2. Part of the input heat is used to perform work by the working
substance of the engine, which is the material within the
engine that actually does the work (e.g., the gasolineair
mixture in an automobile engine).
3. The remainder of the input heat is rejected at a temperature
lower than the input temperature to a place called the cold
reservoir

Pernyataan Hukum Kedua

Ada dua pernyataan klasik mengenai Hukum Kedua yang

dikenal luas. Yang pertama adalah mengenai efisiensi konversi
dari panas menjadi kerja dan yang kedua adalah ireeversibilitas
pada proses alam.
Pernyataan pertama dari Kelvin:
Tidak mungkin ada sebuah proses yang dapat mengkonversi
panas menjadi kerja secara sempurna
T
1

T1
Q1 =100 J
Mesin
Kalor

Q1

Mesin
Kalor

W1 =100 J

Q2

T2

Pernyataan kedua dari Clausius:

Tidak mungkin ada proses yang dapat memindahkan panas

dari daerah dingin ke daerah panas tanpa bantuan kerja

T1

T1
Q1

Mesin
Kalor

Q2

T2

Q1

Mesin
Kalor

Q2

T2

Heat Engine
This schematic representation
of a heat engine shows the input
heat (magnitude = QH) that
originates from the hot
reservoir, the work (magnitude
= W) that the engine does, and
the heat (magnitude = QC ) that
the engine rejects to the cold
reservoir.

HEAT ENGINE

REFRIGERATOR

TH

TH

QH

system

System of
interest

Weng

Wref

QC

QC
TC

TC

Q = U - W
QH - QC

QH

Q = U - W
QC - QH

QH - QC = -W = Weng

QH - QC = + W = Wref

for a heat engine

for refrigerator

HEAT ENGINE

REFRIGERATOR

TH

TH

QH

QH
Weng

QC

Wref
QC

TC
QH - QC = Weng

TC
QH - QC = Wref

Eff = Weng / QH

COPrefrig= QC / Wref = QC / (QH - QC)

Eff = 1 - QC / QH

COPht. pump= QH / Weng = QH / (QH - QC)

COP ---coefficient of performance

Heat Engine: Carnot Cycle

Qc
Tc
Eff 1
1
Qh
Th

No real engine operating

between two energy
reservoirs can be more
efficient than a Carnot
engine operating between
the same two temperatues.
- Sadi Carnot

Heat Pumps & Refrigerators

Adiabatic
expansion

Heat engines operated backward

Work done to transfer heat from cold to hot reservoir
Reverse path in the PV diagram compared to Carnot cycle

Carnot Cycle

efisiensi termal () dari mesin kalor adalah perbandingan antara

panas yang diserap dan kerja yang dihasilkan.
=

ker ja keluar
kalor masuk

W
=
Q1

Q1 dan W masing-masing kalor yang diserap dan kerja yang

dihasilkan dalam satu proses lingkar. Karena W = Q1 Q2, dimana
Q2 adalah kalor yang dilepaskan, maka:
QC
Q2
=1=
Q1 QH

Efisiensi di atas merupakan efisiensi Carnot dan merupakan

bagian dari lingkar Carnot.

Efficiency of a Carnot Engine

QC
1
QH

Isothermal
U int 0

Isothermal:
AB QH WAB nRTH ln VB / VA
CD

U int Q W

QC WCD nRTC ln VC / VD

dW pdV
pV nRT

Adiabatic
1
TV
= const.

Adiabatic:
BC

TH VB 1 TC VC 1

DA

1
TH VA

1
TC VD

VB VC

VA VD

Efficiency of an Ideal Engine

ln VB / VA ln VC / VD
QC TC

QH TH
Thermal efficiency:

QH nRTH ln VB / VA
QC nRTC ln VC / VD

QC
TC
1
1
QH
TH

QC
1
QH

A refrigerator is a heat engine in reverse.

A refrigerator is a device that carries a working
substance through a cyclic process, during which it
Absorbs thermal energy from a low-temperature source

Work is done on it

Expels thermal energy to a high-temperature source

Natural Limits on the Efficiency of a Heat Engine

Consider a hypothetical engine that receives 1000 J of heat
as input from a hot reservoir and delivers 1000 J of work,
rejecting no heat to a cold reservoir whose temperature is
above 0 K. Decide whether this engine violates the first or
the second law of thermodynamics, or both.
The first law of thermodynamics is an expression of energy
conservation. From the point of view of energy
conservation, nothing is wrong with an engine that converts
1000 J of heat into 1000 J of work.
Energy has been neither created nor destroyed; it has only
been transformed from one form (heat) to another (work).

This engine does, however, violate the second law of

thermodynamics. Since all of the input heat is converted into
work, the efficiency of the engine is 1, or 100%.
Since we know that TC is above 0 K, it is clear that the ratio
TC/TH is greater than zero, so the maximum possible
efficiency is less than 1, or less than 100%.

A Heat Pump
An ideal or Carnot heat pump is used to heat a house to a
temperature of TH = 294 K (21 C). How much work must
be done by the pump to deliver QH = 3350 J of heat into the
house when the outdoor temperature TC is (a) 273 K (0 C)
and (b) 252 K (-21 C)?

Reasoning
The conservation of energy (QH = W + QC) applies to the
heat pump. Thus, the work can be determined from W =
QH - QC, provided we can obtain a value for QC, the heat
taken by the pump from the outside. To determine QC, we
use the fact that the pump is a Carnot heat pump and
operates reversibly. Therefore, the relation QC/QH = TC/TH
applies. Solving it for QC, we obtain QC = QH(TC/TH). Using
this result, we find that

Solution
(a) At an indoor temperature of TH = 294 K and an
outdoor temperature of TC = 273 K, the work needed
is

(b) This solution is identical to that in part (a), except

that it is now cooler outside, so TC = 252 K. The
necessary work is
, which is more than in part
(a).

Performance of an Ideal Refrigerator

Coefficient of performance:

QC
TC
K

QH QC TH TC

Real Engines vs Carnot Engines

All real engines are less efficient than

the Carnot engine

Real engines are irreversible because of
friction
Real engines are irreversible because
they complete cycles in short amounts of
time

Reversible Process: a process that at the conclusion,

the system and its surrounding return to the exact initial
conditions.
Irreversible: The process can not be reversed. For
example, the process of the universe is irreversible. It
moves in the direction of time. When you try to reverse it, it
would appear like a movie playing back.

HRW.AnidealheatengineoperatesinaStirlingcyclebetween
235Cand115C.Itabsorbs6.30x104Jpercycleatthehigher
temperature.(a)Whatistheefficiencyoftheengine?(b)Howmuch
workpercycleisthisenginecapableofperforming?

(a)

(a)

TH TC (235 115) K

23.6%
TH
(235 273) K
W

QH

W QH 0.236 6.30 10 4 J
1.49 10 4 J

QH

TC
1
TH

HRW.Onemoleofanidealmonatomicgasistakenthroughthe
cycleshown.Assumethatp=2p0,V=2V0,p0=1.01x105Pa,andV0
=0.0225m3.Calculate(a)theworkdoneduringthecycle,(b)the
heataddedduringstrokeabc,and(c)theefficiencyofthecycle.(d)
Whatistheefficiencyofanidealengineoperatingbetweenthe
highestandlowesttemperaturesthatoccurinthecycle?Howdoes
thiscomparetotheefficiencycalculatedin(c)?
c
V,p

(a) W Area p0V0 2.27 103 J

(b)

3
Eint Q W nRT
2

Pressure

b
V0,p0

Volume

PV nRT

HRW.Onemoleofanidealmonatomicgasistakenthroughthe
cycleshown.Assumethatp=2p0,V=2V0,p0=1.01x105Pa,andV0
=0.0225m3.Calculate(a)theworkdoneduringthecycle,(b)the
heataddedduringstrokeabc,and(c)theefficiencyofthecycle.(d)
Whatistheefficiencyofanidealengineoperatingbetweenthe
highestandlowesttemperaturesthatoccurinthecycle?Howdoes
thiscomparetotheefficiencycalculatedin(c)?

Pressure

b
V0,p0

c
V,p

Volume

Eint Q W

HRW.Onemoleofanidealmonatomicgasistakenthroughthe
cycleshown.Assumethatp=2p0,V=2V0,p0=1.01x105Pa,andV0
=0.0225m3.Calculate(a)theworkdoneduringthecycle,(b)the
heataddedduringstrokeabc,and(c)theefficiencyofthecycle.(d)
Whatistheefficiencyofanidealengineoperatingbetweenthe
highestandlowesttemperaturesthatoccurinthecycle?Howdoes
thiscomparetotheefficiencycalculatedin(c)?
b
1

Ta
pV
1 a a
Tc
pcVc

Pressure

(d)

V0,p0

Volume

Largerthan15%.

c
V,p

T
1 C
TH

HRW.Anidealheatpumpisusedtoheatabuilding.Theoutside
temperatureis5.0Candthetemperatureinsidethebuildingistobe
maintainedat22C.Thecoefficientofperformanceis3.8andthe
heatpumpdelivers7.54MJofheattothebuildingeachhour.At
whatratemustworkbedonetoruntheheatpump?

Foracompletecycle,Eint=0

QC
QH Won
K

Won
Won

QC QH Won 0
Won

QH

K 1

ENTROPI
Entropy is a measure of disorder.
Entropy is a state function like p, T, and Eint. A state
function describes the thermodynamic state of a system,
which is independent of the history.
The change in entropy S for an infinitesimal
process:

dQr
dS
T

The subscript r stands for

reversible process

ENTROPY
To introduce the idea of entropy we recall the relation
QC/QH = TC/TH that applies to a Carnot engine. This
equation can be rearranged as QC/TC = QH/TH, which
focuses attention on the heat Q divided by the Kelvin
temperature T. The quantity Q/T is called the change in
the entropy S:

the SI unit for entropy is a joule per kelvin (J/K).

For a finite process from an initial state i to a final

state f, the change in entropy is

dQr
S dS
T
i
i

Unit:J/K

Theintegrationisalongapaththat
representsareversibleprocess
Note: Even if the actual process is irreversible, you need to
follow a reversible process to reach the same final state to
obtain Entropy

Q
r

S
T

Entropy

This applies only to the reversible path, even if the

system actually follows an irreversible path
To calculate the entropy for an irreversible
process, model it as a reversible process
When energy is absorbed, Q is positive and entropy
increases
When energy is expelled, Q is negative and entropy
decreases

More About Entropy

Note, the equation defines the change in entropy

The entropy of the Universe increases in all natural
processes
This is another way of expressing the Second Law of
Thermodynamics
There are processes in which the entropy of a system
decreases
If the entropy of one system, A, decreases it will be
accompanied by the increase of entropy of another
system, B.
The change in entropy in system B will be greater than
that of system A.

Question
Heat is applied to ice-water mixture and a portion of the ice
melts. Which of the following quantities increase?
The mixtures temperature and internal energy.
The mixtures temperature and entropy.
correct
The mixtures entropy and internal energy.
The mixtures temperature, entropy and internal
energy.
None of the above three quantities increase

Perpetual Motion Machines

A perpetual motion machine would operate

continuously without input of energy and without any
net increase in entropy
Perpetual motion machines of the first type would
violate the First Law, giving out more energy than
was put into the machine
Perpetual motion machines of the second type would
violate the Second Law, possibly by no exhaust
Perpetual motion machines will never be invented

Entropy and Disorder

Entropy can be described in terms of disorder

A disorderly arrangement is much more probable
than an orderly one if the laws of nature are allowed
to act without interference
This comes from a statistical mechanics
development

Entropy and Disorder, cont.

Isolated systems tend toward greater disorder, and

entropy is a measure of that disorder
S = kB ln W
kB is Boltzmanns constant
W is a number proportional to the probability that
the system has a particular configuration
This gives the Second Law as a statement of what is
most probably rather than what must be
The Second Law also defines the direction of time of all
events as the direction in which the entropy of the
universe increases

Entropy Question
Suppose your roommate is Mr. Clean and tidies up
your messy room after a big party. What happens to
the entropy of the room (assume that room and its
contents are isolated from rest of the universe)?
Decreases
Stays the same
Increases

Adiabatic Compression
During adiabatic compression of an ideal
gas, the entropy of the gas
Decreases.
Stays constant.
Increases.
No heat is transferred in or out of the system
during an adiabatic process - therefore, entropy
remains constant.

Heat Death of the Universe

The entropy of the Universe always increases

The entropy of the Universe should ultimately reach a
maximum
At that time, the Universe will be at a state of
uniform temperature and density
That state of perfect disorder implies no energy
will be available for doing work
That state is called the heat death of the Universe

Grades of Energy

The tendency of nature to move toward a state of

disorder affects a systems ability to do work
Various forms of energy can be converted into
internal energy, but the reverse transformation is
never complete
If two kinds of energy, A and B, can be completely
interconverted, they are of the same grade

Grades of Energy, cont.

If form A can be completely converted to form B, but

the reverse is never complete, A is a higher grade of
energy than B
When a high-grade energy is converted to internal
energy, it can never be fully recovered as high-grade
energy
Degradation of energy is the conversion of highgrade energy to internal energy
In all real processes, the energy available for doing
work decreases

Lecture 23, Preflight 3,4

Consider a hypothetical refrigerator that

takes 1000 J of heat from a cold
reservoir at 100K and ejects 1200 J of
correct
heat to a hot reservoir
at 300K.

As a result of this operation, what happens to the

REFRIGERATOR
entropy of the universe?
T
1. Decreases There is an increase in entropy
any system undergoing an
2. Increases for
Q
irreversible process.
3. Remains the
same
Total
entropy either increases
H

or remains constant in any

process; never decreases.

W
QC
TC

Lecture 23, Preflight 5,6

Consider a hypothetical refrigerator that

takes 1000 J of heat from a cold
reservoir at 100K and ejects 1200 J of
heat to a hotcorrect
reservoir at 300K.REFRIGERATOR
T
Does this refrigerator violate second law of
thermodynamics?
Q
1. Yes
2. No
H

QC
TC

Lecture 23, Preflight 7

Which of the following violates the second

law of thermodynamics?
1. Heat flows into a gas and temperature falls.

correct

2.The temperature of a gas rises without any

heat flowing into it.
3. Heat spontaneously flows from a cold to
hot body.
4. All of the above

To be highly efficient, a heat engine must produce

a relatively large amount of work from as little
input heat as possible. Thus, the efficiency e of a
heat engine is defined as the ratio of the work W
done by the engine to the input heat QH:

If the input heat were converted entirely into

work, the engine would have an efficiency of
1.00, since W = QH; such an engine would be
100% efficient.

What is it that allows a heat engine to

operate with maximum efficiency?
The French engineer Sadi Carnot (17961832)
proposed that a heat engine has maximum
efficiency when the processes within the engine
are reversible. 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.

In a reversible process, both the system and

its environment can be returned to their initial
states.
A process that involves an energy-dissipating
mechanism, such as friction, cannot be
reversible because the energy wasted due to
friction would alter the system or the
environment or both.

THE SECOND LAW OF

THERMODYNAMICS STATED IN
TERMS OF ENTROPY
The total entropy of the universe does not
change when a reversible process occurs
(Suniverse = 0 ) and increases when an
irreversible process occurs (Suniverse 0 ).

The Entropy of the Universe Increases

This Figure shows 1200 J of
heat flowing spontaneously
through a copper rod from a hot
reservoir at 650 K to a cold
reservoir at 350 K. Determine
the amount by which this
irreversible process changes the
entropy of the universe,
assuming that no other changes
occur.

Reasoning

The hot-to-cold heat flow is irreversible, so

the relation S = (Q/T)R is applied to a
hypothetical process whereby the 1200 J of
heat is taken reversibly from the hot
reservoir and added reversibly to the cold
reservoir.

Solution
The total entropy change of the universe is the
algebraic sum of the entropy changes for each
reservoir:

Order to Disorder
Find the change in entropy that results when a
2.3-kg block of ice melts slowly (reversibly)
at 273 K (0 C).

Reasoning & Solution

Since the phase change occurs reversibly at a constant
temperature, the change in entropy can be found by
using, S = (Q/T)R, where Q is the heat absorbed by
the melting ice. This heat can be determined by using
the relation Q = mLf, where m is the mass and Lf =
3.35 105 J/kg is the latent heat of fusion of water.

THE THIRD LAW OF THERMODYNAMICS

It is not possible to lower the temperature of any
system to absolute zero in a finite number of
steps.