SECOND LAW OF THERMODYNAMICS II

Intended Learning Outcomes – after this lecture you will learn:

1. reversible processes, reversible engine and the Carnot cycle
2. efficiency of the Carnot engine as an upper bound for other heat engines
3. definition of absolute temperature by Carnot efficiency
4. consistency of ideal gas temperature and absolute temperature
5. entropy and the second law of thermodynamics (optional)
Textbook Reference: Ch 20.6

Reversible Processes
A reversible thermodynamic process is an idealized process whose direction can be reversed by
making only an infinitesimal change in the conditions of the system.
Throughout a reversible process the system must be very close to equilibrium at any instant,
called an equilibrium process (but not exactly in equilibrium, otherwise no change, no
process)
Heat flow due to a finite temperature difference is necessarily irreversible because an
infinitesimal change in the temperatures cannot reverse heat flow.
How to understand reversible isothermal heat flow – the temperature difference must be
infinitesimal so that as heat flows, the two bodies are still infinitesimally close to equilibrium.
The rate of heat flow is infinitesimally small, and the time taken to finish the process is
infinitely long!

Reversible engine and Carnot cycle

Recall: heat flow between two objects with different temperatures is irreversible.
Suppose all processes in a cycle of an engine are reversible, then:
1. Heat flow between the reservoirs and the working substance of the engine must take place
when the working substance is in thermal equilibrium with the reservoirs (isothermal
processes) – Processes 𝑎𝑎 → 𝑏𝑏 and 𝑐𝑐 → 𝑑𝑑
2. When the working substance and the reservoirs are not in thermal equilibrium (i.e., not at the
same temperature) with the reservoirs, heat flow must be forbidden (adiabatic) – Processes
𝑏𝑏 → 𝑐𝑐 and 𝑑𝑑 → 𝑎𝑎
Such a reversible cycle (𝑎𝑎 → 𝑏𝑏 → 𝑐𝑐 → 𝑑𝑑) is called a Carnot cycle.

PHYS1112 Lecture 24 Second Law of Thermodynamics II P. 1

 isothermal
expansion
adiabatic
compression

adiabatic
expansion
isothermal
compression

Conclusion: A reversible cycle involving two fixed reservoirs is a Carnot cycle

An engine running a Carnot cycle is called a Carnot engine.

Maximum efficiency
Theorem: No engine can be more efficient than a reversible (Carnot) engine operating
between the same two reservoirs
Proof:
- If such a superefficient engine exists, then compared to a Carnot engine operating between
the same reservoirs and dump the same amount of heat |𝑄𝑄𝐶𝐶 | to the cold reservoir, it takes
more heat 𝑄𝑄𝐻𝐻 + Δ from the hot reservoir and does more work 𝑊𝑊 + Δ (by comparing their
𝑄𝑄 𝑄𝑄𝐶𝐶
efficiency 1 − �𝑄𝑄 𝐶𝐶 � < 1 − �𝑄𝑄 �)
𝐻𝐻 𝐻𝐻 +Δ
- since Carnot engine is reversible, turn it into a refrigerator with the same |𝑄𝑄𝐻𝐻 |, |𝑄𝑄𝐶𝐶 |, and |𝑊𝑊|
( doesn’t work for any other irreversible engine)
- operate the superefficient engine alongside with the Carnot refrigerator:

violates second
law of
thermodynamics

PHYS1112 Lecture 24 Second Law of Thermodynamics II P. 2

 A Carnot engine is the most efficient heat engine operating between the two heat reservoirs,
but the most impractical one. Since the working substance is assumed to be in thermal
equilibrium in every step, it runs very slowly to allow time to establish thermal equilibrium.

Carnot efficiency and definition of absolute temperature

𝑄𝑄C
𝑒𝑒carnot = 1 − � �
𝑄𝑄H
Carnot showed that the efficiency of a Carnot engine depends only on the two reservoirs chosen.
(For example, it does not depend on the working substance chosen) For two given reservoirs
𝑄𝑄H
� � = Constant
𝑄𝑄C
Define absolute temperatures of the two reservoirs by
𝑇𝑇H 𝑄𝑄H
=� �
𝑇𝑇C 𝑄𝑄C
this definition of temperature is “absolute” in the sense that it depends on “absolutely”
nothing besides the two reservoirs
Hence,
𝑇𝑇C 𝑇𝑇H − 𝑇𝑇C
𝑒𝑒Carnot = 1 − =
𝑇𝑇H 𝑇𝑇H
It defines the temperature ratio only. To fix the scale, choose the triple point of water and
define its temperature to be 273.16 K exactly.
𝑒𝑒Carnot < 1 unless 𝑇𝑇C = 0, which is forbidden by the Third Law of Thermodynamics

Carnot Refrigerator
The coefficient of performance
|𝑄𝑄C | 𝑇𝑇C
𝐾𝐾 = =
|𝑄𝑄H | − |𝑄𝑄C | 𝑇𝑇H − 𝑇𝑇C
Example 20.2 P. 683
A Carnot engine takes 2000 J of heat from the hot reservoir and discards 1400 J of heat to the
cold reservoir. The temperature ratio of the two reservoirs should be defined as
𝑇𝑇H 𝑄𝑄H 2000 J 10
=� �= =
𝑇𝑇C 𝑄𝑄C 1400 J 7
The Carnot efficiency is
𝑇𝑇C
𝑒𝑒Carnot = 1 − = 30%
𝑇𝑇H

PHYS1112 Lecture 24 Second Law of Thermodynamics II P. 3

Absolute temperature and ideal gas temperature
Previously we defined ideal gas temperature (as measured by a constant volume gas
thermometer) by 𝑝𝑝𝑝𝑝 = 𝑛𝑛𝑛𝑛𝑛𝑛.
Here we will show that this is consistent with the definition of absolute temperature defined
through a Carnot engine.

Suppose working substance is an ideal gas. Consist of 4 steps:

4. 1.
compressed expands
adiabatically isothermally
back to 𝑇𝑇H at 𝑇𝑇H ,
absorbing
heat 𝑄𝑄H

3.
2.
compressed
expands
isothermally
adiabatically
at 𝑇𝑇C ,
until
rejecting
temperature
heat |𝑄𝑄C |
drops to 𝑇𝑇C

In steps (1) and (3),

𝑉𝑉𝑏𝑏
𝑄𝑄H = 𝑊𝑊𝑎𝑎𝑎𝑎 = 𝑛𝑛𝑛𝑛𝑇𝑇H ln ⎫
𝑉𝑉𝑎𝑎 𝑄𝑄H 𝑇𝑇H ln(𝑉𝑉𝑏𝑏 ⁄𝑉𝑉𝑎𝑎 ) 𝑇𝑇H ln(𝑉𝑉𝑏𝑏 ⁄𝑉𝑉𝑎𝑎 )
⟹ = =−
𝑉𝑉𝑑𝑑 𝑄𝑄C 𝑇𝑇C ln(𝑉𝑉𝑑𝑑 ⁄𝑉𝑉𝑐𝑐 ) 𝑇𝑇C ln(𝑉𝑉𝑐𝑐 ⁄𝑉𝑉𝑑𝑑 )
𝑄𝑄C = 𝑊𝑊𝑐𝑐𝑐𝑐 = 𝑛𝑛𝑛𝑛𝑇𝑇C ln ⎬
𝑉𝑉𝑐𝑐 ⎭
Need to eliminate the volumes. From steps (2) and (4)
𝛾𝛾−1 𝛾𝛾−1 𝛾𝛾−1 𝛾𝛾−1
𝑇𝑇H 𝑉𝑉𝑏𝑏 = 𝑇𝑇C 𝑉𝑉𝑐𝑐 𝑉𝑉𝑏𝑏 𝑉𝑉𝑐𝑐 𝑉𝑉𝑏𝑏 𝑉𝑉𝑐𝑐
𝛾𝛾−1 𝛾𝛾−1 � ⟹ 𝛾𝛾−1 = 𝛾𝛾−1 ⟹ =
𝑇𝑇H 𝑉𝑉𝑎𝑎 = 𝑇𝑇C 𝑉𝑉𝑑𝑑 𝑉𝑉𝑎𝑎 𝑉𝑉𝑑𝑑 𝑉𝑉𝑎𝑎 𝑉𝑉𝑑𝑑

Therefore
𝑇𝑇H 𝑄𝑄H 𝑄𝑄H
=− =� �
𝑇𝑇C 𝑄𝑄C 𝑄𝑄C
Here 𝑇𝑇H and 𝑇𝑇C are ideal gas temperatures, but expression is identical to the previous one in
terms of absolute temperature. Since both scales set the water triple point temperature to be
273.16 K exactly, the ideal gas temperature is the same as the absolute temperature.

PHYS1112 Lecture 24 Second Law of Thermodynamics II P. 4

Exercise
Work out Example 20.3 P. 684 in your textbook on the Carnot cycle
carefully. You can find a video solution here.
Suppose 0.200 mol of an ideal diatomic gas (𝛾𝛾 = 1.40) undergoes a Carnot cycle between 227℃
and 27℃, starting at 𝑝𝑝𝑎𝑎 = 10.0 × 105 Pa at point a in the pV-diagram below.
The volume doubles during the isothermal expansion step 𝑎𝑎 → 𝑏𝑏.
(a) Find the pressure and volume at points a, b, c, and d.
(b) Find 𝑄𝑄, 𝑊𝑊, and Δ𝑈𝑈 for each step and for the entire cycle.
(c) Find the efficiency.

isothermal
expansion
adiabatic
compression

adiabatic
expansion
isothermal
compression

Ans:

PHYS1112 Lecture 24 Second Law of Thermodynamics II P. 5

Entropy (optional, will not appear in final exam)

Thermodynamic definition: the entropy 𝑆𝑆 is defined by

𝑏𝑏
𝑑𝑑𝑑𝑑
Δ𝑆𝑆 = �
𝑎𝑎 𝑇𝑇
Like 𝑈𝑈, it is a state function, Δ𝑆𝑆 = 𝑆𝑆𝑏𝑏 − 𝑆𝑆𝑎𝑎
For a slow isothermal process, Δ𝑆𝑆 = Δ𝑄𝑄/𝑇𝑇

Example (entropy as a measure of randomness/disorderness)

In changing 1 kg of ice at 0 ℃ into water at 0 ℃, needs 𝑄𝑄 = 𝑚𝑚𝐿𝐿𝑓𝑓 = 3.34 × 105 J. The
associated entropy change is
𝑄𝑄 3.34 × 105 J
Δ𝑆𝑆 = = = 1.22 × 103 J/K
𝑇𝑇 273 K
in this process the randomness of the system (ice molecules vs water molecules) increases, so
is the entropy
In general, can interpret entropy as a measure of the randomness of the thermodynamic
system

Example (entropy change in reversible/irreversible processes)

If the net result of a certain thermodynamic process is that an amount of heat Q > 0 flows from
an object with temperature Ta to another object with temperature Tb without change in
temperature.
isolated
if 𝑇𝑇𝑎𝑎 = 𝑇𝑇𝑏𝑏 , isothermal heat flow, reversible, Δ𝑆𝑆 = 0
𝑄𝑄
𝑇𝑇𝑎𝑎 𝑇𝑇𝑏𝑏 if 𝑇𝑇𝑎𝑎 > 𝑇𝑇𝑏𝑏 , spontaneous, irreversible, Δ𝑆𝑆 > 0

if 𝑇𝑇𝑎𝑎 < 𝑇𝑇𝑏𝑏 , forbidden by 2nd law, Δ𝑆𝑆 < 0

−𝑄𝑄 𝑄𝑄
Δ𝑆𝑆 = +
𝑇𝑇𝑎𝑎 𝑇𝑇𝑏𝑏

Second law of thermodynamics in terms of entropy

The entropy of an isolated system never decreases: ∆𝑆𝑆 ≥ 0
If ∆𝑆𝑆 = 0, process is reversible.
If ∆𝑆𝑆 > 0, process is irreversible.

PHYS1112 Lecture 24 Second Law of Thermodynamics II P. 6

Clicker Question:

Ans: Q20.2) B, Q20.7) A

PHYS1112 Lecture 24 Second Law of Thermodynamics II P. 7

For more detail see http://en.wikipedia.org/wiki/Rudolf_Clausius

PHYS1112 Lecture 24 Second Law of Thermodynamics II P. 8