Contents

1. The second law

2. Entropy
Chapter 3 3. Calculation of Entropy changes of processes
4. Absolute entropy
The second law of 5. Thermodynamic functions
6. Relations of thermodynamic functions
Thermodynamics 7. Effects of parameters on thermodynamic functions

1. The second law

3 4

Applications Cyclic processes

• To identify whether a process can take place
• To predict the degree of completion of
chemical reactions.
U = 0:
• To be used in determining the theoretical
limits for the performance of commonly used Q = -W?
engineering systems, such as heat engines
and refrigerators

5 6
 Heat reservoirs Heat engines

• converting heat to
work requires the
use of some
special devices.
These devices are
called heat
• A hypothetical body with a relatively large thermal engines.
energy capacity (mass x specific heat) that can
supply or absorb finite amounts of heat without
undergoing any change in temperature.

7 8

Heat engines Heat engines

Heat engines can be characterized

by the following : • Heat engines and
1. They receive heat from a high- other cyclic
temperature source (solar energy,
oil furnace, nuclear reactor, etc.). devices usually
2. They convert part of this heat to involve a fluid to
work.
3. They reject the remaining waste and from which
heat to a low-temperature sink (the heat is transferred
atmosphere, rivers, etc.).
4. They operate on a cycle. while undergoing a
cycle. This fluid is
called the working
fluid.

9 10

Heat engines

• The net work

output is the
difference between
the total work output
of the plant and the
• a closed system total work input:
undergoing a cycle: U =0

11 12
 Heat engines Heat engines
• Thermal efficiency:
Heat engines operate between:
• a high-temperature medium (or reservoir) at temperature TH
• a low-temperature medium (or reservoir) at temperature TL.
• QH : magnitude of heat transfer between the cyclic device and
the high-temperature medium at temperature TH
• QL : magnitude of heat transfer between the cyclic device and the
low-temperature medium at temperature TL

Notice: both QL and QH are defined as magnitudes  positive.

13 14

Heat engines Heat engines

• Thermal
efficiency:

 The thermal
efficiency of a
heat engine is
always less than
unity

15 16

Heat engines Kelvin statement (2nd law)

• It is impossible for
any device that
operates on a cycle
Is it possible that to receive heat from
“Thermal efficiency = 100%” ??? a single reservoir
and produce a net
amount of work.

(or) no heat engine can

have a thermal
efficiency of 100%

17 18
 Heat engines THE CARNOT CYCLE
• The best known reversible cycle proposed in
1824 by French engineer Sadi Carnot.
• The theoretical heat engine that operates on
What is the maximum thermal efficiency? the Carnot cycle is called the Carnot heat
engine.
• The Carnot cycle is composed of four
reversible processes—two isothermal and two
adiabatic

19 20

Reversible/ Irreversible Reversible/ Irreversible

Reversible process: A process that can be reversed without leaving
any trace on the surroundings. P
Irreversible process: A process that is not reversible.
• All the processes occurring in nature are irreversible.
P2 P1
1
WMax = WRev
• Why are we interested in reversible processes?
(1) they are easy to analyze and (2) they serve as
idealized models (theoretical limits) to which actual
processes can be compared.
• We try to approximate reversible processes. Why?
2
P1, P2
V1

v1 v2 v

Two familiar reversible

processes.
Reversible processes deliver the most and consume the least WORK. 21
22

Reversible/ Irreversible THE CARNOT CYCLE

• The factors that cause a process to be irreversible are called
irreversibilities.
• They include friction, unrestrained expansion, mixing of two
fluids, heat transfer across a finite temperature difference,
electric resistance, inelastic deformation of solids, and
chemical reactions.
• The presence of any of these effects renders a process
irreversible.

(a) Heat transfer

through a temperature
difference is
irreversible, and (b) the Friction renders a Irreversible compression
reverse process is process irreversible. and expansion processes.
impossible. 23
24
 THE CARNOT CYCLE THE CARNOT CYCLE
• Carnot principles: • The efficiency of a Carnot engine, or any
1. The efficiency of an irreversible
heat engine is always less than
reversible heat engine, becomes:
the efficiency of a reversible one
operating between the same two
reservoirs. (Carnot efficiency)

2. The efficiencies of all reversible

heat engines operating between the
same two reservoirs are the
same. Note: TL and TH are absolute
temperatures (K).

25 26

Heat engines Refrigerators

• Heat engines are built for the purpose of converting heat • The transfer of heat from a low-
temperature medium to a high-
to work, and engineers are constantly trying to improve
temperature one requires special
the efficiencies of these devices less fuel consumption devices called refrigerators.
and less pollution. • Refrigerators, are cyclic
Examples: devices. The working fluid used
– 25% for ordinary spark-ignition automobile engines in the refrigeration cycle is called
a refrigerant.
– 40% for diesel engines
– 60% for large combined gas-steam power plants.

27 28

Refrigerators Heat Pumps

• Coefficient of Performance • device that transfers heat from a
– The efficiency of a refrigerator is expressed low-temperature medium to a high-
temperature one.
in terms of the coefficient of performance
• Refrigerators and heat pumps
(COP), denoted by COPR:
operate on the same cycle but differ
in their objectives
– Refrigerator: maintain the refrigerated
space at a low temperature by removing
– 1st law for a cyclic device: heat from it.
– Heat pump: maintain a heated space at
a high temperature.

29 30
 Heat Pumps Heat Pumps
• Coefficient of performance COPHP:

COPHP is always greater than unity!!!

31 32

Refrigerators/heat pumps Clausius Statement (2nd law)

• It is impossible to construct
• Can they operate a device that operates in a
cycle and produces no
without external work effect other than the
transfer of heat from a
supply??? lower-temperature body to
a higher-temperature body.

(or) a refrigerator cannot

operate unless its
compressor is driven by an
external power source,
such as an electric motor.

33 34

The Quality of Energy

• These efficiency values
Ex 1: An automobile engine has an efficiency of 22.0% and produces 2510 J of
show that energy has work. How much heat is rejected by the engine?
quality as well as
Ans: 8900 J
quantity.
• It is clear from the
thermal efficiency
values that more of the
high-temperature
thermal energy can be
converted to work.
 the higher the
temperature, the
higher the quality of
the energy

35
 2. Entropy

38

Entropy Entropy

Cyclic integral
For heat engines: 𝜂𝑡ℎ = 1 −
𝑄𝐿 • The cyclic integral indicates
𝑄𝐻
that the integral should be
𝑇𝐿
𝜂𝑡ℎ,𝑟𝑒𝑣 = 1 − performed over the entire
𝑇𝐻
cycle and over all parts of
According to Carnot principles: 𝜂𝑡ℎ ≤ 𝜂𝑡ℎ,𝑟𝑒𝑣 the boundary.

𝑄𝐿 𝑇𝐿
Therefore: 1− ≤1−
𝑄𝐻 𝑇𝐻
2
Q 3
Q 4
Q 1
Q
Or: 𝑄𝐻 𝑄𝐿
−
𝑇𝐻 𝑇𝐿
≤0    
1
T 2
T 3
T 4
T
40
39

Entropy Entropy

Cyclic integral
2
Q 3
Q 4
Q 1
Q QH Q • Two important thermodynamic parameters derived
     0 L 0
1
T 2
T 3
T 4
T TH TL from the Clausius inequality:

– Entropy (S): a state function

Q
T 0 – Entropy generation (Sg): entropy generated during
a process

41 42
42
 Entropy Entropy

• A thermodynamic (energy) function that describes the • Nature spontaneously proceeds toward the state that
degree of randomness or probability of existence. has the highest probability of (energy) existence –
highest entropy
• The more disordered the system, the larger its entropy. • Entropy is used to predict whether a given
process/reaction is thermodynamically possible
• As a state function – entropy change depends only on
the initial and final states, but not on how the change
occurs.

43 44

Entropy Entropy
For reversible cycle A-B
 Q   Q  δQ is a thermodynamic property
T
2 1
      0 
1
T A 2  T B we call it entropy  S
For reversible cycle C-B
 Q   Q   Q  2  Q 
integrating S 2  S1    
2 1
  dS   
T C 2  T  B
    0
1
  rev
T 1
 T  rev

 Q   Q 
2 2
Subtracting gives   T   
 1

T C
All paths are arbitrary S2 – S1 depends on the end states only Entropy (the unit)
1 A and not on the path, S = entropy (kJ/K);
 it is same for any path reversible or s = specific entropy (kJ/kg K)
Since paths A and C are arbitrary, it follows that the integral of Q/T has the irreversible
same value for ANY reversible process between the two states. Entropy is a state property, it has fixed values at fixed states. Therefore, the entropy change S
Q between two specified states is the same no matter what path, reversible or irreversible.
 the quantity  is independent of the path and dependent on the end states only
T 45 46

Entropy Entropy
A,B: reversible processes
C: irreversible process
δQ 2 δQ equality for reversible
For reversible process A-B: dS  or S 2  S 1  
2 1 T 1 T inequality for irreversible
𝛿𝑄 𝛿𝑄 𝛿𝑄
ර =න +න =0
𝑇 1 𝑇 𝐴 2 𝑇 𝐵 This can be written out in a common form as an equality
2 1
𝛿𝑄 𝛿𝑄
For irreversible process C-B: න >න Q 2 Q for any process,
dS    S gen S 2  S1  
𝑇 𝑇
1 𝐴 2 𝐶 or  S gen 
 with Sgen  0
2 1
ර
𝛿𝑄
=න
𝛿𝑄
+න
𝛿𝑄
<0
T 1 T
𝑇 1 𝑇 2 𝑇
𝐶 𝐵
2nd law of thermodynamics for a closed system
Besides: Entropy Balance Equation for a closed system
2
𝛿𝑄 2 2 2 2  δQ    0 for irreversible process
න = න 𝑑𝑆𝐴 = න 𝑑𝑆𝐶   dS C     S gen  entropy generation 
 0 for a reversible process
𝑇
1 𝐴 1 1 1 1
 T C
In any irreversible process entropy is always generated (Sgen > 0) due to
47 48
irreversibilities occurring inside the system.
 Entropy Entropy

There is some entropy generated during an 2

Q
irreversible process such that S 2  S1  
1
T
 S gen
2
Q

 The entropy change can be evaluated independently of the
S 2  S1   S gen process details.

1
T  However, the entropy generation depends on the process, and
thus it is not a property of the system.
 The entropy generation is always a positive quantity or zero and
Entropy Entropy transfer Entropy generation this generation is due to the presence of irreversibilities.
change with heat due to irreversibility

This is the entropy balance for a closed system.

49 50
49

Entropy Entropy

• Now suppose the system is not adiabatic.

• For an isolated (or simply an adiabatic closed system), the heat
transfer is zero, then
• We can make it adiabatic by extending the
surrounding until no heat, mass, or work are
Q
 S adiabatic  Sgen
2 crossing the boundary of the surrounding.
S  S 2  S 1    Sgen
1 T • This way, the system and its surroundings can be
viewed again as an isolated system.
 This means that the entropy of an adiabatic system during a
process always increases or, In the limiting case of a • The entropy change of an isolated system is
the sum of the entropy changes of its
reversible process, remains constant. components (the system and its surroundings),
and is never less than zero.
 In other words, it never decreases.
• Now, let us apply the entropy balance for an
 This is called “Increase of entropy principle”. isolated system:

S gen  Stotal  S sys  S surr  0

51 52

Entropy Entropy

• Processes can occur in a certain direction only , not in any

 0 irreversib le process
direction. A process must proceed in the direction that
complies with the increase of entropy principle. A process
 that violates this principle is impossible.
S gen  0 reversible process • Entropy is a non-conserved property. Entropy is conserved

 0 imposible process during the idealized reversible process only and increases

 during all actual processes.

• The performance of engineering systems is degraded by the
presence of irreversibilities, and the entropy generation is a
measure of the magnitude of the irreversibilities present
during a process.

53 54
53
 Consequence of 2nd law
• The most important consequence of the second law
of thermodynamics:
“For any adiabatic process, the entropy
of the system cannot decrease.” 3. Calculation of
Entropy changes of processes
Reversible adiabatic process: S=0

• The universe: only adiabatic processes

In any reversible process, the entropy of the universe
remains constant.
In any irreversible process, the entropy of the universe
increases.
55 56

Entropy change Entropy change

S  S 2  S 1    Q  S  S 2  S 1    Q 
2 2

1  T  rev 1  T int rev

a. Heating (cooling) process at constant pressure/constant volume: a. Heating (cooling) process at constant pressure/constant volume:

T2
dT
 QTN C dT • Rev. isobaric: Qrev = Cp.dT S   C P
Isobaric process: S    P T1
T
T T
T2
Qrev = Cv.dT S  CV dT
Isochoric process: S  
 QTN

CVdT • Rev. volume-constant:
 T1
T
T T 57 58

Entropy change Irreversible processes

 Q REV Q REV Separate into reversible processes (1),

b. Isothermal process: S    (2), (3),..
T T
QT V P
Ideal gas expansion: S   nR ln 2  nR ln 1 S = S(1) + S(2) + S(3) + …
T V1 P2
QT 
Phase transfer S  
T T

Chemical reaction ΔS°reaction = ΣnpS°products – ΣnrS°reactants

59 60
 Absolute entropy

S = k lnW
• States, S.
4. Absolute entropy – The microscopic energy levels
available in a system.
• Microstates, W.
– The particular way in which particles are distributed
amongst the states. Number of microstates = W.
• The Boltzmann constant, k = 1.38x10-23 J/K
– Effectively the gas constant per molecule = R/NA.

W2
S  S2  S1  k ln
W1
61

Absolute entropy Absolute entropy

Entropy at 298 K: (So, J/mol.K)

So  limST  0
Gases:
H2(g) 130.6 N2(g) 191.5
T 0 O2(g) 205.0 C6H6(g) 269.2
3rd law of thermodynamics: The entropy of a perfect crystal Liquids:
at 0 K is zero. H2O(l) 69.9 C6H6(l) 172.8
Because:
- all molecular motion stops Solids:
- all particles are in their place Li(s) 29.1 Fe(s) 27.23
FeCl3(s) 142.3 NaCl(s) 72.3
C(diamond) 2.43 C(graphite) 5.69
S = ST – So = ST
63 64

Absolute entropy Example

Entropy at 298 K: (So, J/mol.K) Entropy change during an isothermal process

65
Example Example

67 68

Example Example

69 70

Example Example

a. Calculate S of rev. process of freezing

C6H6 at 1atm, 5oC, given:
f = -2370 cal/mol

b. Calculate S of irrev. process of

freezing C6H6 at 1atm, -5oC, given:
CC6H6 (l)=30,3 cal/mol.K;
CC6H6 (s)=29,3 cal/mol.K

71 72
 Example Example

Solution: b. Freezing at -5oC: Irreversible  convert to rev. processes

a. Freezing at 5oC: Rev. isothermal isobaric:
C6H6 (l) Irrev. C6H6 (s)
 f  2370
S Freezing    8,52cal / mol.K -5o C S -5o C
T f 5  273 Raise
Decrease
S1 S3 temperature
temperature
Rev. isobaric
Rev. isobaric S2
C6H6 (l) C6H6 (s)
5o C Freezing 5o C
Rev.
isothermal
isobaric

73 74

Example
S2 = -8,52 cal/mol.K
278 278
CP l 
dT dT
S1  
268
  30,3
T 268 T
 1,11 cal / mol.K
S = S1 +S2 + S3
= -8,48 cal/mol.K
268 268
5. Thermodynamic functions
S3   CP l 
dT dT
  29,3  1,07 cal / mol.K
278
T 278 T

75 76

Math. Review 5. Thermodynamic functions

G  G( P,T )
 G   G  Thermodynamic function Symbol Definition unit

dG    dP    dT Gibbs free energy (isothermal, isobaric G = H –TS

 P T  T P thermodynamic potential)
G Cal or J

If : dG  A.dP  B.dT Helmholtz free energy (isothermal,

isochoric thermodynamic potential) F
F = U – TS Cal or J

Then : Internal energy U Cal or J

Enthalpy H
H = U + PV Cal or J
 G   G 
A  and, B   
 P T  T  P

77 78
5. Thermodynamic functions 1. Thermodynamic functions

U   U 
Relationship between state function and T   
H  U  PV  U  V  
 V  S
state variable  S V
U = f(V, S) H = f(P, S)  U   U   U 
F = f(V, T) G = f(P, T) P    G  H  TS  U  V    S 
 V S  V  S  S V

  2U   U 
CV   
U
Due to state function, we have total differential:  S2  F  U  TS  U  S 
 S V  V  S V
 G   G 
Ex: G = f(P,T), dG =
  dP    dT
 P T  T  P
80
79 80

 QV  CV .dTV
 QV  dUV
CV  dUV / dTV
U  U (V , S)
 U   U 
dU    dS    dV
Next :

 S V  V S  U 
dU  
 U   U 
 dS    dV  dUV    dS
 S V  V  S  S V
If : dU   Q   W  T .dS  P.dV
Then :  U 
T    f (S,V )
 U   U   S V
T   and, P      U  
 S V  V  S   2U 
 
S V

dT   2  dS     dV  dT    U  dS
2

 S V  V  V
 S V
2

 
 S
81

1. Thermodynamic functions 1. Thermodynamic functions

𝜕𝑈 𝜕𝐹
• 𝑃=− =−
𝜕𝑉 𝑆 𝜕𝑉 𝑇
𝜕𝑈 𝜕𝐻
• 𝑇= =
𝜕𝑆 𝑇 𝜕𝑆 𝑇
𝜕𝐺 𝜕𝐻
• 𝑉= =
𝜕𝑃 𝑇 𝜕𝑃 𝑆
𝜕𝐹 𝜕𝐺
• 𝑆=− = −
𝜕𝑇 𝑉 𝜕𝑇 𝑃

83 84
1. Thermodynamic functions 1. Thermodynamic functions

Characteristics of thermodynamic functions:

• Internal energy U: minimum at a given S, V.
• Entropy S: maximum at a given U, V.
• Gibbs function G: minimum at a given T, P.
• Helmholtz function F: minimum at a given T, V.
• Enthalpy H: minimum at a given S, P.

85 86

6. Relations of thermodynamic functions

G = H –TS
H = U + PV
6. Relations of
thermodynamic functions
Josiah Willard Gibbs

Hermann von Helmholtz

87 88

6. Relations of thermodynamic functions 6. Relations of thermodynamic functions

If we have a function F = F(x,y)

We need to transform function F(x,y) into:
 Function G(x,w) where w is a conjugate variable of variable y. Therefore 𝑑𝐺(𝑥, 𝑤) = 𝑢 × 𝑑𝑥 − 𝑦 × 𝑑𝑤
 Function H(u,y) where u is a conjugate variable of variable x.
 Function L(u,w) where u, w are conjugate variables of x, y respectively. where: 𝜕𝐺
𝑦=−
𝜕𝑤 𝑥
Prove:
𝐹 = 𝐹(𝑥, 𝑦) In summary, Legendre transform is a method to converse a function F(x,y) into a new function
G(x,w), where y and w are a couple of conjugate variable.
𝜕𝐹 𝜕𝐹 𝝏𝑭 𝝏𝑭
𝑑𝐹 = × 𝑑𝑥 + × 𝑑𝑦 where: 𝒖= 𝒘=
𝜕𝑥 𝜕𝑦 𝝏𝒙 𝝏𝒚
𝑦 𝑥 𝒚 𝒙 𝑮 𝒙, 𝒘 = 𝑭 𝒙, 𝒚 − 𝒘 × 𝒚
𝑑𝐹 = 𝑢 × 𝑑𝑥 + 𝑤 × 𝑑𝑦 (1) 𝜕𝐹
𝑤=
𝑑 𝑤 × 𝑦 = 𝑤 × 𝑑𝑦 + 𝑦 × 𝑑𝑤 (2) 𝜕𝑦 𝑥

Equation (1) – equation (2), having : 𝑑 𝑭 − 𝒘 × 𝒚 = 𝑢 × 𝑑𝑥 − 𝑦 × 𝑑𝑤 𝜕𝐺

𝑦=−
𝜕𝑤 𝑥
𝑑 𝑮 = 𝑢 × 𝑑𝑥 − 𝑦 × 𝑑𝑤 𝑤ℎ𝑒𝑟𝑒: 𝑮 𝒙, 𝒘 = 𝑭 𝒙, 𝒚 − 𝒘 × 𝒚
89 90
6. Relations of thermodynamic functions 6. Relations of thermodynamic functions
𝜕𝑇 𝜕𝑃
=− (1)
𝜕𝑉 𝑆 𝜕𝑆 𝑉
𝜕𝑇 𝜕𝑉
= (2)
𝜕𝑃 𝑆 𝜕𝑆 𝑃
𝜕𝑆 𝜕𝑃
H = (3)
𝜕𝑉 𝑇 𝜕𝑇 𝑉
From function U = U(S, V), we 𝜕𝑆 𝜕𝑉
can transform to different state U PV 𝜕𝑃 𝑇
=−
𝜕𝑇 𝑃
(4)
functions as follows:
• H(S, P) = U(S, V) + PV
• F(T, V) = U(S, V) – TS
TS F PV
• G(T, P) = U(S, V) – TS + PV Determining the change in entropy, which cannot
TS G be measured directly, by simply measuring the
changes in properties P, v, and T.

Maxwell relations are extremely valuable in

thermodynamic analysis!!!
91

6. Relations of thermodynamic functions

𝜕𝑇
− How to prove?

𝜕𝑉 𝑆
• Euler’s equation:

z = z(x,y)
𝜕𝑧 𝜕𝑧
 𝑑𝑧 = 𝑑𝑥 + 𝑑𝑦 = 𝑀𝑑𝑥 + 𝑁𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑦 𝑥

𝜕𝑃 And:
𝜕 𝜕𝑧
𝜕𝑦 𝜕𝑥
=
𝜕 𝜕𝑧
𝜕𝑥 𝜕𝑦

𝜕𝑆
𝜕𝑀 𝜕𝑁
 =
𝜕𝑦 𝑥 𝜕𝑥 𝑦

𝑉 94

6. Relations of thermodynamic functions 6. Relations of thermodynamic functions

a. For U:
• 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 = 𝑀𝑑𝑥 + 𝑁𝑑𝑦 c. For F:
𝜕𝑇 𝜕𝑃
•  =− • 𝑑𝐹 = −𝑆𝑑𝑇 − 𝑃𝑑𝑉 = 𝑀𝑑𝑥 + 𝑁𝑑𝑦
𝜕𝑉 𝑆 𝜕𝑆 𝑉
𝜕𝑆 𝜕𝑃
•  =
𝜕𝑉 𝑇 𝜕𝑇 𝑉
b. For H:
• 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 = 𝑀𝑑𝑥 + 𝑁𝑑𝑦 d. For G:
𝜕𝑇 𝜕𝑉
•  = • 𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 = 𝑀𝑑𝑥 + 𝑁𝑑𝑦
𝜕𝑃 𝑆 𝜕𝑆 𝑃
𝜕𝑆 𝜕𝑉
•  =−
𝜕𝑃 𝑇 𝜕𝑇 𝑃

95 96
 6. Relations of thermodynamic functions 6. Relations of thermodynamic functions

 U   H 
    T
 S V  S  P
 U   F 
     P
 V  S  V T
 F   G 
     S
 T V  T  P
 H   G 
    V
 P  S  P T

98

7. Effects of parameters on thermodynamic functions

7. Effects of parameters on 𝑑𝑢 = 𝑐𝑣 . 𝑑𝑇 + 𝑇
𝜕𝑃
− 𝑃 𝑑𝑣
𝜕𝑇
thermodynamic functions 𝑣

𝜕𝑣
𝑑ℎ = 𝑐𝑃 . 𝑑𝑇 + 𝑣 − 𝑇 𝑑𝑃
𝜕𝑇 𝑃

𝑑𝑇 𝜕𝑣
𝑑𝑠 = 𝑐𝑃 − 𝑑P
𝑇 𝜕𝑇 𝑃

𝑑𝑇 𝜕𝑃
𝑑𝑠 = 𝑐𝑣 + 𝑑𝑣
𝑇 𝜕𝑇 𝑣

99

6. Relations of thermodynamic functions 6. Relations of thermodynamic functions

𝜕𝑢 𝜕𝑢
u = u(T, v): 𝑑𝑢 = 𝑑𝑇 + 𝑑𝑣 (1a) h = h(T, P): 𝑑ℎ =
𝜕ℎ
𝑑𝑇 +
𝜕ℎ
𝑑𝑃 (1b)
𝜕𝑇 𝑣 𝜕𝑣 𝑇
𝜕𝑇 𝑃 𝜕𝑃 𝑇
𝜕𝑢
𝑑𝑢 = 𝑐𝑣 𝑑𝑇 + 𝑑𝑣 (2a) 𝑑ℎ = 𝑐𝑝 𝑑𝑇 +
𝜕ℎ
𝑑𝑃 (2b)
𝜕𝑣 𝑇
𝜕𝑃 𝑇
𝜕𝑠 𝜕𝑠
With: s = s(T, v): 𝑑𝑠 = 𝑑𝑇 + 𝑑𝑣 (3a) s = s(T, P): 𝑑𝑠 =
𝜕𝑠
𝑑𝑇 +
𝜕𝑠
𝑑𝑃 (3b)
𝜕𝑇 𝑣 𝜕𝑣 𝑇
𝜕𝑇 𝑃 𝜕𝑃 𝑇
Because: 𝑑𝑢 = 𝑇𝑑𝑠 − 𝑃𝑑𝑣 (4a) Because: 𝑑ℎ = 𝑇𝑑𝑠 + 𝑣𝑑𝑃 (4b)
𝜕𝑠 𝜕𝑠
𝑑𝑢 = 𝑇 𝑑𝑇 + 𝑇 − 𝑃 𝑑𝑣 (5a)  𝑑ℎ = 𝑇
𝜕𝑠
𝑑𝑇 + 𝑣 + 𝑇
𝜕𝑠
𝑑𝑃 (5b)
𝜕𝑇 𝑣 𝜕𝑣 𝑇
𝜕𝑇 𝑃 𝜕𝑃 𝑇
𝜕𝑢 𝜕𝑠
From (1a) and (5a)  =𝑇 (6a) 𝜕ℎ 𝜕𝑠
𝜕𝑇 𝑣 𝜕𝑇 𝑣
From (1b) and (5b): = 𝑇 (6b)
𝜕𝑢 𝜕𝑠 𝜕𝑇 𝑃 𝜕𝑇 𝑃
and = 𝑇 − 𝑃 (7a) 𝜕ℎ 𝜕𝑠
𝜕𝑣 𝑇 𝜕𝑣 𝑇
and = 𝑣+𝑇 (7b)
𝜕𝑃 𝑇 𝜕𝑃 𝑇
𝜕𝑢 𝜕𝑠 𝑐
Because: 𝑐𝑣 =  = 𝑣 (8a) 𝜕ℎ 𝜕𝑠 𝑐𝑝
𝜕𝑇 𝑣 𝜕𝑇 𝑣 𝑇
Because: 𝑐𝑝 =  = (8b)
𝜕𝑠 𝜕𝑃 𝜕𝑢 𝜕𝑃 𝜕𝑇 𝑃 𝜕𝑇 𝑃 𝑇
Maxwell’s relation: =  = 𝑇 −𝑃 (9a) 𝜕𝑠 𝜕𝑣 𝜕ℎ 𝜕𝑣
𝜕𝑣 𝑇 𝜕𝑇 𝑣 𝜕𝑣 𝑇 𝜕𝑇 𝑣
Maxwell’s relation: =−  = 𝑣−𝑇 (9b)
𝜕𝑃 𝑇 𝜕𝑇 𝑃 𝜕𝑃 𝑇 𝜕𝑇 𝑃

𝜕𝑃
Substitute (9a) into (2a): 𝑑𝑢 = 𝑐𝑣 𝑑𝑇 + 𝑇 𝜕𝑇 𝑣
− 𝑃 𝑑𝑣 (10a)
𝜕𝑣
Substitute (9b) into (2b): 𝑑ℎ = 𝑐𝑝 𝑑𝑇 + 𝑣 − 𝑇 𝜕𝑇 𝑃
𝑑𝑃 (10b)
𝑇 𝑣 𝜕𝑃 𝑇 𝑃 𝜕𝑣
 𝑢2 − 𝑢1 = ‫ 𝑇׬‬2 𝑐𝑣 𝑑𝑇 + ‫ 𝑣׬‬2 𝑇 − 𝑃 𝑑𝑣 (11a)  ℎ2 − ℎ1 = ‫ 𝑇׬‬2 𝑐𝑝 𝑑𝑇 + ‫ 𝑃׬‬2 𝑣 − 𝑇 𝑑𝑃 (11b)
1 1 𝜕𝑇 𝑣 1 1 𝜕𝑇 𝑃
 6. Relations of thermodynamic functions Joule – Thomson coefficient

Calculation bases on volume:

𝑐𝑣 𝜕𝑃
𝑑𝑠 = 𝑑𝑇 + 𝑑𝑣 (1c)
𝑇 𝜕𝑇 𝑣
𝑻 𝒄 𝒗 𝝏𝑷
𝒔𝟐 − 𝒔𝟏 = ‫ 𝑻𝒅 𝒗𝑻 𝟐 𝑻׬‬+ ‫𝒗𝒅 𝑻𝝏 𝟐 𝒗׬‬ (2c)
𝟏 𝟏 𝒗

Calculation bases on pressure:

𝑐𝑃 𝜕𝑣
𝑑𝑠 = 𝑑𝑇 − 𝑑𝑃 (3c)
𝑇 𝜕𝑇 𝑃
𝑻𝟐 𝒄 𝑷 𝑷 𝝏𝒗
𝒔𝟐 − 𝒔𝟏 = ‫ 𝑻𝒅 𝑻 𝑻׬‬− ‫𝑷𝒅 𝑻𝝏 𝟐 𝑷׬‬ (4c)
𝟏 𝟏 𝑷

Either relation can be used to determine the entropy change. The proper
choice depends on the available data.

Joule – Thomson coefficient Joule – Thomson coefficient

A throttling process proceeds along a
The temperature behavior of a fluid during a throttling (h = constant) process is
constant-enthalpy line in the direction
described by the Joule-Thomson coefficient
of decreasing pressure, that is, from
right to left.
Therefore, the temperature of a fluid
increases during a throttling process
that takes place on the right-hand
side of the inversion line.
However, the fluid temperature
The Joule-Thomson coefficient decreases during a throttling process
represents the slope of h = constant that takes place on the left-hand side
lines on a T-P diagram. of the inversion line.
It is clear from this diagram that a
cooling effect cannot be achieved by
throttling unless the fluid is below its
maximum inversion temperature.
This presents a problem for
Constant-enthalpy lines of a substance substances whose maximum
The temperature of a fluid may increase,
on a T-P diagram. inversion temperature is well below
decrease, or remain constant during a The development of an h = constant room temperature.
throttling process. line on a P-T diagram.

Joule – Thomson coefficient

𝜕𝑣
𝑑ℎ = 𝑐𝑝 𝑑𝑇 + 𝑣 − 𝑇 𝑑𝑃
𝜕𝑇 𝑃

1 𝜕𝑣
𝐽𝑇 = − 𝑣−𝑇
𝑐𝑝 𝜕𝑇 𝑃

End

The temperature of an ideal gas

remains constant during a throttling
process since h = constant and T =
constant lines on a T-P diagram
coincide.
107
108