The Second Law of Thermodynamics

For the free expansion, we have S > 0. It is an irreversible process

in a closed system.
For the reversible isothermal process, for the gas S > 0 for
expansion and S < 0 for compression. However, the gas itself is not
a closed system. It is only a closed system if we include both the gas
and the reservoir.
|Q| |Q|
during expansion: Sgas = and Sres =
T T
So: Stotal = 0

S 0 (Second Law of Thermodynamics)

If a process occurs in a closed system, the entropy of the system
increases for irreversible processes and remains constant for reversible
processes. It never decreases.

Calculate S for the reversible isothermal

process. since T = constant:
1 f Q
S = Sf Si = dQ =
T i T
In isothermal expansion, Q > 0,
therefore S > 0
that means S > 0 for free expansion

For a process that T is small

compared to T :
Q
S = Sf Si
Tavg

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 Entropy in real world: Engines
Lets explore how entropy affects energy
flow in devices -- (i.e., engines). 1

A heat engine is a device that: 2

absorbs heat from a hot reservoir (1)
3
does work on something (2)
then expels heat to a cold reservoir (3) to return to the
engines starting conditions.
This constitutes one cycle (and the process repeats itself).

In an ideal engine, all processes are reversible.

Entropy in real world: Engines

A heat engine is a device that extracts
heat from its environment and does
useful work.
Consider a p-V diagram with an ideal gas
as the working substance for our engine.

p A
The cycle starts at A and must
return to A at the end of the cycle.
W

The area enclosed by the cycle is the

net work the engine does. V

2
 Engines p A
So..., What cycle will produce
the maximum work (W) for the W
minimum cost (QH) and the
minimum waste (QL)? V

Note that TH and TL are fixed by external conditions such

as the type of fuel used, surrounding environment, etc.

A A
A
p p p

W TL W
TH W TH
TH
TL TL
V V V
Test Problem Stirling Cycle Carnot Cycle

Engines p A
So..., What cycle will produce the
maximum work (W) for the W
minimum cost (QH) and the
minimum waste (QL)? V

Note that TH and TL are fixed by external conditions such

as the type of fuel used, surrounding environment, etc.
A A
p p
W TH W TH
TL TL
V V
(Internal combustion engine) Otto Cycle Diesel Cycle

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 Answer: The Carnot Cycle
Carnot Engine: The most efficient heat engine.
The Carnot cycle consists of four processes:
a-b: isothermal expansion, working substance gets heat
QH from the high-temperature reservoir

b-c: adiabatic expansion. Q = 0

c-d: isothermal compression,

working substance gives heat QL
to the low temperature reservoir

d-a: adiabatic compression. Q = 0

The work done by the gas:

a-b-c: positive work
c-d-a: negative work

Net work done in one cycle: area enclosed by cycle abcda.

For a complete cycle, Eint = 0 (since Eint is a state

function) that is: Q W = 0, since Q = |QH| |QL|
Therefore: W = Q = |QH| |QL|

For a complete cycle, S = 0 ( since S is a state function.)

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Thermal efficiency of an engine:
energy we get out | W | | Q H | | Q L | |Q |
= = = = 1 L
energy we pay for | Q H | | QH | | QH |

For Carnot engine: since the process is reversible, for the

closed system (high-T reservoir + work substance + low-T
reservoir), S = 0 ( 2nd law of thermodynamics)
| QH | |Q | | Q L | TL TL
+0+ L = 0 = = 1
TH TL | Q H | TH TH

For real engine: since the process is irreversible, S > 0

| QH | |Q | | Q L | TL TL
+0+ L > 0 > < ( 1 )
TH TL | Q H | TH TH

Temperature - Entropy Graph for the

Carnot Engine

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 Is there a perfect engine, which converts all QH to work so that
QL = 0 and = 1, possible?

The entropy change for the closed system:

| QH | |Q |
S = +0+0 = H < 0
TH TH

This violates the 2nd law of thermodynamics!

TL
= 1
TH
Also, for = 1, we need TL = 0 or TH to be infinity, either of which
is impossible.

Conclusion: Perpetual motion machines are impossible!!

Daily Quiz, December 03, 2004

An inventor claims to have invented an engine that operates between

constant temperature reservoirs of 600K and 300K. The data per
cycle of the engines are listed. Which (if any) are possible engines?

(1) QH = 200J, QL = 100J, W=50J

(2) QH = 400J, QL = 100J, W=300J
(3) QH = 400J, QL = 200J, W=200J
(4) All three engines are not possible.

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 Daily Quiz, December 03, 2004
1st Law of Thermodynamics: W = QH QL
Engine 1 violates this law, but 2 & 3 obey it.

2nd Law of Thermodynamics:

max = W/QH = 1 QL/QH = 1 TL/TH = 1 300/600 = 1/2

An inventor claims to have invented an engine that operates between

constant temperature reservoirs of 600K and 300K. The data per
cycle of the engines are listed. Which (if any) are possible engines?

(1) QH = 200J, QL = 100J, W=50J

(2) QH = 400J, QL = 100J, W=300J 2 = W/QH = 3/4
(3) QH = 400J, QL = 200J, W=200J 3 = W/QH = 2/4 = 1/2
(4) All three engines are not possible.