AE 231 Thermodynamics

Chapter 8
Entropy for a Control Mass

Instructor: Assoc. Prof. Dr. Sinan Eyi

 Clausius Inequality

δQ
∫ T
≤0 Clausius inequality

Clausius inequality is valid for both reversible and irreversible

cycles
Clausius inequality is valid for any cyclic device (heat engine,
refrigerator and heat pumps)
 Clausius Inequality

• Consider a reversible Carnot heat engine opearting between

reaseravoirs at TH and TL

∫ δQ = Q H − QL ≥ 0

• In all reversible heat engines

QH QL
=
TH TL Reversible Heat Engine

δQ QH QL
∫ T
= −
TH TL
=0

3
 Clausius Inequality

• In all reversible heat engines

∫ δQ ≥ 0
δQ
∫ T
=0

4
 Clausius Inequality

• Consider an irreversible heat engine operating between

reservoirs at TH and TL

Wirrev < Wrev

QH − QL ,irrev < QH − QL , rev

• Therefore

QL ,irrev > QL , rev

5
 Clausius Inequality
• For all reversible heat engines

∫ δQ = Q H − QL , rev ≥ 0
δQ QH QL , rev
∫ T
=
TH
−
TL
=0

• Since we know that QL,irrev > QL,rev

• We can show that for irreversible heat engines

∫ δQ = Q H − QL ,irrev ≥ 0
δQ QH QL ,irrev
∫ T
=
TH
−
TL
<0

6
 Clausius Inequality
• For all reversible an irreversible heat engines

∫ δQ ≥ 0
δQ
∫ T
≤0

7
 Clausius Inequality

• Consider a reversible Carnot refrigerator operating between

reservoirs at TH and TL

∫ δ Q = −Q H + QL < 0

• In all reversible reversible refrigerator

QH QL
=
TH TL Reversible Refrigerator

δQ QH QL
∫ T
=− +
TH TL
=0

8
 Clausius Inequality

• In all reversible refrigerators

∫ δQ ≤ 0
δQ
∫ T
=0

9
 Clausius Inequality

• Consider an irreversible refrigerator operating between

reservoirs at TH and TL

Wirrev > Wrev

QH ,irrev − QL > QH , rev − QL

• Therefore

QH ,irrev > QH , rev

10
 Clausius Inequality
• For all reversible refrigertors

∫ δ Q = −Q H , rev + QL ≤ 0
δQ QH , rev QL
∫ T
=−
TH
+
TL
=0

• Since we know that QH,irrev > QH,rev

• We can show that for irreversible refrigertors

∫ δ Q = −Q H ,irrev + QL ≤ 0
δQ QH ,irrev QL
∫ T
=−
TH
+
TL
<0

11
 Clausius Inequality
• For all reversible an irreversible refrigerators

∫ δQ ≤ 0
δQ
∫ T
≤0

12
 Clausius Inequality
For all reversible and irreversible cyclic devices

∫ δQ ≥ 0 for heat engines

∫ δQ ≤ 0 for refrigerators

δQ
∫ T
≤0 for heat engines and refrigerators

13
 Clausius Inequality

Steam Power Plant

Assume that the

δQ δQ  δQ  temperature remains
∫ T
= ∫ 
 T  boiler
+∫  
 T  condenser constant in boiler and
condenser
δQ 1
2
1 1 Q2
4
3 Q4
∫ = ∫δQ + ∫δQ = +
T T1 1 T3 3 T1 T3
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 Entropy a Property of a System

δQ δQ 
2
δQ 
1

∫ T
= 0 = ∫
1
T
 +∫ 
A 2  T

B

δQ 2
δQ 
δQ 
1

∫ T
= 0 = ∫
1
T
 +∫ 
C 2  T

B

δQ  δQ 
2 2

∫1  T  A ∫1  T C
=

δQ 
2

∫1  T  rev has the same value for all reversible paths

15
 Entropy a Property of a System

δQ 
2

∫1  T  rev is independent of path

δQ 
  is a state varible and it is called the entropy S
 T  rev

The change in entropy can be calculated as

δQ 
2
S 2 − S1 = ∫  
1  rev
T

16
Entropy a Pure System

s = (1 − x ) s f + xs g

s = s f + xs fg

17
Mollier Diagram

18
 Entropy Change in Reversible Processes

Carnot Cycle
δQ 
2
S 2 − S1 = ∫  
1  T  rev

2
1 In Carnot Cycle, the process from state 1
S 2 − S1 = ∫ δQ
TH 1 to 2 is an isothermal expansion.
In this process, heat transfer takes place in
1 Q2 QH
S 2 − S1 = = infinitesimally small temperature
TH TH
difference. Hence, the process is reversible.
19
 Entropy Change in Reversible Processes

δQ 
3
In Carnot cycle, from state 2 to state 3,
S3 − S 2 = ∫   the process is adiabatic expansion.
2  rev
T
Hence, there is no heat transfer. The
process is reversible.
S3 − S 2 = 0

δQ 
4
In Carnot Cycle, the process from state 3
S 4 − S3 = ∫   to 4 is an isothermal compression.
3  rev
T

Q4 QL
S 4 − S3 = 3
=−
TL TL

20
Entropy Change in Reversible Processes

Carnot heat engine Carnot refrigerator

Cycle on T-S diagram. Cycle on T-S diagram.

21
Thermodynamic Property Relations

We are going to derive two important thermodynamic

relations for a simple compressible substance .

TdS = dU + PdV (1)

TdS = dH − VdP (2)

22
 Thermodynamic Property Relations
The fist law of thermodynamics for closed systems
δ Q = dU + δ W
For a reversible process
δ Q = TdS
Boundary Work
δ W = pdV
Eq. (1) can be obtained by substituting dQ and dW in
to the first equation.
TdS = dU + pdV (1)
23
 Thermodynamic Property Relations
From the defition of enthalpy
H = U + PV
Differentiate both sides
dH = dU + pdV + VdP
or
dU = dH − pdV − VdP

Substitue dU in to Eq. (1)

TdS = dH − pdV − VdP + pdV

TdS = dH − VdP (2)

24
 Thermodynamic Property Relations

We can also show that

TdS dU PdV ⇒
= + Tds = du + Pdv
m m m

TdS dH VdP ⇒ Tds = dh − vdP

= −
m m m

TdS dU PdV
= + ⇒ Tds = du + Pdv
N N N

TdS dH VdP
= − ⇒ Tds = dh − vdP
N N N
25
 Entropy Changes of Ideal Gases
We have developed
Tds = du + Pdv
In ideal gases,
du = Cv 0 dT
where the subscript 0 denotes the specific heat of an ideal gas
Pv = RT ⇒ P = RT / v
Substitue the relations for du and p into the first equation

Tds = Cv 0 dT + RTdv / v

ds = Cv 0 dT / T + Rdv / v
26
 Entropy Changes of Ideal Gases
Intergrate the previous equation
2 2
dT dv
s2 − s1 = ∫ Cv 0 +∫R
1
T 1
v
In general, Cv0 is function of temperature
2
dT v2
s2 − s1 = ∫ Cv 0 + R ln
1
T v1
If we assume that Cv0 is constant
T2 v2
s2 − s1 = Cv 0 ln + R ln
T1 v1

27
 Entropy Changes of Ideal Gases
We have developed
Tds = dh − vdP
In ideal gases,
dh = C p 0 dT
where the subscript 0 denotes the specific heat of an ideal gas
Pv = RT ⇒ v = RT / p
Substitue the relations for du and p into the first equation

Tds = C p 0 dT − RTdP / P

ds = C P 0 dT / T − RdP / P
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 Entropy Changes of Ideal Gases
Intergrate the previous equation
2 2
dT dP
s2 − s1 = ∫ C P 0 −∫R
1
T 1
P
In general, Cp0 is function of temperature
2
dT P2
s2 − s1 = ∫ C p 0 − R ln
1
T P1
If we assume that Cp0 is constant

T2 P
s2 − s1 = C p 0 ln − R ln 2
T1 P1

29
 Standard Entropy
In general, Cp0 is function of temperature
2 T
dT P2 2
C p0 P2
s2 − s1 = ∫ C p 0 − R ln =∫ dT − R ln
1
T P1 T1 T P1
Lets define the standard entropy, sT0
T
C p0
s = ∫
0
T dT
T0
T
Standard entropy is tabulated in tables
T2 T2 T1
C p0 C p0 C p0
∫
T1
T
dT = ∫
T0
T
dT − ∫
T0
T
dT =sT02 − sT01

30
 Entropy Changes of Ideal Gases
Similarly, we can show that
2
dT v2
s2 − s1 = ∫ Cv 0 + Ru ln
1
T v1
2
dT P2
s2 − s1 = ∫ C p 0 − Ru ln
1
T P1
For the constant values of specific heats
T2 v2
s2 − s1 = Cv 0 ln + Ru ln
T1 v1
T2 P2
s2 − s1 = C p 0 ln − Ru ln
T1 P1
31
 Isentropic Process in Ideal Gases
In isentropic process, entropy is constnat

ds = Cv 0 dT / T + Rdv / v = 0

dT R dv C p 0 − Cv 0 dv dv
=− =− = − ( k − 1)
T Cv 0 v Cv 0 v v
Integrate above equation
2 2
dT dv
∫1 T = − ( k − 1) ∫1 v
( k −1)
T2 v2 ⇒ T2  v1  ⇒ T2 v2 (
k −1)
= T1v1(
k −1)
ln = − ( k − 1) ln = 
T1 v1 T1  v2 
32
 Isentropic Process in Ideal Gases
In isentropic process, entropy is constnat

ds = C p 0 dT / T − RdP / P = 0

dT R dP C p 0 − Cv 0 dP  1  dP  k − 1  dP
= = = 1 −  = 
T CP 0 P C p0 P  k P  k  P

Integrate above equation

dT  k − 1  dP
2 2

∫1 T =  k  ∫1 P
 1− k 
   1− k   1− k 
T  k − 1  P2 T2  P1   k 
⇒ TP    
ln 2 =   ln ⇒ =   k 
=TP  k 
T1  k  P1 T1  P2  2 2 1 1
33
 Isentropic Process in Ideal Gases
For isentropic process, we have derived

 1− k   1− k 
( k −1) ( k −1)
T2 v2 = T1v1 and T2 P2

 k 

=TP

 k 

1 1

By using the equation of state for ideal gas, above

equations can be written as:

P2 v2 k = Pv
1 1
k

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 Entropy Change of a Control Mass
During an Irreversible Process
From the Clausius equality of reversible cycles
δQ δQ 
2
δQ 
1

∫ T
= ∫
1
 ∫
+  =0
T  A 2  T B

δQ  δQ 
1 2

⇒ ∫2  T  B = − ∫1  T  A
From the Clausius inequality of irreversible cycles
δQ 2
δQ 
δQ 
1

∫ T
= ∫
1
 +∫   <0
T C 2  T  B
δQ  δQ  δQ  δQ 
2 2 2 2

∫1  T C − ∫1  T  A < 0 ⇒ ∫1  T C < ∫1  T  A

35
Entropy Change of a Control Mass
During an Irreversible Process
δQ  δQ 
2 2

∫1  T  A > ∫1  T C

δQ 
2 2 2

∫1  T  A = ∫1 ( dS ) A = ∫1 ( dS )C

δQ 
2 2

⇒ ∫ ( dS )
1
C
> ∫
1

T C

36
 Entropy Change of a Control Mass
During an Irreversible Process
In irreversible process,
δQ  δQ 
dS >   ⇒ S 2 − S1 >  
 T  irrev  T  irrev
In reversible process,
δQ  δQ 
dS =   ⇒ S 2 − S1 =  
 T  rev  T  rev
In general,

δQ δQ
dS ≥ ⇒ S 2 − S1 ≥
T T
37
 Entropy Generation
In irreversible process,
δQ
dS = + δ S gen
T
where δSgen is the entropy generation
δ S gen ≥ 0

In irreversible process,
δ Qirrev ⇒ δ Qirrev = TdS − T δ S gen (1)
dS = + δ S gen
T

38
 Entropy Generation
In closed systems, the first Law of thermodynamics for
irreversible process
δ Qirrev = dU + δ Wirrev (2)
Property relation is valid in irreversible process
TdS = dU + PdV ⇒ dU = TdS − PdV ( 3 )

Substitute Eqs. (1) and (3) into Eq. (2)

TdS − T δ S gen = TdS − PdV + δ Wirrev

⇒ δ Wirrev = PdV − T δ S gen

39
 Entropy Generation
• The work for an irreversible process is not
equal to ∫PdV
• The heat transfer for an irreversible
process is not equal to ∫TdS
• In irreversible process, it is difficult to
define the exact state.
• In general, irreversible process are shown
with dashed lines
40
 Principle of Increase of Entropy

The entropy change of an isolated system

is the sum of the entropy changes of its
components, and is never less than zero.

A system and its surroundings

The increase of form an isolated system.
entropy
principle 41
Some Remarks about Entropy
1. Processes can occur in a certain direction only,
not in any direction. A process must proceed in
the direction that complies with the increase of
entropy principle, that is, Sgen ≥ 0. A process that
violates this principle is impossible.
2. Entropy is a nonconserved property, and there is
no such thing as the conservation of entropy
principle. Entropy is conserved during the
idealized reversible processes only and
increases during all actual processes.
3. The performance of engineering systems is
degraded by the presence of irreversibilities,
and entropy generation is a measure of the
magnitudes of the irreversibilities during that
The entropy change of a process. It is also used to establish criteria for
system can be negative, but the performance of engineering devices.
the entropy generation
cannot.

42
 Entropy as a Rate Equation
Change of entropy with respect to time
∆S 1 ∆Q ∆S gen
= +
∆t T ∆t ∆t
If we have more than one heat sources
dS c .m 1ɺ ɺ
= ∑ Q + S gen
dt T

43
WHAT IS ENTROPY?
Boltzmann
relation

A pure crystalline substance at absolute zero temperature

is in perfect order, and its entropy is zero (the third law of
thermodynamics).

The level of molecular

disorder (entropy) of a
substance increases as it Disorganized energy does not create much
melts or evaporates. useful effect, no matter how large it is.
44
 The paddle-wheel work done on a gas increases the level
of disorder (entropy) of the gas, and thus energy is
degraded during this process.

In the absence of During a heat transfer

friction, raising a process, the net
weight by a rotating entropy increases.
shaft does not (The increase in the
create any disorder entropy of the cold
(entropy), and thus body more than
energy is not degraded offsets the decrease in
during this the entropy of
process. the hot body.)
45