19 Fis - Mek Pan - Entropy Thermody II - UAS

9/22/2020
Aljalal-Phys.102-15 Mar 2008-Ch20-page 1
Chapter 20
Entropy
and
the Second Law of Thermodynamics
20-1 Some One-Way Processes Objective

20-2 Change in Entropy
20-3 The Second Law of Thermodynamics
20-4 Entropy in the Real World: Engines
20-5 Entropy in the Real World: Refrigerator
20-1 Some One-Way Processes

Breaking
Egg Egg
Irreversible
process
Ok Wrong way
Why not?
Does not violate conservation of energy!
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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!

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”
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Entropy must not decrease for a process to occur
Entropy decreases. Egg

Process does not occur.
Wrong way

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
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Formula - change of entropy
Change in Final state Heat transfer to
entropy the system
f
For reversible dQ
S = Sf -Si =
processes T
i
Temperature
in kelvin
Initial state
Entropy is measured in J/K
When the change in temperature T is small relative to the initial and final
temperatures (in kelvins) of the process, the entropy change can be approximated as
f f
dQ 1
S = 
i
T

Tavg  dQ
i
Q
S  Average
Tavg temperature

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
Q
(a), then (b), then (c) S 
Tavg
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Entropy is a state property
Entropy is a state property.

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

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
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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.
Isotherm In a free expansion process, Tf = Ti

Pressure
i We will replace the free expansion

process with an isothermal process.
f
Volume

Change in entropy of a free expansion process
f f
dQ 1 Q
S =   dQ 
i
T T i T
V
For isothermal procss, Q = W = nRT ln f
Vi
Vf
S = nR ln Weight
Vi (Lead shot) Piston
Isotherm
Pressure
Insulating
i Gas cylinder
f Thermal
Reservoir
at T
Volume
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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
f
dQ
S = 
i
T

Change in entropy for gas, liquid, and solid
f
dQ
S = 
i
T
For an ideal gas Vf T
S = nR ln + nCv ln f
Vi Ti
For a solid or liquid substance for which the temperature changes by T
(no phase transition) Tf
S = mc ln
Ti
For a solid or liquid substance that undergoes phase transition at
temperature T
Lm
S =
T
Example
Lv m Lv m
liquid to gas S = gas to liquid S = -
T T
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Derivation - change in entropy for an deal gas
Vi Ti
Derivation Eint = Q - W
For small changes dEint = dQ - dW
dQ = dW + dEint
dQ = pdV + nCV dT
f f f
dQ pdV nCV dT
S = =  
i
T i T i
T
pV=nRT
f f f
dQ nRdV nCV dT
S = =  
i
T i
V i
T
Vf T
Vi Ti

Derivation - change in entropy for liquid or solid
For a solid or liquid substance for which the temperature changes by T

(no phase transition) Tf
S = mc ln
Ti
Derivation f f f
dQ mcdT dT
S = = i T = mc i T
i
T
T
S = m c ln f
Ti
For a solid or liquid substance that undergoes phase transition at
temperature T
Lm
S =
T
Derivation f f
dQ 1 Q Lm
S = =  dQ = 
i
T T i
T T
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Example 1
Free expansion
Valve Valve
Gas Vacuum Gas Gas

P=0
Initial Final
one mole of Vf= 2 Vi
nitrogen gas Insulation
What is the change in entropy?

Solution

Vi Ti
For free expansion Tf = Ti
2Vi
S = nR ln = (1 mol)(8.31 J/mol  K) ln 2 = 5.76 J/K
Vi

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
Tf 40+273
SL = mc ln = (1.5kg)(386J/kg  K) ln =-35.86J/K
TLi 20+273
T 40+273
SR = mc ln f = (1.5kg)(386J/kg  K) ln =38.23J/K
TRi 60+273
S = SL + SR = 2.4 J/K
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Checkpoint 2
a T2
Pressure
T2>T1.
For an ideal gas, is the entropy change T2
T1
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
Vf T
Smaller Vi Ti

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
S > 0 irreversible processes
S = 0 reversible processes
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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
TH
QH
Heat engine W
Working substance
QL Steam engine Water-gas
TL Car engine Gasoline-air
Low-Temperature
reservoir
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Ideal engine
Ideal engine
In an ideal engine, all processes are reversible and no
wasteful energy transfer 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”

Carnot engine - starting
Weight
(Lead shot) Piston
Start at state a
Insulating
a cylinder
Gas
Pressure
Thermal
Reservoir
at TH
TH
Volume
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Carnot engine - first stroke
Remove shot slowly

Piston
Stroke a  b isothermal
Insulating
a Gas cylinder
Pressure
Thermal
Reservoir
QH at TH
b TH
Volume

Carnot engine - second stroke
Remove shot slowly Piston
Stroke b  c adiabatic
Insulating
a Gas cylinder
Pressure
Thermal
Reservoir
at TH
b TH
c
Volume
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Carnot engine - third stroke
Put shot slowly 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
Put shot slowly

Piston
Stroke d  a adiabatic
Insulating
a Gas cylinder
Pressure
Thermal
Reservoir
at TL
b TH
d c
TL
Volume
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Entropy change for a Carnot engine
T-S diagram
QH
Temperature
a b
TH
a TL
d c
Pressure
P-V diagram QL
Entropy
QH
b TH
c
d
TL
QL Volume

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

For a cyclic process Eint = 0
0=Q-W
a W=Q
Pressure
W = QH + QL
QH W = Area inside W = |QH| - |QL|
b TH
d c
TL
QL Volume
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Entropy change of a Carnot engine per cycle = 0
QH
Temperature
S SH + SL a b
TH
QH Q
S= - L
TH TL TL
d c
QL
Heat is removed
Entropy
For a cyclic process S 
QH Q
0= - L
TH TL
QH Q
= L
TH TL

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

temperature reservoir than delivered to the low-
temperature reservoir
TH > TL  |QH| > |QL|
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Thermal efficiency
Thermal efficiency of an engine
energy we get |W|

= = Any engine
energy we pay for |QH |
Thermal efficiency of a Carnot engine QH Q

= L
W |QH | - |QL | |Q | TH TL
C =  T
= 1- L = 1- L
|QH | |QH | |QH | TH
TL
 C = 1- Carnot engine
TH

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

of a Carnot engine
 C = 1-
TH 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
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Carnot engine and real engines
Thermal efficiency TL Always less than unity

of a Carnot engine
 C = 1-
TH (less than 100%)
No real engine can have efficiency greater than C.
Real engines have efficiencies less than C 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 S < C
d
b
QL Q
TH
c TL
Va Vb Volume
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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
400
 C =1- =0.2
500
(c), then (b), then (a) 600
 C =1- =0.25
800
400
 C =1- =0.33
600

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
300 transfer to it from the high-
 C =1- = 0.65 = 65% temperature reservoir ?
850
What is the average power of QH 1855 J
SH =  = 2.18 J/K
this engine? TH 850 K
W 1200 J
P= = =4.8KW What is the entropy change of the
t 0.25 s
working substance for the energy
How much energy |QH| is extracted
transfer to it from the low-
as heat from the high-temperature
temperature reservoir ?
reservoir every cycle?
W W 1200 J QL -655 J
=  |QH |= = =1855 J SL =  = -2.18 J/K
|QH|  0.647 TL 300 K
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Example 4
Is it possible for an engine operated between the boiling

and freezing points of water to have an efficiency of 75%?
Solution
TL (0+273)K
 =1- =1- = 0.27=27%
TH (100+273) K
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
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Coefficient of performance
Ideal refrigerator
In an ideal refrigerator, all processes are reversible and no
wasteful energy transfer occur due, say, friction and
turbulence.
Coefficient of performance
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 What we want |QL |
K= =
performance What we pay |W|
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
QH Q
W = |QH| - |QL| = L
TH TL
|QL | |QL | TL
KC =  
|W| |QH|-|QL | TH -TL
TL Coefficient of performance
KC =
TH -TL 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.
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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
Q Q
S= -
TH TL
Since TH > TL  S < 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.
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Different statements of the second law of thermodynamics
The second law of thermodynamics

closed system
S > 0 irreversible processes
S = 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
TL +dT TL
a- KC = 1 c- KC = 3
TH -(TL +dT) TH + dT -TL
TL - dT TL
b- KC = 4 d- KC = 2
TH -(TL - dT) TH - dT -TL
23

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9/22/2020

Aljalal-Phys.102-15 Mar 2008-Ch20-page 1

20-1 Some One-Way Processes Objective

Aljalal-Phys.102-15 Mar 2008-Ch20-page 2

20-1 Some One-Way Processes

Aljalal-Phys.102-15 Mar 2008-Ch20-page 3

20-1 Some One-Way Processes

Aljalal-Phys.102-15 Mar 2008-Ch20-page 4

20-1 Some One-Way Processes

The direction of the process is setup by a property called

If an irreversible process occurs in a closed system,

Aljalal-Phys.102-15 Mar 2008-Ch20-page 5

20-1 Some One-Way Processes

Entropy decreases. Egg

Aljalal-Phys.102-15 Mar 2008-Ch20-page 6

20-1 Some One-Way Processes

For reversible processes the system is always close to

Aljalal-Phys.102-15 Mar 2008-Ch20-page 7

20-2 Change in Entropy

Aljalal-Phys.102-15 Mar 2008-Ch20-page 8

20-2 Change in Entropy

Water is heated on a stove.

Aljalal-Phys.102-15 Mar 2008-Ch20-page 9

20-2 Change in Entropy

Entropy is a state property.

Aljalal-Phys.102-15 Mar 2008-Ch20-page 10

20-2 Change in Entropy

Free expansion Insulation

Gas Vacuum Gas Gas

We do not know the volume

Aljalal-Phys.102-15 Mar 2008-Ch20-page 11

20-2 Change in Entropy

Since entropy is a state property,

Isotherm In a free expansion process, Tf = Ti

i We will replace the free expansion

Aljalal-Phys.102-15 Mar 2008-Ch20-page 12

20-2 Change in Entropy

Aljalal-Phys.102-15 Mar 2008-Ch20-page 13

20-2 Change in Entropy

To find the entropy change for an irreversible process occurring

Aljalal-Phys.102-15 Mar 2008-Ch20-page 14

20-2 Change in Entropy

Aljalal-Phys.102-15 Mar 2008-Ch20-page 15

20-2 Change in Entropy

Aljalal-Phys.102-15 Mar 2008-Ch20-page 16

20-2 Change in Entropy

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

Aljalal-Phys.102-15 Mar 2008-Ch20-page 17

20-2 Change in Entropy

Gas Vacuum Gas Gas

What is the change in entropy?

For an ideal gas Vf T

Aljalal-Phys.102-15 Mar 2008-Ch20-page 18

20-2 Change in Entropy

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

Aljalal-Phys.102-15 Mar 2008-Ch20-page 19

20-2 Change in Entropy

Aljalal-Phys.102-15 Mar 2008-Ch20-page 20

20-3 The Second Law of Thermodynamics

Second Law of Thermodynamics

Aljalal-Phys.102-15 Mar 2008-Ch20-page 21

20-3 The Second Law of Thermodynamics