Ch.

19 The Second Law of

Thermodynamics

• The second law of thermodynamics, which limits our ability to

extract useful work from thermal energy.
• Thermodynamics of heat engines, refrigerators, and heat pumps
– calculation of efficiency
• Energy quality and entropy
Reversibility and Irreversibility

Reversible: Bouncing ball Irreversible: Heating by friction

• Contacting hot water with cold water cannot be reversed

• Organized states (rare) → disorganized state (common)
• It is very unlikely to assume “spontaneously” a more organized
state.
• Irreversibility is a probabilistic notion: Events that could occur
without violating the principles of Newtonian physics
nevertheless don’t occur because they’re too improbable.
Reversibility and Irreversibility

Reversible: Bouncing ball Irreversible: Heating by friction

• Contacting hot water with cold water cannot be reversed

• Organized states (rare) → disorganized state (common)
• It is very unlikely to assume “spontaneously” a more organized
state.
• Irreversibility is a probabilistic notion: Events that could occur
without violating the principles of Newtonian physics
nevertheless don’t occur because they’re too improbable.
Reversibility and Irreversibility

Reversible: Bouncing ball Irreversible: Heating by friction

• Contacting hot water with cold water cannot be reversed

• Organized states (rare) → disorganized state (common)
• It is very unlikely to assume “spontaneously” a more organized
state.
• Irreversibility is a probabilistic notion: Events that could occur
without violating the principles of Newtonian physics
nevertheless don’t occur because they’re too improbable.
Got it? 19.1

• Which of these processes is irreversible?

(a) stirring sugar into coffee
(b) building a house
(c) demolishing a house with a wrecking ball
(d) demolishing a house by taking it apart piece by piece
(e) harnessing the energy of falling water to drive machinery
(f) harnessing the energy of falling water to heat a house
Got it? 19.1

• Which of these processes is irreversible?

(a) stirring sugar into coffee
(b) building a house
(c) demolishing a house with a wrecking ball
(d) demolishing a house by taking it apart piece by piece
(e) harnessing the energy of falling water to drive machinery
(f) harnessing the energy of falling water to heat a house
The 2nd law of thermodynamics
“Systems naturally tend toward more disorganized states”
The 2nd law of thermodynamics
“Systems naturally tend toward more disorganized states”
(Applied to heat engines, the Kelvin-Planck statement of the second law says )
“It is impossible to construct a heat engine operating in a cycle
that extracts heat from a reservoir and delivers an equal
amount of work.”
The 2nd law of thermodynamics
“Systems naturally tend toward more disorganized states”
(Applied to heat engines, the Kelvin-Planck statement of the second law says )
“It is impossible to construct a heat engine operating in a cycle
that extracts heat from a reservoir and delivers an equal
amount of work.”
The heat engine efficiency

The 2nd law of thermodynamics

in energy flow diagram

• The 2nd law of thermodynamics states that it is not possible to

draw all internal energy out and turn into work
• The perfect engine is not possible! Then how close can we make?
 The heat engine efficiency

The 2nd law of thermodynamics

in energy flow diagram

• The 2nd law of thermodynamics states that it is not possible to

draw all internal energy out and turn into work
• The perfect engine is not possible! Then how close can we make?
𝑊 𝑄ℎ − 𝑄𝑐 𝑄𝑐 𝑊: work done by the engine
Efficiency of engine 𝑒 = = =1− 𝑄ℎ : heat extracted from high T
𝑄ℎ 𝑄ℎ 𝑄ℎ
𝑄𝑐 : heat rejected to low T
 The heat engine efficiency

The 2nd law of thermodynamics

in energy flow diagram

𝑄ℎ = heat added to the system

𝑄𝑐 = heat taken from the system

Δ𝐸𝑖𝑛𝑡 = 𝑄 + 𝑊
𝑸𝒉 ↔ 𝑸, 𝑸𝒄 ↔ −𝑸

• The 2nd law of thermodynamics states that it is not possible to

draw all internal energy out and turn into work
• The perfect engine is not possible! Then how close can we make?
𝑊 𝑄ℎ − 𝑄𝑐 𝑄𝑐 𝑊: work done by the engine
Efficiency of engine 𝑒 = = =1− 𝑄ℎ : heat extracted from high T
𝑄ℎ 𝑄ℎ 𝑄ℎ
𝑄𝑐 : heat rejected to low T
 The Carnot engine
• Two adiabatic + two isothermal steps (Carnot cycle).
• A reversible engine ( thermodynamic equilibrium is maintained)
• Ideal gas is the working fluid
• The most efficient engine operating between the two temperatures

cf. diesel
cycle
The efficiency of the Carnot engine
𝑉𝐵
𝑄ℎ = 𝑛𝑅𝑇ℎ ln cf. Δ𝐸𝑖𝑛𝑡 = 𝑄 + 𝑊 = 0
𝑉𝐴

𝑸𝒉

𝑸𝒄
 Recall: Isothermal processes: constant T

• One way to achieve this is to keep the system

in thermal contact with a heat reservoir*.
*Reservoir: a much larger system held at constant temperature

• Work done:
𝑉2 𝑉2
𝑑𝑉 𝑉2
𝑊 = − න 𝑝𝑑𝑉 = −𝑛𝑅𝑇 න = −𝑛𝑅𝑇 ln
𝑉1 𝑉1 𝑉 𝑉1

1 2 3
• 1st law recall. 𝑚 𝑣ҧ = 2 𝑘𝑇
2

Constant temperature ➔ ∆𝑬𝒊𝒏𝒕 = 𝟎

𝑉2
𝑄 = −𝑊 = 𝑛𝑅𝑇 ln
𝑉1
The efficiency of the Carnot engine
𝑉𝐵
𝑄ℎ = 𝑛𝑅𝑇ℎ ln cf. Δ𝐸𝑖𝑛𝑡 = 𝑄 + 𝑊 = 0
𝑉𝐴

𝑸𝒉 note for the sign

𝑉𝐷 𝑉𝐶
𝑄𝑐 = −𝑛𝑅𝑇𝑐 ln = 𝑛𝑅𝑇𝑐 ln
𝑉𝐶 𝑉𝐷
𝑸𝒄
𝑄𝑐 𝑇𝑐 ln(𝑉𝐶 /𝑉𝐷 )
=
𝑄ℎ 𝑇ℎ ln(𝑉𝐵 /𝑉𝐴 )
The efficiency of the Carnot engine
𝑉𝐵
𝑄ℎ = 𝑛𝑅𝑇ℎ ln cf. Δ𝐸𝑖𝑛𝑡 = 𝑄 + 𝑊 = 0
𝑉𝐴

𝑸𝒉 note for the sign

𝑉𝐷 𝑉𝐶
𝑄𝑐 = −𝑛𝑅𝑇𝑐 ln = 𝑛𝑅𝑇𝑐 ln
𝑉𝐶 𝑉𝐷
𝑸𝒄
𝑄𝑐 𝑇𝑐 ln(𝑉𝐶 /𝑉𝐷 )
=
𝑄ℎ 𝑇ℎ ln(𝑉𝐵 /𝑉𝐴 )

BC and DA :adiabatic processes 𝑇ℎ 𝑉𝐵 𝛾−1 = 𝑇𝑐 𝑉𝐶 𝛾−1 , 𝑇ℎ 𝑉𝐴 𝛾−1 = 𝑇𝑐 𝑉𝐷 𝛾−1

𝛾−1 𝛾−1
𝑉𝐵 𝑉𝐶 𝑉𝐵 𝑉𝐶 𝑄𝑐 𝑇𝑐 ln(𝑉𝐶 /𝑉𝐷 ) 𝑇𝑐
= = = =
𝑉𝐴 𝑉𝐷 𝑉𝐴 𝑉𝐷 𝑄ℎ 𝑇ℎ ln(𝑉𝐵 /𝑉𝐴 ) 𝑇ℎ
The efficiency of the Carnot engine
𝑉𝐵
𝑄ℎ = 𝑛𝑅𝑇ℎ ln cf. Δ𝐸𝑖𝑛𝑡 = 𝑄 + 𝑊 = 0
𝑉𝐴

𝑸𝒉 note for the sign

𝑉𝐷 𝑉𝐶
𝑄𝑐 = −𝑛𝑅𝑇𝑐 ln = 𝑛𝑅𝑇𝑐 ln
𝑉𝐶 𝑉𝐷
𝑸𝒄
𝑄𝑐 𝑇𝑐 ln(𝑉𝐶 /𝑉𝐷 )
=
𝑄ℎ 𝑇ℎ ln(𝑉𝐵 /𝑉𝐴 )

BC and DA :adiabatic processes 𝑇ℎ 𝑉𝐵 𝛾−1 = 𝑇𝑐 𝑉𝐶 𝛾−1 , 𝑇ℎ 𝑉𝐴 𝛾−1 = 𝑇𝑐 𝑉𝐷 𝛾−1

𝛾−1 𝛾−1
𝑉𝐵 𝑉𝐶 𝑉𝐵 𝑉𝐶 𝑄𝑐 𝑇𝑐 ln(𝑉𝐶 /𝑉𝐷 ) 𝑇𝑐
= = = =
𝑉𝐴 𝑉𝐷 𝑉𝐴 𝑉𝐷 𝑄ℎ 𝑇ℎ ln(𝑉𝐵 /𝑉𝐴 ) 𝑇ℎ

𝑄𝑐 𝑇𝑐
𝑒Carnot =1− =1−
𝑄ℎ 𝑇ℎ
Recall: Cyclic process for diesel engine

The work done (by the system) and heat absorbed during each of the four processes

1 → 2 (adiabatic) 𝑊12 = (𝑝1 𝑉1 − 𝑝2 𝑉2 )/(𝛾 − 1), 𝑄12 = 0 Work done on the system

2 → 3 (isobaric) 𝑊23 = 𝑝2 (𝑉3 − 𝑉2 ), 𝑄23 = 𝑛𝐶𝑝 (𝑇3 − 𝑇2 ) ≡ 𝑄ℎ 𝑝2 𝑉2 − 𝑝1 𝑉1

𝑊=
𝛾−1
3 → 4 (adiabatic) 𝑊34 = (𝑝3 𝑉3 − 𝑝4 𝑉4 )/(𝛾 − 1), 𝑄34 = 0
4 → 1 (isovolumic) 𝑊41 = 0, 𝑄41 = 𝑛𝐶𝑉 (𝑇1 − 𝑇4 ) ≡ −𝑄𝑐

For the whole cycle, the work done

𝑝1 𝑉1 − 𝑝2 𝑉2 + 𝑝3 𝑉3 − 𝑝4 𝑉4 𝛾(𝑝3 𝑉3 − 𝑝2 𝑉2 ) − 𝑝4 𝑉4 + 𝑝1 𝑉1
𝑊= + 𝑝3 𝑉3 − 𝑝2 𝑉2 =
(𝛾 − 1) (𝛾 − 1)
 The 2nd law of thermodynamics
Clausius statement: It is impossible to construct a refrigerator
operating in a cycle whose sole effect is to transfer heat from a
cooler object to a hotter one.

Perfect refrigerator
 The 2nd law of thermodynamics
Clausius statement: It is impossible to construct a refrigerator
operating in a cycle whose sole effect is to transfer heat from a
cooler object to a hotter one.
Heat can never pass from a colder to a warmer body without some other change,
connected therewith, occurring at the same time.
(from Wikipedia, [Link]

Perfect refrigerator
 The 2nd law of thermodynamics
Clausius statement: It is impossible to construct a refrigerator
operating in a cycle whose sole effect is to transfer heat from a
cooler object to a hotter one.
Heat can never pass from a colder to a warmer body without some other change,
connected therewith, occurring at the same time.
(from Wikipedia, [Link]

Real refrigerator Perfect refrigerator

 The 2nd law of thermodynamics
Clausius statement: It is impossible to construct a refrigerator
operating in a cycle whose sole effect is to transfer heat from a
cooler object to a hotter one.
Suppose the Clausius statement were
false. Then we could build …

100% engine
60% engine Perfect heat engine???
reversed
 The 2nd law of thermodynamics
Clausius statement: It is impossible to construct a refrigerator
operating in a cycle whose sole effect is to transfer heat from a
cooler object to a hotter one.
Suppose the Clausius statement were Then, perfect heat engine is possible
false. Then we could build …

100% engine
60% engine Perfect heat engine???
reversed
Carnot’s theorem

𝑊 𝑄𝑐 𝑇𝑐
𝑒= =1− ≤ 𝑒Carnot = 1 −
𝑄ℎ 𝑄ℎ 𝑇ℎ

• All Carnot engines operating between temperature 𝑇ℎ and 𝑇𝑐 have the same
efficiency
• No other engine operating between the same two temperatures can be more
efficient than the Carnot engine
Carnot’s theorem

𝑊 𝑄𝑐 𝑇𝑐
𝑒= =1− ≤ 𝑒Carnot = 1 −
𝑄ℎ 𝑄ℎ 𝑇ℎ

• All Carnot engines operating between temperature 𝑇ℎ and 𝑇𝑐 have the same
efficiency
• No other engine operating between the same two temperatures can be more
efficient than the Carnot engine
Carnot’s theorem

𝑊 𝑄𝑐 𝑇𝑐
𝑒= =1− ≤ 𝑒Carnot = 1 −
𝑄ℎ 𝑄ℎ 𝑇ℎ

• All Carnot engines operating between temperature 𝑇ℎ and 𝑇𝑐 have the same
efficiency
• No other engine operating between the same two temperatures can be more
efficient than the Carnot engine
• Carnot efficiency = thermodynamic efficiency
 Limitations on heat engines

• The second law limitations on efficiency show that we can’t

convert thermal energy to mechanical work with 100% efficiency.
– The efficiency depends on the highest and lowest available
temperatures:
• The former is set by the limitations of materials.
• The latter is, at minimum, the temperature of the ambient
environment.
– Technologies affected include
• Electric power plants
• Gasoline engines
• Jet aircraft engines
 Limitations on heat engines

• The second law limitations on efficiency show that we can’t

convert thermal energy to mechanical work with 100% efficiency.
– The efficiency depends on the highest and lowest available
temperatures:
• The former is set by the limitations of materials.
• The latter is, at minimum, the temperature of the ambient
environment.
– Technologies affected include
• Electric power plants
• Gasoline engines
• Jet aircraft engines
 Limitations on heat engines

• The second law limitations on efficiency show that we can’t

convert thermal energy to mechanical work with 100% efficiency.
– The efficiency depends on the highest and lowest available
temperatures:
• The former is set by the limitations of materials.
• The latter is, at minimum, the temperature of the ambient
environment.
– Technologies affected include
• Electric power plants
• Gasoline engines
• Jet aircraft engines
Limitations on heat engines

Schematic diagram of an electric power plant

𝑸𝒉 →
𝑾→

→ 𝑸𝒄
 Limitations on heat engines

Maximum 𝑇ℎ : fossil-fuel plant ∼ 650 K (376.85°𝐶),

nuclear plant ∼ 570 K (296.85°𝐶)

Minimum 𝑇𝑐 : Cooling water ∼ 310 K (36.85°𝐶)

310𝐾 310𝐾
𝑒fossil =1− = 52%, 𝑒nuclear =1− = 46%
650𝐾 570𝐾

In reality, the efficiency is lower than ideal Carnot engine efficiency.

Fossil plant has ∼ 40%, and nuclear plant has ∼ 34% efficiency.
* Car engines have ∼ 25-40% efficiency.
 Limitations on heat engines

Maximum 𝑇ℎ : fossil-fuel plant ∼ 650 K (376.85°𝐶),

nuclear plant ∼ 570 K (296.85°𝐶)

Minimum 𝑇𝑐 : Cooling water ∼ 310 K (36.85°𝐶)

310𝐾 310𝐾
𝑒fossil =1− = 52%, 𝑒nuclear =1− = 46%
650𝐾 570𝐾

In reality, the efficiency is lower than ideal Carnot engine efficiency.

Fossil plant has ∼ 40%, and nuclear plant has ∼ 34% efficiency.
* Car engines have ∼ 25-40% efficiency.
 Example 19.2 A combined-cycle power plant
The gas turbine in a combined-cycle power plant operates at 1450°𝐶. Its waste heat
at 500°𝐶 is the input for a conventional steam cycle, with its average condenser
temperature at 40°𝐶. Find the thermodynamic efficiency of the combined cycle, and
compare with the efficiencies of the individual components if they were operated
independently.
 Example 19.2 A combined-cycle power plant
The gas turbine in a combined-cycle power plant operates at 1450°𝐶. Its waste heat
at 500°𝐶 is the input for a conventional steam cycle, with its average condenser
temperature at 40°𝐶. Find the thermodynamic efficiency of the combined cycle, and
compare with the efficiencies of the individual components if they were operated
independently.
 Example 19.2 A combined-cycle power plant

Gas turbine not efficient

because exhaust also hot.

773
𝑒gas = 1 − = 55%
1723
 Example 19.2 A combined-cycle power plant

Gas turbine not efficient

because exhaust also hot.

773
𝑒gas = 1 − = 55%
1723

281
𝑒steam = 1 − = 64%
773
 Example 19.2 A combined-cycle power plant

Gas turbine not efficient

because exhaust also hot.
𝑊1 + 𝑊2 𝑄ℎ − 𝑄𝑖 + 𝑂𝑖 − 𝑄𝑐
𝑒= =
𝑄ℎ 𝑄ℎ

𝑄𝑐 𝑇𝑐
773 =1− =1−
𝑄ℎ 𝑇ℎ
𝑒gas =1− = 55%
1723

281
𝑒steam = 1 − = 64%
773
 Example 19.2 A combined-cycle power plant

Gas turbine not efficient

because exhaust also hot.
𝑊1 + 𝑊2 𝑄ℎ − 𝑄𝑖 + 𝑂𝑖 − 𝑄𝑐
𝑒= =
𝑄ℎ 𝑄ℎ

𝑄𝑐 𝑇𝑐
773 =1− =1−
𝑄ℎ 𝑇ℎ
𝑒gas =1− = 55%
1723

281
281 𝑒combined = 1 − = 84%
𝑒steam = 1 − = 64% 1723
773

Modern combined-cycle power plants achieve efficiencies approaching 60%

by combining a conventional steam system.
Refreshment
Refreshment

According to the US Department of Energy’s Office of Energy

Efficiency and Renewable Energy, “EVs convert about 59%–62% of
the electrical energy from the grid to power at the wheels.
Conventional gasoline vehicles only convert about 17%–21% of the
energy stored in gasoline to power at the wheels.”
- Evs efficiency: ~ 60% (from the grid energy to power at the wheels)
(The efficiency of an electric motor is typically between 85% and 90%.)
- Combined-cycle power plant efficiency: 60%
- Average loss in electric power transmission and distribution: 8%
Refreshment

According to the US Department of Energy’s Office of Energy

Efficiency and Renewable Energy, “EVs convert about 59%–62% of
the electrical energy from the grid to power at the wheels.
Conventional gasoline vehicles only convert about 17%–21% of the
energy stored in gasoline to power at the wheels.”
- Evs efficiency: ~ 60% (from the grid energy to power at the wheels)
(The efficiency of an electric motor is typically between 85% and 90%.)
- Combined-cycle power plant efficiency: 60%
- Average loss in electric power transmission and distribution: 8%
 Refreshment

According to the US Department of Energy’s Office of Energy

Efficiency and Renewable Energy, “EVs convert about 59%–62% of
the electrical energy from the grid to power at the wheels.
Conventional gasoline vehicles only convert about 17%–21% of the
energy stored in gasoline to power at the wheels.”
- Evs efficiency: ~ 60% (from the grid energy to power at the wheels)
(The efficiency of an electric motor is typically between 85% and 90%.)
- Combined-cycle power plant efficiency: 60%
- Average loss in electric power transmission and distribution: 8%

Total efficiency (from power plant to the wheel) of EVs : 0.6 x (1-0.08) x 0.6 ➔ ~ 33%
Refrigerators and heat pumps

The coefficient of performance describes the relative amount of work

needed for heat pump
What we want
COP =
What we put in
Refrigerators and heat pumps

The coefficient of performance describes the relative amount of work

needed for heat pump
What we want
COP =
What we put in
– For a summer heat pump, “what we want” is
cooling: Carnot(max) efficiency
↓
𝑄c 𝑄c 𝑇c
COPrefrigerator = = =
W 𝑄h − 𝑄c 𝑇h − 𝑇c

– For a winter heat pump, “what we want” is

heating:

– The larger the temperature difference, the lower

the COP and the more work that’s needed.
Refrigerators and heat pumps

The coefficient of performance describes the relative amount of work

needed for heat pump
What we want
COP =
What we put in
– For a summer heat pump, “what we want” is
cooling: Carnot(max) efficiency
↓
𝑄c 𝑄c 𝑇c
COPrefrigerator = = =
W 𝑄h − 𝑄c 𝑇h − 𝑇c

– For a winter heat pump, “what we want” is

heating: Carnot(max) efficiency
↓
𝑄h 𝑄h 𝑇h
COPheat pump = = =
W 𝑄h − 𝑄c 𝑇h − 𝑇c

– The larger the temperature difference, the lower

the COP and the more work that’s needed.
Refrigerators and heat pumps

The coefficient of performance describes the relative amount of work

needed for heat pump
What we want
COP =
What we put in
– For a summer heat pump, “what we want” is
cooling: Carnot(max) efficiency
↓
𝑄c 𝑄c 𝑇c
COPrefrigerator = = =
W 𝑄h − 𝑄c 𝑇h − 𝑇c

– For a winter heat pump, “what we want” is

heating: Carnot(max) efficiency
↓
𝑄h 𝑄h 𝑇h
COPheat pump = = =
W 𝑄h − 𝑄c 𝑇h − 𝑇c

– The larger the temperature difference, the lower

the COP and the more work that’s needed.
Energy quality

E1 E2

E1+E2
Energy quality (≈ versatility)

Mechanical Energy, 𝑊 Thermal Energy, 𝑄

𝐸 = 100𝐽 𝐸 = 100𝐽

High Energy Quality Low Energy Quality

Low disorder High disorder

Low entropy High entropy

Energy quality (≈ versatility)

Mechanical Energy, 𝑊 Thermal Energy, 𝑄

𝐸 = 100𝐽 𝐸 = 100𝐽

High Energy Quality Low Energy Quality

Low disorder High disorder

Low entropy High entropy

Entropy, 𝑺

𝑻𝒉 𝑻𝒄 𝑻𝒊𝒏𝒕
Entropy, 𝑺

𝑻𝒉 𝑻𝒄 𝑻𝒊𝒏𝒕
Entropy, 𝑺

𝑻𝒉 𝑻𝒄 𝑻𝒊𝒏𝒕
𝐸before = 𝐸after

𝑊before > 𝑊after ≈ 0

Entropy, 𝑺

𝑻𝒉 𝑻𝒄 𝑻𝒊𝒏𝒕
𝐸before = 𝐸after

𝑊before > 𝑊after ≈ 0

Entropy, 𝑺

• “A quantitative measure of energy quality”

• Formally, 𝑆 describes the degree of disorder in a system.
• Mathematically, the change in entropy Δ𝑆 associated with a
thermodynamic process between states 1 and 2 is given by
(to be seen below)

2
𝑑𝑄
Δ𝑆 = න
1 𝑇

Unit: 𝐽/𝐾

• Entropy is a function of state

(state variable) like 𝑇 or 𝑝
Carnot cycle

𝑊 𝑄𝑐 𝑇𝑐 𝑄𝑐 𝑇𝑐
𝑒= =1− ≤ 𝑒Carnot = 1 − =
𝑄ℎ 𝑄ℎ 𝑇ℎ 𝑄ℎ 𝑇ℎ

Qh

Qc
Carnot cycle

𝑊 𝑄𝑐 𝑇𝑐 𝑄𝑐 𝑇𝑐
𝑒= =1− ≤ 𝑒Carnot = 1 − =
𝑄ℎ 𝑄ℎ 𝑇ℎ 𝑄ℎ 𝑇ℎ

From the derivation of Carnot engine efficiency

The heat rejected The heat added
Qh from the system
𝑄𝑐 𝑄ℎ to the system
=
𝑇𝑐 𝑇ℎ

Qc
Carnot cycle

𝑊 𝑄𝑐 𝑇𝑐 𝑄𝑐 𝑇𝑐
𝑒= =1− ≤ 𝑒Carnot = 1 − =
𝑄ℎ 𝑄ℎ 𝑇ℎ 𝑄ℎ 𝑇ℎ

From the derivation of Carnot engine efficiency

The heat rejected The heat added
Qh from the system
𝑄𝑐 𝑄ℎ to the system
=
𝑇𝑐 𝑇ℎ
If we define 𝑄 as
𝑄𝑐 → −𝑄𝑐 the heat added
to the system
W

Qc
Carnot cycle

𝑊 𝑄𝑐 𝑇𝑐 𝑄𝑐 𝑇𝑐
𝑒= =1− ≤ 𝑒Carnot = 1 − =
𝑄ℎ 𝑄ℎ 𝑇ℎ 𝑄ℎ 𝑇ℎ

From the derivation of Carnot engine efficiency

The heat rejected The heat added
Qh from the system
𝑄𝑐 𝑄ℎ to the system
=
𝑇𝑐 𝑇ℎ
If we define 𝑄 as
𝑄𝑐 → −𝑄𝑐 the heat added
to the system
W
𝑄𝑐 𝑄ℎ
+ =0
𝑇𝑐 𝑇ℎ

Qc
Carnot cycle

𝑊 𝑄𝑐 𝑇𝑐 𝑄𝑐 𝑇𝑐
𝑒= =1− ≤ 𝑒Carnot = 1 − =
𝑄ℎ 𝑄ℎ 𝑇ℎ 𝑄ℎ 𝑇ℎ

From the derivation of Carnot engine efficiency

The heat rejected The heat added
Qh from the system
𝑄𝑐 𝑄ℎ to the system
=
𝑇𝑐 𝑇ℎ
If we define 𝑄 as
𝑄𝑐 → −𝑄𝑐 the heat added
to the system
W
𝑄𝑐 𝑄ℎ
+ =0
𝑇𝑐 𝑇ℎ

𝑑𝑄 𝑄𝑐 𝑄ℎ
Qc ∆𝑆 = ර = + =0
𝑇 𝑇𝑐 𝑇ℎ
Carnot cycle
Carnot cycle

𝑊 𝑄𝑐 𝑇𝑐 𝑄𝑐 𝑇𝑐
𝑒= =1− ≤ 𝑒Carnot = 1 − =
𝑄ℎ 𝑄ℎ 𝑇ℎ 𝑄ℎ 𝑇ℎ

From the derivation of Carnot engine efficiency

The heat rejected The heat added
Qh from the system
𝑄𝑐 𝑄ℎ to the system
=
𝑇𝑐 𝑇ℎ
If we define 𝑄 as
𝑄𝑐 → −𝑄𝑐 the heat added
to the system
W
𝑄𝑐 𝑄ℎ
+ =0
𝑇𝑐 𝑇ℎ

𝑑𝑄 𝑄𝑐 𝑄ℎ
Qc ∆𝑆 = ර = + =0
𝑇 𝑇𝑐 𝑇ℎ
Carnot cycle

[𝑆 is a state variable!]
Entropy change of reversible cycle

Note: Entropy change

2
𝑑𝑄
∆𝑆12 =න
1 𝑇

cf. heat transfer occurs only during

the isothermal steps
Entropy change of reversible cycle

Note: Entropy change

2
𝑑𝑄
∆𝑆12 =න
1 𝑇

Any reversible cycle :

𝑑𝑄
ර =0
𝑇

𝐵
c.f. ‫𝐹 ׯ‬Ԧ ∙ 𝑑 𝑟Ԧ = 0 for conservative force, Δ𝑈𝐴𝐵 = − ‫𝐹 𝐴׬‬Ԧ ∙ 𝑑𝑟Ԧ
 Entropy change of reversible cycle

Note: Entropy change

2
𝑑𝑄
∆𝑆12 =න
1 𝑇

Any reversible cycle :

𝑑𝑄
ර =0
𝑇

𝐵
c.f. ‫𝐹 ׯ‬Ԧ ∙ 𝑑 𝑟Ԧ = 0 for conservative force, Δ𝑈𝐴𝐵 = − ‫𝐹 𝐴׬‬Ԧ ∙ 𝑑𝑟Ԧ

• Entropy is a state variable: entropy change of irreversible process can

be calculated using reversible process that goes between two states.
Adiabatic free expansion

• Insulated box: No heat flow ➔ adiabatic

• But it is irreversible process.
(not exact adiabatic process in chapter 18.)
𝑉1

𝑉2
Adiabatic free expansion

• Insulated box: No heat flow ➔ adiabatic

• But it is irreversible process.
(not exact adiabatic process in chapter 18.)
𝑉1
• The vacuum doesn’t exert pressure to
oppose the gas. (No work done by the gas)
No change of internal energy

𝑉2
Adiabatic free expansion

• Insulated box: No heat flow ➔ adiabatic

• But it is irreversible process.
(not exact adiabatic process in chapter 18.)
𝑉1
• The vacuum doesn’t exert pressure to
oppose the gas. (No work done by the gas)
No change of internal energy

How about the change of entropy?

𝑉2

⇒ Same amount of internal energy, but different quality

 Adiabatic free expansion

Entropy is a thermodynamic state variable.

➔ A reversible process that takes the gas
between the same two states results in the
same entropy change.

Irreversible,
free expansion
Δ𝑆 > 0
No work done
 Adiabatic free expansion

Entropy is a thermodynamic state variable.

➔ A reversible process that takes the gas
between the same two states results in the
same entropy change.

Irreversible,
free expansion
Δ𝑆 > 0
No work done Isothermal expansion
𝑄 = −𝑊
Different process, but same initial and final state
 Adiabatic free expansion

Entropy is a thermodynamic state variable.

➔ A reversible process that takes the gas
between the same two states results in the
same entropy change.

Isothermal expansion (no 𝑇 change)

𝑉2
𝑄 = −𝑊 = 𝑛𝑅𝑇 ln
𝑉1

Irreversible,
free expansion
𝑑𝑄 1 𝑄 𝑉2
Δ𝑆 = න = න𝑑𝑄 = = 𝑛𝑅 ln >0
Δ𝑆 > 0 𝑇 𝑇 𝑇 𝑉1
No work done Isothermal expansion
𝑄 = −𝑊
Different process, but same initial and final state
Entropy and the availability of work
work done by the system
↓
𝑉2 𝑑𝑄 1 𝑄 𝑉2
𝑊 = 𝑄 = 𝑛𝑅𝑇 ln Δ𝑆 = න = න𝑑𝑄 = = 𝑛𝑅 ln
𝑉1 𝑇 𝑇 𝑇 𝑉1

After the irreversible free expansion, the gas can no longer do the
work done by isothermal expansion, even though its internal
energy is unchanged.
Entropy and the availability of work
work done by the system
↓
𝑉2 𝑑𝑄 1 𝑄 𝑉2
𝑊 = 𝑄 = 𝑛𝑅𝑇 ln Δ𝑆 = න = න𝑑𝑄 = = 𝑛𝑅 ln
𝑉1 𝑇 𝑇 𝑇 𝑉1

After the irreversible free expansion, the gas can no longer do the
work done by isothermal expansion, even though its internal
energy is unchanged.

By comparing 𝑊 and Δ𝑆 shown above,

During an irreversible process (Δ𝑆 increase)

→ The energy becomes unavailable to work is

𝐸unavailable = 𝑇min Δ𝑆

where 𝑇min is the lowest temperature available to the system.

Example 19.4 The loss of energy quality
2.0-L cylinder contains 5.0 mol of compressed gas at 300 K.
If the cylinder is discharged into a 150-L vacuum chamber and its temperature
remains at 300 K, how much energy has become unavailable to do work?
Example 19.4 The loss of energy quality
2.0-L cylinder contains 5.0 mol of compressed gas at 300 K.
If the cylinder is discharged into a 150-L vacuum chamber and its temperature
remains at 300 K, how much energy has become unavailable to do work?
Isothermal free expansion:
𝑑𝑄 1 𝑄 𝑉2
Δ𝑆 = න = න𝑑𝑄 = = 𝑛𝑅 ln
𝑇 𝑇 𝑇 𝑉1
Example 19.4 The loss of energy quality
2.0-L cylinder contains 5.0 mol of compressed gas at 300 K.
If the cylinder is discharged into a 150-L vacuum chamber and its temperature
remains at 300 K, how much energy has become unavailable to do work?
Isothermal free expansion:
𝑑𝑄 1 𝑄 𝑉2
Δ𝑆 = න = න𝑑𝑄 = = 𝑛𝑅 ln
𝑇 𝑇 𝑇 𝑉1

Δ𝑆 ∼ energy quality:

𝐸 = 𝑇min ΔS
Evaluate
V 
Eunavailable = Tmin S = Tmin nR ln  2 
 V1 
 152 L 
= ( 300 K )( 5.0 mol )( 8.314 J / K  mol ) ln  
 2.0 L 
= 54kJ
Entropy S: irreversible heat transfer

Irreversible mixing of hot and cold water

T2
⇓
To compute Δ𝑆, use a reversible process

1. Slowly/reversibly cooling or heating

T1 each water to 𝑇1 → 𝑇𝑓 and 𝑇2 → 𝑇𝑓
2. Then, directly mix them.
Entropy S: irreversible heat transfer

Irreversible mixing of hot and cold water

T2
⇓
To compute Δ𝑆, use a reversible process

1. Slowly/reversibly cooling or heating

T1 each water to 𝑇1 → 𝑇𝑓 and 𝑇2 → 𝑇𝑓
2. Then, directly mix them.
Entropy S: irreversible heat transfer

T2

T1

2
𝑑𝑄
Δ𝑆 = න 𝑑𝑄 = 𝑚𝑐𝑑𝑇
1 𝑇
Entropy S: irreversible heat transfer

𝑇𝑓 𝑇𝑓
𝑑𝑄1 𝑑𝑄2
Δ𝑆 = න +න
T2 𝑇 𝑇
𝑇1 𝑇2
𝑇𝑓 𝑇𝑓
𝑚1 𝑐1 𝑑𝑇 𝑚2 𝑐2 𝑑𝑇
= න +න
𝑇 𝑇
𝑇1 𝑇2
T1
𝑇𝑓 𝑇𝑓
= 𝑚1 𝑐1 ln + 𝑚2 𝑐2 ln
2
𝑑𝑄 𝑇1 𝑇2
Δ𝑆 = න 𝑑𝑄 = 𝑚𝑐𝑑𝑇
1 𝑇
 Entropy S: irreversible heat transfer

𝑇𝑓 𝑇𝑓
𝑑𝑄1 𝑑𝑄2
Δ𝑆 = න +න
T2 𝑇 𝑇
𝑇1 𝑇2
𝑇𝑓 𝑇𝑓
𝑚1 𝑐1 𝑑𝑇 𝑚2 𝑐2 𝑑𝑇
= න +න
𝑇 𝑇
𝑇1 𝑇2
T1
𝑇𝑓 𝑇𝑓
= 𝑚1 𝑐1 ln + 𝑚2 𝑐2 ln
𝑑𝑄2 𝑇1 𝑇2
Δ𝑆 = න 𝑑𝑄 = 𝑚𝑐𝑑𝑇
1 𝑇
Example: m1=25 kg, c1=4.2 kJ/kg K , T1= 95°C
→ Tf = 60°C
m2=35 kg, c2=4.2 kJ/kg K , T2= 35°C
333 333
Δ𝑆 = 25 ∙ 4200 ∙ ln + 35 ∙ 4200 ∙ ln = 978.5 𝐽/𝐾
368 308
 Entropy S: irreversible heat transfer

𝑇𝑓 𝑇𝑓
𝑑𝑄1 𝑑𝑄2
Δ𝑆 = න +න
T2 𝑇 𝑇
𝑇1 𝑇2
𝑇𝑓 𝑇𝑓
𝑚1 𝑐1 𝑑𝑇 𝑚2 𝑐2 𝑑𝑇
= න +න
𝑇 𝑇
𝑇1 𝑇2
T1
𝑇𝑓 𝑇𝑓
= 𝑚1 𝑐1 ln + 𝑚2 𝑐2 ln
𝑑𝑄2 𝑇1 𝑇2
Δ𝑆 = න 𝑑𝑄 = 𝑚𝑐𝑑𝑇
1 𝑇
Example: m1=25 kg, c1=4.2 kJ/kg K , T1= 95°C
→ Tf = 60°C
m2=35 kg, c2=4.2 kJ/kg K , T2= 35°C
333 333
Δ𝑆 = 25 ∙ 4200 ∙ ln + 35 ∙ 4200 ∙ ln = 978.5 𝐽/𝐾
368 308
If environmental temperature: 15°C
𝐸unavailable = 𝑇min Δ𝑆 = 288 ∙ 978.5 = 281.8 𝑘𝐽
A statistical interpretation of entropy

𝑆 = 𝑘𝐵 ln Ω
Ω : # of microstates

22 microstates ← indistinguishable

• A gas with two identical molecules in a box

• 4 microstates and 3 macrostates are possible.
 A statistical interpretation of entropy

24 microstates

• Probability of finding all the gas molecules on one side : 2/16 (2/4
in case of 2 molecules)
23
2100
microstates 210 microstates

100 molecules 1023 molecules

 optional
Water in a bottle

What is the final state for the water in the bottles?

Why don’t the water molecules in the closed bottle evenly disperse in
the space as vapor form?
Gibbs free energy:
the thermodynamic potential
that is minimized when a
system reaches chemical
equilibrium at constant
pressure and temperature.

𝐺 𝑝, 𝑇 = 𝑈 + 𝑝𝑉 − 𝑇𝑆
U is the internal energy
Entropy and the Second Law of Thermodynamics

• The second law of thermodynamics

The entropy of a closed system cannot decrease.
• At best, entropy can remain constant (ideal reversible process).
• Irreversible processes and dissipative forces like friction lead to
entropy increase.
• When the system enlarges to include the entire universe, the
second law reads
The entropy of the universe cannot decrease.
• Any situation that appears to involve an increase in order and thus a
decrease in entropy (i) can’t be closed, and (ii) is always
accompanied by a corresponding and greater increase in entropy.
Q: 𝑆 in living things?
 Chapter summary
• The second law of thermodynamics is fundamentally a statement
about the tendency of systems to evolve toward more disordered
states.
– The Kelvin-Planck statement of the second law asserts that it’s impossible to
build a perfect heat engine, one that cyclically converts thermal energy into
work with 100% efficiency.
• The maximum efficiency is the Carnot efficiency: eCarnot = 1 – Tc / Th.
– The Clausius statement says that it’s impossible to build a perfect
refrigerator, one whose sole effect is to transfer energy from a cooler to a
hotter object.
• Real refrigerators therefore require mechanical energy input.
– In its most general statement, the second law says that the entropy of a
closed system cannot decrease.
• Entropy is a measure of disorder: the higher the entropy, the more disorder.
• High entropy is associated with low-quality energy, and vice versa.
2 𝑑𝑄
• ∆𝑆12 = ‫׬‬1 𝐸unavailable = 𝑇min Δ𝑆
𝑇