THERMODYNAMICS

Chapter Eight Entropy

Chapter -8-
ENTROPY
Up to this point in our consideration of the second law of thermodynamics, we
have dealt only with thermodynamic cycles. Although this is a very useful approach,
we are often interested in the second-law
second law analysis of processes rather than cycles. In
1854, Clausius attempt to make possible the application of the second law in a
quantitative way (process)), by introducing a new property,, which he named entropy.
The objective of this chapter is to introduce entropy and show its use for
thermodynamic analysis.

8.11 The Inequality of Clausius

st step in our consideration of the property we call entropy,
The first entropy is to establish

the inequality of Clausius (1822–1888). It is expressed as: ∮  0.


Figure 8.1: Reversible and irreversible heat engines operating between the same TH and TL.
inequality consider first a reversible
To demonstrate the validity of the Clausius inequality,
(Carnot) heat engine cycle operating between reservoirs at TH and TL [Fig. (8.1)].( For
this cycle, the cyclic integral of the heat transfer, ∮ , is greater than zero:
zero
       0
From the definition of the absolute temperature scale:
scale
     

      
 0
     

Since TH and TL are constant, from the definition of the absolute temperature scale and
from the fact that this is a reversible cycle, it follows that:
that
   1 1  
         0
      
Thus, for all reversible or just internally reversible heat engine cycles, as such, it can
be reversed:




=0 ………..…
………..………………………...……………………………….
………………………………. (8.1)
(

Now consider an irreversible cyclic heat engine operating between the same TH and
TL as the reversible engine [Fig. (8.1)] and receiving the same quantity of heat QH. For
this cycle, the cyclic integral of the heat transfer, ∮ , is greater than zero:
zero
     !   0
From the second law we know that: ! " 
Since     for both the reversible and irreversible cycles, we conclude that:
that

-1- Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
   !  <  −   
  #$$
 ! >  
−  < 0, thus;
 
   ! 1 1   !
 = − =   −   ! = % − &<0
      
Thus, we conclude that for all irreversible heat engine cycles:


 <0 ………..………………………...………………………………. (8.2)
 !
Thus, for all cycles we can write:

 ≤0 …..……..………………………...………….………………………. (8.3)

which is the Clausius inequality. This inequality is the mathematical representation
of the second law and it valid for all possible cycles, including both reversible (or just
internally reversible) and irreversible heat engines and refrigerators.

8.2 Entropy—A Property of a System

Let a system (control mass) undergo a reversible process from state 1 to
state 2 along a path A, and let the cycle be completed along path B,
which is also reversible. Because this is a reversible cycle, we can write:
 ,  + 
∮
  = 0 = '+
  + ',
 
 ( *
Now consider another reversible cycle, which proceeds first along path C and is then
completed along path B. For this cycle we can write:
 ,  + 
∮
  = 0 = '+
  + ',
 
 - *
,  , 
Subtracting the second equation from the first .'+
  = '+
  /
( - 
Since ∮⁄ is the same for all reversible paths between states 1 and 2, we
conclude that this quantity is independent of the path and is a function of the end
states only; it is therefore a property. This property is called entropy (S), and the
entropy per unit mass is designated (s):

12 ≡
  (kJ/K) [For a reversible process only] ………...…..…………. (8.4)

The entropy change of a system during a process can be determined by integrating
Eq. (8.4) between the initial and the final states:
, 
∆2 = 2, − 2+ = '+
  (kJ/K) [For a reversible process only] ...………. (8.5)

where;
• 2, − 2+= entropy change of the system.
, 
• '+
  = entropy transfer with heat during a reversible process.


To perform this integration, we must know the relation between Q and T (often not
available). For the majority of cases we have to rely on tabulated data for entropy.

Since entropy is a property, the change in the entropy is the same for all processes,
both reversible and irreversible, between two states. Thus, from Eq. (8.5);
,

∆2 = 2, − 2+ ! = 2, − 2+  =  % &
+  
Therefore, for an irreversible process, ∆2 must be evaluated along an imaginary
internally reversible path between the actual end states.
-2- Dr. Mohammed A. Nima
 THERMODYNAMICS
Chapter Eight Entropy

We have actually defined the change in entropy instead of entropy itself. It is quite
adequate to give values of entropy relative to some arbitrarily selected reference
state, such as was done earlier when tabulating values of internal energy and
enthalpy. In each case, whatever reference value is chosen, it will cancel out when
the change of property is calculated between any two states.

8.3 Entropy Change in Internally Isothermal H.T. Reversible Processes

Recall that isothermal heat transfer processes are internally reversible,
reversible thus; the
entropy change can be determined by performing the integration in Eq. (8.5):
+ , 
'+ !56 
,  , 
∆2 = '+
 = '+

8 8
(kJ/K) ….……. (8.6)
(
 !56  8 !56 

• T0 = the constant temperature of the system.

• Q = the heat transfer for the internally reversible process.
• ∆2 can be positive (heat transfer to the system) or negative (heat transfer
from the system).
• In fact, losing heat is the only way the entropy of a system can be decreased.
• Equation (8.6) is particularly
rticularly useful for determining the entropy changes of thermal
energy reservoirs that can absorb or supply heat at a constant temperature.

8.4 Entropy Change of a Control Mass During an Irreversible Process

Consider a cycle that is made up of two processes: process 1-2, which is
irreversible, and process 2-1,
2 which is internally reversible, so that the
two processes form an irreversible cycle. From the Clausius inequality::
,  + 
.'+

  ) ',
  /"0
 
∮ <0
 ! !56 
The second integral is recognized as the entropy change 2+  2, (as it
internally reversible). Thus;
+ 2+ − 2, /
/ "
< 0, which can be rearranged as:
, 
.'+
 
!
, 
2, − 2+  > '+
 …………… …………...…………………..…………. (8.7)
……………...…………...…………………..…………. (
 !
• 2, − 2+= entropy change of the system.
, 
• '+
  = entropy transfer with heat during an irreversible process.
!
Combining Eqs.(8.5)
.5) and (8.7),
( gives;
, 
2, − 2+  7 '+ ………..…………… ………...…………………..…………. (8.8)
………..…………….………...…………………..…………. (

It can also be expressed in differential form as:
as

12 7 …….………..………………………...…………………..…………. (8.9)
(

, 
• The equality "=" holds for an internally reversible process .2,  2+ = '+
  /.
!56 
, 
• The inequality ">" holds for an irreversible process .2,  2+   '+
  /.
!
• This is one of the most important equations of thermodynamics,, which state that
entropy change of a closed system during an irreversible process is always greater
than the entropy transfer. That is some entropy is generated or created during an
entirely due to the presence of irreversibilities such as friction).
irreversible process (entirely

-3- Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
8.5 Entropy Generation and the Increase of Entropy Principle
The entropy generated during a process is called entropy generation and is
denoted by 295 , which is equal to the difference between the entropy change of a
closed system 2,  2+  and the entropy transfer '+ ⁄ . Equation
,
uation (8.8) can be
rewritten as equality by adding the entropy generation to the right-hand
hand side:
side
, 
∆2 2,  2+ '+ )2295 ……………....…………………..…......……….

…......………. (8.10)
(
Some important conclusions
onclusions can be drawn from Eq. (8.10):
• 295 0, for a reversible process.
process
2  2 
∵ 22  21 = '1
  2 2  21 '1

  )0
OPQ RST OPQ RST
• 295  0, for an irreversible process.
process
,  , 
∵ 2,  2+   '+
  2,  2+ '+
  ) 295
! !
• Entropy of a system can be increased by:
1) Transferring
ransferring heat to the system.
2) Having
aving an irreversible process.
For an adiabatic process, δQ = 0, the increase in entropy is due to irreversibilities
only such as friction.
• Since 295 is always positive,
positive then the only way in which the entropy of a system
can be decreased, is to transfer heat from the system ( < 0.

For an isolated (adiabatic)) system,  0, and Eq. (8.8) reduces to:

∆2!<= >6? 2,  2+  7 0 ………………......…..…….…………......………. ………......………. (8.11)
(
Equation (8.11)) states that entropy never decreases (we can generate but not destroy
entropy).. This is known as the increase of entropy principle.

 A system and its surroundings can be viewed as the two subsystems of

an isolated system (universe),
(universe) and from Eq. (8.10) the entropy change
of this isolated system (universe) during a process is:
, 
∆2@5! '+
  ) U295 V ∆2< ) ∆2<@
0
< @5! < <
@5! <
Since 295 7 0,, then the above equation can be written as:
295 ∆2@5! < ∆26=6> U∆2< < ) ∆2<@ V 7 0 …………... (8..12)

The equality "=" holds for reversible processes and the inequality ">" for
irreversible ones.

The entropy change of a system U∆2< < V can be negative during a process, but the
total entropy generation (∆2@5! < ) must be positive.

The increase of entropy principle can be summarized as follows:
 0 Irreversible process
295 A 0 Reversible process W ………..……....…………...
……...…. (8.13)
" 0 Impossible process
This relation serves as a criterion in determining whether a process is reversible,
irreversible, or impossible.
impossible

-4- Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
8.6 Entropy Change of Pure Substances
Entropy S (kJ/K) is an extensive property of a system, as the total entropy of a
system is equal to the sum of the entropies of the parts of the system U∆2@5! < =
∆2< < + ∆2<@  . Values of specific entropy s (kJ/kg K) are given in tables of
thermodynamic properties relative to an arbitrary reference state. In the steam tables
the entropy of saturated liquid at 0.01°C is given the value of zero. For many
refrigerants, the entropy of saturated liquid at −40°C is assigned the value of zero. In
the saturation region the entropy may be calculated using the quality as:
s = sf + x sfg (kJ/kg K) …………………………………………...…… (8.14)
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:
X@,[ ≅ X]@ (kJ/kg K) ...….…………………………………………...…… (8.15)
The entropy change of a specified mass m (a closed system) during a process is:
∆2 = ^ ∆X = ^X, − X+  (kJ/ K) ...….………………………………...….… (8.16)
When studying the second-law aspects of processes, entropy is used as a coordinate
on diagrams such as the T-s diagram and h-s diagram (Mollier diagram) [Fig. (8.2)].

(a) T-s diagram (b) h-s diagram

Figure 8.2: T-s and h-s diagrams for steam.

8.7 Isentropic Processes

The entropy of a fixed mass can be changed by (1) heat transfer and (2)
irreversibilities. Then it follows that the entropy of a fixed mass does not change
during a process that is internally reversible and adiabatic. A process during which the
entropy remains constant is called an isentropic process. From Eq. (8.10):
, 
∆2 = 2, − 2+ = '+ 
+ 295
Thus; 0 (adiabatic) 0 (reversible)
Isentropic process: ∆2 = 0 or 2, 2+ ...….….....….… (8.17)
Or in other words;
Isentropic process = adiabatic process + internally reversible process
It should be recognized that a reversible adiabatic process is necessarily isentropic
(2, 2+), but an isentropic process is not necessarily a reversible adiabatic process.
For example, the entropy increase of a substance during a process as a result of
irreversibilities may be offset by a decrease in entropy as a result of heat losses, which
result in an isentropic process.
-5- Dr. Mohammed A. Nima
 THERMODYNAMICS
Chapter Eight Entropy
8.8 Property Diagrams Involving Entropy
In the second-law analysis, it is very helpful to plot the processes on diagrams for
which one of the coordinates is entropy. The two diagrams commonly used in the
second-law analysis are the T-s and the h-s diagrams. Consider the defining equation
of entropy [Eq. (8.4), 12 ≡ ⁄ ]. It can be rearranged as:
!56   12 (kJ) ……………………….………(8.18)
The total heat transfer during an internally reversible process is
determined by integration to be:
,
!56  '+  12 (kJ) …….………………………. (8.19)
Therefore, we conclude that the area under the process curve on a T-S
diagram represents heat transfer during an internally (or totally)
reversible process. The area has no meaning for irreversible processes.
• An isentropic process on a T-s diagram is easily recognized as a vertical
line segment. This is expected since an isentropic process involves no
heat transfer, and therefore the area under the process path must be zero.

Carnot power cycle (heat engine) is represented graphically in Fig. (8.3) on

the T-S and the P-V diagrams. Now we will analyze the four reversible processes:
1. Reversible Isothermal Expansion (Process 1-2, TH = constant).
,  + ,
Eq. (8.5): ∆2 = 2, − 2+ = '+
 = '+  = 1Q2/ =  /
   
Thus;  =  2, − 2+ 
2. Reversible Adiabatic Expansion (Process 2-3, temperature drops from TH to TL).
` 
Eq. (8.5): ∆2 = 2` − 2, = ',
  =0 2` = 2, (isentropic process)

3. Reversible Isothermal Compression (Process 3-4, TL = constant).
a  + a
Eq. (8.5): ∆2 = 2a − 2` = '`
 = '`  = 3Q4/ =  /
 

Thus;  =  2a − 2` 
4. Reversible Adiabatic Compression (Process 4-1, temperature rises from TL to TH).
+ 
Eq. (8.5): ∆2 = 2+ − 2a = 'a
  = 0 2+ = 2a (isentropic process)

Then the efficiency of a Carnot engine (on the T-S diagram) can be written as:
PSQ,deQ   −  gRSg 1−2−3−4−1  l mn lmo  
b6c = f
= 
= gRSg 1−2−j−k−1 =  mn lmo 
= 1 −   ….…. (8.21)


Figure 8.3: T-S and P-V diagrams for a Carnot heat engine.
-6- Dr. Mohammed A. Nima
 THERMODYNAMICS
Chapter Eight Entropy
8.9 The Thermodynamic Property Relation
The entropy change for a process ∆2 can be evaluated by integrating ⁄ along
some imaginary internally reversible path between the actual end states p∆2 =
'⁄!56  q. When the temperature varies during the process ( ≠ sdPXQgPQ),
we have to have a relation between  and T to perform this integration.
Consider a closed stationary system (a fixed mass) containing a simple compressible
substance. The first law for an internally reversible process can be expressed as:
!56  − !56  ,=@6 = 1t, [!56  = 12 and !56  ,=@6 = u1v]
Thus;
12 = 1t + u1v (kJ)
…………………………………………...…… (8.22)
1X = 1e + u1T (kJ/kg)
The second relation is obtained by eliminating du from Eq. (8.22) by using the
definition of enthalpy (ℎ = e + uT):
h = u + Pv 1ℎ = 1e + u1T + T1x
.......…… (8.23)
Eq. (8.22) 1X = 1e + u1T
• Equations (8.22) and (8.23) are known as Gibbs equations.
• For a closed system, the electrical work and the shaft work are irreversible. Thus,
the boundary work p = u1vq, is the only type of work that may be considered
during an internally reversible process.
• Equations (8.22) and (8.23) are relations between thermodynamic properties and
the change in a property between two states is independent of the type of process.
Thus, they are valid for both reversible and irreversible processes and for both
closed and open systems.
• The entropy change during a process can be determined by integrating either of
these equations between the initial and the final states.

8.10 Entropy Change of Liquids and Solids

Liquids and solids can be approximated as incompressible substances. Thus,
1T ≅ 0 for liquids and solids, and Eq. (8.22) can be rearranged by solving for ds:
1X = 1e⁄ + u1T⁄ ≅ 1e⁄ + 0 ≅ y1⁄ ...….….....………….… (8.24)
since yz{ = y { = y and 1e = y1 for incompressible substances. Then the entropy
change during a process is determined by integration to be:
, ?
Liquids, solids: X, − X+ = '+ y ≅ y |P, ⁄+  (kJ/kg K) ….…......…… (8.25)

y is the specific heat for solid or liquid. Specific heats for various solids and liquids
are listed in Tables A.3, A.4. A relation for isentropic processes of liquids and solids
is obtained by setting the entropy change relation above equal to zero. It gives:
X, − X+ = y|P, ⁄+  = 0 , = + ….....……..….....………….… (8.26)
That is, the temperature of a truly incompressible substance remains constant during
an isentropic process (which explains why pumping liquid does not change the
temperature). Therefore, the isentropic process of an incompressible substance is also
isothermal.

-7- Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
8.11 The Entropy Change of Ideal Gases
Two very useful equations for computing the entropy change of an ideal gas can be
developed from Eqs. (8.22) and (8.23) by substituting 1e = y { 1 and 1ℎ = yz{ 1:
Eq. (8.22): 1X = 1e + u1T [for an ideal gas 1e = y { 1 and u⁄ = } ⁄T]
Thus;
?@ [? ? ?
1X = + =y {  +} ….....….....…......…………………….….… (8.27)
 
, ?
X, − X+ = '+ y {  + } |P
n  ………………………………...….…......…… (8.28)
o
Eq. (8.23): 1X = 1ℎ − T1u [for an ideal gas 1ℎ = yz{ 1 and T⁄ = } ⁄u]
Thus;
?c ?[ ? ?[
1X = − = yz{  − } [ ….....…….…......…………………….….… (8.29)
 
, ? [n
X, − X+ = '+ yz{  − } |P
[  ………………………………...….…......…… (8.30)
o
To integrate Eqs. (8.28) and (8.30), we must know the temperature dependence of the
specific heats. There are three possibilities to examine, which are presented next.

1. Constant Specific Heats (Approximate Analysis)

The simplest of which is the assumption of constant specific heat but with some loss
in accuracy, and ∆2 can be found by integrating Eqs. (8.28) and (8.30) directly to:

X, − X+ = y { |P
n  + } |P
n  (kJ/kg K) ………………...….…......…… (8.31)
o o
 [
X, − X+ = yz{ |P
n  − } |P
[n  (kJ/kg K) ………………...….…......…… (8.32)
o o
The values of constant y { and yz{ can be found by:
• Acquiring the constant values of y { & yz{ from Table (A.5) [less accurate values].
• Using the empirical equation for yz{ (general equation for various gases) as a
function of temperature from Table (A.6) [more accurate values]:
yz{ = sdPXQgPQ = y{ + y+ ~ + y, ~ , + y` ~ ` (kJ/kg K), ~ = > 9 S|TOP/1000
Then y { can be found as: y { = yz{ − }

2. Variable Specific Heats (Approximate Analysis)

The second possibility for the specific heat is to integrate the empirical equation of
yz{ in Table (A.6) (assuming large temperature change during the process), and ∆2
can be found by integrating Eq. (8.30) as [more accurate values]:
 ? [  +{{{ ? [
X, − X+ = ' n yz{ 
− } |P
[n  = ' n yz{ ~ × − } |P
[n 
o o o +{{{  o
n - ‚- ‚- n ‚-ƒ ƒ [n
= ' . 8 o n / 1~ − } |P
[ 
o o
Thus;
-n -ƒ n [
X, − X+ = .y{ |P~ + y+ ~ + ~, + ~`/ − } |P
[n  (kJ/kg K) .......…… (8.33)
, ` o o

where;
~+ = + S|TOP/1000 & ~, = , S|TOP/1000

-8- Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
3.. Variable Specific Heats (Exact Analysis)
The third possibility is to integrate the results of the calculations of statistical
thermodynamics from reference temperature T0 to any other temperature T and define
the standard entropy:
 ?
X{ = ' yz{
8 
The entropy change between any two states 1 and 2 is then given by:
[
X, − X+ = X,
{ { 
− X+ − } |P
n  [o
(kJ/kg K) ……………...….…......…… (8.34)
(
The values of X{ are tabulated in the single-entry
single (temperature) ideal-gas
gas table, as for
air in Table (A.7.1) or for other gases in Table (A.8) and Table (A.9) [for ˆˆˆ
X { values]. 
Equation (8.34)) would give the most accurate results.

8.12 T-s Diagram for an Ideal Gas

The constant property lines (P ( and v) on the T-s diagram for an Ideal gas are
shown in Fig. (8.4). We must know that that P2>P1, but v2<v1. As the pressure rises
the temperature rises and the volume decreases; conversely as the pressure and
temperature fall the volume increases.
Another observation is made from Fig. (8.4), that is:
slope of the isochoric lines > slope of the isobaric lines.
This cann be proved easily by applying Eqs. (8.22)
( and (8.23) as:
Eq. (8.22): 1X = 1e + u1T y { 1 ) u1T
0

W
„ 
„< -†8
slope of the isochoric lines
1X = 1ℎ − T1u yz{ 1  T1u
0
Eq. (8.23):
W
„ 
„< z -‡8
slope of the isobaric lines Figure 8.4: Ideal gas T-s diagram.
since yz{ > y {
WW
„
 W„
„< z
„<
.

8.13 Particular Process Undergoes by an Ideal Gas (Constant

Specific Heats) and Vapor.
Vapor
1. Reversible constant
onstant volume (or isochoric) process (V = constant):
The work done during an isochoric process for an ideal is;
'+ u1v = 0
,
1W2=

Applying the first law of thermodynamics to the process, gives:

t,  t+  )1W2
0
1Q2

1Q2= t
 ,  t+  ^e,  e+  ^y { ,  + 
The entropy change can be calculated by using Eq. (8.31)
( as follows:

X,  X+ y { |P
n  ) } |P
n 
o o
,
0
X,  X+ y { |P % &
+

-9- Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy

Reversible isochoric process for vapor
The work done during an isochoric process for vapor is;
'+ u1v = 0
,
1W2=

Applying first law of thermodynamics to the process, gives:

1Q2 t,  t+  )1W2 0
1Q2 t,  t+  ^e,  e+ 
e, and e+ can be evaluated from steam tables.
The entropy change can be calculated by using Eq. (8.16):
(
∆2 ^ ∆X ^X,  X+ 
X, and X+ can be evaluated from steam tables.

2. Reversible constant pressure (or isobaric) process (P = constant):

The work done during an isobaric process for ideal is;
'+ u1v = u v,  v+ 
,
1W2=

Applying the first law of thermodynamics to the process, gives:

1Q2 t,  t+  )1W2
1Q2 t,  t+  ) u, v,  u+ v+ 
t, ) u, v,   t+ ) u+ v+ 
1Q2 f,  f+  ^w,  w+ 
^yz{ ,  + 
The entropy change can be calculated by using Eq. (8.32)
( .32) as follows:
 [
X,  X+ yz{ |P
n   } |P
n 
o [o
,
0
X,  X+ yz{ |P % &
+

Reversible isobaric process for vapor

The work done during an isobaric process for vapor is;
'+ u1v = u v,  v+ 
,
1W2=

Applying first law of thermodynamics to the process, gives:

1Q2 t,  t+  )1W2 ^w,  w+ 
w, and w+ can be evaluated from steam tables.
The entropy change can be calculated by using Eq. (8.16):
(
∆2 ^ ∆X ^X,  X+ 
X, and X+ can be evaluated from steam tables.

- 10 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
3. Reversible constant temperature process (T = constant, isothermal) or hyperbolic
process (PV = constant):
constant
The work done during an isothermal process (or hyperbolic process) for ideal gas is:
Œ
= u+ v+ ln
n 
Œo
1W2

Applying the first law to the process with (T=constant), gives:

1Q2 t,  t+  )1W2
Œ
^y { ,  +  ) u+ v+ |P
n 
0
Œo
1Q2

Œn
u+ v+ ln
 ^ } + |P
n 
Œo
1Q2
o
The entropy change can be calculated by using Eq. (8.31)
( .31) as follows:

X, − XX+ y { |P
n  ) } |P
n  } |P
n 
o o o
0
1Q2 can be calculated as the area under the curve in the T-S diagram:
1Q2 + 2,  2+  ^ } + |P
n 
o

In vapor, the isothermal process and the hyperbolic process are not identical.
Therefore, we must analyze each one alone:
• Reversible isothermal process for vapor
Applying the first law of thermodynamics to the process, gives:
1Q2 t,  t+  )1W2
1W2 = 1Q2 ^e,  e+ 
e, and e+ can be evaluated from steam tables.
The entropy change can be calculated by using Eq. (8.16):
∆2 ^ ∆X ^X,  X+ 
X, and X+ can be evaluated from steam tables.
1Q2 can be calculated as the area under the curve in the T-S diagram:

1Q2 ^ + X,  X+ 

• Reversible hyperbolic process for vapor

The work done during a hyperbolic process for vapor is:
Œ
1W2 = u+ v+ ln
Œn 
o
Applying the first law of thermodynamics to the process, gives:
1Q2 t,  t+  )1W2
The entropy change can be calculated by using Eq. (8.16):
(
∆2 ^ ∆X ^X,  X+ 
X, and X+ can be evaluated from steam tables.

- 11 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
4. Reversible adiabatic (or
or isentropic) process (S = constant):
The
he isentropic relations for ideal gases are obtained by setting Eqs. (8.31) and
(8.32) equal to zero:
 [
Eq. (8.32): X, − X+ = 0 = yz{ |P
n   } |P
n 
o [o
Thus;
  [ n [  ⁄-‡8
|P
n  |P
n 
n
o -‡8 [o o [o
However,
} yz{  y { Ž  1
yz{ yz{ Ž
where k,, the ratio of the specific heats [Table (A.5)], is defined as:
-‡8
Ž -†8
……………...…………………………………… (8.35)
(
Thus; we can write:
n [ l+⁄

o

[n  ………...………………………
………...……………………….......…… (8.36)
o

Eq. (8.31): X,  X+ 0 y { |P
n  ) } |P
n 
o o
  n  ⁄-†8
|P
n  - |P
n 
o
o †8 o o n
Thus; we can write:
n l+

o
o
………..…...………………………………………….…......…… (8.37)
(
n
Finally we can substitute Eq. (8.37)
( into Eq. (8.36) to get:
[n 
[o

o ………..…...………………………………………….….......…… (8.38)
(
n
From this last expression [Eq. (8.38)],
( we note that for this process:
uT 
sdPXQgPQ ………..………………………………………….….......…… (8.39) (
We know that for any reversible process:
process
,
1W2= '+ u1v
For a process in which uv
v  = y, we have u = y/v  , where C is a constant. Thus;
2
= Wy
Ž)1 
Œ ‘’o y
Uv +l  v++l V
, , 1v
1W2= '+ u1v = y '+ 1Ž ,
Œ 1
From the process uv  = y, then C can be written as u+ v+ or as u, v
v,, and the work
done can be written as:
, u2 v2 u1 v1 ^}2 1 
1W2= '+ u1v = 1Ž 1Ž
(only for an Ideal gas) .......….…… (8.40)
The isentropic relations [(88.36), (8.37), (8.38), (8.39) and (8.40)], are strictly valid for:
• Ideal gas.
• Isentropic processes.
• Constant-specific-heat.

- 12 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy

Reversible adiabatic (or
or isentropic) process for vapor
Applying the first law of thermodynamics to the process, gives:
1Q2= t, − t+  +1W2
0

1W2 = ^e+ − e, 
X, = X+
e, and e+ can be evaluated from steam tables.

5. Reversible polytropic process (“”• = –—•˜™š•™):

The work done during a polytropic process for ideal gas is;
, u2 v2u1v1 ^}2 1
1W2= '+ u1v = 1P 1P
Applying
pplying first law of thermodynamics to the process, gives:
1Q2 t,  t+  )1W2
u2 v2 u1 v1
^e,  e+  )
1Q2
1P
^}2 1
) +l5 2 −
 1 

1Q2= ^y { 
,  +  )
1P
^
y {

 2  1   2  1 
-†8 5‚-‡8 l-†8 -‡8 l-†8 5
^

-†8 l-
1Q2= ^

+l5 +l5

 2  1  ^ y {
+l5 2  1 

-‡8 l-†8 5
- l5
1Q2= ^


+l5
1Q2= ^ y5{ 2  1  ….……………..……..……….…………....……
….…… ..…… (8.41)
(
where,
l5
y5{ y {
+l5 ….……………………………………………....……
….…… ..…… (8.42)
(
when n = 0 (P = constant)
constant y5{ yz{
when n = 1 (T = constant)
constant y5{ ∞
when n = ∞ (V = constant)
constant y5{ y {
when n = k (S = constant)
constant y5{ 0
The entropy change can be found by integrating Eq. (8.5),
( with the use of Eq. (8.41)
(
as follows:
,  , -œ8 ? , ? 
X, − X+ = '+
  '+ 
y5{ '+ 
y5{ |P
n  ….………….
….… (8.43)
!56  o
• Recall that for a polytropic process the following relations are valid:
œ‘o
5 n 5l+ n [n



[n
u+ v+5 u, v,5 ,
 ,
o o œ
[o o o [o
, ….……….
….…..…. (8.44)
n n

Figure 8.5:: Polytropic process for an ideal gas on P–v and T–s diagrams.
diagrams

- 13 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy

Reversible polytropic process for vapor
The work done during a polytropic process for vapor is;
, u2 v2u1v1
1W2= '+ u1v = 1P
Applying first law of thermodynamics to the process, gives:
1Q2 ^e,  e+  )1W2
e, and e+ can be evaluated from steam tables.
The entropy change can be calculated by using Eq. (8.16):
(
∆2 ^ ∆X ^X,  X+ 
X, and X+ can be evaluated from steam tables.

u, T+ 5
• Recall that for a polytropic process the following relations are valid:
u+ v+5
u, v, ,
5
% &
u+ T,

8.14 What Is Entropy?

Entropy can be viewed as a measure of molecular disorder, or molecular
randomness. As a system becomes more disordered, the positions of the molecules
become less predictable and the entropy increases. Thus, it is not surprising that the
entropy of a substance
ance is lowest in the solid phase and highest in the gas phase.
The entropy of a system (viewed microscopically) is related to the total number of
possible microscopic states of that system, called thermodynamic probability p, by the
Boltzmann relation, expressed
xpressed as:
S = k ln p
where k is the Boltzmann constant. Therefore, the entropy of a system increases
whenever the molecular randomness of a system increases. A pure crystalline
substance at absolute zero temperature is in perfect order, and therefore, the entropy
zero. This statement is
of a pure crystalline substance at absolute zero temperature is zero.
known as the third law of thermodynamics.
thermodynamics. The third law of thermodynamics
provides an absolute reference point for the determination of entropy. The entropy
determined relative to this point is called absolute entropy. With the increases of
entropy (disorder increase), less work can be extracted from the system because
disorganized energy does not create much useful effect, no matter how large it is.
However, we know that no matter how large their kinetic energies are, the gas
molecules do not rotate a paddle wheel inserted into the container and produce work.
This is because the gas molecules, and the energy they possess, are disorganized.
disorganized

- 14 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
Example (8-1)
A heat engine has a high temperature of 1200 K and a low temperature of 400 K.
What does the inequality of Clausius say about each of the four cases?
a)  = 6 kW,  = 4 kW b)  = 6 kW,  = 0 kW
c)  = 6 kW,  = 2 kW d)  = 6 kW,  = 6 kW
Solution

Example (8-2)
Consider a Carnot-cycle heat engine with water as the working fluid. The heat transfer
to the water occurs at 300°C, during which process the water changes from saturated
liquid to saturated vapor. The heat is rejected from the water at 40°C. Show the cycle
on a T–s diagram and find the quality of the water at the beginning and end of the heat
rejection process. Determine the net work output per kilogram of water and the cycle
thermal efficiency.
Solution

- 15 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy

Example (8-3)
Consider a Carnot-cycle heat pump with R-134a as the working fluid. Heat is rejected
from the R-134a at 40°C, during which process the R-134a changes from saturated
vapor to saturated liquid. The heat is transferred to the R-134a at 0°C.
a) Show the cycle on a T–s diagram.
b) Find the quality of the R-134a at the beginning and end of the isothermal heat
addition process at 0°C.
c) Determine the coefficient of performance for the cycle.

Solution

- 16 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy

Example (8-4)
One kilogram of ammonia in a piston/cylinder at 50°C, 1000 kPa is expanded in a
reversible isothermal process to 100 kPa. Find the work and heat transfer for this
process.
Solution

T=C

P1
P2
T1 = T2

- 17 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
Example (8-5)
A cylinder/piston contains water at 200 kPa, 200°C with a volume of 20 L. The piston
is moved slowly, compressing the water to a pressure of 800 kPa. The loading on the
piston is such that the product PV is a constant. Assuming that the room temperature
is 20°C, show that this process does not violate the second law.
Solution

- 18 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
Example (8-6)
A closed tank, V = 10 L, containing 5 kg of water initially at 25°C, is heated to 175°C
by a heat pump that is receiving heat from the surroundings at 25°C. Assume that this
process is reversible. Determine:
a) The heat transfer to the water.
b) The change in entropy of the tank.
c) Work input to the heat pump.
Solution

- 19 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy

1Q2

Example (8-7)
One kilogram of ammonia in a piston/cylinder at 50°C, 1000 kPa is expanded in a
reversible adiabatic process to 100 kPa. Find the work and heat transfer for this
process.
Solution

- 20 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy

P1
P2
T1

T2

Example (8-8)
A piston cylinder has 2.5 kg ammonia at 50 kPa, -20°C. Now it is heated to 50°C at
constant pressure through the bottom of the cylinder from external hot gas at 200°C.
Find the heat transfer to the ammonia and the total entropy generation.
Solution

- 21 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
Example (8-9)
A piston/cylinder contains 1 kg water at 150 kPa, 20°C. The piston is loaded so
pressure is linear in volume. Heat is added from a 600°C source until the water is at
1 MPa, 500°C. Find the heat transfer and the total change in entropy.
Solution

P2
P1

- 22 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
Example (8-10)
A device brings 2 kg of ammonia from 150 kPa, -20°C to 400 kPa, 80°C in a
polytropic process. Find the polytropic exponent, n, the work and the heat transfer.
Find the total entropy generated assuming a source at 100°C.
Solution

T2
P2
T1
P1

- 23 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
Example (8-11)
A piston/cylinder of total 1 kg steel contains 0.5 kg ammonia at 1600 kPa both masses
at 120°C. Some stops are placed so a minimum volume is 0.02 m3. Now the whole
system is cooled down to 30°C by heat transfer to the ambient at 20°C, and during the
process the steel keeps same temperature as the ammonia. Find the work, the heat
transfer and the total entropy generation in the process.
Solution

- 24 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy

P1a= P1

P1a= P1

Example (8-12)
Oxygen is heated from 300 to 1500 K. During this process the pressure dropped from
200 to 150 kPa. Calculate the change in entropy per kilogram, assuming:
a) Constant specific heat, value from Table A.5.
b) Constant specific heat, value at an intermediate temperature from Table A.6.
c) Variable specific heat, Table A.6.
d) Variable specific heat, Table A.8.

Solution

- 25 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy

Example (8-13)
A cylinder/piston contains 1 kg methane gas at 100 kPa, 20°C. The gas is compressed
reversibly to a pressure of 800 kPa. Calculate the work required, heat transfer, and the
entropy change if the process is:
a) Adiabatic b) Isothermal c) Polytropic, with exponent n = 1.15
Solution

Isentropic process
2 k
PV =Const.
S= Const.

1 W2 1

2 Isentropic
process
k
PV =Const.
1 S= Const.

- 26 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy

2 T=Const.
PV=Const.

1 W2 1
T=Const.
PV=Const.
2 1
1 Q2

2 n
PV =Const.

1 W2
1

2 n
PV =Const.

1 Q2
1

- 27 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
Example (8-14)
A rigid tank contains 2 kg of air at 200 kPa and ambient temperature, 20°C. An
electric current now passes through a resistor inside the tank. After a total of 100 kJ of
electrical work has crossed the boundary, the air temperature inside is 80°C. Is this
possible?
Solution

Air

V = Const.

- 28 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy
Example (8-15)
Consider a Carnot-cycle heat pump having 1 kg of nitrogen gas in a cylinder/piston
arrangement. This heat pump operates between reservoirs at 300 K and 400 K. At the
beginning of the low-temperature heat addition, the pressure is 1 MPa. During this
process the volume triples. Analyze each of the four processes and determine:
a) The pressure, volume, and temperature at each point.
b) The work and heat transfer for each process.
Solution

- 29 - Dr. Mohammed A. Nima

 THERMODYNAMICS
Chapter Eight Entropy

- 30 - Dr. Mohammed A. Nima