Advanced Thermodynamics (M2794.

007900)

Chapter 5

Consequences of the First Law

Min Soo Kim

Seoul National University
A.1 Partial Derivatives

Consider a function of three variables, 𝑓 𝑥, 𝑦, 𝑧 = 0

since only two variables are independent, we can write

𝑥 = 𝑥 𝑦, 𝑧 , 𝑦 = 𝑦 𝑥, 𝑧

𝜕𝑥 𝜕𝑥
Then d𝑥 = ( ) 𝑑𝑦 +( ) 𝑑𝑧, and
𝜕𝑦 𝑧 𝜕𝑧 𝑦

𝜕𝑦 𝜕𝑦
d𝑦 = ( 𝜕𝑥 )𝑧 𝑑𝑥 + ( 𝜕𝑧 )𝑥 𝑑𝑧

We obtain,
𝜕𝑥 𝜕𝑦 𝜕𝑦 𝜕𝑥
d𝑥 = ( 𝜕𝑦 )𝑧 ( 𝜕𝑥 )𝑧 𝑑𝑥 + ( 𝜕𝑧 )𝑥 𝑑𝑧 + ( 𝜕𝑧 )𝑦 𝑑𝑧

2/24
A.1 Partial Derivatives

𝜕𝑥 𝜕𝑦 𝜕𝑦 𝜕𝑥
d𝑥 = ( 𝜕𝑦 )𝑧 ( 𝜕𝑥 )𝑧 𝑑𝑥 + ( 𝜕𝑧 )𝑥 𝑑𝑧 + ( 𝜕𝑧 )𝑦 𝑑𝑧

𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑥
= ( 𝜕𝑦 )𝑧 ( 𝜕𝑥 )𝑧 𝑑𝑥 + ( 𝜕𝑦 )𝑧 ( 𝜕𝑧 )𝑥 + ( 𝜕𝑧 )𝑦 𝑑𝑧

If d𝑧 = 0 and d𝑥 ≠ 0 ,

𝜕𝑥 1
= 𝜕𝑦 . This expression is known as the reciprocal relation.
𝜕𝑦 𝑧
𝜕𝑥 𝑧

If d𝑥 = 0 and d𝑧 ≠ 0 ,

𝜕𝑥 𝜕𝑦 𝜕𝑥
=−
𝜕𝑦 𝑧 𝜕𝑧 𝑥 𝜕𝑧 𝑦

3/24
A.1 Partial Derivatives

𝜕𝑥 𝜕𝑦 𝜕𝑥
=− (previous slide)
𝜕𝑦 𝑧 𝜕𝑧 𝑥 𝜕𝑧 𝑦

𝜕𝑥 1
= 𝜕𝑧 (using reciprocal relation)
𝜕𝑧 𝑦
𝜕𝑥 𝑦

Substituting these equations yield,

𝜕𝑥 𝜕𝑦 𝜕𝑧
= −1. The cyclical rule, or cyclical relation.
𝜕𝑦 𝑧 𝜕𝑧 𝑥 𝜕𝑥 𝑦

4/24
A.1 Partial Derivatives

Consider a function 𝑢 of three variables x, y, z can be written as a function of only

two variables and those two variables are independent.
𝑢 = 𝑢 𝑥, 𝑦

Alternatively,
𝑥 = 𝑥 𝑢, 𝑦

Then

𝜕𝑥 𝜕𝑥
d𝑥 = 𝑑𝑢 + 𝑑𝑦.
𝜕𝑢 𝑦 𝜕𝑦 𝑢

If we divide the equation by d𝑧 while holding 𝑢 constant,

𝜕𝑥 𝜕𝑥 𝜕𝑦
= . The chain rule of differentiation.
𝜕𝑧 𝑢 𝜕𝑦 𝑢 𝜕𝑧 𝑢

5/24
5.1 The Gay-Lussac-Joule Experiment

In general, 𝑢 = 𝑢 𝑇, 𝑣

using the cyclical and reciprocal relations,

𝜕𝑢
𝜕𝑇 ( )
𝜕𝑣 𝑇
( ) =−
𝜕𝑣 𝑢 𝜕𝑢
( 𝜕𝑇 )𝑣

𝜕𝑢
for a reversible process, 𝑐𝑣 = ( )
𝜕𝑇 𝑣

𝜕𝑢 𝜕𝑇
∴ ( ) = −𝑐𝑣 ( )
𝜕𝑣 𝑇 𝜕𝑣 𝑢

Then how can we keep 𝑢 constant during the expansion?

6/24
5.1 The Gay-Lussac-Joule Experiment

𝑑𝑢 = 𝛿𝑞 − 𝛿𝑤 ⇒ free expansion
=0 =0
(adiabatic) (no work)

gas diaphragm
sample

𝒗𝟎 , 𝑻𝟎 𝒗𝟏 − 𝒗𝟎

vacuum
thermal insulation

𝑣 𝜕𝑇 𝜕𝑇
𝑇1 = 𝑇0 + ‫ 𝑣׬‬1( )𝑢 𝑑𝑣, 𝜂≡( ) : Joule’s coefficient
𝜕𝑣
0 𝜕𝑣 𝑢

From Joule’s experimental result,

𝜕𝑇
𝜂 = < 0.001 K kilomole m−3
𝜕𝑣 𝑢

7/24
5.1 The Gay-Lussac-Joule Experiment

for a Van der Waals gas, (Problem 5-3)

𝑎
𝜂=−
𝑣 2 𝑐𝑣

for an ideal gas,

by using the equation 𝑑𝑢 = 𝑇𝑑𝑠 − 𝑃𝑑𝑣,

𝜕𝑢 𝜕𝑠 𝜕𝑃 𝜕 𝑅𝑇
=𝑇 −𝑃 =𝑇 −𝑃 =𝑇[ ]𝑣 − 𝑃
𝜕𝑣 𝑇 𝜕𝑣 𝑇 𝜕𝑇 𝑣 𝜕𝑇 𝑣

𝑅𝑇
= −𝑃 =0
𝑣
Then 𝑢 = 𝑢(𝑇)

8/24
5.1 The Gay-Lussac-Joule Experiment

for a real gas,

𝜕𝑢 𝜕𝑢
by using the equation 𝑑𝑞 = 𝑑𝑇 + + 𝑃 𝑑𝑣 divide by the
𝜕𝑇 𝑣 𝜕𝑣 𝑇

temperature T,

𝑑𝑞 1 𝜕𝑢 1 𝜕𝑢
= 𝑑𝑇 + + 𝑃 𝑑𝑣
𝑇 𝑇 𝜕𝑇 𝑣 𝑇 𝜕𝑣 𝑇

𝜕 1 𝜕𝑢 𝜕 1 𝜕𝑢
= +𝑃
𝜕𝑣 𝑇 𝜕𝑇 𝜕𝑇 𝑇 𝜕𝑣

1 𝜕2 𝑢 1 𝜕𝑢 1 𝜕2 𝑢 1 𝜕𝑃
= − 2 +𝑃 + +
𝑇 𝜕𝑣𝜕𝑇 𝑇 𝜕𝑣 𝑇 𝜕𝑣𝜕𝑇 𝑇 𝜕𝑇

𝜕𝑢 𝜕𝑃
=𝑇 −𝑃
𝜕𝑣 𝑇 𝜕𝑇 𝑣

9/24
5.2 The Joule-Thomson Experiment

Since the process takes place in an insulated cylinder,

Initial state Final state

𝑷𝟐 , 𝒗𝟐 , 𝑻𝟐
𝑷𝟏 , 𝒗𝟏 , 𝑻𝟏

Porous plug

δ𝑞 = 0
0
specific work done in forcing the gas through the plug, 𝑤1 = ‫𝑃 𝑣׬‬1 𝑑𝑣 = −𝑃1 𝑣1
1

𝑣
specific work done by the gas in the expansion, 𝑤2 = ‫׬‬0 2 𝑃2 𝑑𝑣 = 𝑃2 𝑣2

10/24
5.2 The Joule-Thomson experiment

The total work, 𝑤 = 𝑤1 + 𝑤2 = 𝑃2 𝑣2 − 𝑃1 𝑣1 = 𝑢1 − 𝑢2

𝑢1 + 𝑃1 𝑣1 = 𝑢2 + 𝑃2 𝑣2 ⟺ ℎ1 = ℎ2
constant

Thus, a throttling process occurs at constant enthalpy.

11/24
5.2 The Joule-Thomson experiment

Joule-Thomson coefficient
𝜕𝑇
𝜇𝐽𝑇 ≡ ( )
𝜕𝑃 ℎ

the point where 𝜇𝐽𝑇 = 0 is called inversion point.

from ℎ = ℎ 𝑇, 𝑃 ,
𝜕ℎ 𝜕ℎ
𝑑ℎ = ( 𝜕𝑇 )𝑃 𝑑𝑇 + ( 𝜕𝑃 ) 𝑇 𝑑𝑃

𝜕𝑇 𝑇2 −𝑇1
𝜇𝐽𝑇 ≡ ( 𝜕𝑃 )ℎ = 𝑃2 −𝑃1 ℎ

𝑇2 = 𝑇1 − 𝜇 𝑃2 − 𝑃1
The gas is cooling when the 𝜇 is positive
and heating when the 𝜇 is negative

12/24
5.2 The Joule-Thomson experiment

Joule-Thomson coefficient

𝜕𝑇 𝜕𝑇 𝜕ℎ 1 𝜕𝑣
𝜇𝐽𝑇 = =− = 𝑇 −𝑣
𝜕𝑃 ℎ 𝜕ℎ 𝑃 𝜕𝑃 𝑇 𝐶𝑃 𝜕𝑇 𝑃

for an ideal gas, 𝜇𝐽𝑇 = 0,

𝜕ℎ
= 0 and ℎ = ℎ 𝑇
𝜕𝑃 𝑇

𝑅𝑇 𝑎
for a Van der Waals gas, 𝑃 = 𝑣−𝑏 − 𝑣 2
2𝑎 𝑏 2
1 𝑅𝑇 1 − 𝑣 − 𝑏
𝜇𝐽𝑇 =
𝑐𝑃 2𝑎 𝑏 2
1− 1−
𝑣𝑅𝑇 𝑣
2𝑎 𝑏 2
If 𝜇𝐽𝑇 = 0, 𝑇𝑖 = 1−
𝑏𝑅 𝑣

13/24
5.3 Heat engines and the Carnot cycle

Carnot cycle

𝑇 𝑇
𝑸 𝑸

𝑾 𝑴 𝑴 𝑾

(a) (b)

Fig. The concept of a heat engine.

In (a), work is done on the system and is converted to heat.

In (b), heat is extracted from a reservoir and is converted to mechanical work.
This configuration is not possible.

14/24
5.3 Heat engines and the Carnot cycle

Carnot cycle

𝑇 𝑇𝑏
𝑸 𝑸𝑯

𝑴 𝑾 𝑴 𝑾

𝑸𝑳

𝑇𝑎
(b) (c)

Fig. The concept of a heat engine.

Can the work done by the system be equal to the heat in?
The second law of thermodynamics states unequivocally that it is impossible to
construct a perfect heat engine.
Thus case (b) must be modified as case (c)

15/24
5.3 Heat engines and the Carnot cycle

Clausius statement
It is impossible to construct a device that operates in a cycle and whose sole
effect is to transfer heat from a cooler body to a hotter body.

Kelvin-Planck statement
It is impossible to construct a device that operates in a cycle and produces no
other effect than the performance of work and the exchange of heat with a
single reservoir.

16/24
5.3 Heat engines and the Carnot cycle

Carnot cycle

𝑇𝑏
𝑸𝑯

𝑸𝑳

𝑇𝑎
Fig. P-V and T-S diagrams of Carnot cycle.

1 – 2 : isothermal expansion
2 – 3 : adiabatic expansion
3 – 4 : isothermal compression
4 – 1 : adiabatic compression

17/24
5.3 Heat engines and the Carnot cycle

The efficiency of the engine,

𝑊 𝑊 output
𝜂= = =
𝑄𝐻 𝑄𝐻 input

Applying the first law to the system,

∆𝑈 = 𝑄𝐻 + 𝑄𝐿 − 𝑊 = 𝑄𝐻 − 𝑄𝐿 − 𝑊

Since the system is in a cyclical process, ∆𝑈 = 0. Then,

𝑊 = 𝑄𝐻 + 𝑄𝐿 or 𝑊 = 𝑄𝐻 − 𝑄𝐿

Substituting the equations,

𝑄𝐿 +𝑄𝐻 𝑄𝐿 𝑄𝐿
𝜂= =1+ =1−
𝑄𝐻 𝑄𝐻 𝑄𝐻

18/24
5.3 Heat engines and the Carnot cycle

for an ideal gas, 𝑃𝑣 = 𝑅𝑇 , 𝑢 = 𝑢 𝑇 ,

𝑉
for isothermal process, 𝑄𝐻 = 𝑊12 = 𝑛𝑅ത 𝑇𝑏 ln 𝑉2
1

𝑉
𝑄𝐿 = 𝑊34 = 𝑛𝑅ത 𝑇𝑎 ln 𝑉4
3

𝑄𝐻 𝑇 𝑇2 𝑣2
⇒ = − 𝑇𝑏 𝑠2 − 𝑠1 = 𝑐𝑣 ln + 𝑅ln
𝑄𝐿 𝑎
𝑇1 𝑣1
for adiabatic process, 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 , 𝑇2 𝑃2
= 𝑐𝑝 ln − 𝑅ln =0
𝑇𝑏 𝑉2 𝛾−1 = 𝑇𝑎 𝑉3 𝛾−1 𝑇1 𝑃1
1 𝜅
𝑇𝑏 𝑉1 𝛾−1 = 𝑇𝑎 𝑉4 𝛾−1 𝑐𝑣 = 𝑅, 𝑐𝑝 = 𝑅
𝜅−1 𝜅−1
𝜅
𝑉2 𝑉3 𝑃2 𝑣2
⇒ = =
𝑉1 𝑉4 𝑃1 𝑣1
𝑄 𝑇
The efficiency of the Carnot cycle, 𝜂 = 1 + 𝑄 𝐿 = 1 − 𝑇𝑎
𝐻 𝑏

19/24
5.3 Heat engines and the Carnot cycle

Carnot engine has the maximum efficiency for any engine that one might design.

1. Carnot engine operates between two reservoirs and that it is reversible.

2. If a working substance other than an ideal gas is used, the shape of curves in
the P-V diagram will be difference.

3. The efficiency would be 100 percent if we were able to obtain a low temperature
reservoir at absolute zero. →However this is forbidden by the third law.

20/24
5.3 Heat engines and the Carnot cycle

Carnot refrigerator
Reverse process of Carnot engine
𝑇𝑏
Coefficient of performance(COP)
𝑸𝑯

𝑾 𝑄𝐿 𝑄𝐿 𝑄𝐿 𝑇1
COP ≡ − = = =
𝑸𝑳 𝑊 𝑊 𝑄2 − 𝑄𝐿 𝑇2 − 𝑇1
𝑇𝑎

We introduce a minus sign in order to make the COP a positive quantity :

The heat 𝑄𝐿 is extracted from the low temperature reservoir and W is the work done
on the system. 𝑄𝐿 is positive (heat flow into the system) and W is negative (work
done on the system)

21/24
5.3 Heat engines and the Carnot cycle

Typical refrigerator (heat out to surrounding)

refrigerant
𝑸𝑯
high (e.g. freon) high
pressure Condenser pressure
liquid vapor

Compressor
Expansion
valve 𝑾

low
pressure low
liquid/ Evaporator pressure
vapor vapor
long capillary tube 𝑸𝑳
(heat in from refrigerator space)
Fig. Schematic diagram of a typical refrigerator

1. The refrigerant is a substance chosen to be a saturated liquid at the pressure and

temperature of condenser.
2. The liquid undergoes a throttling process in which it is cooled and is partially
vaporized.

22/24
5.3 Heat engines and the Carnot cycle

Typical refrigerator (heat out to surrounding)

refrigerant
𝑸𝑯
high (e.g. freon) high
pressure Condenser pressure
liquid vapor

Compressor
Expansion
valve 𝑾

low
pressure low
liquid/ Evaporator pressure
vapor vapor
long capillary tube 𝑸𝑳
(heat in from refrigerator space)
Fig. Schematic diagram of a typical refrigerator

3. The vaporization is completed in the evaporator: the heat is absorbed by the

refrigerant from the low temperature reservoir (the interior refrigerator space).
4. The low pressure vapor is then adiabatically compressed and isobarically cooled
until it becomes a liquid once again.

23/24
5.3 Heat engines and the Carnot cycle

Typical refrigerator

Refrigerator are designed to extract as much heat as possible from a cold reservoir

with small expenditure of work.

The coefficient of performance of a household refrigerator is in the range of 5 to 10.

24/24