Thermodynamics

Chapter five

Entropy
By: Hailemariam Mulugeta
 ENTROPY
❖ One of the ideas involved in the concept of entropy is that nature tends from order to
disorder in isolated systems. This tells us that the right hand box of molecules happened
before the left.

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➢ The second law of thermodynamics often leads to expressions that involve inequalities.
➢ An irreversible (i.e., actual) heat engine is less efficient than a reversible one
operating between the same two thermal energy reservoirs.

➢ Likewise, an irreversible refrigerator or a heat pump has lower coefficient of performance

(COP) than a reversible one operating between the same temperature limits.
➢ Another important inequality that has a major consequences in thermodynamics is the
Clausius inequality.
➢ It was first stated by the German physicist R. J. E. Clausius (1822–1888), one of the

𝛿𝑄
founders of thermodynamics, and is expressed as: ‫𝑇 ׯ‬ ≤0
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➢ That is, the cyclic integral of 𝛿Q/T is always less than or equal to zero.

➢ Then the cyclic integral of dQ/T can be viewed as the sum of all these differential amounts of
heat transfer divided by the temperature at the boundary.

𝛿𝑄
‫𝑇 ׯ‬ ≤0

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➢ To demonstrate the validity of the Clausius inequality, consider
a system connected to a thermal energy reservoir at a constant
thermodynamic (i.e., absolute) temperature of 𝑇𝑅 through a
reversible cyclic device.
➢ The cyclic device receives heat 𝛿𝑄𝑅 from the reservoir and
supplies heat 𝛿𝑄 to the system whose temperature at that part of
the boundary is T (a variable) while producing work 𝛿𝑄𝑟𝑒𝑣 .
The system produces work 𝛿𝑄𝑠𝑦𝑠 as a result of this heat
transfer. Applying the energy balance to the combined system
identified by dashed lines yields: 𝛿𝑊𝑐 = 𝛿𝑄𝑅 - 𝑑𝐸𝑐
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➢ where 𝛿𝑊𝑐 is the total work of the combined system (𝛿𝑊𝑟𝑒𝑣 + 𝛿𝑊𝑠𝑦𝑠𝑡 ) and 𝑑𝐸𝑐 is the
change in the total energy of the combined system. Considering that the cyclic device is a
reversible one, we have
𝛿𝑄𝑅 𝛿𝑄
=
𝑇𝑅 𝑇
➢ Therefore, the quantity (dQ/T )int, rev must represent a property in the differential form

➢ Clausius realized in 1865 that he had discovered a new thermodynamic property, and he
chose to name this property entropy. It is designated S and is defined as:
𝛿𝑄
d S=( )𝑖𝑛𝑡,𝑟𝑒𝑣 . . . . . . . . . . (3) (KJ/k)
𝑇

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The entropy change of a system during a process can
be determined by integrating Eq. 3 between the initial
and the final states:

2 𝛿𝑄
∆S= 𝑆2 - 𝑆1 =‫׬‬1 ( )𝑖𝑛𝑡,𝑟𝑒𝑣
𝑇

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Example 1.A piston-cylinder device contains a liquid–vapor mixture of water at 27℃. During a
constant-pressure process, 750 kJ of heat is transferred to the water. As a result, part of the liquid
in the cylinder vaporizes. Determine the entropy change of the water during this process.
Required
Given
✓ ∆S=?
✓ Q=750KJ
✓ T= 27℃ = 27℃ +273 =300k
Solution

𝑄 750𝐾𝐽
∆S= =
𝑇 300𝐾

∆S=2.5 KJ/k

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 THE INCREASE OF ENTROPY PRINCIPLE
❖ Consider a cycle that is made up of two processes: process 1-2,
which is arbitrary (reversible or irreversible), and process 2-1,
which is internally reversible, as shown in this figure. From the
Clausius inequality;

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✓ The second integral in the previous relation is recognized as the entropy change 𝑆1 - 𝑆2 .
Therefore,

which can be rearranged as

It can also be expressed in differential form as

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➢ The entropy generated during a process is called entropy generation and is denoted by 𝑆𝑔𝑒𝑛 .

➢ Noting that the difference between the entropy change of a closed system and the entropy
transfer is equal to entropy generation,

➢ Note that the entropy generation 𝑆𝑔𝑒𝑛 is always a positive quantity or zero.

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❖ A system and its surroundings can be viewed as the two subsystems of an isolated system,
and the entropy change of this isolated system during a process is the sum of the entropy
changes of the system and its surroundings, which is equal to the entropy generation since
an isolated system involves no entropy transfer. That is,

❖ The increase of entropy principle can be summarized as follows:

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Example 2. A heat source at 800 K loses 2000 kJ of heat to a sink at (a) 500 K and (b) 750 K.
Determine which heat transfer process is more irreversible?
Since each reservoir undergoes an internally reversible, isothermal process.
(a) For the heat transfer process to a sink at 500 K:

➢ Therefore, 1.5 kJ/K of entropy is generated during this process. Noting that both reservoirs
have undergone internally reversible processes, the entire entropy generation took place in
the partition.
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(b) Repeating the calculations in part (a) for a sink temperature of 750 K, we obtain

➢ The total entropy change for the process in part (b) is smaller, and therefore it is less
irreversible. This is expected since the process in (b) involves a smaller temperature
difference and thus a smaller irreversibility.

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 ENTROPY CHANGE OF PURE SUBSTANCES
❖ Entropy is a property, and thus the value of entropy of a system is fixed once the state of the
system is fixed. Specifying two intensive independent properties fixes the state of a simple
compressible system, and thus the value of entropy, as well as the values of other properties
at that state.

❖ The value of entropy at a specified state is determined just like any other property. In the
compressed liquid and superheated vapor regions, it can be obtained directly from the tables
at the specified state. In the saturated mixture region, it is determined from

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✓ In the absence of compressed liquid data, the entropy of the
compressed liquid can be approximated by the entropy of
the saturated liquid at the given temperature:

✓ The entropy change of a specified mass m (a closed

system) during a process is simply

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 Example 3.A rigid tank contains 5 kg of refrigerant-134a initially at 20℃ and 140 kPa. The
refrigerant is now cooled while being stirred until its pressure drops to 100 kPa. Determine the
entropy change of the refrigerant during this process.

Solution The refrigerant in a rigid tank is cooled while being stirred. The entropy change of
the refrigerant is to be determined.
Assumptions The volume of the tank is constant and thus 𝑉1 = 𝑉2 .
Recognizing that the specific volume remains constant during this process, the properties of
the refrigerant at both states are
Table, A-13

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 Table, A-12

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 Property Relationships
 T2   v2 
s = Cv ln  + R ln   ds =
du CdT
=
 T1   v1  T T
2


dT P2
s2 − s1 = C p (T ) − R ln
1
T P1
k −1 k
 T2   v1  k −1
 v1   P2 
   =    T2
 
  P2
 = 


k
  =  
 T1   v2   T1   P1   v2   P1 
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 The T-ds relations:
Qint rev − Wint rev = dU
Qint rev = TdS Wint rev = PdV

TdS − PdV = dU
Tds = du + Pdv
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 Second T-ds (Gibbs) relationship
Recall that… h = u + Pv
Take the differential for both sides

dh = du + Pdv + vdP
Rearrange to find du Tds = dh − vdP
du = dh − Pdv − vdP dh vdP
Divide by T, .. ds = −
T T
Recall that…
Tds = du + Pdv
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Thus We have two equations for ds
du Pdv dh vdP
ds = + & ds = −
T T T T
Entropy Change of Liquids and Solids

Solids and liquids do not change specific volume appreciably with pressure. That
means that dv=0, then:-
0
du Pdv du
ds = + Thus For solids and liquids ds =
T T T
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Recall also that For solids and liquids, du = CdT
du CdT
 ds = =
T T
Only true
 T2 
Integrate to give…
s = C ln
T 

for solids
 1  and liquids!!
What if the process is isentropic? Hence, for solids and

T1 = T2
 T2  liquids, isentropic
s = 0,  C ln  = 0 processes are also
 T1  isothermal.
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Example 4.A 50-kg block of iron casting at 500 K is dropped in a large lake that is
at 285 K. The block reaches thermal equilibrium with lake water.
Assuming an average specific heat of 0.45 kJ/kg and ignore work done by or on the
system . for the iron, determine:
(a) The entropy change of the iron block,
(b) The entropy change of the water lake,
(c) the entropy generated during this process.
Given Required Solution
✓ 𝒎𝒊𝒓𝒐𝒏 =50 kg • ∆𝑆𝑖𝑟𝑜𝑛 =?
✓ 𝑻𝒊𝒓𝒐𝒏 =500K • ∆𝑆𝑙𝑎𝑘𝑒 =?
✓ 𝑻𝒍𝒂𝒌𝒆 =285K • 𝑆𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 =?
✓ C=0.45kJ/Kg
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 Solution
(a) The entropy change of the iron block,
 T2   285 
Siron = mC ln  = 50  0.45  ln  = −12.65 kj / K
 T1   500 
we need also to find Q coming out of the system.
Q − W = U Q − 0 = mC (T2 − T1 )
Q = 50  0.45(285 − 500) = −4838 kJ
(b) The entropy change of the water lake,
Q 4838
Slake = = = 16.97 kJ / K
Tlake 285

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 The Entropy Change of Ideal Gases, first relation
✓ The entropy change of an ideal gas can be obtained by substituting du = CvdT and
P /T= R/ into Tds relations:
d
Tds = du + pd  ds =
du Pd 
+ ds = Cv
dT
+R
T T T 

2
2


dT
By integrating  s2 − s1 = Cv (T ) +R ln
1
T 1

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➢ A second relation for the entropy change of an ideal gas for a process can
be obtained by substituting dh = CpdT and /T= R/P into Tds relations:

Tds = dh −vdp dh vdp dT dp

ds = − ds = C p −R
T T T p


dT P2
integrating s2 − s1 = C p (T ) − R ln
1
T P1

 T2   v2 
s = Cv ln  + R ln 
 T1   v1 
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 2
2  T2   v2 
s2 − s1 =  Cv (T )
dT
+R ln s = Cv ln  + R ln 
1
T 1  T1   v1 

2
 T2   P2 

dT P2
s2 − s1 = C p (T ) − R ln s = C p ln  − R ln 
1
T P1  T1   P1 

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 Constant specific heats (1st relation)
Recall  T2   v2 
s = Cv ln  + R ln 
 T1   v1 
For the isentropic case, S=0. Thus
R
 T2   v2   T2  R  v2   v1 
Cv ln  = − R ln 
Cv
ln  = − ln  = ln 
 T1   v1   T1  Cv  v1   v2 
R = C p − Cv  R / Cv = C p / Cv − 1 = k − 1
k −1
 T2   v1  Only applies to ideal gases, with constant

T 
=
v  
 1   2 specific heats

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 Constant specific heats (2𝑛𝑑 relation)
R
 T2   P2   T2  R  P2   P2 
s = C p ln  − R ln  = 0
Cp
ln  = ln  = ln 
 T1   P1   T1  C p  P1   P1 
Recall..… that k −1
R /C p =
k
k −1
 T2   P2  k
   =   Only applies to ideal gases, with constant specific heats

 T1   P1 

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 k −1 k −1
Since…  T2   v1   T2   P2  k
  =   &   =  
 T1   v2   T1   P1 

k −1
k −1
 v1   P2  k
  =  
 v2   P1 
k
 v1   P2 
Which can be simplified to…   =  
 v2   P1 
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 ISENTROPIC PROCESSES
❖ A process during which the entropy remains constant is called an isentropic process.

➢ During an internally reversible, adiabatic (isentropic)

process, the entropy remains constant.

➢ It should be recognized that a reversible adiabatic process

is necessarily isentropic ( 𝑆2 = 𝑆1 ), but an isentropic
process is not necessarily a reversible adiabatic process.

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 Isentropic Efficiency of Turbines
➢ Remember, if KE and PE are ignored in the energy balance equation, then the work is
w = h1 − h2
actual turbine work
Turbine =
isentropic turbine work
wa
Turbine =
ws

h1 − h2 a
Turbine =
h1 − h2 s
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 Isentropic Efficiency of Compressors
Isentropic compressor work ws
isen ,comp  =
Actual compressor work wa
Remember, if KE and PE are ignored in the
energy balance equation, then the work is

w = h2 − h1
h2 s − h1
isen ,comp 
h2 a − h1

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EXAMPLE-5

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EXAMPLE-6

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Example 7.
Steam enters an adiabatic turbine at 5 MPa and 450℃ and leaves at a pressure of
1.4 MPa. Determine the work output of the turbine per unit mass of steam if the
process is reversible.
Solution Steam is expanded in an adiabatic turbine to a specified pressure in a reversible
manner. The work output of the turbine is to be determined.

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❖ The inlet state is completely specified since two properties are given. But only one property
(pressure) is given at the final state, and we need one more property to fix it. The second
property comes from the observation that the process is reversible and adiabatic, and thus
isentropic. Therefore, 𝑆1 = 𝑆2 , and

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EXAMPLE 8

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EXAMPLE 9

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EXAMPLE -10

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EXAMPLE -11

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