Entropy and The Second Law of Thermodynamics

Aljalal-Phys.
102-142-Ch20-page 1
Chapter 20
Entropy
and
the Second Law of Thermodynamics
20-1 Entropy Objective

20-2 Entropy in the Real World: Engines
20-3 Entropy in the Real World: Refrigerator
Aljalal-Phys.102-142-Ch20-page 2
20-1 Entropy
Breaking
Egg Egg
Irreversible
process
Ok Wrong way
Why not?
Does not violate conservation of energy!
20-1 Entropy
Cooling
Irreversible
process
A B ok A B
30 0C 50 0C 40 0C 40 0C
A B A B
40 0C 40 0C 30 0C 50 0C
Wrong way
Why not?
Does not violate conservation of energy!
20-1 Entropy
Direction is determined by entropy
The direction of the process is setup by a property called

entropy S
If an irreversible process occurs in a closed system,

the entropy S of the system always increases;
it never decreases.
Some times,
the change in entropy is called “the arrow of time”
20-1 Entropy
Entropy must not decrease for a process to occur
Entropy decreases. Egg

Process does not occur.
Wrong way
20-1 Entropy
Reversible processes
For reversible processes the system is always close to

equilibrium along the path connecting the initial and final points.
Pressure
i system is always
close to equilibrium
Volume
20-1 Entropy
Formula - change of entropy
Change in entropy Final state
Heat transfer to the system
For reversible
processes
Temperature in kelvin
Initial state
Entropy is measured in J/K
When the change in temperature ΔT is small relative to the initial and final
temperatures (in Kelvins) of the process, the entropy change can be approximated as
Average temperature
20-1 Entropy
Checkpoint 1
Water is heated on a stove.

Rank the entropy changes of the water as the
temperature rises
(a) from 20 0C to 30 0C,
(b) from 30 0C to 35 0C, and
(c) from 80 0C to 85 0C.
Solution
(a), then (b), then (c)

20-1 Entropy
Entropy is a state property
Entropy is a state property.

The change in entropy between states i and f depends only
on these states and not on the way the system takes from
one state to the other.
Same ΔS State properties:
i Pressure
Pressure
Volume
A Temperature
Internal energy
Entropy
B f
Work and heat are not
Volume state properties. They
depend on the path.
20-1 Entropy
Free expansion
Free expansion Insulation

Valve Valve
Gas Vacuum Gas Gas

P=0
Initial Final
Pressure
We do not know the volume

i
and pressure at points between
the initial and final states
f
Volume
20-1 Entropy
Replace the free expansion process with an isothermal process
Since entropy is a state property,

we will get the same change in entropy,
if we replace the free expansion process (irreversible)
with a reversible process
that connects the initial and final states.
In a free expansion process, Tf = Ti

Isotherm
Pressure
i We will replace the free expansion

process with an isothermal process.
f
Volume
20-1 Entropy
Change in entropy of a free expansion process
Weight
(Lead shot) Piston
Isotherm
Pressure
Insulating
i Gas cylinder
f Thermal
Reservoir
at T
Volume
20-1 Entropy
Change in entropy of irreversible processes
To find the entropy change for an irreversible process occurring

in a closed system,
replace that process with any reversible process that connects
the same initial and final states.
Calculate the entropy change for this reversible process using
20-1 Entropy
Change in entropy for gas, liquid, and solid
For an ideal gas
For a solid or liquid substance for which the temperature changes by ΔT

(no phase transition)
For a solid or liquid substance that undergoes phase transition at

temperature T
Example
liquid to gas gas to liquid
20-1 Entropy
Derivation - change in entropy for an deal gas
For an ideal gas
Derivation
For small changes
20-1 Entropy
Derivation - change in entropy for liquid or solid
For a solid or liquid substance for which the temperature changes by ΔT

(no phase transition)
Derivation
For a solid or liquid substance that undergoes phase transition at

temperature T
Derivation
20-1 Entropy
Example 1
Free expansion
Valve Valve
Gas Vacuum Gas Gas

P=0
Initial Final
one mole of V f= 2 V i
nitrogen gas Insulation
What is the change in entropy?

Solution
For an ideal gas

For free expansion Tf = T i
20-1 Entropy
Example 2
Final
Initial equilibrium
L R L R
20 0C 60 0C 40 0C 40 0C
Copper Copper
m = 1.5 Kg m = 1.5 Kg
What is the change in entropy of the two-block system?

Solution
20-1 Entropy
Checkpoint 2
a T2
Pressure
T2>T1.
For an ideal gas, is the entropy change
T1 T2
along the path to a is i
larger than, b
smaller than,
or the same as Volume
that along the path to state b.
Solution
Smaller
20-1 Entropy
The law statement
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.
closed system
ΔS > 0 irreversible processes
ΔS = 0 reversible processes
20-1 Entropy
Real world processes are irreversible
In real world,
almost all processes are irreversible.
Processes in which the system’s entropy remains

constant are always idealization.

Engine diagram
High-Temperature
reservoir
A heat engine is a device that extracts
TH
energy from its environment in the form
of heat and does useful work.
QH
Heat engine W
Working substance
QL Steam engine Water-gas
TL Car engine Gasoline-air
Low-Temperature
reservoir

Ideal engine
Ideal engine
In an ideal engine, all processes are reversible and no
wasteful energy transfers occur due, say, friction and
turbulence.
Carnot engine
• Carnot engine is an ideal engine.

• Carnot engine is the best engine in using energy as
heat to do useful work.
• You cannot build more efficient heat engine than a
Carnot engine.
Carnot Pronounced “Car-no”


Work done by a Carnot engine during a cycle
Piston Insulating
a cylinder
Gas
Pressure
Isothermal
QH
W = Area inside
Adiabatic Adiabatic
b TH
d c
Isothermal Volume TL
QL

Carnot engine - first stroke
move slowly up
Stroke a 🡪 b isothermal
Piston
Insulating
a Gas cylinder
Pressure
Thermal
Reservoir
QH at TH
b TH
Volume

Carnot engine - second stroke
move slowly up
Piston
Stroke b 🡪 c adiabatic
Insulating
a Gas cylinder
Pressure
Thermal
Reservoir
at TH
b TH
c
Volume

Carnot engine - third stroke
move slowly down
Piston
Stroke c 🡪 d isothermal
Insulating
a Gas cylinder
Pressure
Thermal
Reservoir
at TL
b TH
d c
TL
QL Volume

Carnot engine - fourth stroke
move slowly down
Stroke d 🡪 a adiabatic Piston
Insulating
a Gas cylinder
Pressure
Thermal
Reservoir
at TL
b TH
d c
TL
Volume

Entropy change for a Carnot engine
Temperature
T-S diagram
QH
a b
TH
a TL
Pressure
d c
P-V diagram QL
Entropy
QH
b c TH
d
QL Volume TL

Work done by a Carnot engine during a cycle
First law of Thermodynamics ΔEint = Q - W

For a cyclic process ΔEint = 0
0=Q-W
W=Q
a
Pressure
W = QH + QL
W = |QH| - |QL|
QH
W = Area inside
b TH
d c
Volume TL
QL

Entropy change of a Carnot engine per cycle = 0
QH
Temperature
ΔS = ΔSH + ΔSL a b
TH
TL c
d
Heat is removed QL
Entropy
For a cyclic process ΔS = 0

Heat extracted and delivered per cycle in a Carnot engine
QH
Temperature
a b
TH
QL
TL c
d
Entropy
Since TH > TL, more energy is extracted from the high

temperature reservoir than delivered to the
low-temperature reservoir
TH > T L 🡪 |QH| > |QL|


Thermal efficiency
Thermal efficiency of an engine
Any engine
Thermal efficiency of a Carnot engine
Carnot engine

Another statement for the second law of thermodynamics
Thermal efficiency εC = 1 when TL = 0 K or TH=∞,

of a Carnot engine which are impossible conditions
Second Law of Thermodynamics – in another form
No series of processes are possible whose sole result is the
transfer of energy as heat from thermal reservoir and the
complete conversion of this energy to work.
TH
There are no QH
perfect engines.
Perfect
engine W

Carnot engine and real engines
Thermal efficiency Always less than unity

of a Carnot engine (less than 100%)
No real engine can have efficiency greater than εC.
Real engines have efficiencies less than εC because

the processes that form their cycles are irreversible.
If your car were powered by a Carnot engine, it would have an

efficiency of bout 55%; its actual efficiency is probably about 25%.

Stirling engine
Stirling engine
It is an ideal engine
Pressure
a It has a smaller efficiency than that of a

Carnot engine operating between the
same temperatures.
Q
QH
d
b
QL Q
TH
c TL
Va Vb Volume

Checkpoint 3
Three Carnot engines operates
between
(a) 400 and 500 K
(b) 600 and 800 K
(c) 400 and 600 K
Rank the engines according to their
thermal efficiencies, greatest first.
Solution
(c), then (b), then (a)


Example 3
How much energy |QL| is delivered
Carnot engine as heat to the low-temperature
reservoir every cycle?
TH = 850 K TL = 300 K
W = |QH| - |QL|
W = 1200 J per cycle
|QL| = |QH| - W = 655 J
Each cycle takes 0.25 s
What is the entropy change of the
What is the efficiency of this engine? working substance for the energy
transfer to it from the
high-temperature reservoir ?
What is the average power of
this engine?
What is the entropy change of the
working substance for the energy
How much energy |QH| is extracted
transfer to it from the
as heat from the high-temperature
low-temperature reservoir ?
reservoir every cycle?
🡪

Example 4
Is it possible for an engine operated between the boiling

and freezing points of water to have an efficiency of 75%?
Solution
It is not possible to have efficiency of 75%.


Refrigerator and heat engine diagrams
High-Temperature High-Temperature
reservoir reservoir
TH TH
QH QH
Refrigerator W Heat engine W
QL QL
TL TL
Low-Temperature Low-Temperature
reservoir reservoir

Coefficient of performance
Ideal refrigerator
In an ideal refrigerator, all processes are reversible and no
wasteful energy transfers occur due, say, friction and
turbulence.
We want to extract as much energy |QL| as possible from
the low-temperature reservoir (what we want) for the least
amount of work |W| (what we pay)
Coefficient of
performance
For typical room air conditioner K ≈ 2.5
For typical household refrigerator K ≈ 5

Carnot refrigerator
Carnot refrigerator
A Carnot refrigerator operates in the reverse of the Carnot
engine
W = |QH| - |QL|
of a Carnot refrigerator
The value of KC is higher the closer the temperatures of the
two reservoirs to each other.
For TH > TL, KC > 1.

Perfect refrigerators
TH
Q
A perfect refrigerator transfer
heat Q from a cold reservoir to Perfect
a warm reservoir without the Refrigerator
need for work.
Q
TL

Why perfect refrigerators are impossible?
Why perfect refrigerators are impossible?

Let us assume it is possible to have a perfect refrigerator
Since TH > TL 🡪 ΔS < 0

This violates the second law of thermodynamics. The
change in entropy for the closed system (refrigerator +
reservoirs) can not be negative.
Perfect refrigerators do not exist.
Perfect refrigerators violate the second law of thermodynamics.

Different statements of the second law of thermodynamics
The second law of thermodynamics

closed system
ΔS > 0 irreversible processes
ΔS = 0 reversible processes
Another formulations of the second law of thermodynamics
No series of processes are possible whose
sole result is the transfer of energy as heat There are no
from thermal reservoir and the complete perfect engines.
conversion of this energy to work.
No series of processes are possible whose
sole result is the transfer of energy as heat There are no
from a reservoir at a given temperature to a perfect refrigerators.
reservoir at a higher temperature.

Checkpoint 4
You want to increase the coefficient of performance of an ideal
refrigerator. You do so by
(a) running the cold chamber at slightly higher temperature,
(b) running the cold chamber at slightly lower temperature,
(c) moving the unit to a slightly warmer room, or
(d) moving the unit to a slightly cooler room.
The magnitudes of the temperature changes are to be the same
in all four cases.
Rank the resulting coefficient of performance, greatest first.
Solution
Let the temperature change = dT
1 3
4 2

Entropy and The Second Law of Thermodynamics

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Aljalal-Phys.

20-1 Entropy Objective

The direction of the process is setup by a property called

If an irreversible process occurs in a closed system,

Entropy decreases. Egg

For reversible processes the system is always close to

Water is heated on a stove.

(a), then (b), then (c)

Entropy is a state property.

Free expansion Insulation

Gas Vacuum Gas Gas

We do not know the volume

Since entropy is a state property,

In a free expansion process, Tf = Ti

i We will replace the free expansion

To find the entropy change for an irreversible process occurring

For an ideal gas

For a solid or liquid substance for which the temperature changes by ΔT

For a solid or liquid substance that undergoes phase transition at

For a solid or liquid substance for which the temperature changes by ΔT

For a solid or liquid substance that undergoes phase transition at

Gas Vacuum Gas Gas

What is the change in entropy?

For an ideal gas

What is the change in entropy of the two-block system?

Second Law of Thermodynamics

Processes in which the system’s entropy remains

20-2 Entropy in the Real World: Engines

QL Steam engine Water-gas

TL Car engine Gasoline-air

20-2 Entropy in the Real World: Engines

• Carnot engine is an ideal engine.

Carnot Pronounced “Car-no”

20-2 Entropy in the Real World: Engines

20-2 Entropy in the Real World: Engines

20-2 Entropy in the Real World: Engines

20-2 Entropy in the Real World: Engines

20-2 Entropy in the Real World: Engines

Stroke d 🡪 a adiabatic Piston

20-2 Entropy in the Real World: Engines

20-2 Entropy in the Real World: Engines

First law of Thermodynamics ΔEint = Q - W

20-2 Entropy in the Real World: Engines

20-2 Entropy in the Real World: Engines

Since TH > TL, more energy is extracted from the high

TH > T L 🡪 |QH| > |QL|

20-2 Entropy in the Real World: Engines

Thermal efficiency of an engine

Thermal efficiency of a Carnot engine

20-2 Entropy in the Real World: Engines

Thermal efficiency εC = 1 when TL = 0 K or TH=∞,

20-4 Entropy in the Real World: Engines

Thermal efficiency Always less than unity

No real engine can have efficiency greater than εC.

Real engines have efficiencies less than εC because

If your car were powered by a Carnot engine, it would have an

20-2 Entropy in the Real World: Engines

a It has a smaller efficiency than that of a

20-2 Entropy in the Real World: Engines

(c), then (b), then (a)

20-2 Entropy in the Real World: Engines

20-2 Entropy in the Real World: Engines